Novel Energetic Phosphazene Polymer Binder Systems for Environmentally Friendly Rocket Motor Propellants

SERDP SEED Project WP-2141

Naval Air Warfare Center Weapons Division China Lake Naval Air Systems Command

Principal Investigator: Joseph Clubb

Synthesis and Formulations Branch (Code 474100D) Energetics Research Division

Naval Air Warfare Center Weapons Division 2400 E. Pilot Plant Rd. MS5202

China Lake, CA 93555-6107

Contributors: Dr. Peter Golding Dr. Alex Contini

Dr. Jeffrey A. Kay

May 26, 2015 Version 2.0

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Final Report 3. DATES COVERED (From - To)

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Novel Energetic Polyphosphazene Polymer Binder Systems for Environmentally Friendly Rocket Motor Propellants (U)

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Clubb, Joseph W. Kay, Jeffrey Golding, Peter

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WP-2141 5f. WORK UNIT NUMBER

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Energetics, Synthesis and Formulations (474100D) Naval Air Warfare Center Weapons Division 2400 E. Pilot Plant road MS5202 China Lake, Ca. 93555-6107

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SERDP

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DISTRIBUTION STATEMENT A. Approved for public release. 13. SUPPLEMENTARY NOTES (U) This report was prepared under contract to the Department of Defense Strategic Environmental Research and Development Program (SERDP). The publication of this report does not indicate endorsement by the Department of Defense, nor should the contents be construed as reflecting the official policy or position of the Department of Defense. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the Department of Defense14. ABSTRACT (U) Solid rocket motor propellants and explosives utilized within the DoD historically have been formulated to provide the most performance over all other operational requirements. Performance requirements needed to be met in order to defeat real and potential threats. As such, a high degree of risk to both the environmental and sensitivity hazards associated with the resulting weapon platforms was accepted. Fielded minimum signature rocket propellants incorporate burn rate catalysts (primarily lead compounds) and RDX; a nitramine, in order to achieve burning rate and performance objectives. It is a well-known fact that chronic or acute exposure to lead has serious health effects on immune, cardiovascular, and central nervous systems. RDX is also known to be acutely toxic to humans. Many studies have shown that accidental ingestion or inhalation has led to central nervous system disorders. (U) It is the author’s contention to introduce novel polymer systems with higher enthalpy functional groups, (nitrato and azido polyphosphazenes), towards the development of the next generation propellants and energetic materials. It is the hope that by introducing these novel polymer systems in conjunction with cutting edge energetic materials as replacements for toxic lead catalysts and RDX explosives, the next generation weapons systems will display a more acceptable environmental and toxicity impact and yet meet performance and sensitivity objectives. Herein are the results of analysis evaluating the levels of hydrofluoric acid and phosphorous compounds that are produced during thermal decomposition of these materials. This work aims to evaluate toxicity and smokiness of the combustion species extrapolated to a rocket motor environment. 15. SUBJECT TERMS Cross-linked binder, double-base propellant, insensitive munitions, minimum smoke rocket propellant, SERDP

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SAR

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222

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Joseph W. Clubba. REPORT

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CONTENTS

Executive Summary ........................................................................................................................ 1 Objective ......................................................................................................................................... 2 Background ..................................................................................................................................... 2 Materials and Methods .................................................................................................................... 3 

Materials ..................................................................................................................................... 3 Experimental Methods ................................................................................................................ 7 

Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) .......... 8 Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR) .......................... 9 

Results and Discussion ................................................................................................................. 10 Formulation Development ........................................................................................................ 11 Energetic Polyphosphazene Propellant Formulation Characterization ..................................... 20 Safety and Thermal Analysis .................................................................................................... 21 Burning Rate ............................................................................................................................. 24 Quantifying Hazardous Emissions From Propellants ............................................................... 25 Decomposition Results ............................................................................................................. 25 

Conclusions and Implications for Future Research ...................................................................... 36 Literature Cited ............................................................................................................................. 38 Appendixes:

A. Supporting Data ...............................................................................................................A-1 B. Propellant Formulation Mix Sheets .................................................................................B-1

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TABLES

1. Physical Properties Comparison of Azido and Nitrato Polyphosphazenes ............................. 4 2. Polynitratrophosphazene Propellant Formulations ................................................................ 11 3. Initial Cure Chemistry of Nitrato Based Polyphosphazene Propellants ................................ 11 4. Nitrato phosphazene Gumstock Cure Study – Individual Propellant Additives ................... 12 5. Nitrato Phosphazene Gumstock Cure Study – Addition of Cure Catalysts .......................... 12 6. Nitrato Phosphazene Gumstock Cure Study – Addition of Acid Catalyst ............................ 13 7. Nitrato Phosphazene Gumstock Cure Study – Isocyanate Curative and Strong Catalyst ..... 14 8. HycatTM Catalysts .................................................................................................................. 15 9. Nitrato Phosphazene Gumstock Cure Study – Epoxy Cure Novel Epoxy Catalysts ............ 15 10. Polynitrato Phosphazene Propellant Formulation Development ........................................... 17 11. Polyazido Phosphazene Propellant Formulation Development ............................................ 18 12. Polyazido Phosphazene Propellant Formulation Development ............................................ 20 13. Formulation Details ............................................................................................................... 21 14. Safety Response of PPZ Propellants ..................................................................................... 21 15. Thermal Properties of PPZ Propellants ................................................................................. 23 16. FTICR Analysis of Major Species Observed During Second Stage of

Decomposition During Isothermal Experiment on Formulation 1 ........................................ 30 17. FTICR Analysis of Major Species Observed During Third Stage of

Decomposition During Isothermal Experiment on Formulation 1 ........................................ 31 18. FTICR Analysis of Major Species Observed During Late Second and

Early Third Stages of Decomposition of Formulation 2 ....................................................... 35 

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FIGURES

1. Polyphosphazene Synthetic Derivatives.................................................................................. 3 2. Polyazido Phosphazene ........................................................................................................... 5 3. Polynitrato Phosphazene ......................................................................................................... 5 4. Molecular Structures of Major Ingredients used in the Propellant Formulations

Investigated in this Study ........................................................................................................ 6 5. Propellant Development Flow Diagram .................................................................................. 7 6. (a) Schematic Diagram of Simultaneous Thermogravimetric Modulated Beam Mass

Spectrometry (STMBMS) Instrument. (b) Schematic Diagram of Reaction Cell Illustrating a Typical Sample Configuration used in an STMBMS Experiment ..................... 9 

7. Chemical Microanalysis Laboratory with FTICR and Surface Analysis System ................. 10 8. Generalized Urethane Reaction ............................................................................................. 13 9. Differential Scanning Calorimetry of Nitrato-PPZ Formulation ........................................... 22 10. Differential Scanning Calorimetry of Azido-PPZ Formulation ............................................ 23 11. Burning Rate Comparison of PPZ Propellants ...................................................................... 24 12. Temperature Profile and Mass Loss for Thermal Ramp Experiment on Formulation 1 ....... 26 13. Mass Spectrum (m/z Versus Time) Acquired During Thermal Ramp Experiment on

Formulation 1. Decomposition proceeds in four stages ........................................................ 26 14. Temperature Profile and Mass Loss for Isothermal Experiment on Formulation 1 .............. 27 15. Mass Spectrum (m/z Versus Time) During Isothermal Experiment on Formulation 1.

Decomposition proceeds in three stages ................................................................................ 27 16. Mass Spectrum of Formulation 1 During First Stage of Isothermal Decomposition,

Plotted Against the Mass Spectrum of BTTN Under Identical Conditions .......................... 29 17. Mass Spectrum of Formulation 1 During Second Stage of Isothermal Decomposition,

Plotted Against the Sum of the Mass Spectra of FOX-7, Polynitrato Phosphazene, and PNO ................................................................................................................................ 29 

18. Mass Spectrum of Formulation 1 During Third Stage of Isothermal Decomposition, Plotted Against the Mass Spectrum of FOX-7 Under Identical Conditions ......................... 31 

19. Temperature Profile Mass Loss for Thermal Ramp Experiment on Formulation 2 .............. 32 20. Mass Spectrum (m/z vs. Time) Acquired During Thermal Ramp

Experiment on Formulation 2. Decomposition proceeds in four stage ................................. 33 21. Mass Spectrum of Formulation 2 During First Stage of Decomposition,

Plotted Against the Mass Spectrum of BTTN Under Identical Conditions .......................... 33 22. Mass Spectrum of Formulation 2 During Second Stage of Decomposition, Plotted

Against the Sum of the Mass Spectra of FOX-7, Polyazido Phosphazene, and BN-7. ......... 34 23. Mass Spectrum of Formulation 2 During Third Stage of Decomposition, Plotted

Against the Mass Spectrum of FOX-7 Under Identical Conditions. ..................................... 34 24. Mass Spectrum of Formulation 2 During Fourth Stage of Decomposition........................... 35 

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ACRONYMS

AWE Atomic Weapons Establishment BAMO 3,3′-bis(azidomethyl oxetane)-1,1′-binaphthalene oxetane BTTN 1,2,4-butanetriol trinitrate CL-20 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane cm centimeters COD cyclooctadiene DIP Direct Insertion Probe DMAC dimethylacetamide DMSO dimethyl sulfoxide DNSA dinitrosalicylic acid DOD Department of Defense DSC differential scanning calorimetry DTCS Dimensional Technology Chemical Systems Inc. EI Electronic Bombardment Ionization ESD electrostatic discharge FOX-7 1,1-diamino-2,2-dinitroethylene FOX-12 guanylurea dinitramide FTICR Fourier Transform Ion Cyclotron Resonance GAP glycidyl azide polymer HF hydrogen fluoride HMX octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine IM insensitive munitions lbf pounds of applied force mm millimeters NAWCWD Naval Air Warfare Center Weapons Division NMC New Materials Committee NMMO 3-nitratomethyl-3-methyl oxetane NMR nuclear magnetic resonance PAP polyazido phosphazene PCP polycaprolactone polymer PLIF Plasma Laser Induced Fluorescence PNO poly-3-nitrato oxetane

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PNP polynitrato phosphazene PPZ-E polyphosphazene, energetic RDX hexahydro-1,3,5-trinitro-1,3,5-triazine SEED SERDP Exploratory Development SERDP Strategic Environmental Research and Development Program SON Statement of Need STBMS Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry T-12 dibutyltin dilaurate TMETN trimethylol ethane trinitrate TMP 2-(hydroxymethyl)-2-ethylpropane-1,3-diol TPB triphenyl bismuth µm micrometers VTS Vacuum Thermal Stability

ACKNOWLEDGMENTS

In addition to the principal investigator, the following individuals conducted the work described in this report: Dr. Jeffrey Kay, Deneille Wiese-Smith, and Aaron Highley (Department of Energy, Sandia National Laboratories); Mr. David A. Turnbaugh and other members of the Synthesis and Formulations Branch, Energetics Research Division, Weapons and Energetics Department, Naval Air Warfare Center Weapons Division [NAWCWD]).

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EXECUTIVE SUMMARY

The Strategic Environmental Research and Development Program (SERDP) Statement of Need (SON) WPSON-11-02 called for a new “ENVIRONMENTALLY BENIGN, INSENSITIVE, CASTABLE, HIGH-PERFORMANCE, MINIMUM-SMOKE ROCKET PROPELLANT” that exhibited the performance requirements associated with the current minimum smoke, double-base propellant. The SON stated the formulation must not contain lead, ammonium perchlorate, or Cyclotrimethylenetrinitramine (RDX); furthermore, the SON stated that the formulation must demonstrate a reduction in toxicity compared to existing propellants while attempting to meet insensitive munition (IM) requirements.

This project was submitted as a SERDP Exploratory Development (SEED) towards that SON; however, this limited scope proposal was directed towards demonstrating a novel binder system using an energetically functionalized polyphosphazene backbone augmented with insensitive energetic fillers as the RDX replacement. The investigation was conducted to ascertain the viability of developing a new class of minimum signature propellants using these nitrato/azido functionalized polyphosphazenes that provide an energetically dense polymer backbone with significantly superior low-temperature properties compared to existing energetic polymers. In addition, the application of a polyphosphazene energetic (PPZ-E) polymer system with a polymer backbone that contains higher enthalpy functional groups (–ONO2, -N3) would allow reaction kinetics and heats of combustion to control burn-rate parameters rather than catalytic kinetics, thus eliminating the need for lead or any other metal burn-rate modifiers. Similarly, RDX nitramine content would also be replaced with significantly more thermodynamically stable energetics that respond more favorably to various stimuli. These energetics would include 1,1-Diamino-2,2-dinitroethylene (FOX-7), Guanylurea dinitramide (FOX-12), or similar ingredients stabilized by hydrogen bonding, overlapping Pi orbitals, and resonance structures.

Many attempts were made to achieve an appropriately cross-linked binder in order to test the project hypotheses, but the resulting formulations would not crosslink effectively. In order to perform the study of record, the investigators chose to use a co-polymer system using similar energetic polymers that would take part in traditional urethane chemistry to augment the polyphosphazene polymers. Although this approach is not ideal when studying the effects of the PPZ-E materials, it was successful in providing cross-linked propellants that subsequently were submitted for testing.

This SEED project constituted only a feasibility demonstration on whether the energetically functionalized polyphosphazene backbone would perform as a viable substitute for propellants without proving more toxic in nature relative to existing materials. Although the material showed no evolution of HF gases or problematic phosphoric species (up to the limits of the experimental detection system), it is noted that the analysis was never fully subjected to pressure and temperatures traditional to rocket motor firings. Secondly, recommendation was made to the manufacturer of record, Atomic Weapons Establishment (AWE), that in order to fully

2

demonstrate the polymer superiority, the cure issues would need to be addressed first and foremost. Note that AWE had already taken this task at hand (upon early notification and consultation with NAWCWD) and successfully claimed a hydroxylated functional polyphosphazene polymer for more traditional cure chemistries.

OBJECTIVE

The Strategic Environmental Research and Development Program (SERDP) Statement of Need (SON) WPSON-11-02 called for new “green chemistry” approaches to the preparation of precursors to important energetic ingredients, such as nitrogenous poly-cycles. The overall main objective of this SEED project was to develop and demonstrate the next generation propellants to be used in weapons systems that display a more acceptable environmental impact and toxicity by introducing cutting edge energetic materials as replacements for toxic lead catalysts and the nitrogenous poly-cyclic RDX explosive.

BACKGROUND

Solid rocket motor propellants and explosives used within the Department of Defense (DOD) historically have been formulated to provide the most performance over all other operational requirements. Performance requirements needed to be met in order to defeat real and potential threats. As such, a high degree of risk to both the environmental and sensitivity hazards associated with the resulting weapon platforms was accepted. Often, reaction products resulting from the ingredients selected to provide the needed energy were overlooked with respect to toxicity and associated sensitivity. In order to achieve burning rate and performance objectives, the current fielded minimum signature rocket propellants need to incorporate metal catalysts (primarily lead compounds) and the nitramine RDX. As is well known, chronic or acute exposure to lead has serious health effects on immune, cardiovascular, and central nervous systems. Health statistics argue that lead poisoning is the leading environmental illness among children in the United States. Currently, there is significant concern to the levels of lead found in imported Chinese toys for children.

RDX is also known to be acutely toxic to humans. Many studies have shown that accidental ingestion or inhalation has led to central nervous system disorders. Although the combustion products of RDX may be rendered benign, the manufacturing, formulation, packing, cleanup, and de-milling processes continue to create the possibility of accidental ingestion. Additionally, RDX is known to react violently to excessive stimuli resulting in loss of life or property when initiated directly or indirectly.

These risks associated with the current fielded solid rocket fuel are no longer viewed as acceptable with regards to environmental and sensitivity concerns. It is in the interest of the DOD to make a concerted effort to protect our warfighters, support personnel, and the public.

3

MATERIALS AND METHODS

MATERIALS

This section describes the various energetic and polymer materials used throughout this study. A generalized description of the synthetic routes along with material properties are noted for the primary polyphosphazene polymers of study. Additionally, brief descriptions of the methods used to characterize the materials, propellant development, and thermal analysis are provided.

These phosphazene polymers are not exclusively novel in application. The generic “backbone” consists of alternating phosphorus and nitrogen atoms with functional groups attached to the phosphorus. These compounds have been used in variety of applications in energy storage, medical, and high-performance polymers. Such uses include permeable cell membranes, bio-medical polymers, and even flame retardants.1-4 The polydichlorophosphazene (Figure 1) is, in fact, unstable in oxygen or moisture environments, and its derivatives of halogenated phosphazenes with chlorine atoms do not lend themselves to be an improvement in toxicity because of their high chlorine content that may form copious amounts of hydrochloric acid. Polyphosphazene derivatives, however, can be achieved by functionalizing the phosphorus backbone with other moieties to tailor in polymer properties as needed, as is the case with the energetic polyphosphazenes proposed in this program.

FIGURE 1. Polyphosphazene Synthetic Derivatives.

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Linear polyphosphazenes functionalized with energetic side-chains were developed by the Atomic Weapons Establishment in the United Kingdom as early as 2001. These polyphosphazenes provided a novel category of ‘energetic’ binders and were developed to address the shortcomings of existing energetic binders. AWE was successful in developing a series of both homo- and mixed-substituent polymers with varying degrees of functionality, percentage, and type of substitution, along with carbon backbone lengths.5,6 AWE conducted a series of synthesis experiments to observe the effect on resulting physical properties in order to tailor the energy-density, heats of combustion, oxygen balance, and/or reduction of glass transition (Tg), relative to the commonly available carbon based energetic polymers such as glycidyl azide (GAP), polyNIMMO, or BAMO/NMMO (BN-7). AWE showed an expanded range of high energy-density materials and low Tg values. Densities and resulting energy-densities were greater with the nitrato functionalized materials (as would be expected), whilst the lower Tg values were noted with the azido functionalized materials (Table 1). Although each set of materials varied in enhanced properties, in general, the materials were an improvement over existing energetic polymers.

TABLE 1. Physical Properties Comparison of Azido and Nitrato Polyphosphazenes.

Polyphosphazene Decomposition Energy (DSC)

(J g-1)

Density (g cm-3)

Energy Density (J cm-3)

Tg (°C)

Homo Polymers bis (C3 di-ONO2) 2690 1.69 4550 -32.5 bis (C4 di-ONO2) 2880 1.65 4750 -23.8 bis (C6 di-ONO2) 2760 1.45 4002 -35.2 bis (C3 N3) 1825 1.35 2465 -73.5 bis (C4 N3) 1665 1.16 1930 -99.5 bis (C6 N3) 1830 1.29 2360 -64.0 Mixed Substituent (C3 di-ONO2/TFE 72% ES) 2020 1.65 3333 -25.0 (C4 di-ONO2/TFE 68% ES) 2370 1.60 3792 -13.0 (C6 di-ONO2/TFE 70% ES) 2430 1.49 3694 -55.0 (C6 mono-N3/TFE 65% ES) 1187 1.23 1460 N/A (C6 di-N3/TFE 44% ES) 1496 1.43 2139 -60.0

TFE = 2,2,2-Trifluoroethan-1-oxy %ES = Percentage of energetic side chain present

Ideally, the homopolymer PPZ-E materials would be selected for characterization and study, as they hold the best in energy-density and low temperature properties. As a proof of concept (and availability), however, the specific PPZ-E materials provided by AWE were both of the azido and nitrato mixed substituent moieties. Those selected materials were chosen based on the best available trade-off balance between energy-density and low-temperature glass transition (Tg) properties. The two PPZ-E materials provided were 4-azidobutan-1-oxy/2,2,2-trifluoroethan-1-oxy phosphazene, ES ca 65%± 3%, and 5,6-dinitratohexan-1-oxy/2,2,2-trifluoroethan1-oxy phosphazene ES ca 68%± 3% (Figures 2 and 3). The substituted carbon backbone side chain and ES percentages were determined by nuclear magnetic spectroscopy (NMR) with an error of ± 3%.

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Although they are not exactly the same as those noted in Table 1, the physical properties are expected to be very similar to those that were measured prior. Due to the level of mixed moieties, the underlying goal of this work is to determine whether hazardous fluorine- or phosphorus-containing compounds are emitted during decomposition of new polyphosphazene-containing propellant formulations developed at NAWCWD China Lake.7

FIGURE 2. Polyazido Phosphazene.

FIGURE 3. Polynitrato Phosphazene.

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In order to study the effect of the PPZ-E materials, a variety of other materials were used during the propellant development. These materials consisted of the energetic oxidizer 2,2-Diamino-1,1-dinitroethylene (better known as FOX-7), 1,2,4- Butanetriol trinitrate (BTTN), and a set of co-polymers, Poly-3 nitrato (PNO) or a mixture of Poly 3,3 -Bisazidomethyl and 3-Nitratomethyl-3- methyl (BAMO/NMMO) oxetanes. These materials were chosen to best match the energetic functionality based on the type of PPZ-E (azido or nitrato) used. Major ingredients in the two formulations are shown in Figure 4.

(C) (D)

(E) (F)

FIGURE 4. Molecular Structures of Major Ingredients used in the Propellant Formulations Investigated in this Study.

(a) 1,1-Diamino-2,2- dinitroethylene (FOX-7). (b) 1,2,4-butanetriol trinitrate(BTTN).

(c) Poly-3-nitratooxetane (PNO). (d) 3,3-bisazidomethyl and 3-nitratomethyl-3-methyl oxetanes (BAMO/NMMO or BN-7).

(e) glycidyl azide polymer. (f) 1,1,1-tris (hydroxymethyl)propane (TMP).

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EXPERIMENTAL METHODS

The formulation development followed traditional methods of propellant development, which is an iterative process beginning at ingredient characterization and 5-gram hand mix scale (Figure 5). Basic safety and thermal properties are evaluated to determine whether the corresponding formulations were safe enough to handle and scale (Figure 5). This would go through a New Materials Committee (NMC) requesting scale-up approval of up to 4X to 5X the original scale. The propellant would then be scaled to 25-gram mechanical mix that would then allow enough material to run window bomb combustion burning rates and thermal degradation studies to evaluate combustion species (specifically any hydrofluoric or phosphoric corrosive species).

PROPELLANT DEVELOPMENT PROTOCOL

PH

AS

E I

PH

AS

E I

I

PH

AS

E I

II

FIGURE 5. Propellant Development Flow Diagram.

Methods used to quantify potential hazardous species evolved during combustion include Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) and Fourier-Transform Ion-Cyclotron-Resonance (FTICR) mass spectrometry. The STMBMS was used to investigate the thermal decomposition chemistry of the propellant formulations at small

DATA REVIEW PROPERTIES ACCEPTABLE

SCALE-UP FORMULATIONS

(1-PINT)

INGREDIENTS

CHARACTERIZATION

THERMOCHEMICAL

CALCULATIONS SMALL-SCALE

FORMULATIONS (5 GRAM)

SCALE-UP FORMULATIONS

(25-50 GRAM)

PROPELLANT

CHARACTERIZATION

DATA REVIEW PROPERTIES ACCEPTABLE

HEAT OF FORMATION DENSITY THERMAL STABILITY MORPHOLOGY (SOLIDS)

SAFE TO SCALE UP

SAFE TO SCALE UP

PROPELLANT

CHARACTERIZATION

CURE CHEMISTIRY SAFETY TESTS - IMPACT - FRICTION - ESD

COMPATIBILITY - VTS - DSC/TGA

SPECIFIC IMPULSE DENSITY IMPULSE COMBUSTION - EXIT PRODUCTS - FLAME TEMPERATURE TRADE-OFFS

YES

SAFETY WINDOW BOMB THERMAL DECOMPOSITION

YES

YES NO

SAFE TO SCALE UP

REFORMULATE

PROCESSABILITY - EOMV

BURNING RATE - STRAND - WINDOW BOMB - ABCC MOTOR

SAFETY/THERMAL - IMPACT/FRICTION/ESD - VTS/DSC/TGA MECHANICAL PROPERTY THERMAL COOKOFF - ARC/SBAT - VCCT/SCO BOMB SHOCK TESTING - IHE/NOL

PROCEED TO 1-GALLON SCALE

YES

YES

NO

REFORMULATE

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scales. References 7 through 10 describe the experimental methods and numerical algorithms used to examine and characterize the reactions of energetic materials at elevated temperatures. The experimental methods use the following: (1) the STMBMS instrument and associated numerical data analysis algorithms to investigate the thermal decomposition processes of compounds and mixtures, and (2) an FTICR mass spectrometer to aid in identifying molecular fragments and decomposition products.

Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS)

The basic features of a thermal decomposition experiment using the STMBMS instrument are illustrated in Figure 6. A small sample of propellant (2 to 10 mg) is placed in an alumina reaction cell (free volume of 0.227 cm3), which is sealed with a cap assembly containing either a disk of 25 µm thick gold foil with a small pinhole (2.5 to 50 μm) at its center or a ceramic cup with a 30 to 1,000 µm orifice at its center. The reaction cell is heated in a controlled manner using a thermocouple and programmable thermal controller to measure and control the temperature of the cell. As the reaction cell is heated, volatile compounds are generated due to sublimation/evaporation and thermal decomposition of the sample. These vapors fill the free volume of the reaction cell, causing it to pressurize. The pressurized vapor flows through the orifice and expands into vacuum, forming a molecular beam. The resulting molecular beam is directed into a quadrupole mass spectrometer, where the relative abundance of each constituent is measured. The reaction cell sits atop a microbalance, which records the change in mass of the sample as it is heated and undergoes sublimation/evaporation and decomposition. Together, these measurements allow identification and determination of the time-and temperature-dependent rate of formation of each gaseous species that evolves from the heated sample.

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(a) (b)

FIGURE 6. (a) Schematic Diagram of Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) Instrument. (b) Schematic Diagram of Reaction Cell Illustrating a

Typical Sample Configuration used in an STMBMS Experiment.

Heating of a sample in the reaction cell of the STMBMS causes evolution of gas-phase products, which form a molecular beam. This molecular beam is directed to a mass spectrometer, where species are ionized and detected using a quadrupole mass spectrometer. The mass of the sample is simultaneously recorded on a microbalance, which allows absolute determination of gas evolution rates for each species.

The pressure of gases within the reaction cell is determined by the diameter of the orifice and the experimental conditions. The gas pressure within the cell is determined by a steady-state balance between the rate of gas formation from the sample and the rate of exhaust through the orifice. Smaller orifices will produce higher pressures for a given gas formation rate from the sample. For compounds in two-phase quasi-equilibrium, the pressure is determined by the temperature of the reaction cell and the properties of the compounds. In this case, a smaller orifice results in less of the gas exiting the reaction cell. The reaction conditions are controlled by altering the sample size, temperature, heating rate, orifice diameter, and volume of the reaction cell.

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR)

A Bruker Daltonics APEX-II FTICR mass spectrometer is used to unambiguously identify compounds that evolve from the samples (Figure 7). It is a high mass resolution (m/Δm >100,000) and mass accuracy (<1 ppm) ion-trap-based mass spectrometer. The high mass accuracy of this instrument allows unambiguous determination of the empirical formula for each mass-value observed in a mass spectrum. Operation of this instrument under conditions similar

10

to the STMBMS instrument allows chemical analysis results from the FTICR to be matched to the temporally correlated product distribution spectra obtained with the STMBMS instrument.

FIGURE 7. Chemical Microanalysis Laboratory with FTICR and Surface Analysis System.

A basic chemical analysis thermal decomposition experiment using the FTICR mass spectrometer is straightforward. A 1 mm ID X 9 mm L quartz tube (internal volume: 0.0071 cm3) is loaded with ca. 1 mg of material and the open end of the tube can be either left open or “necked-down” with a methane-oxygen flame to produce an exit aperture as small as 5 μm in diameter. The resulting reaction cell is mounted in the heated tip of a direct insertion probe (DIP) whose temperature is controlled by a programmable temperature controller (Omega model CN3000). The DIP probe is inserted into the FTICR mass spectrometer with the tip of the probe positioned at the entrance of an electron-bombardment ionization (EI) source. Neutral gaseous species exiting the quartz reactor are ionized in the EI source and extracted into the FTICR mass spectrometer for analysis.

RESULTS AND DISCUSSION

The following sections provide description and discussion of various efforts undertaken to develop and characterize the resulting propellant formulations with respect to curability, safety and thermal analysis, burning rate, and thermal decomposition. These studies are traditional in early development of novel propellants and required to view acceptability with respect to basic propellant metrics. The thermal decomposition analysis is both crucial in observing and quantifying decomposition species as well as in answering critical questions regarding the evolution of toxic and/or smoky species of the phosphazene containing propellants.

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FORMULATION DEVELOPMENT

Original formulation development began at the 5-gram scale first with the polynitrato phosphazene (C6) material, and ingredients found to be the most promising needed to meet the performance/IM balance (Table 2). These ingredients were chosen based on thermochemical calculations and previously demonstrated properties in alternate development. Six separate formulations were initially formulated using alternate cure chemistry developed by Golding et. al.11 This chemistry followed an epoxy ring opening using 1,2,7,8 – diepoxyoctane and eliminated the need for isocyanates.

Unfortunately, the cure chemistry showed no actual rubber development, as all formulations remained uncured (Table 3). The investigators took a step back and began an in-depth cure and compatibility study on gumstocks with the nitrato phosphazene and selectively introducing the remaining proposed propellant ingredients.

TABLE 2. Polynitratrophosphazene Propellant Formulations.

Formulation Ingredient Weight % 1 FOX-7 78 BTTN Polynitrato phosphazene 10.935 NC 0.906 2 CL20 78 BTTN Polyazido phosphazene 23.0 NC 0.772 3 CL20/FOX12 78 BTTN Polynitrato phosphazene 10.935 NC 0.906

TABLE 3. Initial Cure Chemistry of Nitrato Based Polyphosphazene Propellants.

Mix# Oxidizer Plasticizer Cure/Catalyst Result HM-PPZ-7-1-0-1 FOX-7 BTTN diepoxyoctane/TPB Did not cure HM-PPZ-7-1-0-1A FOX-7 BTTN diepoxyoctane Did not cure HM-PPZ-7-2-0-1 CL-20 BTTN diepoxyoctane/TPB Did not cure HM-PPZ-7-2-0-1A CL-20 BTTN diepoxyoctane Did not cure HM-PPZ-7-2-1-1 CL-20/FOX-12 BTTN diepoxyoctane/TPB Did not cure HM-PPZ-7-2-1-1A CL-20/FOX-12 BTTN diepoxyoctane Did not cure

A series of gumstocks were prepared with varying additives, cure ratios, cure types, and cure catalyst to observe the cure chemistry. The first matrix looked to isolate the individual

12

ingredients (without solids loading) used in the matrix propellants (Table 4) to observe which material(s) may have contributed to the lack of ability in producing a rubbery matrix. Observation of this effort appeared to show that a gelled material would take shape (cure chemistry) when using only the nitrato PPZ with the curative. Better cohesiveness was observed when adding the nitrocellulose (used as a co-polymer energetic additive), yet the material remained deformable. When the BTTN was added, the gumstock would not cure.

TABLE 4. Nitrato phosphazene Gumstock Cure Study – Individual Propellant Additives.

Mix# Curative Catalyst Additive Result GS-PPZ-1-1-1 diepoxyoctane none None Gelled but very soft GS-PPZ-1-1-2 diepoxyoctane none nitrocellulose Gelled better cohesiveness, no shapeGS-PPZ-1-1-3 diepoxyoctane none BTTN Did not cure, remained fluid

Consecutive matrices (Table 5 and 6) were made to observe effect of cure catalyst using traditional catalysts triphenyl bismuth (TPB), dibutyltin dilaurate (T-12), and mild acid dinitrosalicylic (DNSA). The additive addition study followed the same process as that used in the first gumstock study. A relatively mild catalyst, TPB is used to delay the reaction over time and increasing pot-life capability. But it has a very poor selectivity, which allows for potentially numerous undesirable side reactions if conditions are not controlled. Whereas T-12 is a strong organo-metallic catalyst that is very selective in reactivity but is sometimes found to be too aggressive and not allowing for sufficient pot-life of the formulated material.

Results showed that the traditional catalysts had little effect on improving the curability over the original formulation when mixing with just the PPZ polymer and nitrocellulose additive and no effect when including the BTTN plasticizer; the gumstock did not cure at all (Table 5). Some improvement, however, was noted when adding mild acid catalyst in attempts to improve activation of the reactive sites (Table 6). This improvement appeared to be enhanced when the level of DNSA acid was increased to 0.50% by weight. The gumstocks with just PPZ polymer and/or nitrocellulose appeared to gel even better but, again, no effect was noted when adding the BTTN plasticizer. Although the acid catalyst appeared to improve the curability, the level needed towards this improvement would become prohibitive in formulation development because of the decrease in other ingredients needed to meet other metrics.

TABLE 5. Nitrato Phosphazene Gumstock Cure Study – Addition of Cure Catalysts.

Mix# Curative Catalyst Additive Result GS-PPZ-1-1-1 diepoxyoctane TPB None Gelled but very soft and deformable GS-PPZ-1-1-2 diepoxyoctane TPB nitrocellulose Similar to iteration 1-1-1 GS-PPZ-1-1-3 diepoxyoctane TPB BTTN Never really gelled GS-PPZ-1-1-1 diepoxyoctane T-12 None Gelled but very soft and deformable GS-PPZ-1-1-2 diepoxyoctane T-12 nitrocellulose Did not completely cure GS-PPZ-1-1-3 diepoxyoctane T-12 BTTN Did not cure still fluid

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TABLE 6. Nitrato Phosphazene Gumstock Cure Study – Addition of Acid Catalyst.

Mix# Curative Catalyst Additive Result

GS-PPZ-1-1-1 diepoxyoctane DNSA (0.15%) none Appears to gel better than TPB or

T-12, yet still soft

GS-PPZ-1-1-2 diepoxyoctane DNSA (0.15%) nitrocellulose Appeared to gel better than TPB or

T-12, yet still soft

GS-PPZ-1-1-3 diepoxyoctane DNSA (0.15%) BTTN Did not cure still fluid

GS-PPZ-1-1-1 diepoxyoctane DNSA (0.50%) none

Increase in DNSA content to 0.5wt.% improved gelling but again not complete

GS-PPZ-1-1-2 diepoxyoctane DNSA (0.50%) nitrocellulose Nearly complete gel, no removable

of uncured material, still too soft

GS-PPZ-1-1-3 diepoxyoctane DNSA (0.50%) BTTN Still wet, did not gel

A third matrix was conducted to test the effect of replacing the non-traditional cure system

of epoxy opening with a traditional polyurethane cure system using di and polyisocyanate curatives (Figure 8). The nitrato-PPZ material is noted to have approximately 5% of free hydroxyls that could potentially be available to take part in hydroxyl-isocyanate cure reactions forming the alkoxide bonds, thus polymerizing the PPZ material.

FIGURE 8. Generalized Urethane Reaction.

Results from this matrix were dramatic starting with the initial gumstock where the PPZ polymer was reacted with N-100 polyisocyanate and catalyzed with strong metal catalyst T-12. The reaction was nearly instantaneous producing a foamed up urethane of the nitrato-PPZ. Although successful in finally producing a cured material, the reaction was orders of magnitude too fast resulting in a hard crosslinked honeycombed foam material rather than a rubbery solid. The second iteration was conducted at a lower cure temperature reducing the cure temperature from 160°F to 120°F. The result was similar. Finally, a cured reaction was successful with the addition of the BTTN; yet again, the reaction time was too fast. The honeycombing of the material was thought to possibly be caused by the reaction sequence of isocyanate with water found in the ambient air through air oxidation producing urea units and carbon dioxide gas. It is conceivable that during the nearly instantaneous reaction, air oxidation reactions competed with urethane catalysis resulting in CO2 evolution blowing up the material as it cured creating a honeycomb like texture.

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Modifications were made in order to slow the reaction time down and reduce competing

reactions. The T-12 was replaced with the less selective catalyst TPB in order to slow the reaction time down, reaction temperature maintained at a lower level of 120°F, and reaction was controlled under both vacuum (to remove air oxidation) or small positive pressure of N2 gas.

Although these experiments (GS-PPZ-1-2-3A and B) retarded the reaction time, it appeared also to retard the overall extent of the reaction and resulted in incomplete cure. A switch to a less reactive isocyanate, dicyclohexylmethane diisocyanate (H12MDI) with only two reactive functionalities was investigated using the strong T-12 catalyst. This approach was successful in retarding the cure chemistry but also resulted in incomplete cures (Table 7).

TABLE 7. Nitrato Phosphazene Gumstock Cure Study – Isocyanate Curative and Strong Catalyst.

Mix# Curative Catalyst Additive Result

GS-PPZ-E-1-2-1 N-100 T-12 none Nearly instantaneous cure, formed a polyurethane like foam, reduce temperature to 120°F

GS-PPZ-E-1-2-2 N-100 T-12 nitrocellulose Same result as iteration 1-2-1 GS-PPZ-E-1-2-3 N-100 T-12 BTTN Finally cured sample, way too fast

GS-PPZ-E-1-2-3A N-100 TPB BTTN/NC Gel time retarded, yet sample not fully cured beyond top ½ layer

GS-PPZ-E-1-2-3B N-3200 TPB BTTN/NC Same result as 1-2-3A GS-PPZ-E-1-2-4 HMDI TPB BTTN/NC Sample did not completely gel GS-PPZ-E-1-2-4 HMDI T-12 BTTN/NC Sample did not completely gel GS-PPZ-E-1-2-5 HMDI T-12 BTTN/NC Sample did not completely gel GS-PPZ-E-1-2-6 HMDI T-12 BTTN/NC Sample did not completely gel

A decision was made to re-investigate the original epoxide reaction but introduce some novel, aggressive, epoxy catalysts. Four experimental HycatTM organo-phosphoric and metal-carboxylate catalysts were purchased from Dimension Technology Chemical Systems Incorporated (DTCS) in efforts to accelerate the epoxy reaction with the nitrato-PPZ. It was proposed that these compounds may help to catalyze the ester linkage of the phosphazenes similarly to other carbonate esters known to react well using these catalytic compounds. The four separate catalysts were 2,000s; 3,000s; SM3; and AO-4. Typical properties of each of these catalysts are noted in Table 8.

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TABLE 8. HycatTM Catalysts.

*HycatTM catalyst Type Catalyst Complex Active Additive

2000S Metal-carboxylate Oxo-trinuclear chromate Chromium III

3000S Metal-carboxylate Oxo-trinuclear chromate Chromium III

SM3 Metal-carboxylate Modified trinuclear chromate Chromium III

AO-4 Organo-metallic Organo-phosphorous phosphorous * All catalysts are proprietary and protected no empirical or chemical formula was provided.

Results of this matrix were mixed (Table 9). It appeared the nitrato-PPZ would gel with each of the HycatTM catalysts except the AO-4, but again soft and deformable. Some improvement was noted when adding BTTN to the gumstock mixture and using the 2000S catalyst. It became apparent that the addition of plasticizer to the nitrato-PPZ polymer negatively hindered the extent of curing. A low-level experimental study into the effect of reactions using alternate plasticizers was conducted to observe whether the reaction rate hindrance was due specifically to the BTTN plasticizer or just a plasticizer effect overall. Gumstocks of the following alternate plasticizers, trimethylol ethane trinitrate (TMETN) and N-butyl-n-(2-nitroxyethyl) nitramine (ButylNena) were mixed with the nitrato-PPZ and the HycatTM 2000S as the catalyst. The resulting materials were observed to try and differentiate the level, or extent, of the reaction and/or no reaction. In the case of both of the nitrate ester plasticizers (BTTN and TMETN), the gumstocks did not cure and some improvement was noted when replacing with the ButylNena plasticizer. This gumstock appeared to be gelling, however, the level of cure was still insufficient.

TABLE 9. Nitrato Phosphazene Gumstock Cure Study – Epoxy Cure Novel Epoxy Catalysts.

Mix# Curative Catalyst Additive Result GS-PPZE-1-1 diepoxyoctane 2000S none Gelled, soft, flexible, weak

GS-PPZE-1-2 diepoxyoctane 3000S none Similar to iteration 1-1, tackier,deformable

GS-PPZE-1-3 diepoxyoctane SM3 none Similar to other iterations, tacky, deformable

GS-PPZE-1-4 diepoxyoctane AO-4 none Sample did not cure, still runs GS-PPZE-1-1-1 diepoxyoctane 2000S BTTN Did not completely cure GS-PPZE-1-1-2 diepoxyoctane 2000S TMETN Still flowed, not gelling enough GS-PPZ-1-1-3 diepoxyoctane 2000S ButylNena Gelled but wet, not completely cure

It became apparent that the cure chemistry was not straight forward and would require a more in-depth analysis and experimentation and/or modification of the polyphosphazene materials in order to achieve a rubbery propellant material. Although a cured material was achievable when using traditional urethane cure techniques, this was only accomplished with polyfunctional isocyanates (N-100 and 3200) and an aggressive metal catalyst, T-12. Even then,

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control of the time and extent of the reaction was not achievable; the resulting material behaved more like urethane foam than a rubbery propellant.

In order to move forward with the amount of material remaining, the investigators chose to approach the curing problem by using a co-polymer system of oxetanes that is similar to the energetic functionality type of the phosphazenes and reacted with traditional cure/catalysts for urethane rubber formation. In addition, a widely used industry short chain triol polymer, 2-(hydroxymethyl)-2-ethylpropane-1,3-diol (TMP) was used to improve crosslinking ability The nitrato-PPZ was co-formulated with equal parts of poly-3-nitrato oxetane (PNO), the azido-PPZ was co-formulated with equal parts of glycidyl azide polymer (GAP) or 3,3-bisazidomethyl - 3-nitratomethyl-3-methyl oxetane (BAMO/NMMO or BN-7).

This study first began with the nitrato-PPZ material and a variety of co-polymer additives that include the PNO, TMP, and a polycaprolactone (PCP) of higher molecular weight. The addition of the PCP was to improve the rubbery quality by increasing polymer chain length. Several formulation variable changes were experimented on in attempts to provide a rubbery material consistent with propellant formulations. All formulations used a polyfunctional isocyanate with the moderate cure catalyst TPB. The energetic oxidizer in all formulations was FOX-7.

The first iteration looked to use a direct 50:50 mixture of the nitrato-PPZ with the PNO at a mass loading of 10.0 wt%. The plasticizer used was a less volatile form of nitrate ester, TMETN, as a replacement for BTTN, which was observed to consistently interfere with the cure chemistry. Subsequent iterations built off of the observed results from the iteration prior with formulation variables adjusted as seen fit.

Propellant iteration 7-2-3 proved to be too soft and was adjusted to increase crosslink density using the short chain TMP. Iterations 4 through 6 showed significant improvement in crosslink density but to the extreme opposite effect resulting in good shore A hardness values but a brittle material with very little elasticity. The curative addition was corrected in iteration 7 but the results were still too brittle. It was decided that a third co-polymer (PCP6000) would be added in attempts to connect together a network of longer chain pre-polymers in efforts to improve elasticity. Additionally, a return to the more energetic BTTN was instituted to improve performance losses caused by adding a third polymer to the formulation.

The formulation variable changes resulted in a reverse of the cure chemistry where the resulting propellant now was too soft. After three iterations where the NCO/OH ratio was increased to improve crosslink density, a suitable rubbery material was produced with a good shore A measurement depicting reasonable stress conditions with the increased elasticity (formulation SERDP-PPZ-7-2-8-3). This formulation was selected as a good candidate for further characterization. Results of this study are noted in Table 10.

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TABLE 10. Polynitrato Phosphazene Propellant Formulation Development.

Mix# Co-polymer % Plasticizer N-3200 NCO/OH Result PNO TMP PCP

SERDP-PPZ-7-2-3 10.0 --- --- TMETN 1.20 gelled but too soft

SERDP-PPZ-7-2-4 10.0 0.20 --- TMETN 1.20 gelled better than iteration 1, shore A of 63 too brittle

SERDP-PPZ-7-2-5 10.0 1.0 --- TMETN 1.20 cured well, very hard but not brittle no elasticity shore A 66

SERDP-PPZ-7-2-6 10.0 0.70 --- TMETN 1.20 cured, no improvement on

rubber quality, noted too much curative was added

SERDP-PPZ-7-2-7 10.0 0.70 --- TMETN 1.20 curative reduced, material gelled but still too brittle

SERDP-PPZ-7-2-8 10.0 0.50 2.50 BTTN 1.15 gelled fairly well, little too hard, continue with candidate

SERDP-PPZ-7-2-8-1 9.0 0.20 3.50 BTTN 1.20 gelled soft and deformable, reduce plasticizer

SERDP-PPZ-7-2-8-2 9.0 0.20 3.50 BTTN 1.60 gelled better but still too soft

SERDP-PPZ-7-2-8-3 8.25 0.50 3.00 BTTN 1.20 cured well, homogeneous, no internal voids, shore A 53-58

SERDP-PPZ-7-2-8-4 8.25 0.50 3.00 BTTN TMETN 1.20 cured well, but internal

voiding, return to iteration 3 *Candidate selected highlighted in red.

The azido-PPZ material also did not follow traditional urethane cure chemistry, and the formulation development of the azido-PPZ proved to be nearly as difficult as the cure chemistry of the nitrato-PPZ but under an opposite direction. Unlike the nitrato-PPZ, where the difficulty in the cure-chemistry was actually achieving an effective cure of a material with rubbery consistency, the azido-PPZ difficulty was in controlling the level, or extent, of the cure reaction to avoid brittle like material. Bala et.al. 12 had shown that the azido functionalized polyphosphazene was curable by use of maleimides, in this instance, methylene (p--phenyl bismaleimide).

The reaction sequence followed a 1,2,3-triazoline ring formation resulting in a rubbery gel material. This reaction would occur in the presence, (or lack of) solvents, tetrahydrofuran, methylene chloride, or chloroform, and required no catalysts. Note was taken, however, that the azido-PPZ tended to homopolymerize in the lack of solvent presence providing a potential obstacle in controlling the extent and rate of reaction. As such, the material was shipped and stored in methylene chloride until formulation work began.

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Initially, formulators attempted to take advantage of this self-curing effect by using solvent assisted mixing and allow the azido-PPZ to provide the crosslinking during the propellant curing process. This was first attempted at room temperature and held overnight, followed by placement into an oven at the initial temperature of 95°F and ramped to 140°F for further curing. Although we were successful in allowing the self-curing to occur, the resulting formulations (iterations 8-2-0 and 8-2-1) showed severe signs of outgassing, probably due to level of entrapped solvent still present (Table 11).

Next, the cure agent methylene (p-phenyl bismaleimide) was used in order to improve the cure chemistry. Lessons learned from the formulation development of the nitrato-PPZ were used by including glycidyl azide polymer (GAP), an energetic co-polymer in attempts to improve both crosslink and rubbery capability. Although the formulations did show improvement in cure chemistry (lack of doming or outgassing), the materials were all too brittle for practical purposes. Subsequently, a series of iterations were performed to address the brittleness by varying the maleimide cure agent, co-polymer (GAP), and plasticizer additives. None of these changes (iterations 3 through 6) resulted in a rubbery material suitable for further characterization.

TABLE 11. Polyazido Phosphazene Propellant Formulation Development.

Mix# PPZ %

Co-polymer % Plasticizer Cure

agent Result GAP

polyol GAP triol

SERDP-PPZ-8-2-0 20.0 15.0 --- --- self-cure Cured but domed and

voided, unable to vacuum cast

SERDP-PPZ-8-2-1 20.0 15.0 --- GAP self-cure Ambient cured overnight

but soft, signs of outgassing again

SERDP-PPZ-8-2-2 20.0 10.0 --- GAP maleimide 5%

Cured well at ambient, tough but brittle, adjust

plasticizer

SERDP-PPZ-8-2-3 10.0 10.0 --- TMETN maleimide 2%

Sample cured again at ambient but extremely

brittle

SERDP-PPZ-8-2-4 10.0 10.0 --- BTTN maleimide 2%

Sample cured at ambient but soft, post cure at

140,no effect

SERDP-PPZ-8-2-5 15.0 --- --- BTTN maleimide 3.75%

Boiled off solvent to fast, remake mix

SERDP-PPZ-8-2-5-1 15.0 --- --- BTTN maleimide

3.75%

Cured again brittle at ambient, increase GAP

plasticizer

SERDP-PPZ-8-2-6 20.0 20.0 --- GAP maleimide 5%

Cured better than prior mixes, very tough and

hard, use isocyanate with BN-7

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A decision was made to incorporate polyfunctional isocyanate, N-3200, as a co-curative

with the bismaleimide in order to improve extent of reaction and the rubber properties of the propellant. The isocyanate would provide traditional urethane cure chemistry with the hydroxyl functionalities of the BN-7. This should allow a knitting of the end-cap hydroxyls of the monomer BN-7, slowing, or decreasing, the extent of the crosslinking and minimize the brittleness of the propellant.

The ratios of the cure agents were varied from high to lower and alternating between the two types of curatives in order to observe the effects on rubbery properties provided by competing cure reactions. In iterations 8-2-7 through 8-2-9, GAP was still the co-polymer of use, and the ratio varied from 100% of the isocyanate to mixtures of high and low levels of maleimide curative. The results of these experiments shown below in Table 12 revealed only improvement when the isocyanate was in high content with respect to the bismaleimide. A better rubber was formed but severe outgassing was observed. A decision was made to switch to BN-7, a larger molecular weight diol, whereas the GAP material is a shorter chain triol. It appeared that the maleimide may have the greater effect on the crosslink density, so it followed that use of less maleimide and lower functional polymer (BN-7) would respond more favorably in reducing crosslink density and creating a longer chain polymer matrix. The initial formulation (iteration 8-3-1) began with higher amount of maleimide than the isocyanate to test whether the maleimide has greater effect on crosslink density and, indeed, the result was a hard brittle material. The cure ratio was switched reducing the amount of maleimide and increasing that of isocyanate. This resulted in a nice rubbery material with shore A value of 30 (iterations 8-3-2 and 8-3-2-1). The maleimide was increase by 0.25 wt%, and the material remained rubbery with a measured shore A increase to a very acceptable 53. The maleimide was increased again to 1.00 wt% looking to optimize the curative ratio with propellant properties. This increase had a negative effect as the propellant again became brittle. As such, iteration 8-3-2-2 was chosen as the best candidate to move forward for further characterization.

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TABLE 12. Polyazido Phosphazene Propellant Formulation Development.

Mix# PPZ %

Co-polymer

% Plasticize

r Cure agent

Cure % Result

BN-7 GAP

SERDP-PPZ-8-2-7 10.0 --- 10.0 BTTN N-3200 1.00 Cured poorly, splits, cracks,

poor integrity, use both cures

SERDP-PPZ-8-2-8 10.0 --- 10.0 BTTN N-3200

maleimide1.687 Cured hard and brittle, adjust

maleimide curative, remake 1.500

SERDP-PPZ-8-2-9 10.0 --- 10.0 BTTN N-3200

maleimide

1.687 Cured better and rubbery, severe outgassing, switch to

BN-7 0.500

SERDP-PPZ-8-3-1 10.0 10.0 --- BTTN N-3200

maleimide

0.695 Cured hard and brittle, reduced level of maleimide

curative 1.500

SERDP-PPZ-8-3-2 10.0 10.0 --- BTTN N-3200

maleimide

0.695 Cured fairly nice rubber, less internal voids or cracks,

repeat 0.500

SERDP-PPZ-8-3-2-1

10.0 10.0 --- BTTN N-3200

maleimide

0.695 Good rubber, slightly better than prior iteration, shore A

of 30 0.500

SERDP-PPZ-8-3-2-2

10.0 10.0 --- BTTN N-3200

maleimide

0.695 Good cure shore A of 53, submit for combustion

analysis 0.750

SERDP-PPZ-8-3-3 10.0 10.0 --- BTTN N-3200

maleimide

0.695 Cured too brittle, too much maleimide, revert prior

iteration 1.00

*Candidate selected highlighted in red.

The formulation development required a great deal of experimentation and improvisation; however, the effort was successful in providing two candidates, one each from the nitrato and azido PPZ materials, for further study. Each candidate was submitted for characterization in safety and thermal properties along with burning rate study. Additionally, a sample of each was provided to Sandia National Laboratories for conducting decomposition studies and look at gaseous species for potential toxic and smoky species.

ENERGETIC POLYPHOSPHAZENE PROPELLANT FORMULATION CHARACTERIZATION

Final nominal propellant formulations for the nitrato and azido-PPZ propellants are defined in the Table 13. Only the major ingredients are noted and only the weight percentages of the polymer system of interest provided. The remaining major energetic percentages are approximations so as to not provide potential disclosure of performance parameters.

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The nitrato-based formulation was formulated with PNO co-polymer mixture and the azido-based formulation with BN-7 co-polymer. Both of these formulations used FOX-7 as the energetic fill and BTTN as the plasticizer.

TABLE 13. Formulation Details.

Formulation Ingredient Weight %

Nitrato-PPZ 1,1-Diamino-2,2-dinitroethylene 78

BTTN

Polynitrato

phosphazene 10.0

PNO 8.3

Azido-PPZ 1,1-Diamino-2,2-dinitroethylene 78

BTTN Polyazido phosphazene 10.0

BN-7 10.0

SAFETY AND THERMAL ANALYSIS

Traditional safety analysis was conducted in order to observe potential sensitivity and handling hazards of each PPZ formulation in impact, friction, and electrostatic stimuli. Thermal analysis was conducted to observe any endothermic behavior along with ultimate decomposition temperature to assess thermal stability. Safety analysis results of each reveal propellants with relatively good impact response and excellent response to both friction and electrostatic discharge (Table 14).

TABLE 14. Safety Response of PPZ Propellants.

Propellant Impact (cm) Friction (lbf) ESD (0.25joules) SERDP-7-2-8-3 30 20/20 NF @ 1000 20/20 NF SERDP-8-2-3 22 20/20 NF @ 1000 20/20 NF

Thermal analysis conducted by differential scanning calorimetry (DSC) revealed that both samples have adequate to good thermal stability with only an endothermic peak occurring at 116°C. This is indicative of the alpha to beta phase change of the FOX-7 material present in both formulations. Concurrently, all the exothermic peaks can be accounted for and assigned to BTTN plasticizer, the two decomposition peaks of FOX-7, and in the instance of the nitrato-PPZ the very high decomposition peak at 311°C (Figures 9 and 10). Additionally, each sample was tested in vacuum thermal stability (VTS) which is used to measure the stability of a material over time. The sample is placed under vacuum at constant temperature and observed for volatility by quantifying gas evolved.

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Results showed that both formulations passed the test with the criteria defined by < 2.0 ml of evolved gas per gram of material held at vacuum/temperature over 48 hours. Although it must be noted that the azido-PPZ formulation had significantly higher values than the nitrato-PPZ, this can be explained due to any occluded methylene chloride solvent that was present during the solvent assisted mix and casting. The solvent would come off readily due to the very high vapor pressure of methylene chloride (349 mm Hg). Table 15 summarizes the thermal and vacuum stability tests conducted.

FIGURE 9. Differential Scanning Calorimetry of Nitrato-PPZ Formulation.

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FIGURE 10. Differential Scanning Calorimetry of Azido-PPZ Formulation.

TABLE 15. Thermal Properties of PPZ Propellants.

Propellant VTS (ml/mg/48hr)

DSC peaks (°C) Assignment

SERDP-PPZ-7-2-8-3 0.521

Endotherm 116

Exotherm 201

234,249 311

FOX-7 phase change

BTTN FOX-7

Nitrato-PPZ

SERDP-PPZ-8-2-3 1.011

Endotherm 115

Exotherm 194

234,247

FOX-7 phase change

BTTN FOX-7

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BURNING RATE

Both PPZ propellants were subjected to ‘window bomb’ burning rate experiments to observe their burning behavior with respect to rate and pressure exponent. Figure 11 shows a direct comparison of the PPZ propellant burning rates. Propellant formulation SERDP-PPZ-7-2-8-3 burning rate was found to be 0.363 in/sec measured at 1,000 psia with a pressure exponent of 0.633. This is a fair rate and typical of traditional composite minimum smoke propellants without burn rate catalysts;, a little slower than nitrocellulose/nitroglycerin double base propellants that do use metal burn rate catalysts like lead to improve their burning rate.

The azido-PPZ formulation, SERDP-PPZ-8-2-3, has a burn rate much faster and with a better pressure slope exponent, with a rate of 0.512in/sec and n = 0.499. This is a nice improved burning behavior without burn rate catalysts, even over double base propellants.

The question remains whether these effects are due to the new energetic PPZ polymers (as theorized) or more due to the use of the energetic co-polymers PNO and BN-7. The author suspects it is the latter, as it is known that PNO burns fairly slow, while BN-7 burns fairly rapidly. At this point we are unable to answer definitively because of the need to formulate with the co-polymers due to the existing difficult cure chemistries. A comparison of both burning behaviors is found in Figure 11.

FIGURE 11. Burning Rate Comparison of PPZ Propellants.

y = 0.0045x0.6355

y = 0.0169x0.4997

0.1

1

10

100 1000 10000

Burning Rate (in/sec)

Pressure (psia)

Polyphosphazene Propellant Burning Rate

Nitrato‐PPZ

Azido‐PPZ

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QUANTIFYING HAZARDOUS EMISSIONS FROM PROPELLANTS

The goal of this work is to determine whether hazardous fluorine- or phosphorus-containing compounds are emitted during decomposition of two new polyphosphazene-containing propellant formulations developed at NAWCWD China Lake. Both formulations employ FOX-7 and BTTN as the main energetic ingredients, and both contain polyphosphazene (polyazido or polynitrato phosphazene) and oxetane (PNO or BN-7) energetic polymers as binders. The polyphosphazene binders contain both phosphorus and fluorine, and may release hazardous compounds during combustion. The compositions of both formulations were shown in Table 13. In this work, mass spectrometry was used to examine the decomposition products that evolve as a function of time and temperature during thermal decomposition of the propellant samples.

Two candidate propellant formulations containing polyphosphazene energetic binders were analyzed using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) to determine whether the formulations emit hazardous fluorine- and/or phosphorus-containing compounds during thermal decomposition. The measurements show a multi-stage decomposition process that includes evaporation of BTTN, decomposition of the CHNO portion of the binder material and sublimation of FOX-7, a rapid reaction, and very slow decomposition of the remaining residue. The experiments were unable to detect any fluorine- or phosphorus-containing compounds, and it appears that the P=N backbone of the polyphosphazene binder does not undergo significant thermal decomposition under the conditions of these experiments.

DECOMPOSITION RESULTS

Thermal decomposition of two formulations were investigated in thermal ramp experiments. In these experiments, the samples are heated from ambient temperature to 500°C at a rate of 1°C/minute. The gaseous products and weight of the samples are monitored as a function of temperature and time using the STMBMS instrument. The temperature profile and mass loss record for Formulation 1 is shown in Figure 12. As the figure shows, the sample gradually loses mass in two phases, followed by an abrupt mass loss event, and very slow mass loss thereafter. The abrupt event around ~205°C is so rapid that the high rate of mass ejection from the reaction cell creates thrust, resulting in an apparent gain in mass.

26

FIGURE 12. Temperature Profile and Mass Loss for

Thermal Ramp Experiment on Formulation 1.

The mass spectrum acquired during this experiment is shown in Figure 13. The mass spectrum clearly shows that the decomposition proceeds in four stages. The first and second show relatively slow evolution of products, and the second stage abruptly terminates into a brief third phase, during which reaction of the sample leads to rapid formation of products and the thrust event. The fourth stage is characterized by minimal evolution of gas-phase products.

FIGURE 13. Mass Spectrum (m/z Versus Time) Acquired During Thermal Ramp

Experiment on Formulation 1. Decomposition proceeds in four stages.

27

The rapid reaction during the third stage of decomposition (~205°C) is too fast to

characterize using STMBMS. We therefore ran an isothermal decomposition experiment just below this temperature (190°C) to fully characterize the decomposition products. The temperature profile, mass loss records, and mass spectra are shown in Figures 14 and 15.

FIGURE 14. Temperature Profile and Mass Loss for

Isothermal Experiment on Formulation 1.

FIGURE 15. Mass Spectrum (m/z Versus Time) During Isothermal Experiment

on Formulation 1. Decomposition proceeds in three stages.

28

The decomposition of the sample is much smoother under isothermal conditions, and proceeds in three steps. The first two are identical to the first two stages of the ramped decomposition experiment. The three stages can be analyzed by comparing the mass spectrum of the decomposing formulation with mass spectra of the individual ingredients under identical conditions.

The first stage of the decomposition process is evaporation of BTTN. BTTN, a liquid at room temperature, evolves readily from the sample at relatively low temperature (<100°C). Figure 16 compares the mass spectrum of the first stage of Formulation 1 decomposition with the mass spectrum of BTTN at the same temperature. The figure clearly shows excellent correspondence between all major mass peaks in Formulation 1 and in BTTN.

The second stage of the decomposition process involves partial decomposition of the energetic polymers, evaporation of FOX-7, and possibly reactions between FOX-7 and the energetic polymers and/or decomposition products. Figure 17 shows the mass spectrum of Formulation 1 during the second stage of decomposition compared with the mass spectra of FOX-7, polynitrato phosphazene, PNO, and their sum. The qualitative agreement between Formulation 1 and the sum of the ingredients indicates that all three ingredients participate in this stage of the decomposition process to some extent. The lack of quantitative agreement suggests that additional reactions occur between the ingredients and may give rise to new products not observed in the decomposition of the individual ingredients.

An FTICR mass analysis of the second stage of decomposition is shown in Table 16. The Table lists the FTICR formula for each of the dominant mass peaks observed in Figure 18.

As the FTICR results show, none of the observed mass peaks correspond to fluorine- or phosphorus-containing compounds or fragments thereof. All mass peaks appear to originate from reactions involving PNO, FOX-7, and the CHNO side chains of the polynitrato phosphazene polymer.

29

FIGURE 16. Mass Spectrum of Formulation 1 During First Stage of Isothermal Decomposition,

Plotted Against the Mass Spectrum of BTTN Under Identical Conditions.

FIGURE 17. Mass Spectrum of Formulation 1 During Second Stage of Isothermal

Decomposition, Plotted Against the Sum of the Mass Spectra of FOX-7, Polynitrato Phosphazene, and PNO.

30

TABLE 16. FTICR Analysis of Major Species Observed During Second Stage of

Decomposition During Isothermal Experiment on Formulation 1.

Nominal m/z

Observed m/z

Theoretical m/z

Error (ppm) Formula

28 28.018174 28.018176 0.0532 C 1 H 2 N 1 30 29.997420 29.997440 0.6683 N 1 O 1 44 43.989291 43.989281 0.2350 C 1 O 2 44 44.036849 44.036900 1.1480 C 1 H 4 N 2 46 45.992355 45.992355 0.0072 N 1 O 2 55 55.017825 55.017841 0.2933 C 3 H 3 O 1 55 55.029068 55.029075 0.1186 C 2 H 3 N 2 55 55.054221 55.054227 0.1025 C 4 H 7 57 57.033477 57.033491 0.2490 C 3 H 5 O 1 57 57.069879 57.069877 0.0402 C 4 H 9 67 67.054222 67.054227 0.0693 C 5 H 7 69 69.008326 69.008339 0.1896 C 2 H 1 N 2 O 1 69 69.033474 69.033491 0.2492 C 4 H 5 O 1 69 69.069885 69.069877 0.1200 C 5 H 9 71 71.023966 71.023989 0.3259 C 2 H 3 N 2 O 1 71 71.049135 71.049141 0.0882 C 4 H 7 O 1 85 85.028335 85.028406 0.8330 C 4 H 5 O 2 85 85.064803 85.064791 0.1372 C 5 H 9 O 1 99 99.044041 99.044056 0.1503 C 5 H 7 O 2 148 148.022784 148.022706 0.5266 C 2 H 4 N 4 O 4

The third stage of decomposition appears to primarily involve reactions of FOX-7. Figure 18 shows the mass spectrum during the third stage of decomposition of Formulation 1, compared with the mass spectrum of FOX-7 under identical conditions. An FTICR analysis of this stage of the decomposition was also performed, and no fluorine- or phosphorus-containing compounds were detected in this stage. FTICR analysis of the major mass peaks are shown in Table 17.

The STMBMS and FTICR analysis on Formulation 1 appear to indicate that only reactions involving CHNO compounds are significant under the conditions of these experiments. The observation of only CHNO compounds and fragments in the mass spectrum, combined with the presence of substantial nonvolatile residue at the end of the experiment (i.e., nonzero final mass in Figures 12 and 14) suggests that the P=N backbone and fluorinated sidechains of the polynitrato phosphazene do not decompose to liberate volatile P- or F-containing compounds at the temperatures encountered in these experiments.

31

FIGURE 18. Mass Spectrum of Formulation 1 During Third

Stage of Isothermal Decomposition, Plotted Against the Mass Spectrum of FOX-7 Under Identical Conditions.

TABLE 17. FTICR Analysis of Major Species Observed During Third Stage

of Decomposition During Isothermal Experiment on Formulation 1.

Nominal m/z

Observed m/z

Theoretical m/z

Error (ppm) Formula

28 28.018174 28.018176 0.0532 C 1 H 2 N 1 30 29.997420 29.997440 0.6683 N 1 O 1 44 43.989291 43.989281 0.2350 C 1 O 2 44 44.036849 44.036900 1.1480 C 1 H 4 N 2 46 45.992355 45.992355 0.0072 N 1 O 2 55 55.017825 55.017841 0.2933 C 3 H 3 O 1 55 55.029068 55.029075 0.1186 C 2 H 3 N 2 55 55.054221 55.054227 0.1025 C 4 H 7 69 69.008326 69.008339 0.1896 C 2 H 1 N 2 O 1 69 69.033474 69.033491 0.2492 C 4 H 5 O 1 69 69.069885 69.069877 0.1200 C 5 H 9 72 72.019232 72.019238 0.0850 C 1 H 2 N 3 O 1 72 72.031813 72.031814 0.0164 C 2 H 4 N 2 O 1 86 86.034903 86.034888 0.1722 C 2 H 4 N 3 O 1 129 129.054626 129.054621 0.0420 C 6 H 9 O 3 129 129.091094 129.091006 0.6811 C 7 H 13 O 2 148 148.022784 148.022706 0.5266 C 2 H 4 N 4 O 4

32

Formulation 2 (azido-PPZ) was also subject to a thermal ramp experiment, and behaves similarly to Formulation 1. The temperature profile, mass loss record, and mass spectrum of the thermal ramp experiment on Formulation 2 are shown in Figures 19 and 20. Formulation 2 also undergoes gradual mass loss in the initial stage of decomposition, followed by a rapid reaction with a thrust event, and slow reaction thereafter. As with Formulation 1, the mass spectrum of Formulation 2 abruptly terminates after the rapid reaction/thrust event, and minimal species are observed in the final stage of decomposition.

The first stage of decomposition of Formulation 2 (shown in Figure 21) corresponds to evaporation of BTTN; the second stage (Figure 22) involves reactions of FOX-7 and the BN-7 and polyazido phosphazene energetic polymers. The third stage of decomposition (Figure 23) is very similar to the third stage of decomposition of Formulation 1 and clearly involves reactions of FOX-7. The fourth stage, during which volatile products evolve very slowly, is shown in Figure 24, and displays only weak mass peaks that are attributable to FOX-7 and BN-7.

An FTICR analysis of the second and third stages of decomposition of Formulation 2 was unable to identify any F- or P-containing compounds (see Table 18). As with Formulation 1, it appears that decomposition of Formulation 2 primarily involves reactions of the CHNO compounds and CHNO moieties of the polyazido phosphazene polymer. As with the polynitrato phosphazene polymer used in Formulation 1, it appears that the P=N backbone and fluorinated sidechains of the polyazido phosphazene polymer of Formulation 2 do not decompose to liberate volatile P- or F-containing compounds at the temperatures encountered in these experiments.

FIGURE 19. Temperature Profile Mass Loss for

Thermal Ramp Experiment on Formulation 2.

33

FIGURE 20. Mass Spectrum (m/z vs. Time) Acquired During Thermal Ramp

Experiment on Formulation 2. Decomposition proceeds in four stages.

FIGURE 21. Mass Spectrum of Formulation 2 During First Stage of Decomposition,

Plotted Against the Mass Spectrum of BTTN Under Identical Conditions.

34

FIGURE 22. Mass Spectrum of Formulation 2 During Second Stage of

Decomposition, Plotted Against the Sum of the Mass Spectra of FOX-7, Polyazido Phosphazene, and BN-7.

FIGURE 23. Mass Spectrum of Formulation 2 During Third Stage of

Decomposition, Plotted Against the Mass Spectrum of FOX-7 Under Identical Conditions.

35

FIGURE 24. Mass Spectrum of Formulation 2

During Fourth Stage of Decomposition.

TABLE 18. FTICR Analysis of Major Species Observed During Late Second and Early Third Stages of Decomposition of Formulation 2.

Nominal m/z

Observed m/z

Theoretical m/z

Error (ppm) Formula

28 28.00561 28.00560 0.3774 N 2 28 28.01819 28.01818 0.4108 C 1 H 2 N 1 30 29.99743 29.99744 0.2349 N 1 O 1 39 39.02295 39.02293 0.5249 C 3 H 3 43 43.01786 43.01784 0.3222 C 2 H 3 O 1 43 43.02909 43.02907 0.3596 C 1 H 3 N 2 44 44.03688 44.03690 0.4669 C 1 H 4 N 2 55 55.02910 55.02907 0.4629 C 2 H 3 N 2 55 55.05426 55.05423 0.6422 C 4 H 7 60 60.02062 60.02058 0.65323 C 2 H 4 O 2 69 69.00838 69.00834 0.5639 C 2 H 1 N 2 O 1 69 69.03355 69.03349 0.7793 C 4 H 5 O 1 69 69.05734 69.05730 0.5843 C 4 H 7 N 1 69 69.06993 69.06988 0.815 C 5 H 9 72 72.01930 72.01924 0.8036 C 1 H 2 N 3 O 1 72 72.03186 72.03181 0.6777 C 2 H 4 N 2 O 1 86 86.03496 86.03489 0.7882 C 2 H 4 N 3 O 1 98 98.06013 98.06004 0.9453 C 5 H 8 N 1 O 1 98 98.07270 98.07262 0.8732 C 6 H 10 O 1 99 99.04416 99.04406 1.021 C 5 H 7 O 2 99 99.06796 99.06787 0.9656 C 5 H 9 N 1 O 1 118 118.02484 118.02472 1.03 C 2 H 4 N 3 O 3 148 148.02294 148.02271 1.553 C 2 H 4 N 4 O 4

36

CONCLUSIONS AND IMPLICATIONS FOR FUTURE RESEARCH

Two alternative energetic polyphosphazene polymers (nitrato and azido functional groups) were tested as potential replacement polymer backbones in rocket motor propellant formulations. After an intensive study to acquire viable propellant candidates, the formulations were characterized via safety/thermal, burning rate, and decomposition properties.

Thermally, the materials behave well and show no signature peaks (early endotherms, large shifts) suggesting incompatibility with the other ingredients in the formulation. Basic safety testing was conducted to assess propellant response to insult or stimuli via impact, friction, and electrostatic discharge. Both propellants performed well within accepted safe handling conditions and showed improved impact results when compared to traditional AP and/or minimum signature propellants. The burning behaviors of both propellants also were within accepted metrics of traditional propellants, with the azido candidate burning exceptionally well.

The decomposition products of two propellant formulations containing polyphosphazene energetic binders were analyzed using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) to determine whether the formulations emit hazardous fluorine- and/or phosphorus-containing compounds during thermal decomposition. The measurements showed a multi-stage decomposition process that includes evaporation of BTTN and reactions involving the CHNO compounds and CHNO side-chains of the polyphosphazene binders. The experiments were unable to detect any fluorine- or phosphorus-containing compounds and it appears that the P=N backbone of the polyphosphazene binder does not undergo significant thermal decomposition under the conditions of these experiments. This observation supported earlier work where Golding et.al. experimented with flame temperature, laser ignition, and decomposition products resulting in the same charred residue which appears to be ‘not fully’ combusted and may potentially trap the fluorine species within the polyphosphazene backbone.13-16 As such, this may explain the lack of phosphoric and fluorine species in the decomposition products.

This was due in part to the limitations of the experimental method utilized to observe decomposition species. It must be noted that the experimental method was not an ‘ignition and combustion’ event under pressure. It was, however, expected that the polymer backbone would decompose and take part in reaction chemistry within the tolerances of the machine, and then this data would be extrapolated to a rocket motor combustion environment. At first glance, this lack of participation in the ‘chemical reactions’ may presume that these polymers would be a detriment with respect to full grain rocket motor propellant performance. Yet, we know they do burn, and fairly well, when exposed to both and ignition source and under pressure (see burning rate section in results). It appears the P=N polymer backbone is quite stable with respect to generalized thermal ramping. This data suggests that the inability of the polyphosphazene backbone to reach complete combustion state during ‘thermal ramping’ may provide an IM solution to thermal cook-off environments.

Ultimately, we were not fully able to answer the main question of evolution of toxic or smoky decomposition species extrapolated to a combustion environment. Alternate detection methods (noted in recommendations) will be needed more closely simulate a rocket motor

37

ignition event in order to address this question. Yet, data results from the characterization of these polymers do suggest an ability to meet most of the metrics required for rocket motor applications and, in turn, may provide a means for replacing more toxic or hazardous ingredients through the method of energy partitioning. Furthermore, if the cure chemistries can be sorted out energetic polyphosphazenes may provide an alternate cure chemistry pathway eliminating traditional isocyanates. It is the author’s contention that ‘Energetic Polyphosphazenes’ warrants further research, either directed or under additional SEED basic research dependent on the following recommendations:

First and foremost, address the cure-chemistry of these new polymers:

The manufacturer (AWE) was made aware of the difficulty in the cure chemistry and had already taken this action item up. They have since claimed success in providing hydroxyl end-capped phosphazenes for use and characterization in traditional urethane chemistry and are willing to provide samples for further characterization.

These materials may still show merit as a SEED directed study under current SERDP WPSEED01-019 for ‘Environmentally Sustainable Binder Systems for Energetic Materials’ to continue investigating both the epoxy and maleimide chemistries as replacements for isocyanic cure chemistries.

Introduce a pathway for technical transition for the synthesis of these polymers to allow CONUS development with another U.S. partner due to the long delay time in receipt of the PPZ materials.

Introduce alternate combustion diagnostics testing, like Plasma Laser Induced Fluorescence (PLIF), or other techniques to mimic rocket motor conditions to capture, observe, and quantify true combustion species evolved from these PPZ materials - answer the critical questions originally outlined in this limited scope SEED proposal.

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LITERATURE CITED

1. Nair, Lakshmi S.; Lee, Duron; and Laurencin, Cato T. Polyphosphazenes as Novel Biomaterials. Handbook of Biodegradable Polymeric Materials and Their Applications. (2006), 1 277-306. CODEN: 69HLHA AN 2005:1082133 CAPLUS.

2. Laurencin, Cato T.; Ambrosio, Archel M. A. Biodegradable Polyphosphazenes for

Biomedical Applications. PBM Series (2003). 2 (Biodegradable Polymers), 153–173. CODEN: PSBEC6 ISSN: 1479-1285. CAN 140:380353 AN 2003:990415 CAPLUS.

3. Lakshmi, S.; Katti, D. S.; and Laurencin, C. T. Biodegradable Polyphosphazenes for Drug

Delivery Applications. Advanced Drug Delivery Reviews (2003), 55 (4), 467-482. CODEN: ADDREP ISSN: 0169-409X. CAN 139: 385926 AN 2003:289916 CAPLUS.

4. Laurencin, Cato T.; Norman, Marie E.; Elgendy, Hoda M.; El-Amin, Saadiq F.;

Allcock, Harry R.; Pucher, Shawn R.; and Ambrosio, Archel A. Use of Polyphosphazenes for Skeletal Tissue Regeneration. Journal of Biomedical Materials Research (1993), 27 (7), 963-73. CODEN: JBMRBG ISSN: 0021-9304. CAN 119: 188536 AN 1993: 588536 CAPLUS.

5. Golding, P.; and Trussell, S. J.. “Energetic Polyphosphazenes – a New Category of Binders

for Energetic Formulations,” NDIA Insensitive Munitions and Energetic Materials Technology Symposium, San Francisco, CA, November 15–17 (2004).

6. Bolton, P. R.; Golding, P.; Murray, C. B.; Till, M. K.; and Trussell, S. J. “Enhanced

Energetic Polyphosphazenes,” NDIA Insensitive Munitions and Energetic Materials Technology Symposium, Thistle Hotel, Bristol, UK, April 24–28, (2006).

7. Behrens, R. “New Simultaneous Thermogravimetry and Modulated Molecular Beam Mass

Spectrometry Apparatus for Quantitative Thermal Decomposition Studies,” Review of Scientific Instruments, Vol. 58, Is. 451 (1987).

8. Behrens, R. “Identification of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)

Pyrolysis Products by Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry and Time-of-Flight Velocity-Spectra Measurements,” International Journal of Chemical Kinetics, Vol. 22, Is. 135 (1990).

9. Behrens, R. “Determination of the Rates of Formation of Gaseous Products from the

Pyrolysis of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry,” International Journal of Chemical Kinetics, Vol. 22, Is. 159 (1990).

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10. Behrens, R. “Thermal Decomposition Processes of Energetic Materials in the Condensed Phase at Low and Moderate Temperatures.” In Overviews of Recent Research on Energetic Materials, Shaw, R. W.; Brill, T. B.; Thompson, D. L., Eds. World Scientific Publishing Co.: Singapore, 2005; pp 29-74.

11. Bala, K.; Bolton, P.; Golding, P.; Hibbert, T.; Till, M.; Trussell, S. J.; and Willcox, M.

“Energetic polyphosphazene binders: Some Non-Isocyanate Cure Options and Use with FOX-7 and FOX-12.” Dinitramide and FOX-7 Seminars, Royal Hotel, San Remo, Italy, 19-20 September 2007.

12. Bala, K.; Golding, P.; Hibbert, T. G.; Jenkins, P.; Till, M. K.; and Willcox, M.

“Non-isocyanate Curable, Energetic (azido) Polyphosphazenes,” 41st International Conference of Fraunhofer ICT, Karlsruhe, Germany, 29 June to 2 July 2010.

13. Bellamy, A. J.; Contini, A. E.; Golding, P.; and Trussell, S. J. “Bomb Calorimetric Study of

a Series of Energetic Linear Polyphosphazenes,” 2004 Insensitive Munitions and Energetic Materials Technology Symposium, Hilton Hotel, San Francisco, California, 15-17 November 2004.

14. Bellamy, A. J.; Contini, A. E.; Golding, P.; and Trussell, S. J. “Bomb Calorimetric Study of

a Series of Energetic Linear Polyphosphazenes,” Eighth Seminar: 'New Trends in Research of Energetic Materials, University of Pardubice, Pardubice, The Czech Republic, 19-21 April 2005, 138, (2005).

15. Bellamy, A. J.; Contini, A. E.; and Golding, P. “Oxygen Combustion Calorimetry of

Samples Containing Phosphorus and Fluorine: Formation of Fluorinated Phosphoric Acids as Non-Ideal Combustion Species,” Combustion Science and Technology, Vol. 180, Is. 2103, (2008).

16. Ahmad, R.; Golding, P.; Padworth, J.; and Russell, A. “Laser Ignition of GUDN

(FOX-12)—Facilitation by an Energetic Polyphosphazene Binder,” 36th International Pyrotechnics Seminar and Symposium, Congress Centre De Doelen, Rotterdam, the Netherlands, 23–28 August 2009.

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Appendix A

SUPPORTING DATA

A1. Polyphosphazene Data Sheets A2. Individual Ingredient Thermal Analysis A3. Propellant Formulation Safety Data

(Reproduced in facsimile)

A-1

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A-2

Provisional Data Sheet

Poly[2,2,2-trifluoroethan-1-oxy/4-azidobutan-1-oxy phosphazene], ES65% Empirical Formula: C6.6H11.8N4.9F2.1O2.0P1.0 Percentage Energetic Side Chains: 65% Energy Content (DSC): 1150Jg-1

Heat of Formation: -1380 +/- 65 KJmol-1; -5240 +/- 240 Jg-1

Molecular Weight: Mw = ca 25,000 Glass Transition Temperature: -91oC Cure Procedure: Reaction with bismaleimide (Unstabilised product is likely to self-cure, once the solvent is removed) NB: This specific product has not yet been cured, but by analogy with its C6 homologue it should cure effectively using methylene bis(p-phenylenemaleimide). Around 1-2% of this bismaleimide is likely to be an appropriate starting point, depending on the required physical properties. Suggested cure conditions would be:- 24h at 35oC, neat or with a solvent (eg THF, CH2Cl2, CHCl2 and possibly H2O, depending on solubility). Hazard Data Small-scale mallet impact and friction: No response (0%) A cured product has not yet been tested, but the C6 analogue (66%ES), cured with 5% bismaleimide, gives no response (0/10) ESD: Not available, but C3 analogue (100%ES) gives no response at 4.5J Ignition by flame: Ignites after ca 0.5seconds, burns quickly then self extinguishes without propagation.

P N

O

OCH2CF 3

N3

n

A-3

Thermal stability: Exothermic decomposition of the azido groups (and/or triazoline functionalities after cure) is likely to occur around 200oC. Further hazard characterization is planned for this specific material. As a high molecular weight polymer this material is likely to have a low vapour pressure. Compatibility Not tested, but by analogy with other azido polyphosphazenes, this binder will probably be satisfactory with HNS, TATB, FOX-7, PETN and GUDN. There may be some compatibility issues with RDX and HMX. (Not tested with red phosphorus.) Notes If this product does not produce an adequately rubbery product using bis(p-phenylenemaleimide, a bismaleimide with a long chain linker may give a superior product. We would expect this material to be miscible with polar (eg energetic) plasticizers This polymer is not telechelically functionalized, so it is unlikely to produce a satisfactory filled rubber if very high levels of solids loading are employed (cf HTPB).

A-4

SUMMARY DATA SHEET

Trifluoroethoxy/5,6-Dinitratohexan-1-oxy polyphosphazene

SMALL- SCALE EXPLOSIVE HAZARD PROPERTIES & GENERAL INFORMATION

Physical state:

.. Tacky viscous liquid (Glass transition temperature: ca -55oC)

Appearance:

.. Yellow/brown in colour.

Designation:

.. Energetic Binder for Propellant Explosive and Pyrotechnic Formulations.

Composition:

.. Nitrate ester functionalised polyphosphazene (Trifluoroethoxy/5,6-Dinitratohexan-1-oxy polyphosphazene)

P N

O

OCH2CF3

ONO2O2NO

n

ca. 70% of side-groups

ca. 30% of side-groups

Empirical Formula: C9.60H16.60O10.40N3.80F1.80P1.00

Density: ca 1.49gcm-3

CHEMICAL STABILITY

Stability statement:

.. This research material has been stored at both ambient temperature and elevated temperature (60oC) for some months without visible alteration/deterioration. Nevertheless, it is anticipated that addition of a stabilizer will be necessary for long term storage and use

Incompatibility: .. Likely to be incompatible with base and strong oxidizing agents

Health hazards: .. The material contains some fluorine which may result in small quantities of toxic products including hydrofluoric acid when heated above 250 deg.C., or when an explosive, propellant, or pyrotechnic containing this material is burned or detonated.

Recommended method of

destruction:

Detonation or burning as HE contaminated solvent waste

A-5

SUMMARY DATA SHEET

EXPLOSIVE PROPERTIES - SENSITIVENESS CHARACTERISTICS

Figure of insensitiveness:

.. F of I (10 Cap Langlie method) = 11.1 (but see notes below)

Mallet friction test: Steel/Steel: 0%

Temperature of ignition:

.. Onset of decomposition (using Differential Scanning Calorimetry) = 186°C

Ignition by electric spark:

.. No ignitions at 4.5 Joules.

Behavior on inflammation:

.. Material burns quietly but is difficult to light (requiring a fair amount of heating before taking fire). The residue was a sintered char.

SUMMARY

Sensitiveness to friction:

.. Insensitive

Sensitiveness to electrostatic spark:

.. Insensitive

Sensitiveness to impact:

.. Although the F of I result is low, the observed response is mild, suggesting low explosiveness. It should be noted that this material is a viscous liquid, not a crystalline solid and that therefore it tends to come into contact with the sides of the cap during the test. Furthermore, as it is contains nitrate ester functionalities the material is likely to decompose at temperatures above ca 200oC. Inspection of the Rotter cap after testing showed minimal consumption of material with noticeable darkening only around the sides of the cap. There was no evidence of reaction on the base of the cap. This indicates ignition by means of a pinching/heating mechanism during impact. (The sides of the cap attain a high temperature as it is crushed). Significantly, the ignition does not propagate through the material, that is, it is self-extinguishing under these conditions. The test therefore suggests that this material has properties closer to those of a double base propellant than a primary explosive.

ADDITIONAL INFORMATION

Attempted Detonation: Under light confinement at a diameter of 16mm this material does not detonate or show any evidence of fast reaction (either deflagration or fast combustion) when in direct contact with a detonating PE4 booster charge (16mm diameter, 15mm length). Although further tests are required, it is thought unlikely that this material will prove to be detonable in its pure form.

Small-Scale Formulation: This material has been formulated with: HMX, TATB, HNS, FOX-7, FOX-12, AP, AN, Al, Mg & P. In most cases compatibility was demonstrated on a small scale using DSC, together with an absence of colour change at manufacture or on storage (24h/20oC, 30min/100oC). The formulations (excluding phosphorus) where also tested using the (small-scale) mallet friction (direct & glancing blow) and (for the high explosives) F of I. No problems were identified. Some additional tests have been performed with HMX, including spark test, trough test, T of I and small-scale (1g) vacuum stability. All were satisfactory.

Thermochemical Data: Heat of Formation: -4268+/-210 J/g; -1758+/-86 KJ/mol Heat of Combustion: -14440+/-210 J/g; -5946+/-86 KJ/mol

A-6

FOX7003Author: Deneille Wiese-Smith

OverviewPurpose

Ë The primary purpose of this experiment is to examine the decomposition of the 30mm FOX-7 20119001 sample for Joseph Clubb,NAWCWD, China Lake. This experiment is identical to FOX7004 except it uses the smallest particle FOX-7 instead of the largest.FOX7002 uses this sample under the same heating profile but under low confinement. Note that FOX-7 is 1,1-diamino-2,2-dintroethene(DADNE); C2H4N4O4, MW 148.08.

Experiment DescriptionË A small alumina type reaction cell, fitted with a alumina style cap assembly having an orifice diameter of 10.5 µm was loaded with the

sample and sealed with a kalrez oring.

The sample is comprised of one compound. The bottom section is loaded with 3.27 mg of Fox7.001-CLPP01 01 (sample ID # TU 122470).

Summary1. The temperature data is virtually free of the noise pick-up that is seen in the weight data, which is more common for the instrument at this

time.2. The ion signal data quality is adequate. The baseline noise is +/-0.04cts/ms and quite large at m/z 2, 32, which is a bit worse than

experiments since August 2012 but similar to recent KCL experiments.a. The early water signal is not seen, rather a more constant baseline background evolve from the start. b. A small, narrow peak is seen at m/z 98 & 99 at around 110°C, which is similar to FOX7004.c. There are a number of peaks that continue to evolve during cooling which are likely from the kalrez o-ring. Grease, which is applied to

seal the taper plug and crucile interface, may also contribute to the ion signals in this experiment.d. The largest ion signlas are at m/z 18 & 30. e. It's interesting, perhaps surpising, that m/z 148 (which I assumed to be the DADNE molecule) is correlated with m/z 176.

3. This data warrants closer analysis.

Thermal Analysis ResultsTA Overview Summary

Ë Heating ProfileË Profile type: simple ramp 2°C/min to 320°C, hold 500 seconds before cooling no faster than -5°c/min.Ë The temperature of the experiment ranged from 19.9 to 321.°C.

Ë Sample mass infoË The experiment started with a sample mass of 3.27mg.Ë The final mass with the sample measured in the experiment is 0.324mg.Ë Residue info is not available at the time of this write-up.

TA Overview Graphs

Thermal Analysis Region #1Ë The time limits for this region was selected and will be used in further analysis in this notebook, unless changed at a later time.Ë The following plots show all thermogravimetric data in this experiment. There is some noise pick-up in the weight data but very little in

the temperature data, which has been common for the instrument at this time. There is also a small thrust event near 8000 seconds that preceeds a rapid mass loss.

"Time range: 23.48 to 13541.8 sec."

A-7

g"Parameters for subset: "

" Minimum Time: 23.48 Maximum Time: 13541.8Minimum Temp: 19.8946 Maximum Temp: 320.953Minimum Weight: 0.315 Maximum Weight: 3.4356No residue is assumed. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.8946 Maximum Temp: 320.953"

" Minimum Weight: 0.315 Maximum Weight: 3.4356"

" Start time = 10.083 Final time =13555. Balance drift factor =0.00002433 mgêsec."

0 2000 4000 6000 8000 10 00012 0000

50

100

150

200

250

300

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 2000 4000 6000 8000 10 00012 0000.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Time HsL

Wei

ghtHm

gL

Weight HmgL

0 2000 4000 6000 8000 10 00012 000-0.08

-0.06

-0.04

-0.02

0.00

0.02

Time HsL

DT

AHCL

DTA HCL

50 100 150 200 250 3000.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Temperature HCLW

eigh

tHmgL

Weight HmgL

Thermal Analysis Region #2Ë The data has been replotted to 6000 seconds for a closer look at the early data. The weight increase during initial heating is common in

STMBMS experiments and is somehow related to adsorbed water in the instrument that is driven off with increasing temperature.

"Time range: 23.48 to 5991.81 sec.""Parameters for subset: "

" Minimum Time: 23.48 Maximum Time: 5991.81Minimum Temp: 19.8946 Maximum Temp: 217.391Minimum Weight: 3.0983 Maximum Weight: 3.4356No residue is assumed. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.8946 Maximum Temp: 320.953"

" Minimum Weight: 0.315 Maximum Weight: 3.4356"

" Start time = 10.083 Final time =13555. Balance drift factor = `0.00002433 mgêsec."

0 1000 2000 3000 4000 5000 60000

50

100

150

200

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 1000 2000 3000 4000 5000 6000

3.10

3.15

3.20

3.25

3.30

3.35

3.40

Time HsL

Wei

ghtHm

gL

Weight HmgL

0 1000 2000 3000 4000 5000 6000

-0.05

-0.04

-0.03

-0.02

-0.01

0.00

0.01

0.02

Time HsL

DT

AHCL

DTA HCL

50 100 150 200

3.10

3.15

3.20

3.25

3.30

3.35

3.40

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

2 FOX7003PreliminaryAnalysis_dws1.nb

A-8

Thermal Analysis Region #3Ë The data has been replotted over the weight loss region of the data while heating (before cooling begins). The thrust occurs at 280°C.

"Time range: 5505.03 to 9491.81 sec.""Parameters for subset: "

" Minimum Time: 5505.03 Maximum Time: 9491.81Minimum Temp: 201.145 Maximum Temp: 320.953Minimum Weight: 0.3559 Maximum Weight: 3.1956No residue is assumed.\n Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.8946 Maximum Temp: 320.953"

" Minimum Weight: 0.315 Maximum Weight: 3.4356"

" Start time = 10.083 Final time =13555. Balance drift factor =0.00002433382 mgêsec."

6000 7000 8000 9000

200

220

240

260

280

300

320

Time HsL

Tem

pera

ture

HCL

Temperature HCL

6000 7000 8000 90000.0

0.5

1.0

1.5

2.0

2.5

3.0

Time HsL

Wei

ghtHm

gL

Weight HmgL

6000 7000 8000 9000-0.025

-0.020

-0.015

-0.010

-0.005

0.000

0.005

0.010

Time HsL

DT

AHCL

DTA HCL

200 220 240 260 280 300 3200.0

0.5

1.0

1.5

2.0

2.5

3.0

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

Temperature Segment AnalysisTemperature Segment Overview Summary

Ë The number of different types of segments identified are as follows:Ë Heating: 3Ë Cooling: 4Ë Isothermal: 0

Display of Temperature Segment Analysis

Temperature Analysis #1: Cluster DisplayË Four cluster group analysis of all temperature data using 150 span points will be plotted twice: as a function of Rate °C/s and of

Temperature °C. The PID control and furnace response are good. The algorithm works well when there is minimal noise in the data.

FOX7003PreliminaryAnalysis_dws1.nb 3

A-9

2000 4000 6000 8000 10 000 12 000

-0.08

-0.06

-0.04

-0.02

0.00

0.02

0.04

Time HsL

Rat

eH°Cê

sL

Ò groups = 4 low index = 1 high index = 151

Temperature Analysis #2: BreakPoint Display

2000 4000 6000 8000 10 000 12 000

0

50

100

150

200

250

300

Time HsL

Tem

pera

ture

H°CL

Temperature Analysis #3: Segment Table

TimeHsL TempH°CL Heat RateH°CêminL DurationHsL Type

10. 19.9 0.28 89. up

99. 19.9 2.01 8960. up

9059. 318.8 0.03 474. up

9533. 319.5 -2.95 38. down

9571. 318.3 -4.70 2091. down

11662. 160.4 -2.11 1893. down

13555. 92.0 -2.11 0. down

General STMBMS Ion SignalsIon Signals Plots #1: time range 0 to 13770sec.Ë Comments: Raw ion signals for all m/z scanned in this experiment have been plotted vs. time. The baseline noise is generally

+/-0.04cts/ms generally and significantly larger at m/z 2 & 32, which is similar to experiment run recently but a bit wider than most experiment run since August 2012. Early water (adsorbed water) is obscured on this scale. As seen in FOX7004, there is an early peak at m/z 98 & 99.

"Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

4 FOX7003PreliminaryAnalysis_dws1.nb

A-10

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.1

0.0

0.1

0.2mêz = 2

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 12

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04mêz = 13

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.04

mêz = 14

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.2

-0.1

0.0

0.1

0.2mêz = 15

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.2

0.00.20.40.60.81.0

mêz = 16

0.0 0.2 0.4 0.6 0.8 1.0 1.20

2

4

6

mêz = 17

0.0 0.2 0.4 0.6 0.8 1.0 1.20

20

40

60

80

mêz = 18

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10

mêz = 19

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.050.000.050.100.150.200.25

mêz = 20

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 21

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 22

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.06-0.04-0.02

0.000.020.040.06

mêz = 23

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 24

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 25

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 26

0.0 0.2 0.4 0.6 0.8 1.0 1.205

101520253035

mêz = 27

0.0 0.2 0.4 0.6 0.8 1.0 1.205

1015202530

mêz = 28

0.0 0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 29

0.0 0.2 0.4 0.6 0.8 1.0 1.20

20

40

60

80

mêz = 30

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

mêz = 31

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.10-0.05

0.000.050.100.150.200.25

mêz = 32

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 33

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 34

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

FOX7003PreliminaryAnalysis_dws1.nb 5

A-11

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.04

mêz = 35

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.15-0.10-0.05

0.000.050.100.15

mêz = 36

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 37

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.10

-0.05

0.00

0.05

0.10

0.15mêz = 38

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

mêz = 39

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 40

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.050.000.050.100.150.200.25

mêz = 41

0.0 0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4mêz = 42

0.0 0.2 0.4 0.6 0.8 1.0 1.20

10

20

30

40

mêz = 43

0.0 0.2 0.4 0.6 0.8 1.0 1.20

10

20

30

40

50mêz = 44

0.0 0.2 0.4 0.6 0.8 1.0 1.20

2

4

6

8

mêz = 45

0.0 0.2 0.4 0.6 0.8 1.0 1.20

10

20

30

40

mêz = 46

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 47

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15

mêz = 48

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 49

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 50

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04mêz = 51

0.0 0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 52

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.0

mêz = 53

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

1.0mêz = 54

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0mêz = 55

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.10.20.30.40.5

mêz = 56

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

mêz = 57

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.10.20.30.40.50.6

mêz = 58

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

6 FOX7003PreliminaryAnalysis_dws1.nb

A-12

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15

mêz = 59

0.0 0.2 0.4 0.6 0.8 1.0 1.205

10152025

mêz = 60

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.10.20.30.40.50.60.7

mêz = 61

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

mêz = 62

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 63

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 64

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15

mêz = 65

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 66

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10

0.15

0.20mêz = 67

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

2.5mêz = 68

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

mêz = 69

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

mêz = 70

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

0.4

mêz = 71

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.25

mêz = 72

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.0

mêz = 73

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 74

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15mêz = 75

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10mêz = 76

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 77

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 78

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

0.4mêz = 79

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5mêz = 80

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.01.2

mêz = 81

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10mêz = 82

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

FOX7003PreliminaryAnalysis_dws1.nb 7

A-13

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

mêz = 83

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

mêz = 84

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.250.30

mêz = 85

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

mêz = 86

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 87

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8mêz = 88

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 89

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 90

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 91

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 92

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 93

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

0.4

0.5mêz = 94

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

mêz = 95

0.0 0.2 0.4 0.6 0.8 1.0 1.20.00.20.40.60.81.01.2

mêz = 96

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 97

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.10.20.30.40.5

mêz = 98

0.0 0.2 0.4 0.6 0.8 1.0 1.20.00.20.40.60.81.0

mêz = 99

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15

mêz = 100

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.06

mêz = 101

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 102

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.06

mêz = 103

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.250.30

mêz = 104

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 105

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

mêz = 106

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

8 FOX7003PreliminaryAnalysis_dws1.nb

A-14

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04mêz = 107

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15mêz = 108

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15

mêz = 109

0.0 0.2 0.4 0.6 0.8 1.0 1.201234567

mêz = 110

0.0 0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.53.0

mêz = 111

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.1

0.0

0.1

0.2

mêz = 112

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

mêz = 113

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

mêz = 114

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 115

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15mêz = 116

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 117

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15mêz = 118

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10mêz = 119

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

0.4

mêz = 120

0.0 0.2 0.4 0.6 0.8 1.0 1.20.00.20.40.60.81.01.2

mêz = 121

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.20

mêz = 122

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 123

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15mêz = 124

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.20

mêz = 125

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15

0.20mêz = 126

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.06

mêz = 127

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.25

mêz = 128

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

mêz = 129

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5mêz = 130

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

FOX7003PreliminaryAnalysis_dws1.nb 9

A-15

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15mêz = 131

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04mêz = 132

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 133

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.06

mêz = 134

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 135

0.0 0.2 0.4 0.6 0.8 1.0 1.20.00.20.40.60.81.0

mêz = 136

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.250.30

mêz = 137

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

1.0mêz = 138

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15

mêz = 139

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

mêz = 140

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 141

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 142

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 143

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 144

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04mêz = 145

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.020.000.020.040.060.08

mêz = 146

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.250.30

mêz = 147

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.01.2

mêz = 148

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

mêz = 149

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 150

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

mêz = 151

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 152

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15

0.20

mêz = 153

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.01.2

mêz = 154

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

10 FOX7003PreliminaryAnalysis_dws1.nb

A-16

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.10.20.30.40.50.6

mêz = 155

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 156

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10mêz = 157

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 158

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.04

mêz = 159

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 160

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 161

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.080.10

mêz = 162

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15

0.20

mêz = 163

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.08

mêz = 164

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.20

mêz = 165

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.06

mêz = 166

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 167

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 168

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 169

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 170

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 171

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04mêz = 172

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 173

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.080.10

mêz = 174

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.06-0.04-0.02

0.000.020.04

mêz = 175

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

mêz = 176

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 177

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.25

mêz = 178

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

FOX7003PreliminaryAnalysis_dws1.nb 11

A-17

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.25

mêz = 179

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.25

mêz = 180

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 181

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 182

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 183

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 184

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.15-0.10-0.05

0.000.050.10

mêz = 185

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

mêz = 186

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 187

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15

0.20mêz = 188

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

mêz = 189

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 190

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 191

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 192

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 193

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 194

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 195

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04mêz = 196

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 197

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15mêz = 198

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 199

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.20

mêz = 200

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.060.080.10

mêz = 201

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 202

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

12 FOX7003PreliminaryAnalysis_dws1.nb

A-18

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10

mêz = 203

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

0.15mêz = 204

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 205

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.02

0.00

0.02

0.04

0.06mêz = 206

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.01.2

mêz = 207

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

mêz = 208

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 209

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04-0.02

0.000.020.040.06

mêz = 210

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 211

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10

mêz = 212

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.00

0.05

0.10mêz = 213

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 214

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 215

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 216

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 217

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 218

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 219

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 220

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00.10.20.30.40.5

mêz = 221

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10

0.15mêz = 222

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10

mêz = 223

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 224

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8mêz = 225

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.20

mêz = 226

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

FOX7003PreliminaryAnalysis_dws1.nb 13

A-19

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.05

0.00

0.05

0.10

0.15mêz = 227

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 228

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.05

0.000.050.100.150.200.25

mêz = 229

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 230

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.060.08

mêz = 231

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04mêz = 232

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 233

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 234

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 235

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 236

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 237

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 238

"Time Hs x10000.L""Data File: FOX7003.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 239

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 240

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 241

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 242

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

mêz = 243

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 244

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.04

mêz = 245

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 246

0.0 0.2 0.4 0.6 0.8 1.0 1.2-0.06-0.04-0.02

0.000.020.040.06

mêz = 247

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 248

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04

-0.02

0.00

0.02

0.04

mêz = 249

0.0 0.2 0.4 0.6 0.8 1.0 1.2

-0.04-0.02

0.000.020.040.06

mêz = 250

"Time Hs x10000.L"Ion Signals Plots #2: time range 0 to 13770sec.Ë Comments: Ion signals greater than 0.1 percent total signal were smoothed and replotted as a function of temperature. For some m/z this

plot is confusing because the signals continue to evolve during cooling. Some of these may be evolving from the kalrez o-ring and/or the grease (i.e. not necessarily from the sample).

"Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

14 FOX7003PreliminaryAnalysis_dws1.nb

A-20

p

0.5 1.0 1.5 2.0 2.5 3.0-0.2

0.00.20.40.60.81.0

mêz = 16

0.5 1.0 1.5 2.0 2.5 3.00

2

4

6

mêz = 17

0.5 1.0 1.5 2.0 2.5 3.00

20

40

60

80

mêz = 18

0.5 1.0 1.5 2.0 2.5 3.005

101520253035

mêz = 27

0.5 1.0 1.5 2.0 2.5 3.005

1015202530

mêz = 28

0.5 1.0 1.5 2.0 2.5 3.00

1

2

3

4

mêz = 29

0.5 1.0 1.5 2.0 2.5 3.00

20

40

60

80

mêz = 30

0.5 1.0 1.5 2.0 2.5 3.00

1

2

3

4mêz = 42

0.5 1.0 1.5 2.0 2.5 3.00

10

20

30

40

mêz = 43

0.5 1.0 1.5 2.0 2.5 3.00

10

20

30

40

50mêz = 44

0.5 1.0 1.5 2.0 2.5 3.00

2

4

6

8

mêz = 45

0.5 1.0 1.5 2.0 2.5 3.00

10

20

30

40

mêz = 46

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.00

1

2

3

4

mêz = 52

0.5 1.0 1.5 2.0 2.5 3.0

0.00.20.40.60.81.0

mêz = 53

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 54

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

2.0mêz = 55

0.5 1.0 1.5 2.0 2.5 3.0

0.00.10.20.30.40.50.6

mêz = 58

0.5 1.0 1.5 2.0 2.5 3.005

10152025

mêz = 60

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

2.0

2.5mêz = 68

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

0.8

mêz = 69

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

2.0

mêz = 70

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.1

0.2

0.3

0.4

mêz = 71

0.5 1.0 1.5 2.0 2.5 3.0

0.00.20.40.60.81.0

mêz = 73

0.5 1.0 1.5 2.0 2.5 3.0-0.05

0.000.050.100.150.200.25

mêz = 77

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

FOX7003PreliminaryAnalysis_dws1.nb 15

A-21

p

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.1

0.2

0.3

0.4mêz = 79

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5mêz = 80

0.5 1.0 1.5 2.0 2.5 3.0

0.00.20.40.60.81.01.2

mêz = 81

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

mêz = 86

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

0.8mêz = 88

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.1

0.2

0.3

0.4

0.5mêz = 94

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

mêz = 95

0.5 1.0 1.5 2.0 2.5 3.00.00.20.40.60.81.01.2

mêz = 96

0.5 1.0 1.5 2.0 2.5 3.0

0.00.10.20.30.40.5

mêz = 98

0.5 1.0 1.5 2.0 2.5 3.00.00.20.40.60.81.0

mêz = 99

0.5 1.0 1.5 2.0 2.5 3.001234567

mêz = 110

0.5 1.0 1.5 2.0 2.5 3.00.00.51.01.52.02.53.0

mêz = 111

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

mêz = 113

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

mêz = 114

0.5 1.0 1.5 2.0 2.5 3.00.00.20.40.60.81.01.2

mêz = 121

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5

2.0

mêz = 129

0.5 1.0 1.5 2.0 2.5 3.00.0

0.5

1.0

1.5mêz = 130

0.5 1.0 1.5 2.0 2.5 3.00.00.20.40.60.81.0

mêz = 136

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 138

0.5 1.0 1.5 2.0 2.5 3.0

0.000.050.100.150.200.250.30

mêz = 147

0.5 1.0 1.5 2.0 2.5 3.0

0.00.20.40.60.81.01.2

mêz = 148

0.5 1.0 1.5 2.0 2.5 3.0

0.00.20.40.60.81.01.2

mêz = 154

0.5 1.0 1.5 2.0 2.5 3.0

0.00.10.20.30.40.50.6

mêz = 155

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

mêz = 176

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

16 FOX7003PreliminaryAnalysis_dws1.nb

A-22

p

0.5 1.0 1.5 2.0 2.5 3.0

0.00.20.40.60.81.01.2

mêz = 207

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.1

0.2

0.3

mêz = 208

0.5 1.0 1.5 2.0 2.5 3.0-0.05

0.000.050.100.150.200.25

mêz = 211

0.5 1.0 1.5 2.0 2.5 3.0

0.00.10.20.30.40.5

mêz = 221

0.5 1.0 1.5 2.0 2.5 3.0

0.0

0.2

0.4

0.6

0.8mêz = 225

"Temperature H°C x100.L"Ion Signals Plots #3: time range 0 to 6000sec.Ë Comments: The data has been replotted vs temperature to better see the early lion signals. We're not seeing the typcal early water peak,

rather a constant baseline background."Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0-0.2-0.1

0.00.10.20.30.40.5

mêz = 17

0.5 1.0 1.5 2.005

1015202530

mêz = 18

0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

mêz = 20

0.5 1.0 1.5 2.00

2

4

6

mêz = 27

0.5 1.0 1.5 2.0

02468

1012

mêz = 28

0.5 1.0 1.5 2.0-0.1

0.00.10.20.30.40.5

mêz = 29

0.5 1.0 1.5 2.00123456

mêz = 30

0.5 1.0 1.5 2.0-0.10

-0.05

0.00

0.05

0.10

mêz = 32

0.5 1.0 1.5 2.0-0.10

-0.05

0.00

0.05

0.10

0.15mêz = 36

0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

0.15mêz = 41

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4mêz = 42

0.5 1.0 1.5 2.00

1

2

3

4mêz = 43

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

FOX7003PreliminaryAnalysis_dws1.nb 17

A-23

p

0.5 1.0 1.5 2.00

5

10

15

20

mêz = 44

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 45

0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

mêz = 46

0.5 1.0 1.5 2.00.0

0.5

1.0

1.5mêz = 52

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 53

0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20

mêz = 54

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 55

0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

0.15

mêz = 56

0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

mêz = 57

0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 58

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

mêz = 60

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

mêz = 68

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 69

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

mêz = 70

0.5 1.0 1.5 2.0

0.000.050.100.150.200.25

mêz = 71

0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 72

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 73

0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 75

0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20

mêz = 80

0.5 1.0 1.5 2.0

0.00.10.20.30.40.5

mêz = 81

0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10mêz = 82

0.5 1.0 1.5 2.0

-0.05

0.00

0.05

mêz = 83

0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10mêz = 84

0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

mêz = 85

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

18 FOX7003PreliminaryAnalysis_dws1.nb

A-24

p

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8mêz = 86

0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15

mêz = 88

0.5 1.0 1.5 2.0

0.00.10.20.30.40.50.6

mêz = 95

0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 96

0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 97

0.5 1.0 1.5 2.0

0.00.10.20.30.40.5

mêz = 98

0.5 1.0 1.5 2.00.00.20.40.60.81.0

mêz = 99

0.5 1.0 1.5 2.0

-0.020.000.020.040.060.080.10

mêz = 100

0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 109

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

mêz = 110

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 111

0.5 1.0 1.5 2.0

-0.10

-0.05

0.00

0.05

0.10mêz = 112

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 113

0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

mêz = 114

0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15mêz = 120

0.5 1.0 1.5 2.0

-0.020.000.020.040.060.08

mêz = 121

0.5 1.0 1.5 2.0

-0.020.000.020.040.060.08

mêz = 123

0.5 1.0 1.5 2.0

-0.020.000.020.040.060.08

mêz = 124

0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 125

0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 127

0.5 1.0 1.5 2.0

-0.020.000.020.040.060.08

mêz = 128

0.5 1.0 1.5 2.0

0.00.10.20.30.40.5

mêz = 129

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 136

0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 137

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

FOX7003PreliminaryAnalysis_dws1.nb 19

A-25

p

0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4mêz = 138

0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 149

0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04

0.06mêz = 150

0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.20

mêz = 154

0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 155

0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 157

0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 163

0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.040.06

mêz = 167

0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 178

0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.20

mêz = 207

0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 213

0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 219

"Temperature H°C x100.L""Data File: FOX7003.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0

-0.050.000.050.100.150.200.25

mêz = 221

0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

mêz = 222

0.5 1.0 1.5 2.0

-0.020.000.020.040.060.080.10

mêz = 223

0.5 1.0 1.5 2.0

0.000.050.100.150.200.25

mêz = 225

"Temperature H°C x100.L"Correlations Analysis of Ion Signals

Correlated Signals #1: time range 0 to 13770sec.Ë Comments: A 95 percent correlation analysis of the 53 smoothed ion signals greater than 0.1 percent total signals is shown below. It's

interesting that m/z 148, which one would think to be the DADNE (Fox-7) molecular ion, is correlated with m/z 176 (larger than the molecular ion).

::98. 99.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

Time Hsec x10000L

Centroid Time =5428.66

, 98

99

0 50 100 150 2000.000.050.100.150.200.250.300.35

Mass

Sig

nalH%

L

Band Ò1 Group Ò 16Limits: 0.95 - 1.0001

>,

20 FOX7003PreliminaryAnalysis_dws1.nb

A-26

:71.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.250.30

Time Hsec x10000L

Centroid Time =6262.58

,

71

0 50 100 150 2000.00

0.05

0.10

0.15

Mass

Sig

nalH%

L

Band Ò1 Group Ò 8Limits: 0.95 - 1.0001

>,

:44. 70. 95.

111.113.

136.138.154.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =6709.19

,

44

70 95 111113 1361381540 50 100 150 200

02468

1012

Mass

Sig

nalH%

LBand Ò1 Group Ò 5

Limits: 0.95 - 1.0001

>,

:86. 114.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

Time Hsec x10000L

Centroid Time =6749.67

,

86114

0 50 100 150 2000.00.10.20.30.40.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 13Limits: 0.95 - 1.0001

>,

:58.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.000.050.100.150.200.250.300.35

Time Hsec x10000L

Centroid Time =6809.5

,

58

0 50 100 150 2000.000.020.040.060.080.10

Mass

Sig

nalH%

L

Band Ò1 Group Ò 7Limits: 0.95 - 1.0001

>,

: 88.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.1

0.2

0.3

0.4

0.5

Time Hsec x10000L

Centroid Time =6882.39

,

88

0 50 100 150 2000.000.020.040.060.080.100.120.14

Mass

Sig

nalH%

L

Band Ò1 Group Ò 14Limits: 0.95 - 1.0001

>,

:18. 27. 28.

52. 53.

68. 80. 110.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =6955.72

,

18

2728

52536880 1100 50 100 150 200

05

10152025

Mass

Sig

nalH%

L

Band Ò1 Group Ò 3Limits: 0.95 - 1.0001

>,

FOX7003PreliminaryAnalysis_dws1.nb 21

A-27

:129.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

Time Hsec x10000L

Centroid Time =7047.73

,

129

0 50 100 150 2000.0

0.2

0.4

0.6

0.8

Mass

Sig

nalH%

L

Band Ò1 Group Ò 17Limits: 0.95 - 1.0001

>,

:29. 45.

54.

55. 69.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =7114.07

,

2945

5455

69

0 50 100 150 2000.00.20.40.60.81.01.21.4

Mass

Sig

nalH%

LBand Ò1 Group Ò 4

Limits: 0.95 - 1.0001

>,

:46.

60.

130.0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =7258.72

,

46

60

1300 50 100 150 200

012345

Mass

Sig

nalH%

L

Band Ò1 Group Ò 6Limits: 0.95 - 1.0001

>,

:148. 176.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

1.0

1.2

Time Hsec x10000L

Centroid Time =7365.86

,

148

176

0 50 100 150 2000.000.050.100.150.200.25

Mass

Sig

nalH%

L

Band Ò1 Group Ò 18Limits: 0.95 - 1.0001

>,

: 16.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

0.4

0.5

Time Hsec x10000L

Centroid Time =7395.35

,

16

0 50 100 150 2000.00

0.05

0.10

0.15

Mass

Sig

nalH%

L

Band Ò1 Group Ò 1Limits: 0.95 - 1.0001

>,

:17. 30. 42.

43.

96.121.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =7443.24

,

17

30

42

43

96 1210 50 100 150 200

02468

1012

Mass

Sig

nalH%

L

Band Ò1 Group Ò 2Limits: 0.95 - 1.0001

>,

22 FOX7003PreliminaryAnalysis_dws1.nb

A-28

: 94.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.00

0.05

0.10

0.15

0.20

0.25

Time Hsec x10000L

Centroid Time =7596.65

,

94

0 50 100 150 2000.000.020.040.060.080.10

Mass

Sig

nalH%

L

Band Ò1 Group Ò 15Limits: 0.95 - 1.0001

>,

: 221.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

Time Hsec x10000L

Centroid Time =7908.62

,

221

0 50 100 150 2000.000.050.100.150.200.25

Mass

Sig

nalH%

LBand Ò1 Group Ò 21Limits: 0.95 - 1.0001

>,

:

77.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

Time Hsec x10000L

Centroid Time =8135.53

,

77

0 50 100 150 2000.000.020.040.060.080.10

Mass

Sig

nalH%

L

Band Ò1 Group Ò 10Limits: 0.95 - 1.0001

>,

:81.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =8223.62

,

81

0 50 100 150 2000.0

0.1

0.2

0.3

0.4

Mass

Sig

nalH%

L

Band Ò1 Group Ò 12Limits: 0.95 - 1.0001

>,

:79.

211.

225.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.1

0.2

0.3

0.4

0.5

0.6

Time Hsec x10000L

Centroid Time =8512.7

,79

211

225

0 50 100 150 2000.000.050.100.150.200.250.300.35

Mass

Sig

nalH%

L

Band Ò1 Group Ò 11Limits: 0.95 - 1.0001

>,

:155.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.1

0.2

0.3

Time Hsec x10000L

Centroid Time =8751.01

,

155

0 50 100 150 2000.00

0.05

0.10

0.15

0.20

Mass

Sig

nalH%

L

Band Ò1 Group Ò 19Limits: 0.95 - 1.0001

>,

FOX7003PreliminaryAnalysis_dws1.nb 23

A-29

:73. 147.

207.

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

1.0

1.2

Time Hsec x10000L

Centroid Time =8765.08

,

73

147

207

0 50 100 150 2000.00.10.20.30.40.50.6

Mass

Sig

nalH%

L

Band Ò1 Group Ò 9Limits: 0.95 - 1.0001

>,

:208.

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.00

0.05

0.10

0.15

0.20

0.25

Time Hsec x10000L

Centroid Time =8885.42

,

208

0 50 100 150 2000.000.020.040.060.080.100.12

Mass

Sig

nalH%

LBand Ò1 Group Ò 20Limits: 0.95 - 1.0001

>>

Tables of Mass Spectral InformationMass Spec Table #1: time range 0 to 13770sec.Ë Comments: Table summary of raw ion signals for all m/z scanned in this experiment:

Ion signals greater than 0.% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L2 0. 71 0.1 131 0. 191 0.

12 0. 72 0.1 132 0. 192 0.

13 0. 73 0.5 133 0. 193 0.

14 0. 74 0. 134 0. 194 0.

15 0. 75 0.1 135 0. 195 0.

16 0.2 76 0. 136 0.2 196 0.

17 1.3 77 0.1 137 0.1 197 0.

18 22.5 78 0. 138 0.2 198 0.

19 0. 79 0.2 139 0. 199 0.

20 0.1 80 0.3 140 0. 200 0.

21 0. 81 0.4 141 0. 201 0.

22 0. 82 0. 142 0. 202 0.

23 0. 83 0. 143 0. 203 0.

24 0. 84 0.1 144 0. 204 0.

25 0. 85 0.1 145 0. 205 0.

26 0. 86 0.5 146 0. 206 0.

27 6.8 87 0. 147 0.1 207 0.6

28 8.9 88 0.1 148 0.2 208 0.1

29 1. 89 0. 149 0.1 209 0.1

30 11.6 90 0. 150 0. 210 0.

31 0. 91 0. 151 0.1 211 0.1

32 0.1 92 0. 152 0. 212 0.

33 0. 93 0. 153 0.1 213 0.

34 0. 94 0.1 154 0.2 214 0.

35 0. 95 0.3 155 0.2 215 0.

36 0 96 0 2 156 0 1 216 0

24 FOX7003PreliminaryAnalysis_dws1.nb

A-30

36 0. 96 0.2 156 0.1 216 0.

37 0. 97 0.1 157 0. 217 0.

38 0. 98 0.2 158 0. 218 0.

39 0. 99 0.3 159 0. 219 0.

40 0. 100 0.1 160 0. 220 0.

41 0.1 101 0. 161 0. 221 0.2

42 0.7 102 0. 162 0. 222 0.1

43 9.4 103 0. 163 0.1 223 0.

44 11.5 104 0.1 164 0. 224 0.

45 1.3 105 0. 165 0. 225 0.3

46 5. 106 0. 166 0. 226 0.1

47 0. 107 0. 167 0. 227 0.1

48 0. 108 0. 168 0. 228 0.

49 0. 109 0. 169 0. 229 0.1

50 0. 110 1.2 170 0. 230 0.

51 0. 111 0.6 171 0. 231 0.

52 1. 112 0.1 172 0. 232 0.

53 0.2 113 0.1 173 0. 233 0.

54 0.2 114 0.4 174 0. 234 0.

55 0.6 115 0. 175 0. 235 0.

56 0.1 116 0. 176 0.1 236 0.

57 0.1 117 0. 177 0. 237 0.

58 0.1 118 0. 178 0.1 238 0.

59 0. 119 0. 179 0. 239 0.

60 2.6 120 0.1 180 0. 240 0.

61 0.1 121 0.1 181 0. 241 0.

62 0. 122 0. 182 0. 242 0.

63 0. 123 0. 183 0. 243 0.

64 0. 124 0. 184 0. 244 0.

65 0. 125 0. 185 0. 245 0.

66 0. 126 0. 186 0. 246 0.

67 0. 127 0. 187 0. 247 0.

68 0.6 128 0.1 188 0. 248 0.

69 0.3 129 0.8 189 0. 249 0.

70 0.4 130 0.2 190 0. 250 0.

Mass Spec Table #2: time range 0 to 13770sec.Ë Comments: Table summary of the 53 smoothed ion signals greater than 0.1 percent total signal:

FOX7003PreliminaryAnalysis_dws1.nb 25

A-31

Ion signals greater than 0.1% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L16 0.2 54 0.2 88 0.1 138 0.2

17 1.3 55 0.6 94 0.1 147 0.1

18 22.5 58 0.1 95 0.3 148 0.2

27 6.8 60 2.6 96 0.2 154 0.2

28 8.9 68 0.6 98 0.2 155 0.2

29 1. 69 0.3 99 0.3 176 0.1

30 11.6 70 0.4 110 1.2 207 0.6

42 0.7 71 0.1 111 0.6 208 0.1

43 9.4 73 0.5 113 0.1 211 0.1

44 11.5 77 0.1 114 0.4 221 0.2

45 1.3 79 0.2 121 0.1 225 0.3

46 5. 80 0.3 129 0.8

52 1. 81 0.4 130 0.2

53 0.2 86 0.5 136 0.2

26 FOX7003PreliminaryAnalysis_dws1.nb

A-32

CL20012Author: Deneille Wiese-Smith

OverviewPurpose

Ë The primary purpose of this experiment is to learn the sublimation signature of the CL-20 sample from Josepth Clubb, NAWCWD, China Lake. CL-20 is 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, also called HNIW, C6H6N12O12, MW 438.1850.

Experiment DescriptionË A small alumina type reaction cell, fitted with a alumina style cap assembly having an orifice diameter of 1006 µm was loaded with the

sample.

The sample is comprised of one compound. The bottom section is loaded with 5.62 mg of CL-20 (sample ID # CL20-CLPP01).

Summary1. The weight and temperature data seem okay.

a. There is a moderate thrust event as temperatures ramp from 210°c to 220°C. This is unusual for a low confinement crucilbe assembly using a 1000µm orifice.

b. The noise in the weight and temperatue data is relatively mild compared to that oberved in experiments earlier this year.c. The final experiment weight of 0.043mg might be off because of the thrust in the experiment. The crucible assembly and any residue

were not examined at the point of the write-up; thus no insight regarding the end-weight at present.2. The ion data ought to provide some useful insight inspite of some uncertainty about the mass offsets used in the QMS data acquisition.

a. The pre-experiment observation of the background water, H2 and CO2 in the STMBMS (unmodulated ion signals at m/z 18, 28 and 44) showed an extreem shift up (0.35amu) compared to the signals at the time calibration and mass offsets were observed.

b. The morning after the experiment the same ion signals were observed 0.2amu lower. This result has been seen a couple of times since the August post maintenance restart.

c. The baseline noise is a bit higher than observed in recent experimnets (+/-0.04cts/ms generally rather than +/- 0.03cts/ms). This suggests that the QMS offsets in the experiment were not optimal.

d. The largest ion signals were at m/z 46 and 30. Here too, the maximum signal intensity was smaller than I would have expected given the thrust observed. This too suggests that we were on the shoulder not center of the ion signal peak.

Thermal Analysis ResultsTA Overview Summary

Ë Heating ProfileË Profile type: simple ramp at 2°C/min to 400°C holding 500 seconds before cooling at no more than -5°C/min.Ë The temperature of the experiment ranged from 19.6 to 400.2°C.

Ë Sample mass infoË The experiment started with a sample mass of 5.62mg.Ë The final mass with the sample measured in the experiment is 0.043mg.Ë Residue info is not available at the time of this write-up.

Display of Thermal Analysis Data

Thermal Analysis Region #1Ë The time limits for this region was selected and will be used in further analysis in this notebook, unless changed at a later time.Ë The noise level in the weight and temperature data is relatively minor (better than recent experiments). There was a sizable thrust event

just after 210°C. This may have affected the ending weight (0.043mg).

"Time range: 22.763 to 17045.1 sec."

A-33

g"Parameters for subset: "

" Minimum Time: 22.763 Maximum Time: 17045.1Minimum Temp: 19.7075 Maximum Temp: 400.18Minimum Weight: -0.0235 Maximum Weight: 6.455A residue of 0.043mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.6348 Maximum Temp: 400.18"

" Minimum Weight: -0.0235 Maximum Weight: 6.455"

" Start time = 10.077 Final time = 17045.1Balance drift factor =`3.75697182*^-7 mgêsec."

0 5000 10 000 15 0000

100

200

300

400

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 5000 10 000 15 0000

1

2

3

4

5

6

Time HsL

Wei

ghtHm

gL

Weight HmgL

0 5000 10 000 15 000-0.08

-0.06

-0.04

-0.02

0.00

0.02

Time HsL

DT

AHCL

DTA HCL

50 100 150 200 250 300 350 4000

1

2

3

4

5

6

Temperature HCLW

eigh

tHmgL

Weight HmgL

Thermal Analysis Region #2Ë Zooming into the data, we see that both the temperature and weight reflected a jump at the same time, which is a bit odd if this is indeed a

thrust event. The ion data will need to be examined closely.

"Time range: 5602.75 to 6193.9 sec.""Parameters for subset: "

" Minimum Time: 5602.75 Maximum Time: 6193.9Minimum Temp: 204.438 Maximum Temp: 224.143Minimum Weight: 0.2259 Maximum Weight: 6.455A residue of 0.043mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.6348 Maximum Temp: 400.18"

" Minimum Weight: -0.0235 Maximum Weight: 6.455"

" Start time = 10.077 Final time = 17045.1Balance drift factor =3.756971824`*^-7 mgêsec."

5600 5700 5800 5900 6000 6100 6200

205

210

215

220

Time HsL

Tem

pera

ture

HCL

Temperature HCL

5600 5700 5800 5900 6000 6100 62000

1

2

3

4

5

6

Time HsL

Wei

ghtHm

gL

Weight HmgL

2 CL20012PreliminaryAnalysis_dws1.nb

A-34

5600 5700 5800 5900 6000 6100 6200

-0.008

-0.006

-0.004

-0.002

0.000

Time HsL

DT

AHCL

DTA HCL

205 210 215 2200

1

2

3

4

5

6

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

Temperature Segment AnalysisTemperature Segment Overview Summary

Ë The number of different types of segments identified are as follows:Ë Heating: 3Ë Cooling: 4Ë Isothermal: 0

Display of Temperature Segment Analysis

Temperature Analysis #1: Cluster DisplayË Four cluster group analysi of all temperature data using 200 span points will be plotted twice: as a function of Rate °C/s and of

Temperature °C. The algorithm does a reasonable job given the periodic noise excursions. We also see reasonable PID control / furnace response.

5000 10 000 15 000

-0.08

-0.06

-0.04

-0.02

0.00

0.02

0.04

Time HsL

Rat

eH°Cê

sL

Ò groups = 4 low index = 1 high index = 221

Temperature Analysis #2: BreakPoint Display

5000 10 000 15 000

0

100

200

300

400

Time HsL

Tem

pera

ture

H°CL

CL20012PreliminaryAnalysis_dws1.nb 3

A-35

Temperature Analysis #3: Segment Table

TimeHsL TempH°CL Heat RateH°CêminL DurationHsL Type

10. 19.6 0.21 76. up

86. 19.8 2.00 11343. up

11429. 397.9 0.22 469. up

11898. 400.0 -2.53 119. down

12017. 395.4 -4.87 2934. down

14951. 164.0 -2.10 2094. down

17045. 88.7 -2.10 0. down

General STMBMS Ion SignalsIon Signals Plots #1: time range 0 to 17320sec.Ë Comments: Raw ion signals for all m/z scanned in this expeirment are plotted as a function of time. The molecular CL-20 ion (m/z 438) is

not seen. The largest ion signals are at m/z 46 and 30. Given the rapid mass loss I expected larger signal intensities. Since the baseline noise level is somewhat larger (+/- 0.045 cts/ms rather and 0.03 cts/ms) I suspect the shifts in the QMS signals were at play. Even so, there is useful information here.

"Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 12

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 13

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 14

0.0 0.5 1.0 1.5-0.2

-0.1

0.0

0.1

0.2

mêz = 15

0.0 0.5 1.0 1.5-0.2-0.1

0.00.10.20.30.4

mêz = 16

0.0 0.5 1.0 1.5

0.0

0.5

1.0

mêz = 17

0.0 0.5 1.0 1.5

0

10

20

30

mêz = 18

0.0 0.5 1.0 1.5-0.10

-0.05

0.00

0.05

0.10mêz = 19

0.0 0.5 1.0 1.5

-0.10

-0.05

0.00

0.05

0.10mêz = 20

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 21

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 22

0.0 0.5 1.0 1.5-0.10

-0.05

0.00

0.05

0.10

mêz = 23

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

4 CL20012PreliminaryAnalysis_dws1.nb

A-36

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 24

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 25

0.0 0.5 1.0 1.5-0.10

-0.05

0.00

0.05

mêz = 26

0.0 0.5 1.0 1.50123456

mêz = 27

0.0 0.5 1.0 1.50

5

10

15

20

25mêz = 28

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

2.0

mêz = 29

0.0 0.5 1.0 1.50

20406080

100120

mêz = 30

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.50.6

mêz = 31

0.0 0.5 1.0 1.5

-0.1

0.0

0.1

0.2

0.3

mêz = 32

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 33

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 34

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 35

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.15-0.10-0.05

0.000.050.100.15

mêz = 36

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 37

0.0 0.5 1.0 1.5

-0.10

-0.05

0.00

0.05

0.10

mêz = 38

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 39

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 40

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.4

mêz = 41

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 42

0.0 0.5 1.0 1.50

2

4

6

8

10mêz = 43

0.0 0.5 1.0 1.505

101520253035

mêz = 44

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

2.5mêz = 45

0.0 0.5 1.0 1.50

50

100

150

mêz = 46

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 47

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 5

A-37

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 48

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 49

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 50

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 51

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 52

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.5

mêz = 53

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 54

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.21.4

mêz = 55

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.5

mêz = 56

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.50.6

mêz = 57

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.4

mêz = 58

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 59

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 60

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 61

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 62

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 63

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 64

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 65

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 66

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 67

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 68

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 69

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 70

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 71

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

6 CL20012PreliminaryAnalysis_dws1.nb

A-38

0.0 0.5 1.0 1.5-0.1

0.0

0.1

0.2

0.3

0.4mêz = 72

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

mêz = 73

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 74

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15

mêz = 75

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 76

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 77

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 78

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 79

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 80

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 81

0.0 0.5 1.0 1.50

5

10

15

20

25mêz = 82

0.0 0.5 1.0 1.50

1

2

3

4mêz = 83

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 84

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 85

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 86

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 87

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15

mêz = 88

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.21.4

mêz = 89

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 90

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 91

0.0 0.5 1.0 1.5-0.10-0.05

0.000.050.100.150.20

mêz = 92

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 93

0.0 0.5 1.0 1.50123456

mêz = 94

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 95

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 7

A-39

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 96

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.21.4

mêz = 97

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 98

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 99

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.60.7

mêz = 100

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 101

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 102

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 103

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 104

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 105

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 106

0.0 0.5 1.0 1.50.00.51.01.52.02.53.03.5

mêz = 107

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.50

2

4

6

8

mêz = 108

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 109

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

2.0

mêz = 110

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

2.0mêz = 111

0.0 0.5 1.0 1.5-0.2

0.0

0.2

0.4

0.6

mêz = 112

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 113

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 114

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 115

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 116

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 117

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 118

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 119

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

8 CL20012PreliminaryAnalysis_dws1.nb

A-40

0.0 0.5 1.0 1.50

2

4

6

8mêz = 120

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 121

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 122

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0mêz = 123

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 124

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.50.6

mêz = 125

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 126

0.0 0.5 1.0 1.50

5

10

15

20

mêz = 127

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

2.5mêz = 128

0.0 0.5 1.0 1.5

-0.1

0.0

0.1

0.2

0.3

mêz = 129

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 130

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 131

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10mêz = 132

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 133

0.0 0.5 1.0 1.50.00.20.40.60.81.01.2

mêz = 134

0.0 0.5 1.0 1.50

1

2

3

4

5

mêz = 135

0.0 0.5 1.0 1.50.00.51.01.52.02.5

mêz = 136

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 137

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 138

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 139

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 140

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 141

0.0 0.5 1.0 1.5

-0.10-0.05

0.000.050.100.150.20

mêz = 142

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0mêz = 143

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 9

A-41

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 144

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 145

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 146

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 147

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 148

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 149

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 150

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 151

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 152

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 153

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 154

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.21.4

mêz = 155

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 156

0.0 0.5 1.0 1.5-0.1

0.0

0.1

0.2

0.3mêz = 157

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 158

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 159

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 160

0.0 0.5 1.0 1.50

1

2

3

4

5

mêz = 161

0.0 0.5 1.0 1.50

1

2

3

4mêz = 162

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.2

mêz = 163

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 164

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 165

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.60.7

mêz = 166

0.0 0.5 1.0 1.50.00.51.01.52.02.5

mêz = 167

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

10 CL20012PreliminaryAnalysis_dws1.nb

A-42

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 168

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 169

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 170

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 171

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 172

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 173

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 174

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 175

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 176

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 177

0.0 0.5 1.0 1.50

2

4

6

mêz = 178

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 179

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.050.000.050.100.15

mêz = 180

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 181

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.21.4

mêz = 182

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 183

0.0 0.5 1.0 1.5

-0.10-0.05

0.000.050.100.15

mêz = 184

0.0 0.5 1.0 1.5-0.15-0.10-0.05

0.000.050.100.15

mêz = 185

0.0 0.5 1.0 1.5-0.1

0.0

0.1

0.2

0.3

mêz = 186

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 187

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15

mêz = 188

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 189

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 190

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 191

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 11

A-43

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 192

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 193

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.60.7

mêz = 194

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 195

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 196

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0mêz = 197

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15

mêz = 198

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 199

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 200

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 201

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 202

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 203

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 204

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 205

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 206

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 207

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 208

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 209

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 210

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 211

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 212

0.0 0.5 1.0 1.502468

1012

mêz = 213

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 214

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 215

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

12 CL20012PreliminaryAnalysis_dws1.nb

A-44

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 216

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 217

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 218

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 219

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 220

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 221

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 222

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 223

0.0 0.5 1.0 1.50

1

2

3

4mêz = 224

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 225

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 226

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 227

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 228

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 229

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 230

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 231

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 232

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 233

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 234

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 235

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 236

0.0 0.5 1.0 1.5

0.00

0.05

0.10

0.15

mêz = 237

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 238

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 239

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 13

A-45

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 240

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10mêz = 241

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 242

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

mêz = 243

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 244

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 245

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 246

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 247

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 248

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 249

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 250

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 251

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 252

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 253

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 254

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 255

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 256

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 257

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 258

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 259

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 260

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 261

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 262

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 263

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

14 CL20012PreliminaryAnalysis_dws1.nb

A-46

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 264

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 265

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 266

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 267

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 268

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 269

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

2.0

mêz = 270

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 271

0.0 0.5 1.0 1.5

-0.2

-0.1

0.0

0.1

mêz = 272

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 273

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 274

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 275

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 276

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 277

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 278

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 279

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 280

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 281

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 282

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 283

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 284

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 285

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 286

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 287

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 15

A-47

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 288

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 289

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 290

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 291

0.0 0.5 1.0 1.5

-0.02

0.00

0.02

0.04

mêz = 292

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 293

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 294

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 295

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 296

0.0 0.5 1.0 1.5

-0.10

-0.05

0.00

0.05

mêz = 297

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 298

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 299

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 300

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 301

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 302

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 303

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 304

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 305

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 306

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 307

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 308

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 309

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 310

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 311

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

16 CL20012PreliminaryAnalysis_dws1.nb

A-48

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 312

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 313

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 314

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 315

0.0 0.5 1.0 1.50

1

2

3

4

5mêz = 316

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 317

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 318

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 319

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 320

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 321

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 322

0.0 0.5 1.0 1.5-0.06

-0.04

-0.02

0.00

0.02

mêz = 323

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

mêz = 324

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 325

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 326

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 327

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 328

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 329

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 330

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 331

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 332

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 333

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

mêz = 334

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 335

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 17

A-49

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 336

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 337

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 338

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 339

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 340

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 341

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 342

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 343

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 344

0.0 0.5 1.0 1.5

-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 345

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 346

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 347

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 348

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 349

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 350

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 351

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 352

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 353

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 354

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 355

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 356

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 357

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 358

0.0 0.5 1.0 1.5-0.10

-0.05

0.00

0.05mêz = 359

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

18 CL20012PreliminaryAnalysis_dws1.nb

A-50

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 360

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 361

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 362

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 363

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 364

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 365

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 366

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 367

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 368

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 369

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 370

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 371

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 372

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 373

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 374

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 375

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 376

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 377

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 378

0.0 0.5 1.0 1.5

-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 379

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 380

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 381

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 382

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 383

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 19

A-51

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 384

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 385

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 386

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 387

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 388

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 389

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 390

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 391

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 392

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 393

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 394

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 395

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 396

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 397

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 398

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 399

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 400

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 401

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 402

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 403

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 404

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 405

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 406

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 407

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

20 CL20012PreliminaryAnalysis_dws1.nb

A-52

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 408

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 409

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 410

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 411

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 412

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 413

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 414

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 415

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 416

0.0 0.5 1.0 1.5-0.10

-0.05

0.00

0.05

mêz = 417

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 418

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 419

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 420

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 421

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 422

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 423

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 424

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 425

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 426

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 427

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 428

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 429

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 430

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 431

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20012PreliminaryAnalysis_dws1.nb 21

A-53

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 432

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 433

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 434

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 435

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 436

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 437

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 438

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 439

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 440

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 441

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 442

0.0 0.5 1.0 1.5-0.10

-0.05

0.00

0.05mêz = 443

"Time Hs x10000.L""Data File: CL20012.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 444

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 445

"Time Hs x10000.L"Ion Signals Plots #2: time range 0 to 17320sec.Ë Comments: Ion signals greater than 0.1 percent total signal were smoothed and replotted as a function of Temperature °C. Signals emerge

at 170°C and most fall abruptly at ~230°C when the sample is depleted."Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

mêz = 17

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0

10

20

30

mêz = 18

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00123456

mêz = 27

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

5

10

15

20

25mêz = 28

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

2.0

mêz = 29

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

20406080

100120

mêz = 30

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0-0.1

0.00.10.20.30.4

mêz = 41

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

mêz = 42

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

8

10mêz = 43

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.005

101520253035

mêz = 44

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0

2.5mêz = 45

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

50

100

150

mêz = 46

22 CL20012PreliminaryAnalysis_dws1.nb

A-54

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

mêz = 47

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 48

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 54

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.21.4

mêz = 55

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0-0.1

0.00.10.20.30.40.5

mêz = 56

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0-0.1

0.00.10.20.30.40.50.6

mêz = 57

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 62

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 66

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

mêz = 68

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 69

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

mêz = 70

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 71

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

mêz = 73

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 80

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

mêz = 81

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

5

10

15

20

25mêz = 82

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4mêz = 83

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 84

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

mêz = 85

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.21.4

mêz = 89

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 93

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00123456

mêz = 94

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 95

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 96

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

CL20012PreliminaryAnalysis_dws1.nb 23

A-55

p

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.21.4

mêz = 97

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 98

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.10.20.30.40.50.60.7

mêz = 100

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 106

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.03.5

mêz = 107

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

8

mêz = 108

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 109

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0

mêz = 110

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

2.0mêz = 111

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0-0.2

0.0

0.2

0.4

0.6

mêz = 112

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

mêz = 113

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

mêz = 119

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

8mêz = 120

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 121

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 122

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 123

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 124

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0-0.1

0.00.10.20.30.40.50.6

mêz = 125

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 126

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

5

10

15

20

mêz = 127

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0

2.5mêz = 128

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.10.20.30.40.5

mêz = 133

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.20.40.60.81.01.2

mêz = 134

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0012345

mêz = 135

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

24 CL20012PreliminaryAnalysis_dws1.nb

A-56

p

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.5

mêz = 136

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 137

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

mêz = 138

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 139

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

mêz = 140

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 143

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 145

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 148

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 151

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 152

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

mêz = 154

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.21.4

mêz = 155

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

mêz = 156

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 160

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5

mêz = 161

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4mêz = 162

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.2

mêz = 163

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 164

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.10.20.30.40.50.60.7

mêz = 166

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.5

mêz = 167

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 170

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 177

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

mêz = 178

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 179

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

CL20012PreliminaryAnalysis_dws1.nb 25

A-57

p

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 181

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.21.4

mêz = 182

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 197

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 207

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

mêz = 209

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.002468

1012

mêz = 213

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 214

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4mêz = 224

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

mêz = 243

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 259

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5

2.0

mêz = 270

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 300

"Temperature H°C x100.L""Data File: CL20012.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5mêz = 316

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8mêz = 317

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 392

"Temperature H°C x100.L"Correlations Analysis of Ion Signals

Correlated Signals #1: time range 0 to 17320sec.Ë Comments: Several groups of correlated ions were found in a 95 percent correlation analysis of smoothed signals greater than 0.1 percent

total signal. The last three plots are odd and should be thrown-out.

::112.

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

Time Hsec x10000L

Centroid Time =4869.19

,

112

0 100 200 300 4000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 13Limits: 0.95 - 1.0001

>,

:85.

0.0 0.5 1.0 1.5

0.000.050.100.150.200.250.30

Time Hsec x10000L

Centroid Time =5097.12

,

85

0 100 200 300 4000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 12Limits: 0.95 - 1.0001

>,

26 CL20012PreliminaryAnalysis_dws1.nb

A-58

:57.

0.0 0.5 1.0 1.5

0.000.050.100.150.200.250.300.35

Time Hsec x10000L

Centroid Time =5284.71

,

57

0 100 200 300 4000.00

0.05

0.10

0.15

Mass

Sig

nalH%

L

Band Ò1 Group Ò 10Limits: 0.95 - 1.0001

>,

:46.

0.0 0.5 1.0 1.50

50

100

150

Time Hsec x10000L

Centroid Time =5669.65

,

46

0 100 200 300 40005

101520253035

Mass

Sig

nalH%

LBand Ò1 Group Ò 7

Limits: 0.95 - 1.0001

>,

:41.

0.0 0.5 1.0 1.5

0.000.050.100.150.200.250.30

Time Hsec x10000L

Centroid Time =5750.05

,

41

0 100 200 300 4000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 4Limits: 0.95 - 1.0001

>,

:82.

0.0 0.5 1.0 1.50

5

10

15

Time Hsec x10000L

Centroid Time =5785.94

,

82

0 100 200 300 4000.0

0.5

1.0

1.5

2.0

Mass

Sig

nalH%

L

Band Ò1 Group Ò 11Limits: 0.95 - 1.0001

>,

:29.45.47.54.55.62.66.68.69.70.71.73.80.81.83.84.89.93.94.95.96.97.98.100.106.107.108.109.

110.111.113.

119.

120.121.

122.

123.124.125.126.128.134.135.136.137.139.140.143.148.151.152.154.155.156.161.162.163.164.166.167.170.177.178.179.181.182.197.207.209.213.214.224.270.316.317.392.

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =5799.85

,

29454754556266686970717380818384899394

95969798100106107

108

109110111113119

120

121122123124125126128134

135136137139140143148151152154155156

161162163164166167170177

178

179181182197207209

213

214224

270316

317 3920 100 200 300 400

0.00.51.01.52.02.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 3Limits: 0.95 - 1.0001

>,

:18. 28. 30. 44. 127.

0.0 0.5 1.0 1.50

20

40

60

80

100

Time Hsec x10000L

Centroid Time =5882.07

, 1828

30

44127

0 100 200 300 40002468

101214

Mass

Sig

nalH%

L

Band Ò1 Group Ò 2Limits: 0.95 - 1.0001

>,

CL20012PreliminaryAnalysis_dws1.nb 27

A-59

:56.

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

Time Hsec x10000L

Centroid Time =6058.

,

56

0 100 200 300 4000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 9Limits: 0.95 - 1.0001

>,

:133.

0.0 0.5 1.0 1.5

0.000.050.100.150.200.250.300.35

Time Hsec x10000L

Centroid Time =6899.01

,

133

0 100 200 300 4000.000.020.040.060.080.100.120.14

Mass

Sig

nalH%

LBand Ò1 Group Ò 14Limits: 0.95 - 1.0001

>,

:17.

27.145.

0.0 0.5 1.0 1.50

1

2

3

Time Hsec x10000L

Centroid Time =7273.98

,17

27

145

0 100 200 300 4000.00.20.40.60.81.01.2

Mass

Sig

nalH%

L

Band Ò1 Group Ò 1Limits: 0.95 - 1.0001

>,

:43.

0.0 0.5 1.0 1.501234567

Time Hsec x10000L

Centroid Time =7603.91

,

43

0 100 200 300 4000.00.51.01.52.02.53.0

Mass

Sig

nalH%

L

Band Ò1 Group Ò 6Limits: 0.95 - 1.0001

>,

:160.

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

Time Hsec x10000L

Centroid Time =7709.67

,

160

0 100 200 300 4000.000.050.100.150.200.25

Mass

Sig

nalH%

L

Band Ò1 Group Ò 15Limits: 0.95 - 1.0001

>,

:42.

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

Time Hsec x10000L

Centroid Time =8204.3

,

42

0 100 200 300 4000.000.050.100.150.200.250.30

Mass

Sig

nalH%

L

Band Ò1 Group Ò 5Limits: 0.95 - 1.0001

>,

28 CL20012PreliminaryAnalysis_dws1.nb

A-60

:259.

0.0 0.5 1.0 1.50.00

0.01

0.02

0.03

0.04

Time Hsec x10000L

Centroid Time =9051.77

,

259

0 100 200 300 4000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 17Limits: 0.95 - 1.0001

>,

:48.

138.

300.

0.0 0.5 1.0 1.5

-0.0050.0000.0050.0100.0150.0200.025

Time Hsec x10000L

Centroid Time =9238.46

,

300

0 100 200 300 4000.000.020.040.060.080.100.12

Mass

Sig

nalH%

LBand Ò1 Group Ò 8

Limits: 0.95 - 1.0001

>,

:243.

0.0 0.5 1.0 1.5

-0.010-0.005

0.0000.0050.0100.015

Time Hsec x10000L

Centroid Time =17736.

,

243

0 100 200 300 4000.0000.0050.0100.0150.0200.025

Mass

Sig

nalH%

L

Band Ò1 Group Ò 16Limits: 0.95 - 1.0001

>>

Tables of Mass Spectral InformationMass Spec Table #1: time range 0 to 17320sec.Ë Comments: Table summary of raw ion signals for all m/z scanned:

Ion signals greater than 0.% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L12 0. 121 0.6 230 0. 339 0.

13 0. 122 0.2 231 0. 340 0.

14 0. 123 0.1 232 0. 341 0.

15 0. 124 0.1 233 0. 342 0.

16 0.1 125 0.1 234 0. 343 0.

17 0.4 126 0.5 235 0. 344 0.

18 5.6 127 1.8 236 0. 345 0.

19 0. 128 0.4 237 0. 346 0.

20 0. 129 0.1 238 0. 347 0.

21 0. 130 0.1 239 0. 348 0.

22 0. 131 0. 240 0.1 349 0.

23 0. 132 0. 241 0. 350 0.

24 0. 133 0.1 242 0. 351 0.

25 0. 134 0.2 243 0.1 352 0.

26 0. 135 1.2 244 0. 353 0.

27 1.1 136 0.6 245 0.1 354 0.

28 2.6 137 0.5 246 0.1 355 0.

29 0.4 138 0.1 247 0. 356 0.

30 12.1 139 0.1 248 0. 357 0.

31 0 1 140 0 1 249 0 358 0

CL20012PreliminaryAnalysis_dws1.nb 29

A-61

31 0.1 140 0.1 249 0. 358 0.

32 0.1 141 0. 250 0. 359 0.

33 0. 142 0. 251 0. 360 0.

34 0. 143 0.2 252 0. 361 0.

35 0. 144 0. 253 0. 362 0.

36 0.1 145 0.2 254 0.1 363 0.

37 0. 146 0.1 255 0. 364 0.

38 0. 147 0.1 256 0. 365 0.

39 0. 148 0.2 257 0. 366 0.

40 0. 149 0.1 258 0. 367 0.

41 0.1 150 0.1 259 0.1 368 0.

42 0.3 151 0.2 260 0. 369 0.

43 2.9 152 0.2 261 0. 370 0.

44 3.8 153 0.1 262 0. 371 0.

45 0.3 154 0.3 263 0. 372 0.

46 31.7 155 0.2 264 0. 373 0.

47 0.5 156 0.2 265 0. 374 0.

48 0.2 157 0. 266 0. 375 0.

49 0. 158 0. 267 0. 376 0.

50 0. 159 0. 268 0. 377 0.

51 0. 160 0.2 269 0. 378 0.

52 0.1 161 1. 270 0.4 379 0.

53 0.1 162 0.6 271 0.1 380 0.

54 0.2 163 0.2 272 0. 381 0.

55 0.3 164 0.1 273 0.1 382 0.

56 0.1 165 0.1 274 0. 383 0.

57 0.1 166 0.1 275 0. 384 0.

58 0.1 167 0.4 276 0. 385 0.

59 0.1 168 0. 277 0. 386 0.

60 0. 169 0. 278 0. 387 0.

61 0. 170 0.2 279 0. 388 0.

62 0.1 171 0.1 280 0. 389 0.

63 0. 172 0. 281 0. 390 0.

64 0. 173 0. 282 0. 391 0.

65 0. 174 0. 283 0. 392 0.2

66 0.2 175 0. 284 0. 393 0.1

67 0.1 176 0.1 285 0. 394 0.

68 0.4 177 0.1 286 0. 395 0.

69 0.2 178 1.3 287 0. 396 0.

70 0.4 179 0.1 288 0. 397 0.

71 0.2 180 0. 289 0. 398 0.

72 0.1 181 0.1 290 0. 399 0.

73 0.3 182 0.2 291 0. 400 0.

74 0. 183 0.1 292 0. 401 0.

75 0. 184 0. 293 0. 402 0.

76 0 185 0 294 0 403 0

30 CL20012PreliminaryAnalysis_dws1.nb

A-62

76 0. 185 0. 294 0. 403 0.

77 0. 186 0.1 295 0. 404 0.

78 0. 187 0. 296 0. 405 0.

79 0. 188 0. 297 0. 406 0.

80 0.2 189 0. 298 0. 407 0.

81 0.7 190 0. 299 0. 408 0.

82 1.9 191 0. 300 0.3 409 0.

83 0.7 192 0.1 301 0. 410 0.

84 0.3 193 0. 302 0. 411 0.

85 0.1 194 0.1 303 0. 412 0.

86 0.1 195 0. 304 0. 413 0.

87 0. 196 0. 305 0. 414 0.

88 0. 197 0.2 306 0. 415 0.

89 0.1 198 0. 307 0. 416 0.

90 0. 199 0. 308 0. 417 0.

91 0. 200 0.1 309 0. 418 0.

92 0. 201 0. 310 0. 419 0.

93 0.5 202 0. 311 0. 420 0.

94 1. 203 0. 312 0. 421 0.

95 0.3 204 0. 313 0. 422 0.

96 0.2 205 0. 314 0. 423 0.

97 0.3 206 0. 315 0. 424 0.

98 0.2 207 0.2 316 1. 425 0.

99 0. 208 0.1 317 0.1 426 0.

100 0.1 209 0.1 318 0. 427 0.

101 0. 210 0. 319 0. 428 0.

102 0. 211 0. 320 0. 429 0.

103 0. 212 0. 321 0. 430 0.

104 0. 213 2.3 322 0. 431 0.

105 0. 214 0.2 323 0. 432 0.

106 0.1 215 0. 324 0. 433 0.

107 0.6 216 0. 325 0. 434 0.

108 1.4 217 0. 326 0. 435 0.

109 0.5 218 0. 327 0. 436 0.

110 0.4 219 0. 328 0. 437 0.

111 0.3 220 0. 329 0. 438 0.

112 0.1 221 0. 330 0. 439 0.

113 0.3 222 0. 331 0. 440 0.

114 0.1 223 0. 332 0. 441 0.

115 0. 224 0.8 333 0. 442 0.

116 0. 225 0.1 334 0. 443 0.

117 0. 226 0. 335 0. 444 0.

118 0.1 227 0.1 336 0. 445 0.

119 0.1 228 0. 337 0.

120 1.3 229 0. 338 0.

CL20012PreliminaryAnalysis_dws1.nb 31

A-63

CL20016Author: Deneille Wiese-Smith

Overviewü Purpose

The primary purpose of this experiment is to learn the MS sublimation signature of the CL-20 sample from China Lake in this 175°C isothermal heating experiment under the low confinement of a 1006µm diameter alumina orifice. This is similar to CL20013, which heated to 195°C. CL-20 is 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, also called HNIW, C6H6N12O12, MW 438.1850.

ü Experiment DescriptionA small alumina type reaction cell, fitted with a alumina style cap assembly having an orifice diameter of 1006 µm was loaded with the sample.

The sample is comprised of one compound. The bottom section is loaded with 5.45 mg of DRIED CL-20 powder (sample ID # CL20-CLPP01).

ü SummaryThe weight and temperature data quality is adequate. There is some noise pickup, which is common at this time in the STMBMS DAQ system.The weight loss rate is almost constant during the initial 9000 seconds (2.5 hours) holding at 175°C then begins to slowly accelerate.

Although it continues to accelerate, it never reaches the point where rapid gas evolution causes a thrust in the microbalance (as we saw in CL20013).At the time of this report, the reaction cell assembly has not yet been removed from the STMBMS and the residue examined. Thus, no description of the residue will be found in this write-up. (Check the database for residue description and condition of the orifice.)The ion signal data quality is adequate. Signals are generally small and, therefore, somewhat noisy.

The baseline noise is 0.03cts/ms generally which is about the same as seen in experiment ran since August 2012 maintenance.

There aren't many ion signals with a constant (flat) profile over the period when the weight loss was constant [characteristic of sublimation]. Most ion signals are either decaying, accelerating or both. Because of this, I would say that the sample was decomposing at this temperature - not subliming.

Thermal Analysis Resultsü Overall TA Resultsü TA Overview Summary

Heating Profile

Profile type: Isothermal. (5°C/min to 165°C, 1°C/min to 170°C, 0.5°C/min to 175°C holding 20,000 seconds before cooling no faster than 5°C/min.The temperature of the experiment ranged from 19.5 to 179.3°C.

Sample mass info

The experiment started with a sample mass of 5.45mg.

The final mass with the sample measured in the experiment is 2.325mg.

Residue info is not available at the time of this report.

A-64

ü TA Overview Graphs

ü Display of Thermal Analysis Data„ Thermal Analysis Region #1

The time limits for this region was selected and will be used in further analysis in this notebook, unless changed at a later time.

The following plots show all thermogravimetric data in the experiment. There is some noise pickup in both the temperature and weight data, which is common for the STMBMS DAQ at this time. Weight loss, which was initially constant, appears to accelerate around 12,000 seconds (after holding at 175°C ~9000 seconds=2.5 hours.

"Time range: 23.041 to 25018.9 sec.""Parameters for subset: "

" Minimum Time: 23.041 Maximum Time: 25018.9Minimum Temp: 19.517 Maximum Temp: 179.331Minimum Weight: 2.3197 Maximum Weight: 5.4662A residue of 2.325mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.517 Maximum Temp: 179.331"

" Minimum Weight: 2.3197 Maximum Weight: 5.4662"

" Start time = 10.081 Final time = 25025.Balance drift factor =9.194505363594589`*^-8 mgêsec."

0 5000 10 000 15 000 20 000 25 000

50

100

150

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 5000 10 000 15 000 20 000 25 0000

1

2

3

4

5

Time HsLW

eigh

tHmgL

Weight HmgL

0 5000 10 000 15 000 20 000 25 000-0.03

-0.02

-0.01

0.00

0.01

0.02

0.03

0.04

Time HsL

DT

AHCL

DTA HCL

50 100 1500

1

2

3

4

5

Temperature HCL

Wei

ghtHm

gLWeight HmgL

„ Thermal Analysis Region #2

The data was replotted to better view the early weight data. There was a slight weight gain as the instrument began heating, which is common in the STMBMS but not well understood.

"Time range: 23.041 to 4994.03 sec.""Parameters for subset: "

" Minimum Time: 23.041 Maximum Time: 4994.03Minimum Temp: 19.517 Maximum Temp: 179.331Minimum Weight: 5.1461 Maximum Weight: 5.4662A residue of 2.325mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.517 Maximum Temp: 179.331"

" Minimum Weight: 2.3197 Maximum Weight: 5.4662"

" Start time = 10.081 Final time = 25025.Balance drift factor = 9.194505363594589`*^-8 mgêsec."

0 1000 2000 3000 4000 50000

50

100

150

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 1000 2000 3000 4000 5000

5.15

5.20

5.25

5.30

5.35

5.40

5.45

Time HsL

Wei

ghtHm

gL

Weight HmgL

2 CL20016PreliminaryAnalysis_dws1.nb

A-65

0 1000 2000 3000 4000 5000

-0.02

-0.01

0.00

0.01

0.02

Time HsL

DT

AHCL

DTA HCL

50 100 150

5.15

5.20

5.25

5.30

5.35

5.40

5.45

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

ü Temperature Segment Analysisü Temperature Segment Overview Summary

The number of different types of segments identified are as follows:

Heating: 4

Cooling: 2

Isothermal: 1

ü Display of Temperature Segment Analysis„ Temperature Analysis #1: Cluster Display

Four cluster group analysis of all temperature data will be plotted twice: as a funciton of Rate °C/s and of Temperature °C. The number of span points was lowered to mitigate the effect of the noise pickup on this algorithm, which worked well enough. The PID control and furnace response was adequate.

5000 10 000 15 000 20 000 25 000

-0.04

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

Time HsL

Rat

eH°Cê

sL

Ò groups = 4 low index = 1 high index = 266

„ Temperature Analysis #2: BreakPoint Display

5000 10 000 15 000 20 000 25 000

50

100

150

Time HsL

Tem

pera

ture

H°CL

CL20016PreliminaryAnalysis_dws1.nb 3

A-66

„ Temperature Analysis #3: Segment Table

TimeHsL TempH°CL Heat RateH°CêminL DurationHsL Type

10. 19.8 0.09 131. up

141. 20.0 1.79 112. up

252. 23.7 5.20 1620. up

1872. 161.6 1.58 423. up

2295. 171.3 0.00 20436. isothermal

22730. 175.3 -2.31 2295. down

25025. 92.0 -2.31 0. down

ü General STMBMS Ion Signalsü Ion Signals Plots #1: time range 0 to 25459sec.

Comments: Raw ion signals for all m/z scanned in the experiment have been plotted vs. time (seconds). The baseline noise is +/-0.03cts/ms generally and much larger at m/z 18 - and where signal is present generally. This is similar to other experiments ran since August 2012. Most of the signals are rather small. The largest are m/z 30, 46,44, 28 and 43.

"Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 12

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 13

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 14

0.0 0.5 1.0 1.5 2.0 2.5-0.10

-0.05

0.00

0.05

0.10

mêz = 15

0.0 0.5 1.0 1.5 2.0 2.5-0.15-0.10-0.05

0.000.050.100.150.20

mêz = 16

0.0 0.5 1.0 1.5 2.0 2.5

-0.1

0.0

0.1

0.2

0.3mêz = 17

0.0 0.5 1.0 1.5 2.0 2.5

012345

mêz = 18

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 19

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 20

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 21

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 22

0.0 0.5 1.0 1.5 2.0 2.5-0.10

-0.05

0.00

0.05

mêz = 23

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

4 CL20016PreliminaryAnalysis_dws1.nb

A-67

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 24

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 25

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 26

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

0.8

mêz = 27

0.0 0.5 1.0 1.5 2.0 2.5-0.5

0.00.51.01.52.02.53.0

mêz = 28

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.5

mêz = 29

0.0 0.5 1.0 1.5 2.0 2.50

5

10

15

mêz = 30

0.0 0.5 1.0 1.5 2.0 2.5

-0.050.000.050.100.15

mêz = 31

0.0 0.5 1.0 1.5 2.0 2.5-0.10-0.05

0.000.050.100.150.20

mêz = 32

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 33

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

mêz = 34

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 35

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

-0.10

-0.05

0.00

0.05

0.10

mêz = 36

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 37

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 38

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 39

0.0 0.5 1.0 1.5 2.0 2.5-0.10

-0.05

0.00

0.05

0.10

mêz = 40

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10

0.15mêz = 41

0.0 0.5 1.0 1.5 2.0 2.5

-0.050.000.050.100.150.200.25

mêz = 42

0.0 0.5 1.0 1.5 2.0 2.50.0

0.5

1.0

1.5

2.0

mêz = 43

0.0 0.5 1.0 1.5 2.0 2.5012345

mêz = 44

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.50.6

mêz = 45

0.0 0.5 1.0 1.5 2.0 2.502468

1012

mêz = 46

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.50.6

mêz = 47

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20016PreliminaryAnalysis_dws1.nb 5

A-68

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 48

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 49

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 50

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 51

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10mêz = 52

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 53

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.250.30

mêz = 54

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 55

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10

0.15mêz = 56

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3mêz = 57

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15

mêz = 58

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 59

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 60

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.5

mêz = 61

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 62

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 63

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 64

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 65

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.25

mêz = 66

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 67

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.250.30

mêz = 68

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 69

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

mêz = 70

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 71

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

6 CL20016PreliminaryAnalysis_dws1.nb

A-69

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.08

mêz = 72

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 73

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.08

mêz = 74

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 75

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 76

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 77

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

mêz = 78

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 79

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 80

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

mêz = 81

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

0.5mêz = 82

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 83

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 84

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 85

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 86

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 87

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.25

mêz = 88

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

mêz = 89

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.08

mêz = 90

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 91

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 92

0.0 0.5 1.0 1.5 2.0 2.50.00.10.20.30.40.50.60.7

mêz = 93

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 94

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20mêz = 95

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20016PreliminaryAnalysis_dws1.nb 7

A-70

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 96

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 97

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 98

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15

mêz = 99

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 100

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 101

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 102

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 103

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 104

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 105

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10mêz = 106

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 107

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

mêz = 108

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

mêz = 109

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 110

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 111

0.0 0.5 1.0 1.5 2.0 2.5

-0.10-0.05

0.000.050.100.15

mêz = 112

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 113

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 114

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 115

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 116

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 117

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 118

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.08

mêz = 119

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

8 CL20016PreliminaryAnalysis_dws1.nb

A-71

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

mêz = 120

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20mêz = 121

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10mêz = 122

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 123

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 124

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 125

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

mêz = 126

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4mêz = 127

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

mêz = 128

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 129

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 130

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 131

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 132

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 133

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 134

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 135

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.25

mêz = 136

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.20

mêz = 137

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.08

mêz = 138

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 139

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 140

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 141

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 142

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 143

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20016PreliminaryAnalysis_dws1.nb 9

A-72

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 144

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 145

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.060.08

mêz = 146

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 147

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 148

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 149

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 150

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 151

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10mêz = 152

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

mêz = 153

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 154

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 155

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 156

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 157

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 158

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 159

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 160

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 161

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.25

mêz = 162

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 163

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 164

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.060.080.10

mêz = 165

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.060.080.10

mêz = 166

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 167

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

10 CL20016PreliminaryAnalysis_dws1.nb

A-73

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 168

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 169

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 170

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 171

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 172

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 173

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 174

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 175

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 176

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.060.080.10

mêz = 177

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.50.6

mêz = 178

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 179

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.08

mêz = 180

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 181

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 182

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

mêz = 183

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 184

0.0 0.5 1.0 1.5 2.0 2.5

-0.10-0.05

0.000.050.100.15

mêz = 185

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 186

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.06

mêz = 187

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 188

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 189

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 190

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.06

mêz = 191

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20016PreliminaryAnalysis_dws1.nb 11

A-74

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 192

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 193

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.060.080.10

mêz = 194

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 195

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04mêz = 196

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 197

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 198

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 199

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.06

mêz = 200

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04mêz = 201

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 202

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

mêz = 203

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.04

mêz = 204

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 205

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 206

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15mêz = 207

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10mêz = 208

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 209

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 210

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 211

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 212

0.0 0.5 1.0 1.5 2.0 2.50.0

0.2

0.4

0.6

0.8

mêz = 213

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

mêz = 214

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 215

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

12 CL20016PreliminaryAnalysis_dws1.nb

A-75

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 216

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 217

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 218

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 219

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 220

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.04

mêz = 221

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 222

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 223

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

mêz = 224

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 225

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 226

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 227

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.04

mêz = 228

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 229

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 230

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 231

0.0 0.5 1.0 1.5 2.0 2.5

-0.02

0.00

0.02

0.04

mêz = 232

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.04

mêz = 233

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 234

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 235

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 236

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 237

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 238

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 239

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20016PreliminaryAnalysis_dws1.nb 13

A-76

0.0 0.5 1.0 1.5 2.0 2.5

-0.020.000.020.040.060.080.10

mêz = 240

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 241

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 242

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 243

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.04

mêz = 244

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 245

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 246

0.0 0.5 1.0 1.5 2.0 2.5-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 247

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 248

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 249

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 250

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 251

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 252

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 253

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10mêz = 254

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 255

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 256

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 257

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 258

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

0.15mêz = 259

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 260

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 261

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 262

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 263

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

14 CL20016PreliminaryAnalysis_dws1.nb

A-77

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 264

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 265

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 266

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 267

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 268

0.0 0.5 1.0 1.5 2.0 2.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 269

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.250.30

mêz = 270

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 271

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 272

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10mêz = 273

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 274

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 275

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 276

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 277

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 278

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 279

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 280

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 281

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 282

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 283

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 284

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 285

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 286

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 287

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

CL20016PreliminaryAnalysis_dws1.nb 15

A-78

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 288

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 289

0.0 0.5 1.0 1.5 2.0 2.5

-0.08-0.06-0.04-0.02

0.000.020.04

mêz = 290

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 291

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 292

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 293

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 294

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.04

mêz = 295

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

mêz = 296

0.0 0.5 1.0 1.5 2.0 2.5-0.10

-0.05

0.00

0.05

0.10mêz = 297

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10mêz = 298

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 299

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 300

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.00

0.05

0.10

mêz = 301

0.0 0.5 1.0 1.5 2.0 2.5-0.06-0.04-0.02

0.000.020.04

mêz = 302

0.0 0.5 1.0 1.5 2.0 2.5

-0.2

-0.1

0.0

0.1

mêz = 315

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

mêz = 316

0.0 0.5 1.0 1.5 2.0 2.5

-0.05

0.00

0.05

0.10

0.15mêz = 317

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 318

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 319

0.0 0.5 1.0 1.5 2.0 2.5

-0.04

-0.02

0.00

0.02

0.04mêz = 320

0.0 0.5 1.0 1.5 2.0 2.5-0.10

-0.05

0.00

0.05

mêz = 321

0.0 0.5 1.0 1.5 2.0 2.5

-0.06-0.04-0.02

0.000.020.04

mêz = 322

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.060.08

mêz = 346

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

16 CL20016PreliminaryAnalysis_dws1.nb

A-79

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.040.06

mêz = 347

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 365

0.0 0.5 1.0 1.5 2.0 2.5-0.04

-0.02

0.00

0.02

0.04

mêz = 390

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 391

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20mêz = 392

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10mêz = 393

0.0 0.5 1.0 1.5 2.0 2.5-0.04-0.02

0.000.020.040.06

mêz = 394

0.0 0.5 1.0 1.5 2.0 2.5

-0.04-0.02

0.000.020.04

mêz = 395

"Time Hs x10000.L"ü Ion Signals Plots #2: time range 0 to 25459sec.

Comments: Ion signals greater than 0.1 percent total signal were smoothed and replotted vs. temperature °C for the sole purpose of seeing what evolves during the ramp to the 175°C isotherm. This format shows both heating and cooling data (which can look odd). It also compresses the isothermal data to a single point (which is the majority of the data) so don't read too much into the data. Besides adsorbed water (m/z 18), there are small signals at m/z 56, 71, 108, 135. It's hard to say whether the signals at m/z 70 and 73 are in the heating or cooling data.

"Data File: CL20016.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5

-0.1

0.0

0.1

0.2

0.3mêz = 17

0.5 1.0 1.5

012345

mêz = 18

0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 27

0.5 1.0 1.5-0.5

0.00.51.01.52.02.53.0

mêz = 28

0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 29

0.5 1.0 1.50

5

10

15

mêz = 30

0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15

mêz = 31

0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 42

0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

mêz = 43

0.5 1.0 1.50

1

2

3

4

5

mêz = 44

0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 45

0.5 1.0 1.502468

1012

mêz = 46

"Temperature H°C x100.L""Data File: CL20016.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

CL20016PreliminaryAnalysis_dws1.nb 17

A-80

p

0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 47

0.5 1.0 1.5

0.00

0.05

0.10

mêz = 48

0.5 1.0 1.5-0.05

0.000.050.100.150.200.250.30

mêz = 54

0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 55

0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15

mêz = 56

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 58

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 62

0.5 1.0 1.5

0.000.050.100.150.200.25

mêz = 66

0.5 1.0 1.5

0.000.050.100.150.200.250.30

mêz = 68

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 69

0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 70

0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 71

"Temperature H°C x100.L""Data File: CL20016.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 73

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 80

0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 81

0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

0.5mêz = 82

0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 83

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 84

0.5 1.0 1.5

0.00

0.05

0.10

0.15

mêz = 89

0.5 1.0 1.5

0.00.10.20.30.40.50.60.7

mêz = 93

0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 94

0.5 1.0 1.5

0.00

0.05

0.10

0.15

0.20mêz = 95

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 96

0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 97

"Temperature H°C x100.L""Data File: CL20016.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

18 CL20016PreliminaryAnalysis_dws1.nb

A-81

p

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 107

0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 108

0.5 1.0 1.5

0.00

0.05

0.10

0.15

mêz = 109

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 110

0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 111

0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 120

0.5 1.0 1.5

0.00

0.05

0.10

0.15

0.20mêz = 121

0.5 1.0 1.5

0.00

0.05

0.10

0.15

0.20

mêz = 126

0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 127

0.5 1.0 1.5

0.00

0.05

0.10

0.15

0.20

mêz = 128

0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 134

0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 135

"Temperature H°C x100.L""Data File: CL20016.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5

0.000.050.100.150.200.25

mêz = 136

0.5 1.0 1.5

0.000.050.100.150.20

mêz = 137

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 145

0.5 1.0 1.5

0.00

0.05

0.10

mêz = 154

0.5 1.0 1.5

0.00

0.05

0.10

mêz = 155

0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 161

0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 162

0.5 1.0 1.5

0.00

0.05

0.10

mêz = 163

0.5 1.0 1.5

0.00

0.05

0.10

0.15mêz = 167

0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 178

0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 179

0.5 1.0 1.5

0.00

0.05

0.10

0.15mêz = 182

"Temperature H°C x100.L""Data File: CL20016.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

CL20016PreliminaryAnalysis_dws1.nb 19

A-82

p

0.5 1.0 1.5

0.00

0.05

0.10

0.15mêz = 197

0.5 1.0 1.5

0.00

0.05

0.10

0.15mêz = 207

0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 209

0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 213

0.5 1.0 1.5

0.00

0.05

0.10

0.15

mêz = 214

0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 224

0.5 1.0 1.5-0.05

0.000.050.100.150.200.250.30

mêz = 270

0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 300

0.5 1.0 1.5

0.0

0.2

0.4

0.6

mêz = 316

0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 317

0.5 1.0 1.5

0.00

0.05

0.10

0.15

0.20mêz = 392

"Temperature H°C x100.L"ü Ion Signals Plots #3: time range 0 to 25459sec.

Comments: The smoothed ions greater than 0.2 percent total signsl were replotted vs. time (seconds). Only a handfull suggest sublimation (have a flat profile where the weight loss was constant.) Most show growth or decay or both.

"Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

-0.1

0.0

0.1

0.2

0.3mêz = 17

0.0 0.5 1.0 1.5 2.0 2.5

012345

mêz = 18

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

0.8

mêz = 27

0.0 0.5 1.0 1.5 2.0 2.5-0.5

0.00.51.01.52.02.53.0

mêz = 28

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.5

mêz = 29

0.0 0.5 1.0 1.5 2.0 2.50

5

10

15

mêz = 30

0.0 0.5 1.0 1.5 2.0 2.50.0

0.5

1.0

1.5

2.0

mêz = 43

0.0 0.5 1.0 1.5 2.0 2.5012345

mêz = 44

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.50.6

mêz = 45

0.0 0.5 1.0 1.5 2.0 2.502468

1012

mêz = 46

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.50.6

mêz = 47

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.250.30

mêz = 54

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

20 CL20016PreliminaryAnalysis_dws1.nb

A-83

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.25

mêz = 66

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.250.30

mêz = 68

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

mêz = 70

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

mêz = 81

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

0.5mêz = 82

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 83

0.0 0.5 1.0 1.5 2.0 2.50.00.10.20.30.40.50.60.7

mêz = 93

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 94

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.20

mêz = 107

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

mêz = 108

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

mêz = 120

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20mêz = 121

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

mêz = 126

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4mêz = 127

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

mêz = 128

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 135

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.25

mêz = 136

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.20

mêz = 137

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

mêz = 161

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.25

mêz = 162

0.0 0.5 1.0 1.5 2.0 2.5

0.00.10.20.30.40.50.6

mêz = 178

0.0 0.5 1.0 1.5 2.0 2.50.0

0.2

0.4

0.6

0.8

mêz = 213

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

mêz = 224

0.0 0.5 1.0 1.5 2.0 2.5-0.05

0.000.050.100.150.200.250.30

mêz = 270

"Time Hs x10000.L""Data File: CL20016.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

mêz = 316

"Time Hs x10000.L"

CL20016PreliminaryAnalysis_dws1.nb 21

A-84

ü Correlations Analysis of Ion Signalsü Correlated Signals #1: time range 0 to 25459sec.

Comments: A 90 percent correlation analysis of the 37 ions greater than 0.2 percent total signal identifies 8 groupings. (Noisy ion signals don't correlate well.)

:: 126.127.

0.0 0.5 1.0 1.5 2.0 2.50.00

0.05

0.10

0.15

0.20

0.25

Time Hsec x10000L

Centroid Time =10185.9

, 126

127

0 50 100 150 200 250 3000.0

0.1

0.2

0.3

0.4

Mass

Sig

nalH%

L

Band Ò1 Group Ò 13Limits: 0.9 - 1.0001

>,

: 107.

108.

135.137.

0.0 0.5 1.0 1.5 2.0 2.5

0.000.050.100.150.200.250.30

Time Hsec x10000L

Centroid Time =10690.

,107

108135

137

0 50 100 150 200 250 3000.00.10.20.30.40.50.6

Mass

Sig

nalH%

L

Band Ò1 Group Ò 10Limits: 0.9 - 1.0001

>,

: 83.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

0.25

Time Hsec x10000L

Centroid Time =11280.5

,

83

0 50 100 150 200 250 3000.00.10.20.30.40.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 9Limits: 0.9 - 1.0001

>,

:213.

224. 316.

0.0 0.5 1.0 1.5 2.0 2.50.0

0.2

0.4

0.6

Time Hsec x10000L

Centroid Time =11325.

,

213

224316

0 50 100 150 200 250 3000.0

0.5

1.0

1.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 18Limits: 0.9 - 1.0001

>,

:270.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

Time Hsec x10000L

Centroid Time =11419.7

,

270

0 50 100 150 200 250 3000.0

0.1

0.2

0.3

0.4

Mass

Sig

nalH%

L

Band Ò1 Group Ò 19Limits: 0.9 - 1.0001

>,

: 136.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.02

0.04

0.06

0.08

0.10

Time Hsec x10000L

Centroid Time =11433.1

,

136

0 50 100 150 200 250 3000.000.050.100.150.200.25

Mass

Sig

nalH%

L

Band Ò1 Group Ò 15Limits: 0.9 - 1.0001

>,

22 CL20016PreliminaryAnalysis_dws1.nb

A-85

:82.

94.

178.

0.0 0.5 1.0 1.5 2.0 2.50.0

0.1

0.2

0.3

0.4

0.5

Time Hsec x10000L

Centroid Time =11442.2

,82

94

178

0 50 100 150 200 250 3000.00.20.40.60.81.01.2

Mass

Sig

nalH%

L

Band Ò1 Group Ò 8Limits: 0.9 - 1.0001

>,

: 162.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

Time Hsec x10000L

Centroid Time =11526.2

,

162

0 50 100 150 200 250 3000.000.050.100.150.200.250.30

Mass

Sig

nalH%

LBand Ò1 Group Ò 17Limits: 0.9 - 1.0001

>,

: 161.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

0.25

Time Hsec x10000L

Centroid Time =11940.9

,

161

0 50 100 150 200 250 3000.00.10.20.30.40.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 16Limits: 0.9 - 1.0001

>,

:121.

0.0 0.5 1.0 1.5 2.0 2.5

0.000.020.040.060.080.100.12

Time Hsec x10000L

Centroid Time =12367.4

,

121

0 50 100 150 200 250 3000.000.050.100.150.200.25

Mass

Sig

nalH%

L

Band Ò1 Group Ò 12Limits: 0.9 - 1.0001

>,

: 70.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

0.20

Time Hsec x10000L

Centroid Time =12848.4

,

70

0 50 100 150 200 250 3000.000.050.100.150.200.250.30

Mass

Sig

nalH%

L

Band Ò1 Group Ò 6Limits: 0.9 - 1.0001

>,

:46.

0.0 0.5 1.0 1.5 2.0 2.50

2

4

6

8

10

12

Time Hsec x10000L

Centroid Time =13135.7

,

46

0 50 100 150 200 250 30005

101520253035

Mass

Sig

nalH%

L

Band Ò1 Group Ò 4Limits: 0.9 - 1.0001

>,

CL20016PreliminaryAnalysis_dws1.nb 23

A-86

: 81.

0.0 0.5 1.0 1.5 2.0 2.50.000.050.100.150.200.250.300.35

Time Hsec x10000L

Centroid Time =13339.4

,

81

0 50 100 150 200 250 3000.00.10.20.30.40.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 7Limits: 0.9 - 1.0001

>,

: 128.

0.0 0.5 1.0 1.5 2.0 2.5

0.00

0.05

0.10

0.15

Time Hsec x10000L

Centroid Time =13715.7

,

128

0 50 100 150 200 250 3000.000.050.100.150.200.25

Mass

Sig

nalH%

LBand Ò1 Group Ò 14Limits: 0.9 - 1.0001

>,

:120.

0.0 0.5 1.0 1.5 2.0 2.50.0

0.1

0.2

0.3

0.4

0.5

0.6

Time Hsec x10000L

Centroid Time =13733.1

,

120

0 50 100 150 200 250 3000.00.10.20.30.40.50.60.7

Mass

Sig

nalH%

L

Band Ò1 Group Ò 11Limits: 0.9 - 1.0001

>,

:68.

93.

0.0 0.5 1.0 1.5 2.0 2.50.0

0.1

0.2

0.3

0.4

0.5

Time Hsec x10000L

Centroid Time =15013.3

, 68

93

0 50 100 150 200 250 3000.00.10.20.30.40.50.6

Mass

Sig

nalH%

L

Band Ò1 Group Ò 5Limits: 0.9 - 1.0001

>,

:17.

29.47.

54.66.

0.0 0.5 1.0 1.5 2.0 2.5

0.0

0.1

0.2

0.3

0.4

0.5

Time Hsec x10000L

Centroid Time =15650.9

, 1729

47

5466

0 50 100 150 200 250 3000.00.10.20.30.40.50.60.7

Mass

Sig

nalH%

L

Band Ò1 Group Ò 1Limits: 0.9 - 1.0001

>,

:18. 28.

30.

0.0 0.5 1.0 1.5 2.0 2.50

5

10

15

Time Hsec x10000L

Centroid Time =16126.9

,

1828

30

0 50 100 150 200 250 30005

1015202530

Mass

Sig

nalH%

L

Band Ò1 Group Ò 2Limits: 0.9 - 1.0001

>,

24 CL20016PreliminaryAnalysis_dws1.nb

A-87

:27. 43.

44. 45.

0.0 0.5 1.0 1.5 2.0 2.50.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =16860.4

,

2743

44

450 50 100 150 200 250 300

01234567

Mass

Sig

nalH%

L

Band Ò1 Group Ò 3Limits: 0.9 - 1.0001

>>

ü Tables of Mass Spectral Informationü Mass Spec Table #1: time range 0 to 25459sec.

Comments: TAble summary of raw ion signals for all m/z scanned in the experiment:

Ion signals greater than 0.% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L12 0. 89 0.1 166 0.1 243 0.1

13 0. 90 0. 167 0.2 244 0.

14 0. 91 0. 168 0. 245 0.1

15 0. 92 0. 169 0. 246 0.

16 0.1 93 0.5 170 0.1 247 0.

17 0.3 94 0.5 171 0.1 248 0.

18 6.9 95 0.2 172 0. 249 0.

19 0. 96 0.1 173 0. 250 0.

20 0. 97 0.1 174 0. 251 0.

21 0. 98 0.1 175 0. 252 0.

22 0. 99 0. 176 0. 253 0.

23 0. 100 0.1 177 0.1 254 0.

24 0. 101 0. 178 1. 255 0.

25 0. 102 0. 179 0.1 256 0.

26 0. 103 0. 180 0. 257 0.

27 1. 104 0. 181 0.1 258 0.

28 4. 105 0. 182 0.1 259 0.1

29 0.4 106 0. 183 0.1 260 0.

30 25.1 107 0.2 184 0. 261 0.

31 0.1 108 0.6 185 0. 262 0.

32 0.1 109 0.1 186 0. 263 0.

33 0. 110 0.1 187 0. 264 0.

34 0. 111 0.1 188 0. 265 0.

35 0. 112 0. 189 0. 266 0.

36 0. 113 0.1 190 0. 267 0.

37 0. 114 0. 191 0. 268 0.

38 0. 115 0. 192 0. 269 0.

39 0. 116 0. 193 0. 270 0.4

40 0. 117 0. 194 0.1 271 0.

41 0.1 118 0. 195 0. 272 0.

42 0.2 119 0. 196 0. 273 0.1

43 2. 120 0.7 197 0.1 274 0.

44 6 5 121 0 2 198 0 275 0

CL20016PreliminaryAnalysis_dws1.nb 25

A-88

44 6.5 121 0.2 198 0. 275 0.

45 0.5 122 0.1 199 0. 276 0.

46 30.5 123 0.1 200 0. 277 0.

47 0.6 124 0.1 201 0. 278 0.

48 0.1 125 0. 202 0. 279 0.

49 0. 126 0.2 203 0. 280 0.

50 0. 127 0.4 204 0. 281 0.

51 0. 128 0.2 205 0. 282 0.

52 0.1 129 0. 206 0. 283 0.

53 0.1 130 0. 207 0.1 284 0.

54 0.2 131 0. 208 0. 285 0.

55 0.2 132 0. 209 0.1 286 0.

56 0.1 133 0. 210 0. 287 0.

57 0.1 134 0.1 211 0. 288 0.

58 0.1 135 0.5 212 0. 289 0.

59 0.1 136 0.2 213 1.4 290 0.

60 0. 137 0.3 214 0.1 291 0.

61 0. 138 0. 215 0. 292 0.

62 0.1 139 0.1 216 0. 293 0.

63 0. 140 0.1 217 0. 294 0.

64 0. 141 0. 218 0. 295 0.

65 0. 142 0. 219 0. 296 0.

66 0.2 143 0. 220 0. 297 0.

67 0.1 144 0. 221 0. 298 0.

68 0.3 145 0.1 222 0. 299 0.

69 0.1 146 0. 223 0. 300 0.2

70 0.3 147 0. 224 0.7 301 0.

71 0.2 148 0.1 225 0.1 302 0.

72 0. 149 0. 226 0. 315 0.

73 0.1 150 0. 227 0.1 316 1.1

74 0. 151 0.1 228 0. 317 0.1

75 0. 152 0.1 229 0. 318 0.

76 0. 153 0. 230 0. 319 0.

77 0. 154 0.1 231 0. 320 0.

78 0. 155 0.1 232 0. 321 0.

79 0. 156 0.1 233 0. 322 0.

80 0.1 157 0. 234 0. 346 0.

81 0.4 158 0. 235 0. 347 0.

82 0.8 159 0. 236 0. 365 0.

83 0.4 160 0.1 237 0. 390 0.

84 0.2 161 0.4 238 0. 391 0.

85 0.1 162 0.3 239 0. 392 0.2

86 0.1 163 0.1 240 0.1 393 0.

87 0. 164 0.1 241 0. 394 0.

88 0. 165 0.1 242 0. 395 0.

26 CL20016PreliminaryAnalysis_dws1.nb

A-89

BTTN001Author: Deneille Wiese-Smith

OverviewPurpose

Ë The primary purpose of this experiment is to acquire the MS sublimation signature of the BTTN sample from Joseph Clubb, NAWCWD, China Lake. BTTN is 1,2,4-butanetriol trinitrate (C4H7N3O9, MW 241), a yellow liquid. This is the first experiment with this sample.

Experiment DescriptionË A small alumina type reaction cell, fitted with a alumina style cap assembly having an orifice diameter of 1007 µm was loaded with the

sample.

The sample is comprised of one compound. The bottom section is loaded with 3.80 mg of BTTN-CLPP01 00 (sample ID # BTTN-CLPP01).

Summary1. The weight and temperature data look okay. There is some noise but not out of the ordinary at this time.

a. The final experimnet weight of -0.014mg is within the error of the balance initially weighing the sample + the STMBMS instruments.b. The sample was depleted before temperatures reached 80°C.

2. The ion signals are okay. The signal at m/z 46 (NO2) is very large a. Baseline noise of +/- 0.03 cts/ms generally but significantly higher at m/z 18, 28, m/z 44 , etc which is similar to recent data. b. The molecular BTTN ion is not seen (m/z 241). The most significant higher molecular weight ion is at m/z 214.

Thermal Analysis ResultsTA Overview Summary

Ë Heating ProfileË Profile type: simple ramp at 2°C/min to 400°C; hold 500 seconds before cooling at less than -5°C/min.Ë The temperature of the experiment ranged from 19.2 to 400.5°C.

Ë Sample mass infoË The experiment started with a sample mass of 3.80mg.Ë The final mass with the sample measured in the experiment is -0.014mg.Ë Residue info is not available at the time of this write-up.

TA Overview Graphs

Thermal Analysis Region #1Ë The time limits for this region was selected and will be used in further analysis in this notebook, unless changed at a later time.Ë The following plots show the temperature and weight data over the entire experiment. The sample was basically depleted before reaching

80°C. There is some noise in the weight data but it is not excessive. The end weight of -0.014mg is within the error of the balance initially weighing the sample + the STMBMS instrument.

"Time range: 23.749 to 17055.1 sec.""Parameters for subset: "

" Minimum Time: 23.749 Maximum Time: 17055.1Minimum Temp: 19.2212 Maximum Temp: 400.504Minimum Weight: -0.0659 Maximum Weight: 3.9462No residue is assumed. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.2212 Maximum Temp: 400.504"

" Minimum Weight: -0.0659 Maximum Weight: 3.9462"

" Start time = 10.077 Final time = 17055.1Balance drift factor =-9.328244922398684`*^-7 mgêsec."

A-90

pp g pp

0 5000 10 000 15 0000

100

200

300

400

Time HsL

Tem

pera

ture

HCLTemperature HCL

0 5000 10 000 15 0000

1

2

3

4

Time HsL

Wei

ghtHm

gL

Weight HmgL

0 5000 10 000 15 000

-0.04

-0.02

0.00

0.02

0.04

Time HsL

DT

AHCL

DTA HCL

50 100 150 200 250 300 350 4000

1

2

3

4

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

Temperature Segment AnalysisTemperature Segment Overview Summary

Ë The number of different types of segments identified are as follows:Ë Heating: 3Ë Cooling: 4Ë Isothermal: 0

Display of Temperature Segment Analysis

Temperature Analysis #1: Cluster DisplayË Four cluster group analysis of all temperature data using 200 span points will be plotted twice: as a function of Rate °C/s then

Temperature°C. There were a few small noise spikes in the data set. The PID control and furnace response was good.

5000 10 000 15 000

-0.08

-0.06

-0.04

-0.02

0.00

0.02

0.04

Time HsL

Rat

eH°Cê

sL

Ò groups = 4 low index = 1 high index = 213

Temperature Analysis #2: BreakPoint Display

2 BTTN001PreliminaryAnalysis_dws1.nb

A-91

5000 10 000 15 000

0

100

200

300

400

Time HsL

Tem

pera

ture

H°CL

Temperature Analysis #3: Segment Table

TimeHsL TempH°CL Heat RateH°CêminL DurationHsL Type

10. 19.2 0.35 56. up

66. 19.3 2.00 11378. up

11443. 398.4 0.15 468. up

11911. 399.9 -2.64 114. down

12025. 395.0 -4.90 2876. down

14901. 166.9 -2.19 2141. down

17042. 88.6 -2.19 0. down

General STMBMS Ion SignalsIon Signals Plots #1: time range 0 to 17340sec.Ë Comments: Raw ion signals for all m/z scanned have been plotted as a function of time. The baseline noise is generally +/- 0.03 cts/ms -

similar to experiment run since August 2012. The molecular ion is not observed (m/z 241). The most significant peak at high m/z is 214. The largest signal - possibly pushing the maximum - is m/z 46 (NO2).

"Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.2

0.00.20.40.60.81.01.2

mêz = 2

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 3

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 4

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 5

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 6

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 7

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 8

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 9

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 10

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 11

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 12

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 13

"Time Hs x10000.L"

BTTN001PreliminaryAnalysis_dws1.nb 3

A-92

"Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 14

0.0 0.5 1.0 1.5

-0.10.00.10.20.30.40.50.6

mêz = 15

0.0 0.5 1.0 1.5-0.20-0.15-0.10-0.05

0.000.050.100.15

mêz = 16

0.0 0.5 1.0 1.5-0.2

-0.1

0.0

0.1

0.2mêz = 17

0.0 0.5 1.0 1.5

-0.50.00.51.01.52.02.5

mêz = 18

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 19

0.0 0.5 1.0 1.5-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 20

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 21

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 22

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 23

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 24

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 25

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 26

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.50.6

mêz = 27

0.0 0.5 1.0 1.5-10-8-6-4-2

0

mêz = 28

0.0 0.5 1.0 1.50

2

4

6

8

mêz = 29

0.0 0.5 1.0 1.50

5

10

15

20mêz = 30

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 31

0.0 0.5 1.0 1.5

-0.1

0.0

0.1

0.2mêz = 32

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 33

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 34

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 35

0.0 0.5 1.0 1.5

-0.10-0.05

0.000.050.100.15

mêz = 36

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 37

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

4 BTTN001PreliminaryAnalysis_dws1.nb

A-93

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 38

0.0 0.5 1.0 1.5

-0.15-0.10-0.05

0.000.050.100.15

mêz = 39

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 40

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

mêz = 41

0.0 0.5 1.0 1.5

0.0

0.5

1.0

mêz = 42

0.0 0.5 1.0 1.502468

101214

mêz = 43

0.0 0.5 1.0 1.5

-0.20.00.20.40.60.81.01.2

mêz = 44

0.0 0.5 1.0 1.50

1

2

3

4

5mêz = 45

0.0 0.5 1.0 1.50

100

200

300

400

mêz = 46

0.0 0.5 1.0 1.50123456

mêz = 47

0.0 0.5 1.0 1.50

1

2

3

4

5

mêz = 48

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 49

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 50

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 51

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 52

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 53

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3mêz = 54

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0mêz = 55

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 56

0.0 0.5 1.0 1.50

1

2

3

4

5

mêz = 57

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 58

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 59

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 60

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 61

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN001PreliminaryAnalysis_dws1.nb 5

A-94

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 62

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

mêz = 63

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 64

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 65

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

0.20mêz = 66

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.250.30

mêz = 67

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 68

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 69

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 70

0.0 0.5 1.0 1.50

5

10

15

mêz = 71

0.0 0.5 1.0 1.5

0.00.20.40.60.81.01.21.4

mêz = 72

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

2.5mêz = 73

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.250.30

mêz = 74

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 75

0.0 0.5 1.0 1.50

20406080

100120140

mêz = 76

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 77

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 78

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

2.5

mêz = 79

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.200.25

mêz = 80

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 81

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 82

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 83

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 84

0.0 0.5 1.0 1.50.00.51.01.52.02.5

mêz = 85

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

6 BTTN001PreliminaryAnalysis_dws1.nb

A-95

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5

mêz = 86

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 87

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 88

0.0 0.5 1.0 1.50.00.51.01.52.02.53.03.5

mêz = 89

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 90

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 91

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.250.30

mêz = 92

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 93

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0mêz = 94

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 95

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 96

0.0 0.5 1.0 1.5

0.000.050.100.150.200.25

mêz = 97

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 98

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 99

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 100

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 101

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0mêz = 102

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 103

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 104

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8mêz = 105

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

2.5mêz = 106

0.0 0.5 1.0 1.5

0.000.050.100.150.200.250.30

mêz = 107

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 108

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 109

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN001PreliminaryAnalysis_dws1.nb 7

A-96

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 110

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 111

0.0 0.5 1.0 1.5

-0.10

-0.05

0.00

0.05

0.10

mêz = 112

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15mêz = 113

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10mêz = 114

0.0 0.5 1.0 1.5

0.00

0.05

0.10

0.15

mêz = 115

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 116

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

0.15

mêz = 117

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 118

0.0 0.5 1.0 1.5

0.00.20.40.60.81.0

mêz = 119

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 120

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10mêz = 121

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.50

1

2

3

4

5mêz = 122

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 123

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

mêz = 124

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 125

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.040.06

mêz = 126

0.0 0.5 1.0 1.5

0.00

0.05

0.10

0.15mêz = 127

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 128

0.0 0.5 1.0 1.5

0.00.10.20.30.40.5

mêz = 129

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 130

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 131

0.0 0.5 1.0 1.50

1

2

3

4mêz = 132

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

0.5mêz = 133

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

8 BTTN001PreliminaryAnalysis_dws1.nb

A-97

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.200.25

mêz = 134

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 135

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 136

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 137

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

mêz = 138

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 139

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 140

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 141

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 142

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 143

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10mêz = 144

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.060.08

mêz = 145

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

0.00

0.05

0.10

mêz = 146

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

mêz = 147

0.0 0.5 1.0 1.5

0.00

0.05

0.10

0.15mêz = 148

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 149

0.0 0.5 1.0 1.5-0.05

0.00

0.05

0.10

mêz = 150

0.0 0.5 1.0 1.50

2

4

6

8mêz = 151

0.0 0.5 1.0 1.50

5

10

15

20mêz = 152

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0mêz = 153

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 154

0.0 0.5 1.0 1.5

0.00

0.05

0.10

0.15

mêz = 155

0.0 0.5 1.0 1.5-0.1

0.00.10.20.30.40.50.6

mêz = 156

0.0 0.5 1.0 1.5

0.0

0.5

1.0

1.5mêz = 157

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN001PreliminaryAnalysis_dws1.nb 9

A-98

0.0 0.5 1.0 1.5

-0.050.000.050.100.150.20

mêz = 158

0.0 0.5 1.0 1.5

0.00

0.05

0.10

mêz = 159

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4mêz = 160

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 161

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.060.080.10

mêz = 162

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 163

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

mêz = 164

0.0 0.5 1.0 1.50

10

20

30

40

50mêz = 165

0.0 0.5 1.0 1.50.00.51.01.52.02.53.0

mêz = 166

0.0 0.5 1.0 1.50

2

4

6

8

mêz = 167

0.0 0.5 1.0 1.50.00.51.01.52.02.53.03.5

mêz = 168

0.0 0.5 1.0 1.50

2

4

6

mêz = 169

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 170

0.0 0.5 1.0 1.5

0.00

0.05

0.10

mêz = 171

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 172

0.0 0.5 1.0 1.5-0.06

-0.04

-0.02

0.00

0.02

0.04mêz = 173

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.080.10

mêz = 174

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 175

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 176

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 177

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 178

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 179

0.0 0.5 1.0 1.50

1

2

3

4

mêz = 180

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

mêz = 181

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

10 BTTN001PreliminaryAnalysis_dws1.nb

A-99

0.0 0.5 1.0 1.5-0.05

0.000.050.100.150.20

mêz = 182

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 183

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 184

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6mêz = 185

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10mêz = 186

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 187

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 188

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 189

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 190

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 191

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 192

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 193

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.04

-0.02

0.00

0.02

0.04mêz = 194

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 195

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

0.15mêz = 196

0.0 0.5 1.0 1.50

1

2

3

4mêz = 197

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 198

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 199

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 200

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 201

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 202

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

mêz = 203

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 204

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 205

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN001PreliminaryAnalysis_dws1.nb 11

A-100

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 206

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 207

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 208

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 209

0.0 0.5 1.0 1.5-0.06

-0.04

-0.02

0.00

0.02

mêz = 210

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 211

0.0 0.5 1.0 1.5

-0.05

0.00

0.05

0.10

mêz = 212

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

mêz = 213

0.0 0.5 1.0 1.505

1015202530

mêz = 214

0.0 0.5 1.0 1.50

1

2

3

4

5

mêz = 215

0.0 0.5 1.0 1.5

0.00.10.20.30.40.50.6

mêz = 216

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.060.08

mêz = 217

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 218

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.06

mêz = 219

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 220

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 221

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 222

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 223

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 224

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 225

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 226

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 227

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 228

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 229

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

12 BTTN001PreliminaryAnalysis_dws1.nb

A-101

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 230

0.0 0.5 1.0 1.5-0.04-0.02

0.000.020.040.06

mêz = 231

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 232

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 233

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 234

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 235

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 236

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04

mêz = 237

0.0 0.5 1.0 1.5

-0.06-0.04-0.02

0.000.020.04

mêz = 238

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 239

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.04

mêz = 240

0.0 0.5 1.0 1.5-0.06-0.04-0.02

0.000.020.04

mêz = 241

"Time Hs x10000.L""Data File: BTTN001.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 242

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 243

0.0 0.5 1.0 1.5

-0.04

-0.02

0.00

0.02

0.04mêz = 244

0.0 0.5 1.0 1.5

-0.04-0.02

0.000.020.040.06

mêz = 245

"Time Hs x10000.L"Ion Signals Plots #2: time range 0 to 17340sec.Ë Comments: Ion signals greater than 0.1 percent total signal were smoothed and replotted as a function of temperature. Most signals emerge

after reaching 50°C. The exceptions are the adsorbed water, m/z 44 and 73. "Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

BTTN001PreliminaryAnalysis_dws1.nb 13

A-102

p

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

-0.50.00.51.01.52.02.5

mêz = 18

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

mêz = 19

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

8

mêz = 29

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

5

10

15

20mêz = 30

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

mêz = 31

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0

mêz = 41

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.002468

101214

mêz = 43

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

-0.20.00.20.40.60.81.01.2

mêz = 44

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5mêz = 45

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

100

200

300

400

mêz = 46

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00123456

mêz = 47

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5

mêz = 48

"Temperature H°C x100.L""Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 55

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5

mêz = 57

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 60

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

mêz = 69

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

5

10

15

mêz = 71

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.01.21.4

mêz = 72

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0

2.5mêz = 73

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

20406080

100120140

mêz = 76

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

mêz = 77

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 78

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.5

mêz = 79

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.5

mêz = 85

"Temperature H°C x100.L""Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

14 BTTN001PreliminaryAnalysis_dws1.nb

A-103

p

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 86

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.03.5

mêz = 89

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 94

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4mêz = 103

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0

2.5mêz = 106

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.00.20.40.60.81.0

mêz = 116

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 118

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.20.40.60.81.0

mêz = 119

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5mêz = 122

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4mêz = 132

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

8mêz = 151

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

5

10

15

20mêz = 152

"Temperature H°C x100.L""Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.0

0.5

1.0

1.5

2.0mêz = 153

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0

0.5

1.0

1.5mêz = 157

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

10

20

30

40

50mêz = 165

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.0

mêz = 166

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

8

mêz = 167

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00.00.51.01.52.02.53.03.5

mêz = 168

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

2

4

6

mêz = 169

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

mêz = 180

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4mêz = 197

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.005

1015202530

mêz = 214

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00

1

2

3

4

5

mêz = 215

"Temperature H°C x100.L"Ion Signals Plots #3: time range 0 to 3500sec.Ë Comments: The ions greater than 0.1 percent total signal were reploted over the first 3500 seconds and plotted v.s. Temperature °C to

better see their temporal behavior. M/z 28 (N2 &/or CO +? ), which had a large negative data excursion, is now seen in this set."Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

BTTN001PreliminaryAnalysis_dws1.nb 15

A-104

p

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.5

mêz = 18

0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.5

1.0

1.5

mêz = 19

0.2 0.4 0.6 0.8 1.0 1.2

-0.20.00.20.40.60.81.01.2

mêz = 28

0.2 0.4 0.6 0.8 1.0 1.20

2

4

6

8

mêz = 29

0.2 0.4 0.6 0.8 1.0 1.20

5

10

15

20mêz = 30

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 31

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

mêz = 41

0.2 0.4 0.6 0.8 1.0 1.202468

101214

mêz = 43

0.2 0.4 0.6 0.8 1.0 1.2-0.2

0.00.20.40.60.81.01.2

mêz = 44

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

5mêz = 45

0.2 0.4 0.6 0.8 1.0 1.20

100

200

300

400

mêz = 46

0.2 0.4 0.6 0.8 1.0 1.20123456

mêz = 47

"Temperature H°C x100.L""Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

5

mêz = 48

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

5

mêz = 57

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.53.0

mêz = 60

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 69

0.2 0.4 0.6 0.8 1.0 1.20

5

10

15

mêz = 71

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

2.5mêz = 73

0.2 0.4 0.6 0.8 1.0 1.20

20406080

100120140

mêz = 76

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 77

0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.5

1.0

1.5mêz = 78

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

2.5

mêz = 79

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.5

mêz = 85

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

mêz = 86

"Temperature H°C x100.L""Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

16 BTTN001PreliminaryAnalysis_dws1.nb

A-105

p

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.53.03.5

mêz = 89

0.2 0.4 0.6 0.8 1.0 1.20.0

0.2

0.4

0.6

0.8

mêz = 90

0.2 0.4 0.6 0.8 1.0 1.2

0.0

0.2

0.4

0.6

0.8

1.0mêz = 94

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 103

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0

2.5mêz = 106

0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.0

mêz = 116

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.53.0

mêz = 118

0.2 0.4 0.6 0.8 1.0 1.2

0.00.20.40.60.81.0

mêz = 119

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

5mêz = 122

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4mêz = 132

0.2 0.4 0.6 0.8 1.0 1.20

2

4

6

8mêz = 151

0.2 0.4 0.6 0.8 1.0 1.20

5

10

15

20mêz = 152

"Temperature H°C x100.L""Data File: BTTN001.dat" "X axis: Temperature H°CL" " X Scale Factor: 100."

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5

2.0mêz = 153

0.2 0.4 0.6 0.8 1.0 1.20.0

0.5

1.0

1.5mêz = 157

0.2 0.4 0.6 0.8 1.0 1.20

10

20

30

40

50mêz = 165

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.53.0

mêz = 166

0.2 0.4 0.6 0.8 1.0 1.20

2

4

6

8

mêz = 167

0.2 0.4 0.6 0.8 1.0 1.20.00.51.01.52.02.53.03.5

mêz = 168

0.2 0.4 0.6 0.8 1.0 1.20

2

4

6

mêz = 169

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

mêz = 180

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4mêz = 197

0.2 0.4 0.6 0.8 1.0 1.205

1015202530

mêz = 214

0.2 0.4 0.6 0.8 1.0 1.20

1

2

3

4

5

mêz = 215

"Temperature H°C x100.L"Correlations Analysis of Ion Signals

Correlated Signals #1: time range 0 to 17340sec.Ë Comments: A large number of the 47 smoothed ion signals that are greater than 0.1 percent total signal were found to be correlated in a 95

percent analysis. Six were not correlated. The results are plotted below:

BTTN001PreliminaryAnalysis_dws1.nb 17

A-106

::73.

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

2.0

Time Hsec x10000L

Centroid Time =1462.72

,

73

0 50 100 150 2000.0

0.1

0.2

0.3

0.4

0.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 5Limits: 0.95 - 1.0001

>,

:122.

0.0 0.5 1.0 1.50

1

2

3

4

Time Hsec x10000L

Centroid Time =1494.84

,

122

0 50 100 150 2000.00.10.20.30.40.50.6

Mass

Sig

nalH%

LBand Ò1 Group Ò 7

Limits: 0.95 - 1.0001

>,

:19.29.

30.

31.

41.

43.45.46.47.48.57.60.69.71.72.76.77.78.79.86.89.94.103.106.116.118.119.132.151.152.153.157.165.166.167.168.169.180.19721421

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x10000L

Centroid Time =1707.06

,

19293031414345

46

47485760697172

76777879868994103106116118119132151152153157165166167168169180197214215

0 50 100 150 2000

1020304050

Mass

Sig

nalH%

L

Band Ò1 Group Ò 2Limits: 0.95 - 1.0001

>,

:85.

0.0 0.5 1.0 1.50.00.20.40.60.81.01.21.4

Time Hsec x10000L

Centroid Time =2663.92

,

85

0 50 100 150 2000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 6Limits: 0.95 - 1.0001

>,

:55.

0.0 0.5 1.0 1.5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Time Hsec x10000L

Centroid Time =2817.82

,

55

0 50 100 150 2000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 4Limits: 0.95 - 1.0001

>,

:44.

0.0 0.5 1.0 1.5

0.0

0.2

0.4

0.6

Time Hsec x10000L

Centroid Time =4111.55

,

44

0 50 100 150 2000.000.020.040.060.080.100.120.14

Mass

Sig

nalH%

L

Band Ò1 Group Ò 3Limits: 0.95 - 1.0001

>,

18 BTTN001PreliminaryAnalysis_dws1.nb

A-107

:18.

0.0 0.5 1.0 1.50.0

0.5

1.0

1.5

Time Hsec x10000L

Centroid Time =5705.71

,

18

0 50 100 150 2000.00.51.01.52.02.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 1Limits: 0.95 - 1.0001

>>

Correlated Signals #2: time range 0 to 3500sec.Ë Comments: A correlation analysis of ions greater than 0.1 percent total signal from 0 - 3500 seconds identifies two groups among the 47

ion subset. The plot of m/z 28, however, is odd. Not sure what's happening here!

::73.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50.0

0.5

1.0

1.5

2.0

Time Hsec x1000L

Centroid Time =1330.43

,

73

0 50 100 150 2000.0

0.1

0.2

0.3

0.4

0.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 6Limits: 0.95 - 1.0001

>,

:46.

76.

122.

152. 165.0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x1000L

Centroid Time =1569.1

,

46

76122 152165

0 50 100 150 2000

102030405060

Mass

Sig

nalH%

L

Band Ò1 Group Ò 5Limits: 0.95 - 1.0001

>,

: 44.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

0.0

0.2

0.4

0.6

Time Hsec x1000L

Centroid Time =1587.3

,

44

0 50 100 150 2000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 4Limits: 0.95 - 1.0001

>,

:19.29.30.31.41.43.45.47.48.57.60.69.

71.77.78.

79.86.

89.

90.

94.

103.106.116.118.119.132.151.153.157.166.167.168161

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x1000L

Centroid Time =1637.7

,

1929

30

3141

43

454748576069

71

77787986899094

103106116118119132

151153157166

167168169180197

214

215

0 50 100 150 2000.00.51.01.52.02.53.0

Mass

Sig

nalH%

L

Band Ò1 Group Ò 2Limits: 0.95 - 1.0001

>,

:18.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50.0

0.5

1.0

1.5

Time Hsec x1000L

Centroid Time =1672.29

,

18

0 50 100 150 2000.00.20.40.60.81.0

Mass

Sig

nalH%

L

Band Ò1 Group Ò 1Limits: 0.95 - 1.0001

>,

BTTN001PreliminaryAnalysis_dws1.nb 19

A-108

:85.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50.00.20.40.60.81.01.21.4

Time Hsec x1000L

Centroid Time =1808.12

,

85

0 50 100 150 2000.000.020.040.060.080.10

Mass

Sig

nalH%

L

Band Ò1 Group Ò 7Limits: 0.95 - 1.0001

>,

:28.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

-0.10

-0.05

0.00

0.05

0.10

Time Hsec x1000L

Centroid Time =13640.5

,

28

0 50 100 150 2000.0000.0010.0020.0030.0040.005

Mass

Sig

nalH%

LBand Ò1 Group Ò 3

Limits: 0.95 - 1.0001

>>

Tables of Mass Spectral InformationMass Spec Table #1: time range 0 to 17340sec.Ë Comments: Table summary of raw ion signals for all m/z scanned:

Ion signals greater than 0.% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L2 0.1 63 0. 124 0. 185 0.

3 0. 64 0. 125 0. 186 0.

4 0. 65 0.1 126 0. 187 0.

5 0. 66 0. 127 0. 188 0.

6 0. 67 0. 128 0. 189 0.

7 0. 68 0. 129 0.1 190 0.

8 0. 69 0.4 130 0. 191 0.

9 0. 70 0.1 131 0. 192 0.

10 0. 71 1.7 132 0.4 193 0.

11 0. 72 0.1 133 0. 194 0.

12 0. 73 0.4 134 0. 195 0.

13 0. 74 0. 135 0. 196 0.

14 0. 75 0. 136 0. 197 0.3

15 0. 76 15. 137 0. 198 0.

16 0. 77 0.5 138 0. 199 0.

17 0. 78 0.2 139 0. 200 0.

18 2.4 79 0.3 140 0. 201 0.

19 0.2 80 0. 141 0. 202 0.

20 0. 81 0. 142 0. 203 0.

21 0. 82 0. 143 0. 204 0.

22 0. 83 0. 144 0. 205 0.

23 0. 84 0. 145 0. 206 0.

24 0. 85 0.1 146 0. 207 0.

25 0. 86 0.2 147 0. 208 0.

26 0. 87 0.1 148 0. 209 0.

27 0.1 88 0.1 149 0.1 210 0.

20 BTTN001PreliminaryAnalysis_dws1.nb

A-109

28 0. 89 0.3 150 0. 211 0.

29 0.8 90 0.1 151 0.8 212 0.

30 1.8 91 0. 152 2. 213 0.

31 0.4 92 0. 153 0.2 214 2.6

32 0. 93 0. 154 0. 215 0.4

33 0. 94 0.1 155 0. 216 0.

34 0. 95 0. 156 0.1 217 0.

35 0. 96 0. 157 0.1 218 0.

36 0. 97 0. 158 0. 219 0.

37 0. 98 0. 159 0. 220 0.

38 0. 99 0. 160 0. 221 0.

39 0. 100 0. 161 0. 222 0.

40 0. 101 0. 162 0. 223 0.

41 0.2 102 0. 163 0. 224 0.

42 0.1 103 0.4 164 0. 225 0.

43 1.3 104 0.1 165 4.6 226 0.

44 0.1 105 0.1 166 0.3 227 0.

45 0.4 106 0.3 167 0.7 228 0.

46 52.1 107 0. 168 0.3 229 0.

47 0.5 108 0. 169 0.7 230 0.

48 0.4 109 0. 170 0.1 231 0.

49 0. 110 0. 171 0. 232 0.

50 0. 111 0. 172 0. 233 0.

51 0. 112 0. 173 0. 234 0.

52 0. 113 0. 174 0. 235 0.

53 0. 114 0. 175 0. 236 0.

54 0. 115 0. 176 0. 237 0.

55 0.1 116 0.1 177 0. 238 0.

56 0.1 117 0. 178 0. 239 0.

57 0.5 118 0.3 179 0.1 240 0.

58 0.1 119 0.1 180 0.4 241 0.

59 0. 120 0.1 181 0.1 242 0.

60 0.3 121 0. 182 0. 243 0.

61 0.1 122 0.6 183 0. 244 0.

62 0. 123 0.1 184 0. 245 0.

BTTN001PreliminaryAnalysis_dws1.nb 21

A-110

BTTN006Author: Deneille Wiese-Smith

Overviewü Purpose

The primary purpose of this experiment is to to capture the sublimation signature of the BTTN sample using the isothermal analog of BTTN001.

ü Experiment DescriptionA small alumina type reaction cell, fitted with a alumina style cap assembly having an orifice diameter of 1007 µm was loaded with the sample.

The sample is comprised of one compound. The bottom section is loaded with 4.22 mg of BTTN sample from China Lake (sample ID # BTTN-CLPP01 00).

ü SummaryThe temperature data after ~5000 seconds is bad.

I'm not sure what caused the oscillation to begin but, at these low temperatures, the standard PID parameters are not optimal. That said, I don't know whether using the low temperature PID parameters would have prevented the temperature swings.The temperature band width during the upswings is rather wide. This is seen from time to time and I don't know the causes - arising in the first place and then simply going away.The sample was effectively depleted by 3200 seconds - well before the temperature control problems occurred.

The small weight loss, ~0.05mg, from 4000 seconds through the end of the experiment appears to be drift. Only the water ion has signal over this period, which doesn't really support the loss since the noise band is big in the large background water signal.The ion signal data is okay. Baseline noise is in the same ballpark as other experiment ran since August 2012.

The largest ion signal is at m/z 46 followed by m/z 76. The BTTN molecular ion (m/z 241) is not seen.

Thermal Analysis Resultsü Overall TA Resultsü TA Overview Summary

Heating Profile

Profile type: 2°C/min to 50°C, 1°C/min to 55°C, 0.5°C/min to 50°C holding 20,000 seconds before cooling no faster than -5°C/min.

The temperature of the experiment ranged from 19.4 to 61.4°C.

Sample mass info

The experiment started with a sample mass of 4.22mg.

The final mass with the sample measured in the experiment is 0.097mg.

Residue info is not available at the time of this report.

A-111

ü TA Overview Graphs

ü Display of Thermal Analysis Data„ Thermal Analysis Region #1

The time limits for this region was selected and will be used in further analysis in this notebook, unless changed at a later time.

The follow plots show all thermogravimetric data in the experiment. The sample was essentially gone shortly after reaching 60°C. There was some problem maintianing the 60°C isothermal temperature. It's difficult to say that use of the low temperature PID controls would have prevented this outcome - perhaps. The program was stable for over an hour before the oscillation occured. The temperature band width during the oscillations is an indicator that something else was going on.

"Time range: 23.244 to 23041.4 sec.""Parameters for subset: "

" Minimum Time: 23.244 Maximum Time: 23041.4Minimum Temp: 19.4183 Maximum Temp: 61.3934Minimum Weight: 0.0658 Maximum Weight: 4.2453A residue of 0.097mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.4183 Maximum Temp: 61.3934"

" Minimum Weight: 0.0658 Maximum Weight: 4.2453"

" Start time = 10.079 Final time = 23055.Balance drift factor = -4.33934756781088`*^-8 mgêsec."

0 5000 10 000 15 000 20 00020

30

40

50

60

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 5000 10 000 15 000 20 0000

1

2

3

4

Time HsLW

eigh

tHmgL

Weight HmgL

0 5000 10 000 15 000 20 000

-0.03

-0.02

-0.01

0.00

0.01

Time HsL

DT

AHCL

DTA HCL

20 30 40 50 600

1

2

3

4

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

„ Thermal Analysis Region #2

The small weight increase as the instrument begins heating is common in the STMBMS although not well understood. On this scale, we can see that the noise in the weight data is about +/-0.01mg.

"Time range: 23.244 to 991.39 sec.""Parameters for subset: "

" Minimum Time: 23.244 Maximum Time: 991.39Minimum Temp: 19.4183 Maximum Temp: 50.2386Minimum Weight: 4.1314 Maximum Weight: 4.2453A residue of 0.097mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.4183 Maximum Temp: 61.3934"

" Minimum Weight: 0.0658 Maximum Weight: 4.2453"

" Start time = 10.079 Final time = 23055.Balance drift factor =-4.33934756781088`*^-8 mgêsec."

2 BTTN006PreliminaryAnalysis_dws1.nb

A-112

pp g pp

200 400 600 800 10000

10

20

30

40

50

Time HsL

Tem

pera

ture

HCLTemperature HCL

200 400 600 800 1000

4.14

4.16

4.18

4.20

4.22

4.24

Time HsL

Wei

ghtHm

gL

Weight HmgL

200 400 600 800 1000

-0.010

-0.008

-0.006

-0.004

-0.002

0.000

0.002

Time HsL

DT

AHCL

DTA HCL

20 25 30 35 40 45 50

4.14

4.16

4.18

4.20

4.22

4.24

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

„ Thermal Analysis Region #3

The sample is essentially depleted just after 3200 seconds.

"Time range: 23.244 to 3991.53 sec.""Parameters for subset: "

" Minimum Time: 23.244 Maximum Time: 3991.53Minimum Temp: 19.4183 Maximum Temp: 60.3723Minimum Weight: 0.1273 Maximum Weight: 4.2453A residue of 0.097mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.4183 Maximum Temp: 61.3934"

" Minimum Weight: 0.0658 Maximum Weight: 4.2453"

" Start time = 10.079 Final time = 23055.Balance drift factor = -4.33934756781088`*^-8 mgêsec."

0 1000 2000 3000 40000

10

20

30

40

50

60

Time HsL

Tem

pera

ture

HCL

Temperature HCL

0 1000 2000 3000 40000

1

2

3

4

Time HsL

Wei

ghtHm

gL

Weight HmgL

0 1000 2000 3000 4000

-0.010

-0.005

0.000

0.005

Time HsL

DT

AHCL

DTA HCL

20 30 40 50 600

1

2

3

4

Temperature HCL

Wei

ghtHm

gL

Weight HmgL

„ Thermal Analysis Region #4

The data has been replotted over the isothermal region following the majority of mass loss. Here the weight does appear to drop another ~0.05mg. The temperature data is of concern.

"Time range: 4005.05 to 22091.4 sec."

BTTN006PreliminaryAnalysis_dws1.nb 3

A-113

g"Parameters for subset: "

" Minimum Time: 4005.05 Maximum Time: 22091.4Minimum Temp: 57.8974 Maximum Temp: 61.3934Minimum Weight: 0.0658 Maximum Weight: 0.2635A residue of 0.097mg remains. Balance drift

factor not applied Gaussian smoothing applied to: DTA"

"Full Dataset Info:"

" Minimum Temp: 19.4183 Maximum Temp: 61.3934"

" Minimum Weight: 0.0658 Maximum Weight: 4.2453"

" Start time = 10.079 Final time = 23055.Balance drift factor = -4.33934756781088`*^-8 mgêsec."

5000 10 000 15 000 20 000

58.0

58.5

59.0

59.5

60.0

60.5

61.0

61.5

Time HsL

Tem

pera

ture

HCL

Temperature HCL

5000 10 000 15 000 20 0000.00

0.05

0.10

0.15

0.20

0.25

Time HsL

Wei

ghtHm

gL

Weight HmgL

5000 10 000 15 000 20 000-0.015

-0.010

-0.005

0.000

0.005

0.010

0.015

Time HsL

DT

AHCL

DTA HCL

58.0 58.5 59.0 59.5 60.0 60.5 61.00.00

0.05

0.10

0.15

0.20

0.25

Temperature HCLW

eigh

tHmgL

Weight HmgL

ü Temperature Segment Analysisü Temperature Segment Overview Summary

The number of different types of segments identified are as follows:

Heating: 2

Cooling: 0

Isothermal: 19

ü Display of Temperature Segment Analysis„ Temperature Analysis #1: Cluster Display

Four cluster group analysis of all temeperature data is usless for this experiment because of the oscillating excursions. The plot below shows the results of the analysis when 150 span points are used and the isothermal drift limit is increased (unreasonably) to 1.0. Again - this analysis is not useful (but the algorithm must be run).

5000 10 000 15 000 20 000-0.01

0.00

0.01

0.02

0.03

0.04

Time HsL

Rat

eH°Cê

sL

Ò groups = 4 low index = 1 high index = 154

4 BTTN006PreliminaryAnalysis_dws1.nb

A-114

ü General STMBMS Ion Signalsü Ion Signals Plots #1: time range 0 to 23460sec.

Comments: Raw ion signals for all m/z scanned in the experiment have been plotted vs. time. The baseline noise is +/-0.03cts/ms generally and significantly larger mat m/z 2, 18, which is similar to other experiments. The largest ion signal is at m/z 46 followed by 76. We do not see a signal at m/z 241 (BTTN molecule).

"Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

-0.2

-0.1

0.0

0.1

0.2mêz = 2

0.0 0.5 1.0 1.5 2.0

-0.06-0.04-0.02

0.000.020.040.06

mêz = 3

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 4

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 5

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 6

0.0 0.5 1.0 1.5 2.0

-0.06-0.04-0.02

0.000.020.04

mêz = 7

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 8

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 9

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 10

0.0 0.5 1.0 1.5 2.0

-0.06-0.04-0.02

0.000.020.04

mêz = 11

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 12

0.0 0.5 1.0 1.5 2.0-0.06

-0.04

-0.02

0.00

0.02

0.04mêz = 13

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 14

0.0 0.5 1.0 1.5 2.0

-0.1

0.0

0.1

0.2

0.3

mêz = 15

0.0 0.5 1.0 1.5 2.0-0.15-0.10-0.05

0.000.050.100.15

mêz = 16

0.0 0.5 1.0 1.5 2.0

-0.15-0.10-0.05

0.000.050.100.15

mêz = 17

0.0 0.5 1.0 1.5 2.0-1.0-0.5

0.00.51.01.52.02.5

mêz = 18

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

mêz = 19

0.0 0.5 1.0 1.5 2.0

-0.06-0.04-0.02

0.000.020.040.06

mêz = 20

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 21

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 22

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

mêz = 23

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 24

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 25

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN006PreliminaryAnalysis_dws1.nb 5

A-115

0.0 0.5 1.0 1.5 2.0

-0.10-0.05

0.000.050.100.15

mêz = 26

0.0 0.5 1.0 1.5 2.0-0.1

0.00.10.20.30.4

mêz = 27

0.0 0.5 1.0 1.5 2.0-0.4-0.2

0.00.20.40.60.8

mêz = 28

0.0 0.5 1.0 1.5 2.00

1

2

3

mêz = 29

0.0 0.5 1.0 1.5 2.00

2

4

6

8mêz = 30

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

mêz = 31

0.0 0.5 1.0 1.5 2.0-0.10-0.05

0.000.050.100.15

mêz = 32

0.0 0.5 1.0 1.5 2.0

-0.06-0.04-0.02

0.000.020.04

mêz = 33

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 34

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 35

0.0 0.5 1.0 1.5 2.0-0.15-0.10-0.05

0.000.050.10

mêz = 36

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 37

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

mêz = 38

0.0 0.5 1.0 1.5 2.0

-0.1

0.0

0.1

0.2

0.3mêz = 39

0.0 0.5 1.0 1.5 2.0-0.15-0.10-0.05

0.000.050.100.15

mêz = 40

0.0 0.5 1.0 1.5 2.0

0.00.20.40.60.81.01.2

mêz = 41

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

mêz = 42

0.0 0.5 1.0 1.5 2.00123456

mêz = 43

0.0 0.5 1.0 1.5 2.0-0.2

0.0

0.2

0.4

0.6

mêz = 44

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

2.5mêz = 45

0.0 0.5 1.0 1.5 2.00

50100150200250300

mêz = 46

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

2.5mêz = 47

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

mêz = 48

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 49

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

6 BTTN006PreliminaryAnalysis_dws1.nb

A-116

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 50

0.0 0.5 1.0 1.5 2.0-0.08-0.06-0.04-0.02

0.000.020.040.06

mêz = 51

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 52

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

0.15mêz = 53

0.0 0.5 1.0 1.5 2.0

-0.10-0.05

0.000.050.100.150.20

mêz = 54

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

mêz = 55

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 56

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

mêz = 57

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4mêz = 58

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.20

mêz = 59

0.0 0.5 1.0 1.5 2.00.00.20.40.60.81.01.21.4

mêz = 60

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.250.30

mêz = 61

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 62

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 63

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15mêz = 64

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 65

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

mêz = 66

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10mêz = 67

0.0 0.5 1.0 1.5 2.0

-0.1

0.0

0.1

0.2

mêz = 68

0.0 0.5 1.0 1.5 2.0

0.0

0.5

1.0

1.5

mêz = 69

0.0 0.5 1.0 1.5 2.0-0.1

0.00.10.20.30.4

mêz = 70

0.0 0.5 1.0 1.5 2.00

2

4

6

8mêz = 71

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4

0.5mêz = 72

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

mêz = 73

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN006PreliminaryAnalysis_dws1.nb 7

A-117

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15

0.20mêz = 74

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 75

0.0 0.5 1.0 1.5 2.00

10

20

30

40

50

mêz = 76

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0mêz = 77

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

mêz = 78

0.0 0.5 1.0 1.5 2.0

0.00.20.40.60.81.01.2

mêz = 79

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 80

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15

mêz = 81

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.040.060.08

mêz = 82

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 83

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10mêz = 84

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8

1.0mêz = 85

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

0.00.10.20.30.40.50.6

mêz = 86

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4

mêz = 87

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3mêz = 88

0.0 0.5 1.0 1.5 2.0

0.00.20.40.60.81.01.21.4

mêz = 89

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4

mêz = 90

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15mêz = 91

0.0 0.5 1.0 1.5 2.0

0.000.050.100.150.20

mêz = 92

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 93

0.0 0.5 1.0 1.5 2.0

0.00.10.20.30.40.5

mêz = 94

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 95

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 96

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 97

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

8 BTTN006PreliminaryAnalysis_dws1.nb

A-118

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.040.06

mêz = 98

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3mêz = 99

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 100

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15

0.20mêz = 101

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 102

0.0 0.5 1.0 1.5 2.00.00.20.40.60.81.01.21.4

mêz = 103

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.250.30

mêz = 104

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4mêz = 105

0.0 0.5 1.0 1.5 2.00.00.20.40.60.81.0

mêz = 106

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15mêz = 107

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 108

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 109

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 110

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04mêz = 111

0.0 0.5 1.0 1.5 2.0-0.15-0.10-0.05

0.000.050.10

mêz = 112

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10mêz = 113

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 114

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 115

0.0 0.5 1.0 1.5 2.0

0.00.10.20.30.40.5

mêz = 116

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.080.10

mêz = 117

0.0 0.5 1.0 1.5 2.00.00.20.40.60.81.0

mêz = 118

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 119

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.250.30

mêz = 120

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 121

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN006PreliminaryAnalysis_dws1.nb 9

A-119

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

mêz = 122

0.0 0.5 1.0 1.5 2.0

0.000.050.100.150.20

mêz = 123

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 124

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 125

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 126

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 127

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 128

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 129

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 130

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.25

mêz = 131

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

mêz = 132

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20

mêz = 133

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 134

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 135

0.0 0.5 1.0 1.5 2.0

0.000.050.100.150.20

mêz = 136

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04

mêz = 137

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 138

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15

mêz = 139

0.0 0.5 1.0 1.5 2.0

-0.020.000.020.040.060.08

mêz = 140

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 141

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 142

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

mêz = 143

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

mêz = 144

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 145

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

10 BTTN006PreliminaryAnalysis_dws1.nb

A-120

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 146

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04

mêz = 147

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

0.20mêz = 148

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4mêz = 149

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

mêz = 150

0.0 0.5 1.0 1.5 2.00.00.51.01.52.02.5

mêz = 151

0.0 0.5 1.0 1.5 2.00

2

4

6

8

10mêz = 152

0.0 0.5 1.0 1.5 2.0

0.00.20.40.60.81.0

mêz = 153

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.25

mêz = 154

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

0.15

0.20mêz = 155

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 156

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

0.8mêz = 157

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

0.15

mêz = 158

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 159

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3mêz = 160

0.0 0.5 1.0 1.5 2.0

-0.020.000.020.040.06

mêz = 161

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 162

0.0 0.5 1.0 1.5 2.0

-0.020.000.020.040.060.08

mêz = 163

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.25

mêz = 164

0.0 0.5 1.0 1.5 2.00

5

10

15

20

mêz = 165

0.0 0.5 1.0 1.5 2.0

0.00.20.40.60.81.01.21.4

mêz = 166

0.0 0.5 1.0 1.5 2.00

1

2

3

4mêz = 167

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0mêz = 168

0.0 0.5 1.0 1.5 2.00.00.51.01.52.02.53.03.5

mêz = 169

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN006PreliminaryAnalysis_dws1.nb 11

A-121

0.0 0.5 1.0 1.5 2.0

0.00.10.20.30.40.50.6

mêz = 170

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

mêz = 171

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 172

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.06

mêz = 173

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.080.10

mêz = 174

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 175

0.0 0.5 1.0 1.5 2.0-0.03-0.02-0.01

0.000.010.020.03

mêz = 176

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

mêz = 177

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04mêz = 178

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.250.30

mêz = 179

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

2.5mêz = 180

0.0 0.5 1.0 1.5 2.0

0.0

0.2

0.4

0.6

mêz = 181

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0-0.05

0.00

0.05

0.10

mêz = 182

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

mêz = 183

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

mêz = 184

0.0 0.5 1.0 1.5 2.0-0.2-0.1

0.00.10.20.30.4

mêz = 185

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10mêz = 186

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.04

mêz = 187

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 188

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04

mêz = 189

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 190

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04mêz = 191

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04

mêz = 192

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 193

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

12 BTTN006PreliminaryAnalysis_dws1.nb

A-122

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

mêz = 194

0.0 0.5 1.0 1.5 2.0-0.04-0.02

0.000.020.040.060.08

mêz = 195

0.0 0.5 1.0 1.5 2.0

0.00

0.05

0.10

0.15

mêz = 196

0.0 0.5 1.0 1.5 2.00.0

0.5

1.0

1.5

2.0

2.5mêz = 197

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4mêz = 198

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.040.06

mêz = 199

0.0 0.5 1.0 1.5 2.0

-0.02

0.00

0.02

0.04

mêz = 200

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 201

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.04

mêz = 202

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10mêz = 203

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 204

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 205

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 206

0.0 0.5 1.0 1.5 2.0

-0.06-0.04-0.02

0.000.020.04

mêz = 207

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.04

mêz = 208

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 209

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 210

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 211

0.0 0.5 1.0 1.5 2.0

-0.05

0.00

0.05

0.10

0.15mêz = 212

0.0 0.5 1.0 1.5 2.0-0.05

0.000.050.100.150.200.25

mêz = 213

0.0 0.5 1.0 1.5 2.00

5

10

15

20

mêz = 214

0.0 0.5 1.0 1.5 2.00.00.51.01.52.02.53.0

mêz = 215

0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4

mêz = 216

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.060.08

mêz = 217

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

BTTN006PreliminaryAnalysis_dws1.nb 13

A-123

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 218

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.040.06

mêz = 219

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 220

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 221

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 222

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 223

0.0 0.5 1.0 1.5 2.0-0.06

-0.04

-0.02

0.00

0.02

0.04mêz = 224

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.04

mêz = 225

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.04

mêz = 226

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 227

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 228

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 229

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 230

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 231

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 232

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04

0.06mêz = 233

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.04

mêz = 234

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 235

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 236

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.040.06

mêz = 237

0.0 0.5 1.0 1.5 2.0-0.06-0.04-0.02

0.000.020.040.06

mêz = 238

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 239

0.0 0.5 1.0 1.5 2.0-0.04

-0.02

0.00

0.02

0.04mêz = 240

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 241

"Time Hs x10000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 10000."

14 BTTN006PreliminaryAnalysis_dws1.nb

A-124

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 242

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04

mêz = 243

0.0 0.5 1.0 1.5 2.0

-0.04-0.02

0.000.020.04

mêz = 244

0.0 0.5 1.0 1.5 2.0

-0.04

-0.02

0.00

0.02

0.04mêz = 245

"Time Hs x10000.L"ü Ion Signals Plots #2: time range 0 to 23460sec.

Comments: Ion signals greater than 0.1 percent total signal were smoothed and replotted vs. Temperature to examine the temporatl behavior of the ions during the ramp to the 60°C isotherm. Note that this compresses all the data around 60°C and these plots show both heating and cooling data. Thus this format has limited usefulness. Most of the signals are similar except m/z 18,44 and 73. The noise level in m/z 28 obscures the real data.

"Data File: BTTN006.dat" "X axis: Temperature H°CL" " X Scale Factor: 10."

2 3 4 5 6-1.0-0.5

0.00.51.01.52.02.5

mêz = 18

2 3 4 5 6

0.0

0.2

0.4

0.6

0.8

mêz = 19

2 3 4 5 6-0.4-0.2

0.00.20.40.60.8

mêz = 28

2 3 4 5 60

1

2

3

mêz = 29

2 3 4 5 60

2

4

6

8mêz = 30

2 3 4 5 60.0

0.5

1.0

1.5

2.0

mêz = 31

2 3 4 5 6

0.00.20.40.60.81.01.2

mêz = 41

2 3 4 5 6

0.0

0.2

0.4

0.6

mêz = 42

2 3 4 5 60123456

mêz = 43

2 3 4 5 6-0.2

0.0

0.2

0.4

0.6

mêz = 44

2 3 4 5 60.0

0.5

1.0

1.5

2.0

2.5mêz = 45

2 3 4 5 60

50100150200250300

mêz = 46

"Temperature H°C x10.L""Data File: BTTN006.dat" "X axis: Temperature H°CL" " X Scale Factor: 10."

BTTN006PreliminaryAnalysis_dws1.nb 15

A-125

p

2 3 4 5 60.0

0.5

1.0

1.5

2.0

2.5mêz = 47

2 3 4 5 60.0

0.5

1.0

1.5

2.0

mêz = 48

2 3 4 5 60.0

0.5

1.0

1.5

2.0

mêz = 57

2 3 4 5 60.00.20.40.60.81.01.21.4

mêz = 60

2 3 4 5 6

0.0

0.5

1.0

1.5

mêz = 69

2 3 4 5 60

2

4

6

8mêz = 71

2 3 4 5 60.0

0.5

1.0

1.5

mêz = 73

2 3 4 5 60

10

20

30

40

50

mêz = 76

2 3 4 5 60.0

0.5

1.0

1.5

2.0mêz = 77

2 3 4 5 6

0.0

0.2

0.4

0.6

mêz = 78

2 3 4 5 6

0.00.20.40.60.81.01.2

mêz = 79

2 3 4 5 6

0.00.10.20.30.40.50.6

mêz = 86

"Temperature H°C x10.L""Data File: BTTN006.dat" "X axis: Temperature H°CL" " X Scale Factor: 10."

2 3 4 5 6

0.00.20.40.60.81.01.21.4

mêz = 89

2 3 4 5 60.00.20.40.60.81.01.21.4

mêz = 103

2 3 4 5 60.00.20.40.60.81.0

mêz = 106

2 3 4 5 60.00.20.40.60.81.0

mêz = 118

2 3 4 5 60.0

0.5

1.0

1.5

2.0

mêz = 122

2 3 4 5 60.0

0.5

1.0

1.5

mêz = 132

2 3 4 5 60.00.51.01.52.02.5

mêz = 151

2 3 4 5 60

2

4

6

8

10mêz = 152

2 3 4 5 6

0.00.20.40.60.81.0

mêz = 153

2 3 4 5 6

0.0

0.2

0.4

0.6

0.8mêz = 157

2 3 4 5 60

5

10

15

20

mêz = 165

2 3 4 5 6

0.00.20.40.60.81.01.21.4

mêz = 166

"Temperature H°C x10.L""Data File: BTTN006.dat" "X axis: Temperature H°CL" " X Scale Factor: 10."

16 BTTN006PreliminaryAnalysis_dws1.nb

A-126

p

2 3 4 5 60

1

2

3

4mêz = 167

2 3 4 5 60.0

0.5

1.0

1.5

2.0mêz = 168

2 3 4 5 60.00.51.01.52.02.53.03.5

mêz = 169

2 3 4 5 6

0.00.10.20.30.40.50.6

mêz = 170

2 3 4 5 60.0

0.5

1.0

1.5

2.0

2.5mêz = 180

2 3 4 5 6

0.0

0.2

0.4

0.6

mêz = 181

2 3 4 5 60.0

0.5

1.0

1.5

2.0

2.5mêz = 197

2 3 4 5 60

5

10

15

20

mêz = 214

2 3 4 5 60.00.51.01.52.02.53.0

mêz = 215

"Temperature H°C x10.L"ü Ion Signals Plots #3: time range 0 to 10000sec.

Comments: Ion signals greater than 0.1 percent total signal have been plotted through 10,000 seconds. There isn't a lot of evidence that the weight loss after 4000 is anything but drift in the balance. (Only m/z 18 has a signal after 4000 seconds, which is difficult to interpret given the large background waterl in the STMBMS and the width of the noise in the signal.

"Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 1000."

0 2 4 6 8 10

-0.50.00.51.01.52.02.5

mêz = 18

0 2 4 6 8 10

0.0

0.2

0.4

0.6

0.8

mêz = 19

0 2 4 6 8 100

1

2

3

mêz = 29

0 2 4 6 8 100

2

4

6

8mêz = 30

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

mêz = 31

0 2 4 6 8 10

0.00.20.40.60.81.01.2

mêz = 41

0 2 4 6 8 10

0.0

0.2

0.4

0.6

mêz = 42

0 2 4 6 8 100123456

mêz = 43

0 2 4 6 8 10-0.2

0.0

0.2

0.4

0.6mêz = 44

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

2.5mêz = 45

0 2 4 6 8 100

50100150200250300

mêz = 46

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

2.5mêz = 47

"Time Hs x1000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 1000."

BTTN006PreliminaryAnalysis_dws1.nb 17

A-127

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

mêz = 48

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

mêz = 57

0 2 4 6 8 100.00.20.40.60.81.01.21.4

mêz = 60

0 2 4 6 8 100.0

0.5

1.0

1.5

mêz = 69

0 2 4 6 8 100

2

4

6

8mêz = 71

0 2 4 6 8 100.0

0.5

1.0

1.5

mêz = 73

0 2 4 6 8 100

1020304050

mêz = 76

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0mêz = 77

0 2 4 6 8 10

0.0

0.2

0.4

0.6

mêz = 78

0 2 4 6 8 10

0.00.20.40.60.81.01.2

mêz = 79

0 2 4 6 8 10

0.00.10.20.30.40.50.6

mêz = 86

0 2 4 6 8 100.00.20.40.60.81.01.21.4

mêz = 89

"Time Hs x1000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 1000."

0 2 4 6 8 100.00.20.40.60.81.01.21.4

mêz = 103

0 2 4 6 8 100.00.20.40.60.81.0

mêz = 106

0 2 4 6 8 100.00.20.40.60.81.0

mêz = 118

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

mêz = 122

0 2 4 6 8 100.0

0.5

1.0

1.5

mêz = 132

0 2 4 6 8 100.00.51.01.52.02.5

mêz = 151

0 2 4 6 8 100

2

4

6

8

10mêz = 152

0 2 4 6 8 100.00.20.40.60.81.0

mêz = 153

0 2 4 6 8 10

0.0

0.2

0.4

0.6

0.8mêz = 157

0 2 4 6 8 100

5

10

15

20

mêz = 165

0 2 4 6 8 10

0.00.20.40.60.81.01.21.4

mêz = 166

0 2 4 6 8 100

1

2

3

4mêz = 167

"Time Hs x1000.L""Data File: BTTN006.dat" "X axis: Time HsL" " X Scale Factor: 1000."

18 BTTN006PreliminaryAnalysis_dws1.nb

A-128

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0mêz = 168

0 2 4 6 8 100.00.51.01.52.02.53.03.5

mêz = 169

0 2 4 6 8 10

0.00.10.20.30.40.50.6

mêz = 170

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

2.5mêz = 180

0 2 4 6 8 10

0.00.10.20.30.40.50.60.7

mêz = 181

0 2 4 6 8 100.0

0.5

1.0

1.5

2.0

2.5mêz = 197

0 2 4 6 8 100

5

10

15

20

mêz = 214

0 2 4 6 8 100.00.51.01.52.02.53.0

mêz = 215

"Time Hs x1000.L"General STMBMS ion signals graphics insertion point

ü Correlations Analysis of Ion SignalsThe correlated groups of m/z values provides information that is used to identify species and determine there sequence of evolution. M/z values that are highly correlated are likely to arise from the same species since they are formed from one species in the ionizer. M/z values that are moderately correlated are likely to be formed at the same time during the thermal decomposition process. These species are likely to be formed in the same portion of the reaction network. M/z values that are not correlated are likely to be in separate regions of the network.

The correlated groups are created by running an autocorrelation on all of the ion signals at the selected m/z values and within the selected time interval. The degree of correlation needed to form a group is determined by the correlation band. The band ranges from a lower value to 1.0. The lower value typically ranges between 0.8 (low correlation) and 0.99 (high correlation).

The signal weighted time (time centroid)is calculated for each group. The ion signals in each group aloing with the groups mass spectra are drawn in a sequence ordered by increasing value of each groups time centroid. Thus, they represent the evolution sequence of speciesduring the course of an experiment.

ü Correlated Signals #1: time range 0 to 5000sec.

Write description of data Comments: A 95 percent correlation analysis of the smoothed ion signals greater than 0.1 percent total signal through 5000 seconds. 41 of the 44 ions are correlated in one of the three groups identified.

::73.

0 1 2 3 4 50.0

0.5

1.0

1.5

Time Hsec x1000L

Centroid Time =1698.43

,

73

0 50 100 150 2000.0

0.1

0.2

0.3

0.4

Mass

Sig

nalH%

L

Band Ò1 Group Ò 5Limits: 0.95 - 1.0001

>,

:18.

0 1 2 3 4 5

0.0

0.5

1.0

1.5

Time Hsec x1000L

Centroid Time =1972.77

,

18

0 50 100 150 2000.0

0.1

0.2

0.3

0.4

0.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 1Limits: 0.95 - 1.0001

>,

BTTN006PreliminaryAnalysis_dws1.nb 19

A-129

:106.

122.151.

152.

153.

0 1 2 3 4 50.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x1000L

Centroid Time =2111.35

,

106122 151

152

1530 50 100 150 200

0.00.51.01.52.02.5

Mass

Sig

nalH%

L

Band Ò1 Group Ò 6Limits: 0.95 - 1.0001

>,

:19.29.30.31.43.

45.46.47.48.57.60.69.

71.

76.77.78.79.86.89.103.118.132.

157.

165.166.167.168.169.

170.

180.181.197.

214.215.

0 1 2 3 4 5

0.0

0.2

0.4

0.6

0.8

1.0

Time Hsec x1000L

Centroid Time =2233.73

,

192930314345

46

474857606971767778798689103118132 157165166167168169170180181197214215

0 50 100 150 2000

102030405060

Mass

Sig

nalH%

LBand Ò1 Group Ò 2

Limits: 0.95 - 1.0001

>,

:

44.

0 1 2 3 4 50.0

0.1

0.2

0.3

0.4

Time Hsec x1000L

Centroid Time =2435.27

,

44

0 50 100 150 2000.000.020.040.060.080.100.12

Mass

Sig

nalH%

L

Band Ò1 Group Ò 4Limits: 0.95 - 1.0001

>,

:41.

42.

0 1 2 3 4 5

0.0

0.2

0.4

0.6

0.8

Time Hsec x1000L

Centroid Time =2496.71

,

4142

0 50 100 150 2000.00

0.05

0.10

0.15

Mass

Sig

nalH%

L

Band Ò1 Group Ò 3Limits: 0.95 - 1.0001

>>

ü Tables of Mass Spectral Informationü Mass Spec Table #1: time range 0 to 23460sec.

Comments: Table summary of raw ion signals at all m/z scanned in the experiment:

Ion signals greater than 0.% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L2 0. 63 0. 124 0. 185 0.1

3 0. 64 0. 125 0. 186 0.

4 0. 65 0.1 126 0. 187 0.

5 0. 66 0. 127 0. 188 0.

6 0. 67 0. 128 0. 189 0.

7 0. 68 0. 129 0.1 190 0.

8 0. 69 0.3 130 0. 191 0.

9 0. 70 0. 131 0. 192 0.

10 0. 71 1.6 132 0.3 193 0.

11 0. 72 0.1 133 0. 194 0.

12 0. 73 0.4 134 0. 195 0.

20 BTTN006PreliminaryAnalysis_dws1.nb

A-130

13 0. 74 0. 135 0. 196 0.

14 0. 75 0. 136 0. 197 0.5

15 0. 76 12. 137 0. 198 0.1

16 0. 77 0.4 138 0. 199 0.

17 0. 78 0.1 139 0. 200 0.

18 0.8 79 0.2 140 0. 201 0.

19 0.2 80 0. 141 0. 202 0.

20 0. 81 0. 142 0. 203 0.

21 0. 82 0. 143 0. 204 0.

22 0. 83 0. 144 0. 205 0.

23 0. 84 0. 145 0. 206 0.

24 0. 85 0.1 146 0. 207 0.

25 0. 86 0.1 147 0. 208 0.

26 0. 87 0.1 148 0. 209 0.

27 0. 88 0. 149 0.1 210 0.

28 0.1 89 0.3 150 0. 211 0.

29 0.7 90 0.1 151 0.6 212 0.

30 1.4 91 0. 152 2.2 213 0.

31 0.4 92 0. 153 0.2 214 4.7

32 0. 93 0. 154 0. 215 0.7

33 0. 94 0.1 155 0. 216 0.1

34 0. 95 0. 156 0.1 217 0.

35 0. 96 0. 157 0.2 218 0.

36 0. 97 0. 158 0. 219 0.

37 0. 98 0. 159 0. 220 0.

38 0. 99 0. 160 0. 221 0.

39 0. 100 0. 161 0. 222 0.

40 0. 101 0. 162 0. 223 0.

41 0.1 102 0. 163 0. 224 0.

42 0.1 103 0.3 164 0. 225 0.

43 1.1 104 0. 165 4.8 226 0.

44 0.1 105 0.1 166 0.3 227 0.

45 0.4 106 0.2 167 0.8 228 0.

46 56.1 107 0. 168 0.4 229 0.

47 0.5 108 0. 169 0.7 230 0.

48 0.4 109 0. 170 0.1 231 0.

49 0. 110 0. 171 0. 232 0.

50 0. 111 0. 172 0. 233 0.

51 0. 112 0. 173 0. 234 0.

52 0. 113 0. 174 0. 235 0.

53 0. 114 0. 175 0. 236 0.

54 0. 115 0. 176 0. 237 0.

55 0.1 116 0.1 177 0. 238 0.

56 0. 117 0. 178 0. 239 0.

57 0.4 118 0.2 179 0.1 240 0.

58 0 1 119 0 1 180 0 5 241 0

BTTN006PreliminaryAnalysis_dws1.nb 21

A-131

58 0.1 119 0.1 180 0.5 241 0.

59 0. 120 0. 181 0.1 242 0.

60 0.3 121 0. 182 0. 243 0.

61 0. 122 0.4 183 0.1 244 0.

62 0. 123 0. 184 0. 245 0.

ü Mass Spec Table #2: time range 0 to 5000sec.Comments: Table summary of the smoothed subset of 44 smoothed ion signals evolving to 5000 seconds:

Ion signals greater than 0.1% of total

Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L Mêz Value SignalH%L18 0.5 47 0.5 86 0.1 165 4.9

19 0.2 48 0.4 89 0.3 166 0.3

29 0.7 57 0.4 103 0.3 167 0.9

30 1.4 60 0.3 106 0.2 168 0.4

31 0.4 69 0.3 118 0.2 169 0.7

41 0.1 71 1.6 122 0.4 170 0.1

42 0.1 73 0.4 132 0.3 180 0.5

43 1.1 76 12.1 151 0.6 181 0.1

44 0.1 77 0.4 152 2.2 197 0.5

45 0.4 78 0.1 153 0.2 214 4.7

46 56.3 79 0.2 157 0.1 215 0.7

22 BTTN006PreliminaryAnalysis_dws1.nb

A-132

Naval Air Warfare CenterProduct Quality Laboratory, Code 474400D

Sample Id: SERDP-PPZ-7-2-8-3 Log#:

Lot/Mix# Date: 10/6/14

Test Form: Solid

Test Color: Yellow

Send Report To: Clubb, J., 474100D, 939-7661

Operator(s): Mann

Safety Sensitivity Tests- Final Report

#1-Impact 50 % Pt: #1-ABL Friction: ABL-Electrostatic

30 CM 20/20 NO FIRES @ 1000 LBS 20/20 NO FIRES @ 0.25 J

#1- Impact Low Fire Pt: #1-ABL Friction Low Fire Pt:

25 CM

#1-Impact 10 TIL: #1-ABL Friction 20 TIL:

Quarterly Standard Results - April-13

Standards are performed quarterly. If a different standard is needed contact the Lab. Safety Sensitivity Test conducted in accordance with: AOP-7 Edition 2, NAWC/NSWC Method ESD Category US/201.03.002/003; AOP-7 Edition 2, ABL Sliding Friction Category US/201.02.005; AOP-7 Edition 2, ERL/Bruceton Impact Test Category US/201.01.001; AOP-7 Edition 2, BAM US/201.02.006. Range in Testing is listed below:

Results

(Pellets) (Powders) (Powders) (Powders) (Powders)Standard ERL Impact 50% Pt #1 ABL Friction 50% Pt #1 ABL Friction 20 TIL BAM Friction ABL ESD

PETN 11 CM 234 LBS 100 LBS -------- 20/20 NF @ 0.25J

RDX Type II, Class 5 19 CM ----- ----- 154 N

13-06-04-01

A-133

Naval Air Warfare CenterProduct Quality Laboratory, Code 474400D

Sample Id: SERDP-PPZ-7-2-8-3 Log#:

Lot/Mix# Test Date:

Test Form: Solid Temperature:

Test Color: Yellow RH%:

Send Report To: Clubb, J., 474100D, 939-7661 Sound Meter:

Operator: Mann

Symbols

X= Fire

Safety Sensitivity Tests- Impact (ERL-Mod Type 12 tool) Variable:

LOG CM Volts 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Sum Typical Fire

1.6 40 X X X X 4 Soft

1.5 32 X O O O X X O X X 9 Flash

1.4 25 O O O X O O 6 None

1.3 20 O 1 Consumed

1.2 16 0 Little

1.1 13 0

1.0 10 0

Average Method of Calculation (Use X and O, Omit first, fill in last)(C=Lowest non-fire)LOG of 50% Point Formula= C + 0.1 (A/N)= ANTI-LOG

1.3 + 0.1 1.8 = 1.48 30

Impact 50 % Pt:30 CM LOG i Ni iNi

1.6 3 4 12

Impact Low Fire Pt: 1.5 2 9 18

25 CM 1.4 1 6 6

1.3 0 1 0

1.2 -1 0 0

Total N 20 1.1 -2 0 0Total A 36 1.0 -3 0 0

Notes: No other anomalies noted.

Standard Test Method Information

13-06-04-01

6/5/2013

O= No Fire

115.5

73

36

The Impact (ERL Model Design) Sensitivity Test is used to determine the sensitivity to impact of energetics, when not under confinement. The machine uses a 2.5 kg. drop weight and type 12 tools. A sample of energetic material is placed onto garnet sandpaper and placed together in the center of the anvil and the striker is lowered to rest on top of the sample. The drop weight is raised to the desired height, dropped and results observed. A positive test is detected by a observance of smoke, odor or sound. After each drop the test sample is removed and a fresh sample is used for the next drop. The modifed Bruceton method is used, defining the 50 percent point at which the sample would fire 50 percent of the time. The Low Fire is the lowest level at which a fire is obtained, approximates the level at which the sample will fire 10 percent of the time. This data is compared to standards of RDX, Comp B and PETN.

A-134

Naval Air Warfare CenterProduct Quality Laboratory, Code 474400D

Sample ID: SERDP-PPZ-7-2-8-3 Log#:

Lot/Mix# Test Date:

Test Form: Solid Temperature:

Test Color: Yellow RH%:

Send Report To: Clubb, J., 474100D, 939-7661

Operator: Mann

Symbols

X= Fire

Safety Sensitivity Tests- #1 ABL Friction O= No Fire

Variable:

LBS LOG CM Volts 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Sum Typical Fire

1000 3.0 O O O O O O O O O O O O O O O O O O O O 20

794 2.9 0 Flash

631 2.8 0

501 2.7 0 Consumed

398 2.6 0

316 2.5 0

251 2.4 0

Average Method of Calculation (Use X and O, Omit first, fill in last)(C=Lowest non-fire)LOG of 50% Point Formula= C + 0.1 (A/N)= ANTI-LOG

3.0 + 0.1 0 = 3 1000

ABL Friction 50 % Pt: LOG i Ni iNi

20/20 NO FIRES @ 1000 LBS 3.0 0 20 0

ABL Friction Low Fire Pt: 2.9 -1 0 0

2.8 -2 0 01.1 -3 0 0

ABL Friction 20 TIL: 2.6 -4 0 0

Total N 20 2.5 -5 0 0Total A 0 2.4 -6 0 0

Notes: No other anomalies noted.

Standard Test Method Information

6/5/2013

13-06-04-01

73

36

The ABL (Alleghany Ballistics Laboratory Design) Sliding Friction Sensitivity Test is used to determine the relative sensitivity of an energetic sample to initiation by friction. The test is conducted using a pendulum drop angle of 90 degrees. This imparts an initial velocity of 8 ft. per second to the sliding steel platen. A sample is placed on the platen and the edge of a 1/8 inch wide steel disc is pressed down on the sample with a selected force obtained by means of a hydraulic ram. The platen is free to slide exactly 1 inch after being struck by the pendulum, and the sample is arranged on the platen so that it is carried between the sliding metal surfaces. The test is performed at a maximum load of 1000lbs . If the sampe shows a negative response 20 tests are performed at this level yielding 20/20 no fires @ 1000lbs. A 20 shot modifed Bruceton method is used defining the 50 percent point if a positive test is detected by visible sparks, visible flame, audible explosion, loud crackling, or the detection of reaction products by a gas analyzer .Low Fire is the lowest level at which a fire is obtained, approximates the level at which the sample will fire 10 percent of the time. This data is compared to standards of RDX and PETN. Extreme caution should be used if the data is below 50 pounds.

A-135

Naval Air Warfare CenterProduct Quality Laboratory, Code 474400D

Sample ID: Log#:

LOT# Test Date:

Test Form: Solid Temperature:

Test Color: Yellow RH%:

Send Report To: Clubb, J., 474100D, 939-7661

Operator: Mann

Symbols

X= Fire

Safety Sensitivity Tests- ABL-Electrostatic Discharge O= No Fire

Variable:

LBS LOG JOULES Volts Test 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Sum Typical Fire

3.7 0.25 5000 O O O O O O O O O O O O O O O O O O O O

3.6 0.16 4000 0 Flash

3.5 0.10 3150 0

3.4 0.06 2500 0 Consumed

3.3 0.04 2000 0

3.2 0.02 1580 0

3.1 0.02 1250 0

3.0 0.01 1000 0

Average Method of Calculation (Use X and O, Omit first, fill in last)(C=Lowest non-fire)LOG of 50% Point Formula= C + 0.1 (A/N)= ANTI-LOG

3.7 + 0.1 0 = 3.7

Electrostatic 50 % Pt: LOG i Ni iNi

20/20 NO FIRES @ 0.25 J 3.7 -1 0 0

Electrostatic Low Fire Pt: 3.6 -2 0 0

3.5 -3 0 0

3.4 -4 0 0

Electrostatic 10 TIL: 3.3 -5 0 0Total N 0 3.2 -6 0 0Total A 0 3.0 -7 0 0

Notes: No other anomalies noted.

Standard Test Method Information

SERDP-PPZ-7-2-8-3

6/5/2013

13-06-04-01

73

36

The Electrostatic Discharge Test is designed to simulate an electrostatically charged person or object discharging through a thin layer of sample to a grounded conductive surface. A sample is placed on a grounded steel button. A capacitor (0.02 microfarad) is charged to a selected voltage by means of a high voltage power supply. The positive side of the capacitor is brought into contact with the sample by means of a steel phonograph needle on the end of a probe and discharges through the sample to the steel button, which is grounded to the other side of the capacitor. Voltages over 5000 volts D.C. are not normally tested because it is estimated that a human body can deliver a max. discharge of 0.001 Joule. The test is begun at the 0.25 joule (0.02 μF) level. If results are negative, i.e., no reaction, the test is continued until 20 consecutive failures are reported. If the test sample has a positive result, i.e., flash, spark, burn, odor, or noise other than instrument noise, then testing is performed at the next lower level until 20 consecutive failures are reported.

A-136

CHINA LAKE VACUUM THERMAL STABILITY (CL-VTS) TEST

Heating Block Temperature: 80 °CLog No.: 13-06-04-01 Customer: J. ClubbSample: SERDP-PPZ-7-2-8-3 Operator: MannForm and color of sampl Solid/Yellow Date(s) 6/8/2013 6/10/2013

Start Time 6:00

Area Atmospheric Pressure (PSI) at start of test 13.61 Stop Time 6:00

Area Atmospheric Pressure (PSI) at end of test: 13.60

Test Method: SOP #14502-004 - China Lake Vacuum Thermal Stability (CL-VTS) Test

SAMPLE #1 SAMPLE #1a

Sample Density 1.644 g/cc Sample Density 1.644 g/cc

Sample Weight 1.0280 grams Sample Weight 1.0190 grams

Start Pressure 0.09 PSIA Start Pressure 0.08 PSIA

Start Temperature 22.3 Deg.C° Start Temperature 22.3 Deg.C°

Final Temperature 22.4 Deg.C° Final Temperature 22.4 Deg.C°

Post Pressure #1 2.56 PSIA Post Pressure #1 2.41 PSIA

Post Pressure #2 4.33 PSIA Post Pressure #2 4.17 PSIA

Corrected Pressure 0.79 PSIA Corrected Pressure 0.65 PSIA

Evolved Gas 0.5721 mL/gram Evolved Gas 0.4702 mL/gram

Average Volume of Evolved Gas: 0.521 mL/gram

Comments: Yellow condensation formed in tubes. No other anomalies noted.

Calculation:

EG = Gas evolved from sample during testing, mL/gramSW = Energetic sample mass in gramsVs = Volume of system in mL (13.99 mL for current test tubes and stoppers)d = Sample density, grams/ccPf = Final corrected pressure (PSI) : Pf = P1- (Ps - P1)Where : P1 = First meter reading at end of test (PSI) Ps = Second meter reading at end of test (PSI)Tf = Ambient temperature at end of test (Celsius)Ti = Ambient temperature at start of test (Celsius)Pi = Pressure reading at start of test (PSI)

+

−

+

−

=

15.27315.273

7.1415.27315.273

7.141

i

i

f

fSLIVE T

PT

Pd

SWVSW

EG

A-137

A-138

A-139

A-140

A-141

CHINA LAKE VACUUM THERMAL STABILITY (CL-VTS) TEST

Heating Block Temperature: 80 °CLog No.: 13-10-16-02 Customer: J. ClubbSample: SERDP-PPZ-8-3-2 Operator: MannForm and color of sampl Solid/Yellow Date(s) 10/22/2013 10/24/2013

Start Time ,0900

Area Atmospheric Pressure (PSI) at start of test 13.72 Stop Time ,0900

Area Atmospheric Pressure (PSI) at end of test: 13.65

Test Method: SOP #14502-004 - China Lake Vacuum Thermal Stability (CL-VTS) Test

SAMPLE #1 SAMPLE #1a

Sample Density 1.655 g/cc Sample Density 1.655 g/cc

Sample Weight 1.0160 grams Sample Weight 1.0020 grams

Start Pressure 0.11 PSIA Start Pressure 0.10 PSIA

Start Temperature 21.9 Deg.C° Start Temperature 21.9 Deg.C°

Final Temperature 21.6 Deg.C° Final Temperature 21.6 Deg.C°

Post Pressure #1 3.10 PSIA Post Pressure #1 2.94 PSIA

Post Pressure #2 4.80 PSIA Post Pressure #2 4.65 PSIA

Corrected Pressure 1.40 PSIA Corrected Pressure 1.23 PSIA

Evolved Gas 1.0709 mL/gram Evolved Gas 0.9518 mL/gram

Average Volume of Evolved Gas: 1.011 mL/gram

Comments: Yellow condensation formed in tubes. No other anomalies noted.

Calculation:

EG = Gas evolved from sample during testing, mL/gramSW = Energetic sample mass in gramsVs = Volume of system in mL (13.99 mL for current test tubes and stoppers)d = Sample density, grams/ccPf = Final corrected pressure (PSI) : Pf = P1- (Ps - P1)Where : P1 = First meter reading at end of test (PSI) Ps = Second meter reading at end of test (PSI)Tf = Ambient temperature at end of test (Celsius)Ti = Ambient temperature at start of test (Celsius)Pi = Pressure reading at start of test (PSI)

+

−

+

−

=

15.27315.273

7.1415.27315.273

7.141

i

i

f

fSLIVE T

PT

Pd

SWVSW

EG

A-142

Appendix B

PROPELLANT FORMULATION MIX SHEETS

Phosphazene Gumstocks Mixes (Reproduced in facsimile)

B-1

This page intentionally left blank.

B-2

B2. Phosphazene Gumstock Mixes

B-3

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/1/2011 Hand Mix GS-PPZ-1-1-1 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of curability and the cure ratio. Thick, very little flow with vibration. After sitting in oven overnight noticed some mild expansion.

11/18/11 - Samples are sticky and more fluid (able to remove material) but appears to be gelling11/28/11 -Still soft and somewhat tacky12/5/11 - Definitely gelling but still very sticky, Tray sample is tacky gelled material, tube still soft12/12/11 -tube still sticky but no removal of material, definitely gelling - tray is cured01/04/12 - gelled but very soft like sticky gum with no memory

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F7-14 days

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

93.580000 4.679 4.6798Polynitrato phosphazene (C6) 092711

6.420000 .321 0.32131,2,7,8-diepoxyoctane S41526V

5Totals: 5.0011100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

140PPZ-E, 1,2,7,8-diepoxyoctane Hand

B-4

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/1/2011 Hand Mix GS-PPZ-1-1-2 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of curability with the inclusion of Nitrocellulose and the cure ratio. Very thick, very little flow with vibration - after sitting overnight noticed some mild expansions.

11/17/11 - Sample is tacky but definitely gelling.11/28/11 - Same as 1-1-1, still soft and somewhat sticky12/05/11 - Tray is tacky gelled material, tube is still soft and not completely gelled12/12/11 - Tube is still sticky but no removal of material, definitely curing - tray is cured01/04/11 - Gelled a little more cohesive than 1-1-1, still like gum, won't hold shape or memory

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F7-14 days

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

90.730000 4.5365 4.5365Polynitrato phosphazene (C6) 092711

6.225000 .31125 0.3121,2,7,8-diepoxyoctane S41526V

3.045000 .15225 0.1807Nitrocellulose 08-4133 (H30)

5Totals: 5.0292100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

140PPZ-E, NC Hand

1401,2,7,8-diepoxyoctane Hand

B-5

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/1/2011 Hand Mix GS-PPZ-1-1-3 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of curability and the addition of BTTN with the cure ratio.

Fluid and runny11/18/11 - Sample has not cured, still fluid but sticky - leave in oven11/28/11 - Runny12/05/11 - Still flows *Not Good, the tray sample does not flow, rubbery, nearly cured, still very tacky01/04/12 - Still Fluid - appears some interference with curing is being caused by BTTN*Scrap mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F7-14 days

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

48.340000 2.417 2.4175Polynitrato phosphazene (C6) 092711

3.320000 .166 0.16631,2,7,8-diepoxyoctane S41526V

48.340000 2.417 2.420BTTN HB04B-PTL-4 AB408

5Totals: 5.0038100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

140PPZ-E, BTTN Hand

1401,2,7,8-diepoxyoctane Hand

B-6

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/21/2011 Hand Mix GS-PPZ-1-1-1TPB 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of TPB catalyst on curability and gel time. Sticky settles some with heat, settles into bottom of vial without vibration when hot.

11/28/11 - Still not cured , very sticky12/5/11 - sticky12/12/11 - Sticky, tacky, removal of material, not cured yet01/04/12 - Definitely gelling but still some removal of material01/09/12 - Sample appeared to be gelled but soft and formable , wont hold shape or memory - TPB catalyst appears ineffective *Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

93.580000 4.679 4.6793Polynitrato phosphazene (C6) 092711

6.420000 .321 0.32141,2,7,8-diepoxyoctane S41526V

0.150000 .0075 0.0076TPB (triphenyl bismuth) 09123BS

5Totals: 5.0083100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, 1,2,7,8-diepoxyoctane, TPB

B-7

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/21/2011 Hand Mix GS-PPZ-1-1-2TPB 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of TPB catalyst on curability and gel time. - Thick and sticky, NC does not seem to go inot solution that well, settles at bottom of vial without vibration or when hot.

11/28/11 - Same consistency as iteration 1-1-1, not cured, very sticky12/05/11 - Again same as 1-1-1 sticky12/12/11 - Sticky, tacky, thicker than iteration 1, but still not cured01/04/12 - Same as 1-1-1, gelling but material is removed01/09/12 - Appears to be curing but very soft02/13/12 - Same as iteration 1-1-1, not as well formed with the NC in it, does not hold shape well *Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

90.730000 4.5365 4.5365Polynitrato phosphazene (C6) 092711

6.225000 .31125 0.311251,2,7,8-diepoxyoctane S41526V

3.045000 .15225 0.15225Nitrocellulose 08-4133 (H30)

0.150000 .0075 0.0075TPB (triphenyl bismuth) 09123BS

5Totals: 5.0075100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC

1,2,7,8-diepoxyoctane, TPB

B-8

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/21/2011 Hand Mix GS-PPZ-1-1-3TPB 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of TPB catalyst on curability and gel time. Runny and was able to poor into vial

11/28/11 - Not cured, runny12/05/11 - Very runny fluid12/12/11- Still flows01/04/12 - Still fluid01/09/12 - Still flows02/13/12 - Never really gelled, again obvious level of BTTN is potentially interfering with cure*Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

48.340000 2.417 2.4171Polynitrato phosphazene (C6) 092711

3.320000 .166 0.1671,2,7,8-diepoxyoctane S41526V

48.340000 2.417 2.420BTTN HB04B-PTL-4 AB408

0.150000 .0075 0.075TPB (triphenyl bismuth) 09123BS

5Totals: 5.0791100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, BTTN

1,2,7,8-diepoxyoctane, TPB

B-9

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/21/2011 Hand Mix GS-PPZ-1-1-1T12 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Density of T-12 is 1.066g/ml. Use the 2-20ul RAINETTE Pipet or similar microliter pipet to add the T-12. Additon should be 7.04ul.

Assess effect of T-12 catalyst on curability and gel time. Thick and sticky, settles at bottom of vial without vibraton and heated

11/28/11 - Same iterations 1 and 2 with TPB, not cured, sticky12/05/11 - Very sticky, gelling, does not run12/12/11 - Sames as TPB iteration 1-1-1, sticky, tacky, removal of material, not completely cured yet01/04/12 - Has not shown improvement over TPB based gum stock01/09/12 - Not completely gelled*Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

93.580000 4.679 4.6799Polynitrato phosphazene (C6) 092711

6.420000 .321 0.3211,2,7,8-diepoxyoctane S41526V

0.150000 .0075 0.008T-12 GE

5Totals: 5.0089100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, 1,2,7,8-diepoxyoctane, T-12

B-10

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/21/2011 Hand Mix GS-PPZ-1-1-2T12 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Density of T-12 is 1.066g/ml. Use the 2-20ul RAINETTE Pipet or similar microliter pipet to add the T-12. Additon should be 7.04ul.

Assess effect of T-12 catalyst on curability and gel time. Thick and Sticky, NC does not seem to go into solution all that well. Settles at bottom of vial without vibration and heat

11/28/11 - Surprisingly more firm than the others, still sticky, lots of air bubbles appear throughout.12/05/11 - Very sticky gel, does not run12/12/11 - Same as TPB based iteration01/04/12 - Has not shown improvement over the TPB based formulation01/09/12 - Not completely cured *Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

90.730000 4.5365 4.5365Polynitrato phosphazene (C6) 092711

6.225000 .31125 0.31141,2,7,8-diepoxyoctane S41526V

3.045000 .15225 0.1524Nitrocellulose 08-4133 (H30)

0.150000 .0075 0.0070T-12 GE

5Totals: 5.0073100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC

1,2,7,8-diepoxyoctane, T-12

B-11

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 11/21/2011 Hand Mix GS-PPZ-1-1-3T12 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Density of T-12 is 1.066g/ml. Use the 2-20ul RAINETTE Pipet or similar microliter pipet to add the T-12. Additon should be 7.04ul.

Assess effect of T-12 catalyst on curability and gel time. Runny, poored into vial

11/28/11 - Runny!12/05/11 - runny fluid12/12/11 - Same as TPB based iteration - still flows01/04/12 - Still fluid!01/09/12 - Again still fluid - no curing action when using BTTN look for stronger catalyst and curatives!

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

48.340000 2.417 2.4172Polynitrato phosphazene (C6) 092711

3.320000 .166 0.1661,2,7,8-diepoxyoctane S41526V

48.340000 2.417 2.4176BTTN HB04B-PTL-4 AB408

0.150000 .0075 0.0072T-12 GE

5Totals: 5.0080100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, BTTN

1,2,7,8-diepoxyoctane, T-12

B-12

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 12/6/2011 Hand Mix GS-PPZ-1-1-1DNSA 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Observe whether the DNSA dissolves in the polymer (use heat as needed)

Assess effect of adding mild acid DNSA on curability and gel time.

12/12/11 -Still sticky/tacky, appears to be gelling01/04/12 - Definitely gelling01/09/12 - Gelling but still soft and gummy02/13/12 - Gelled better than TPB, soft but with form, yet not as well as the extra addition of DNSA. Increase level of acid and observed to see if there is a corresponding improvement in curability *Scrap

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

93.580000 4.679 4.6791Polynitrato phosphazene (C6) 092711

6.420000 .321 0.32141,2,7,8-diepoxyoctane S41526V

0.150000 .0075 0.0073DNSA 121881

5Totals: 5.0078100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

hand 140 DNSA dissolved inPPZ-E, DNSA

hand 140 PPZE easily1,2,7,8-diepoxyoctane,

B-13

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 12/6/2011 Hand Mix GS-PPZ-1-1-2DNSA 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Observe whether DNSA dissolves in the polymer mixture first (heat as needed)

Assess effect of adding mild acid DNSA on curability and gel time.

12/12/11 - Still sticky/tacky, appears to be gelling, tray appears almost cured01/04/12 - Definetly gelling01/09/12 - not fully cured, still gummy02/13/12 - still tacky and material removes it did gel better than the TPB version soft but more form *Eventually scrapped as never completely gelled full

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

90.730000 4.5365 4.5369Polynitrato phosphazene (C6) 092711

6.225000 .31125 0.31131,2,7,8-diepoxyoctane S41526V

3.045000 .15225 0.1532Nitrocellulose 08-4133 (H30)

0.150000 .0075 0.0078DNSA 121881

5Totals: 5.0092100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

140 NC,DNSA incorporatedPPZ-E, DNSA, NC

140 easily with heat1,2,7,8-diepoxyoctane,

B-14

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 12/6/2011 Hand Mix GS-PPZ-1-1-3DNSA 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Observe whether DNSA dissolves in polymer/BTTN mixture (use heat as needed)

Assess effect of adding mild acid DNSA on curability and gel time.

12/12/11- Still flows and wet01/04/12 - Still fluid01/09/12 - Still flows - some effect of BTTN interfering with cure? *Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

48.340000 2.417 2.4172Polynitrato phosphazene (C6) 092711

3.320000 .166 0.16601,2,7,8-diepoxyoctane S41526V

48.340000 2.417 2.4177BTTN HB04B-PTL-4 AB408

0.150000 .0075 0.0075DNSA 121881

5Totals: 5.0084100.15

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

140 BTTN and DNSAPPZ-E, BTTN,DNSA

140 incorporated fairly well1,2,7,8-diepoxyoctane,

easily with heat

B-15

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 12/12/2011 Hand Mix GS-PPZ-E-1-1-1DNSA 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Observe whether the DNSA dissolves in the polymer (use heat as needed)

Assess effect of increasing addition of mild acid DNSA on curability and gel time. Cast into wider handmix cups

01/04/12 - Definitely gelling01/09/12 - Gelling but still soft and gummy02/13/12 - Still tacky and material does remove02/23/12 - Sample nearly gelled, material still pulls up but no longer removealbe - increase in DNSA to 0.50 wt% appears to show improve curing time and development yet still times are too long - need to look for stronger catalysts *Scrap mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

93.580000 4.679 4.678Polynitrato phosphazene (C6) 092711

6.420000 .321 0.3251,2,7,8-diepoxyoctane S41526V

0.500000 .025 0.0251DNSA 12981A

5Totals: 5.0281100.5

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, DNSA

1,2,7,8-diepoxyoctane,

B-16

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 12/12/2011 Hand Mix GS-PPZ-E-1-1-2DNSA 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Observe whether DNSA dissolves in the polymer mixture first (heat as needed)

Assess effect of adding additional mild acid DNSA on curability and gel time. Cast into wider hand mix cups

01/04/12 - Definitely gelling01/09/12 - gelling but still soft and gummy02/13/12 - still tacky and material removes02/23/12 - Sample nearly gelled, materials still pulls up but no longer removeable - sample behaved similar to iteration 1-1-1 and NC had little effect on curing or cure time.

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

90.730000 4.5365 4.536Polynitrato phosphazene (C6) 092711

6.225000 .31125 0.3121,2,7,8-diepoxyoctane S41526V

3.045000 .15225 0.1500Nitrocellulose 08-4133 (H30)

0.500000 .025 0.0250DNSA 12981A

5Totals: 5.0230100.5

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, DNSA, NC

1,2,7,8-diepoxyoctane,

B-17

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 12/12/2011 Hand Mix GS-PPZ-E-1-1-3DNSA 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Observe whether DNSA dissolves in polymer/BTTN mixture (use heat as needed)

Assess effect of increasing addition of mild acid DNSA on curability and gel time. Cast into wider handmix cups

01/04/12 - Still fluid, but definitely gelling in the sample tray01/09/12 - Still flows, tray appears cured but sticky to touch. No transfer of material02/23/12 - Still flows02/23/12 - Still wet (not gelling) - appears consistent with all other gumstock studies with BTTN - need to look for new stronger catalysts even though at lower level of material (sample tray) the GS does cure somewhat.

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160FViscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

48.340000 2.417 2.418Polynitrato phosphazene (C6) 092711

3.320000 .166 0.1721,2,7,8-diepoxyoctane S41526V

48.340000 2.417 2.417BTTN HB04B-PTL-4 AB408

0.500000 .025 0.0257DNSA 12981A

5Totals: 5.0327100.5

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, BTTN,DNSA

1,2,7,8-diepoxyoctane,

B-18

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 2/22/2012 Hand Mix GS-PPZ-E-1-2-1 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

N-100 = 182.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use heat as needed

Assess effect of utilizing isocyanates on the curability and gel time. Cast into wider handmix cups

Sample cured up nearly immediately and foamed up pretyy spectacularly, much like a polyurethane foam

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

160FViscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

65.463000 3.27315Polynitrato phosphazene (C6) 092711

34.238000 1.7119N-100 C321000072

0.299000 .01495T-12 GE

5Totals: 100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, N-100, T-12

B-19

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 2/22/2012 Hand Mix GS-PPZ-E-1-2-2 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

N-100 = 182.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use heat as needed

Assess effect of utilizing isocyanates on the curability and gel time. Cast into wider handmix cups

02/23/12 - Sample cured up too fast again even at 120F cure temperature. Sample foamed up spectacularly like a polyurethane foam!!

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

120F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

60.821000 3.04105 3.0448Polynitrato phosphazene (C6) 092711

33.862000 1.6931 1.69N-100 91004

0.278000 .0139 0.0152T-12 GE

5.039000 .25195 0.2562Nitrocellulose 08-4133 (H30)

5Totals: 5.0062100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC

N-100, T-12

B-20

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 2/29/2012 Hand Mix GS-PPZ-E-1-2-3 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

N-100 = 182.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use heat as needed

Assess effect of utilizing isocyanates on the curability and gel time. Cast into wider handmix cups

02/28/13 - Sample cured up way too fast (1/2 hour) at least it cured though. *Scrap Mix

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

120F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

44.428000 2.2214 2.2254Polynitrato phosphazene (C6) 092711

11.047000 .55235 0.55N-100 C321000072

0.097000 .00485 .00486T-12 GE

44.428000 2.2214 2.2264BTTN IHM10K320-001 AB408

5Totals: 5.0067100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, BTTN

N-100, T-12

B-21

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 4/19/2012 Hand Mix GS-PPZE-1-2-3A 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

N-100 = 182.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use dried NC first then use heat as needed when mixing. Cure under vacuum.

Assess effect of curing under pressure utilizing polyfunctional isocyanate with TPB catalyst on the curability and gel time. Cast into wider handmix cups

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

110FViscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

23.000000 1.15 1.1501Polynitrato phosphazene (C6) 092711

11.047000 .55235 0.5526N-100 C321000072

0.043000 .00215 0.0023TPB (triphenyl bismuth) 09123BS

23.000000 1.15 1.1507BTTN IHM10K320-001 AB408

0.772000 .0386 0.0394Nitrocellulose 08-4133 (H30)

5Totals: 2.895157.862

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC, BTTN

N-100, TPB

B-22

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb Hand Mix GS-PPZE-1-2-3B

PPZ-E = 401.7 ewNC = 357 ew

N-3200 = 182.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use dried NC first then use heat as needed when mixing. Cure under vacuum.

Assess effect of curing under pressure utilizing polyfunctional isocyanate with TPB catalyst on the curability and gel time. Cast into wider handmix cups

05/30-12 - Put in oven in pressure cooker at 9psi05/31/12 - Pressure rasied to 11psi, bled back down to 9psiSame results as iteration 1-2-3A

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

135F7-days

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

23.000000 1.15 1.1569Polynitrato phosphazene (C6) 092711

11.047000 .55235 0.55N-3200 C322000037

0.043000 .00215 0.0037TPB (triphenyl bismuth) 09123BS

23.000000 1.15 1.1582BTTN IHM10K320-001 AB408

0.772000 .0386 0.038Nitrocellulose 08-4133 (H30)

5Totals: 2.906857.862

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC, BTTN

N-3200, TPB

B-23

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 3/19/2012 Hand Mix GS-PPZ-E-1-2-4TPB 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

HMDI = 132.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use heat as needed

Assess effect of utilizing di functional isocyanates on the curability and gel time with TPB catalyst. Cast into wider handmix cups

Sample did not completely gel

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

110FViscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

41.587000 2.07935 2.0803Polynitrato phosphazene (C6) 092711

15.387000 .76935 0.7707HMDI(Dicyclohexylmeth. Diisocyanate) C316000286 (Desmodur W)

0.043000 .00215 .0022TPB (triphenyl bismuth) 09123BS

41.587000 2.07935 2.0813BTTN IHM10K320-001 AB408

1.396000 .0698 0.0698Nitrocellulose 08-4133 (H30)

5Totals: 5.0043100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC, BTTN

HNMDI, TPB

B-24

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: Hazard Classification: Inert

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 3/19/2012 Hand Mix GS-PPZ-E-1-2-4T12 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

HMDI = 132.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Use heat as needed

Assess effect of utilizing di functional isocyanates on the curability and gel time along with T-12 catalyst. Cast into wider handmix cups

Sample did not completely gel.

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

110FViscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

41.587000 2.07935 2.0793Polynitrato phosphazene (C6) 092711

15.387000 .76935 0.7658HMDI(Dicyclohexylmeth. Diisocyanate) C316000286 (Desmodur W)

0.043000 .00215 0.0066T-12 DJ-120

41.587000 2.07935 2.0794BTTN IHM10K320-001 AB408

1.396000 .0698 0.0715Nitrocellulose 08-4133 (H30)

5Totals: 5.0026100

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC, BTTN

HMDI, T-12

B-25

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 4/19/2012 Hand Mix GS-PPZE-1-2-5T12 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

HMDI = 132.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Used dried NC first then use heat as needed to mix. Use 2-20ul microliter pipet and inject .751ul of T-12. Density of T-12 is 1.066g/ml. Cure under vacuum.

Assess effect of utilizing di functional isocyanates with reduced T-12 on the curability and gel time. Cast into wider handmix cups

Sample never did gel.

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

110FViscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

23.000000 1.15 1.1509Polynitrato phosphazene (C6) 092711

15.387000 .76935 0.7695HMDI(Dicyclohexylmeth. Diisocyanate) C316000286 (Desmodur W)

0.001500 .00008 .00008T-12 DJ-120

23.000000 1.15 1.1536BTTN IHM10K320-001 AB408

0.772000 .0386 0.0389Nitrocellulose 08-4133 (H30)

5Totals: 3.113062.1605

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC, BTTN

HMDI, T-12

B-26

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Danny White Joey Clubb 5/29/2012 Hand Mix GS-PPZE-1-2-6T12 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

HMDI = 132.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Used dried NC first then use heat as needed to mix. Use 2-20ul microliter pipet and inject .751ul of T-12. Density of T-12 is 1.066g/ml. Cure under vacuum.

Assess effect of curing under pressure and utilizing di functional isocyanates with reduced T-12 on the curability and gel time. Cast into wider handmix cups

05/30/12 - Put in oven in pressure cooker at 9psi05/31/12 - Pressure raised to 11psi. Bled back to 9psiSample never did completely gel

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

135F7-days

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

23.000000 1.15 1.1547Polynitrato phosphazene (C6) 092711

15.387000 .76935 0.7694HMDI(Dicyclohexylmeth. Diisocyanate) C316000286 (Desmodur W)

0.001500 .00008 0.00008T-12 DJ-120

23.000000 1.15 1.155BTTN IHM10K320-001 AB408

0.772000 .0386 0.38Nitrocellulose 08-4133 (H30)

5Totals: 3.459262.1605

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, NC, BTTN

HMDI, T-12

B-27

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/19/2012 Hand Mix GS-PPZE-1-1 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of Hycat 2000S as a cure catalyst with the epoxy curative. Cast into wider handmix cups

Looked like it started to get stringy while mixing (gelling). Somewhat of an oily type base but not really separation.07/23/12 - Sample has gelled, no running of material, sample is soft and pipet leaves slight indentation, but does not stick, firmer than the other iterations07/30/12 - Same state no real hardening or toughening *Good Sample to begin work with plasticizer study07/31/12 - Sample shows same response, cured soft, very flexible, not much memory and will tear apart - will it improve with solids loading?

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

167F4-days

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45 3.450Polynitrato phosphazene (C6) 092711

4.830000 .2415 0.2411,2,7,8-diepoxyoctane S41526V

1.380000 .069 .069Hycat 2000S N-205-137

5Totals: 3.760075.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, diepoxyoctane, Hycat 2000S

B-28

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/19/2012 Hand Mix GS-PPZE-1-2 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of Hycat 3000S as a cure catalyst with the epoxy curative. Cast into wider handmix cups

material seemed to have an oily base -did not stick to cup, pooled and pulled to itself.07/23/12 - Sample has gelled, no running of material, sot and sticky pulls up with pipet but does not stick to pipet and pulls away.07/31/12 - Material is a little tackier than iteration 1, fairly similar in consistency, deformable but will respond with memory if not stressed to much.

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45 3.450Polynitrato phosphazene (C6) 092711

4.830000 .2415 0.2411,2,7,8-diepoxyoctane S41526V

1.380000 .069 0.069Hycat 3000S 1059214

5Totals: 3.760075.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, diepoxyoctane, Hycat 3000S

B-29

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/19/2012 Hand Mix GS-PPZE-1-3 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of Hycat SM3 as a cure catalyst with the epoxy curative. Cast into wider handmix cups

Seemed to have an oily base - much like the other Hycat catalysts.07/23/12 - Sample has gelled, soft but cured with no material running, pipet leaves indentation but reforms, does not stick to pipet07/31/12 - Similar results to other iterations, tacky, deformable, some memory

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45 3.451Polynitrato phosphazene (C6) 092711

4.830000 .2415 0.2411,2,7,8-diepoxyoctane S41526V

1.380000 .069 0.069Hycat AO-4 N-205-131

5Totals: 3.761075.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, diepoxyoctane, Hycat SM3

B-30

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/19/2012 Hand Mix GS-PPZE-1-4 100000462206 0010

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of organophosphorous Hycat AO-4 as a cure catalyst with the epoxy curative. Cast into wider handmix cups

Seemed to have an oily base much like the other Hycat materials.07/23/12 - Sample still runs and has not gelled yet.

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 1.00

160F???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45 3.450Polynitrato phosphazene (C6) 092711

4.830000 .2415 0.2411,2,7,8-diepoxyoctane S41526V

1.380000 .069 0.069Hycat AO-4 N-205-131

5Totals: 3.760075.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, diepoxyoctane, Hycat AO-4

B-31

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/31/2012 Hand Mix GS-PPZE-1-1-1

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of adding the BTTN at 5% by wt. With the Hycat 2000S cure catalyst with the epoxy curative. Cast into wider handmix cups

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 0.217

75C???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45Polynitrato phosphazene (C6) 092711

4.830000 .24151,2,7,8-diepoxyoctane S41526V

1.380000 .069Hycat 2000S N-205-137

15.000000 .75BTTN IHM10K320-001 AB408

5Totals: 90.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, BTTN

diepoxyoctane, Hycat 2000S

B-32

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/31/2012 Hand Mix GS-PPZE-1-1-2

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of adding the TMETN at 15% by wt. With the Hycat 2000S cure catalyst with the epoxy curative. Cast into wider handmix cups

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 0.217

75C???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45Polynitrato phosphazene (C6) 092711

4.830000 .24151,2,7,8-diepoxyoctane S41526V

1.380000 .069Hycat 2000S N-205-137

15.000000 .75TMETN IH91B120-019/113 AB854

5Totals: 90.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, TMETN

diepoxyoctane, Hycat 2000S

B-33

SMALL SCALE PROPELLANT / EXPLOSIVES MIX SHEET

Card #: AD974 Hazard Classification: Class 1.1C

COG ENG DATE MIXED MIXER USED MIX NUMBER PJ NUMBEROPERATOR (S)

Dave Turnbaugh Joey Clubb 7/31/2012 Hand Mix GS-PPZE-1-1-3

PPZ-E = 401.7 ewNC = 357 ew

diepoxyoctane = 142.2 mw68%ES group

95% nitration - 5% free hydroxyl

CATALYST EQUIV.

Assess effect of adding the BuNENA at 15% by wt. With the Hycat 2000S cure catalyst with the epoxy curative. Cast into wider handmix cups

REQUIRED TESTING

TECH COMMENTS

MIX INSTRUCTIONS

0

Page #

OH/epoxide ratio: 5.7equiv. =(142.2 x .68 x .05) x 5.7

PL/PO = 0.217

75C???

Viscosity:

Cure Time:Cure Temp:

Rel Humidity

Building Location: Sample Identifier

% By Wt gm Needed gm Added LOT NUMBER NALCMATERIAL

69.000000 3.45Polynitrato phosphazene (C6) 092711

4.830000 .24151,2,7,8-diepoxyoctane S41526V

1.380000 .069Hycat 2000S N-205-137

15.000000 .75Butyl NENA Lot 3

5Totals: 90.21

MIXING TIME VAC TEMP

MIXING STOPSTART MAT MIX SPEED CONDITIONJACKETmm HgLive?INGREDIENT MIX ORDER

PPZ-E, Butyl NENA

diepoxyoctane, Hycat 2000S

B-34