lfCFILE Copy'$

FADAD-E 401 739

Contractor Report Number ARAED-CR-87024

NOVEL ANALYTICAL X-RAY NON-DESTRUCTIVE EVALUATION (NDE)TOOL FOR QUALITY CONTROL OF ENERGETIC MATERIALS

Dr. Ronald G. Rosemelerr. T.S. Ananthanarayanan(v) Dr. Sudhir B. Trived;N Alfred L. Wiltrout

Douglas C. LeepaN. Bruce E. Harrison A L A

Jolanta I. Soos l 06Brimrose Corporation of America 0 6

7720 Belair RoadBaltimore, MD 21236 z

James PintoProject Engineer

ARDEC

(12 OCT "987 )

U.S. ARMY ARMAMENT RESEARCH, DEVELOPMENT ANDENGINEERING CENTER

Armament Engineering DirectoratePicatinny Arsenal, New Jemey

WUs~*~Muamy

Approved for public release; distribution unlimited.

87 10 20 074

II

The views, opinions, and/or findings contciined in this report are those of theauthor(s) and should not be construed as an official Department of the Armyposition, policy, or decision, unless so designated by other documentation.

The citation in this report of the names; of commercial firms or commerciallyavailable products or services does not constitute official endorsement by orapproval of the U.S. Government.

Destroy this report when no longer needed by any method that will preventdisclosure of contents or reconstruction of the document. Do not return to theoriginator.

1

jr

II

C / SVURITtCLASSIFICATION OF THIS PAGE

REPORT DOCUMENTATION PAGE

Ii REPORT SEGUIITY CLASSIFICAIION lb. RESTRICTIVE MARKINGS

2. SECURITY CLASSIFICATION AUTHORITY 3. OISTRIBUTION/AVAILABILITY OF REPORT

APPROVED FOR PUBLIC RELEASE; DISTRIBUTION

2b DECLASSIFICATION/DOWNGRADING SCHEDULE UNLIMITED

4 PERFORMING ORGANIZATION REPORT NUMBER(S) 5. MONITORING ORGANIZATION REPORT NUMBER(S)

ARAED-CR-87024

"6a. NAME OF PERFORMING ORGANIZATION lb. OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION

Brimrose Corp. of America (ifapplicable) ARDEC, AED

6c ADDRESS (City, State and ZIP Code) 7b. ADDRESS (City. Stlate and ZIP Code)

7720 Belair Road Energetics and Warheads Div. (SMCAR-AEE-WW)Baltimore, MD 21236 Picatinny Arsenal, NJ 07806-5000

"Go. NAME OF FUNDINGISPONSORING 0b. OFFICE SYMBOL 9. PROCUREMENT INSTRUMENT IDENTIFICATION NUMBERORGANIZATION (if applicable) DAAA21-86-C-0271ARDEC, IMD

Sc. ADDRESS (City. Statl and ZIP Code) 10. SOURCE OF FUNDING NOS.

STINFO Br (SMCAR-IMI-I) PROGRAM PROJECT TASK WORK UNITSIFBr(MA-M-)ELEMENT NO. NO. NO. NO.

Picatinny Arsenal, NJ 07806-5000

11. TITLE (include Security Clasification) Novel AnalyticalX-rayvon-Destructive (NDE) Tool for Quality('ont- tol__ofFn~rapti r _terlaig a

12. PERSONAL AUTHOR(S) R. G. Rosemeier, T. S. Ananthanarayanan, S. B. Trivedi, A. L. Wiltrout,D. C. Leepa, B. Harrison, J. I. Soos, Brimrose Corp., J. Pinto, Proiect Engineer, ARDEC

13& TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Yr.. Mo.. Day) 1Is. PAGE COUNT

FINAL FROM 8/28/86 To 2/28/87 10/05/87 116. SUPPLEMENTARY NOTATION

17. COSATI CODES 18. SUBJECT TERMS (Continue on reuerse if neceuary and identify by block number)cIELO GROUP SUB. GR. RDX, HMX, explosives, propellants, quality control,

real time, x-ray

19. ABSTRACT (Continue on reverse If necessarJ and idmntiy by block number)

Particle size, segregation and composite homogeniety are some of the criticalparameters affecting propellant performance. Several investigations have been undertakento resolve this issue. The current study involves the use of real time x-ray diffractionexperiments to quantify the above mentioned parameters.

2-D x-ray detectors in combination with state-of-the-art image processinghardware/software have significantly enhanced the analytical capabilities. Severalcaposites and simulants have been examined using these techniques. A procedure for x-ray"finger printing" individual constituents in composites has been successfully implemented.Algorithms have also been developed for particle size and distribution analysis. Some ofthe initial results have been presented to show the efficacy of such techniques in rapidon-line production oriented applications. Additionally, these techniques can also be usedto determine micro-lattice strain states in various constituents in the composites.

All x-ray methods used are firmly based on 1st principles (Bragg's Law of x-raydiffraction). Integration with digital imaging and advanced computing techniques makesexpert system design viable and extremely lucrative for production feed back control.

20. DISTRISUTION/AVAILABILITY OF ABSTRACT 21. ABSTRACT SECURITY CLASSIFICATION

UNCLASSIFIED/UNLIMITED E SAME AS RPT. 0 OTIC USERS Q Unclassified

22a. NAME OF RESPONSIBLE INDIVIDUAL 22b. TELEPHONE NUMBER 22c. OFFICE SYMBOL"'• ~(include Arco Code) •

"I. Haznedari (STINFO's) point of contact"with DTIC) AV880-3316 SMCAR-IMI-I

DD FORM 1473. 83 APR EOi. 4OF I JAN 73 IS OBSOLETE. UNCLASSIFIEDSECURITY CLASSIFICATiON OF THIS PAGE

_3o

PACE#

Introduction 1

Technical Approach 2

X-ray Diffractcmetry, Powder DiffractionRocking Curve Topography

Results and Discussion 4

Micro-lattice Strain Measurements

Propellant Mixing and Distribution

Solid Propellant CharacterizationConstituent Phase AnalysisReal Time Particle Size & Phase Analysis

Process Induced Damage in Propellants

Phase I Conclusion 6

Future Directions: Novel Concept in X-ray Powder Analysis 7

References 8

Distribution List f ric

Accesion Fo

DTIC TAB ujUnano;,.:iced

By ...................................

Byu- .;-.............

Di~ itto

-- t

LIST OF FIGURES

1 PIXI Portable Image X-ray Intensifier 10

2 DIXIE Digital Intensity X-ray Image Enhancer. 10

3 Geometry of Conventional X-ray Diffractameter from 11Cullity, B. D., "Elements of X-ray Diffraction,"Addison-Wesley Publishing Co. Inc., Reading MA.

4 Diffraction Geometry for White Beam Rocking Curve 11Topography.

5a Schematic of a Digital Rocking Curve Analyzer. 12

5b Digital Autamated Rocking Curve To~pographty. 13

5c Digital Autucmated Rocking Curve Topography. 13

6 NaCI White Rocking Curv. 1Lpography Cu Radiation (510) 14Reflection, Surface Orientation (100), 2-Theta = 57.225,Incidence Angle = 30 - 40, AQ (Angular Increment)between Frames = 0.100.

7 NaCl Hardness Indentation (222) Reflection 15Perspective of Rocking Curve Topograph.

8 ZnCdTe Epi/InSb (111), 010 Reflection, Cu Radiation 15(white).

9 Rapid X-ray Diffraction Pattern of tMX and RDX. 16

10 Showing Partial X-ray Diffraction Profiles to 17RDX & HMX with Appropriate Windows for ConstituentPhase Identification and Ccnposition Analysis.

11 Schematic of Proposed System. 17

12a Real Time Laue Diffraction Pattern fran Sugar 18Particles 74-149pm.

12b Real Time Laue Diffraction Pattern fran Sugar 19Particles 44-74pm.

12c Real Time Laue Diffraction Pattern from Sugar 20Particles 0-44pm.

13a Real Time Transmission Laue of Several Prcpellant 21Camposites, 74pm RDX, RDX and Al Camposites in PBX,10% Al/HTP• Ccnposite.

13b Real Time Laue Transmission of RDX and Al Composites 22with Al Fbil.

ivII-

13c Schematic of Real Time Transmission Laue. 23

14 Real Time Transmission Laue of Al Foil. 24

15 Real Time Transmission Laue of Al, Cu, Brass, Ni 24Foils.

16a Effect of Crushing on Pure RDX (Cr Radiation). 25

l1b Production RDX (Lot X661) US. Pure RDX. 26

16c Production RDX (Lot A597) US. Pure PDX. 27

16d Production RDX (Lot A984) US. Pure RDX. 28

16e RDX Sample Lot 78 (Cr Radiation). 29

17 Formation of X-ray (Debye-Scherrer) Powder Pattern in a 30Cylindrical Camera.

18 Improved Real Time Powder Diffraction Technique. 30

v

Factors affecting the stability of energetic materials are notwell understood. Knowledge of these factors is essential for thepredictability and hence the successful dpplicatiops of energeticmaterials as explosives and/or propellants. This in turn involvesstudy of energetic reactions and reaction parameters. The effects oflattice defects, particle size, tem-perature, radiation and mechanicalimpact on the initiation and subsequent propagation of solid-statedecomposition reaction have been studied by several researchers.(rLef-s _-hr-ough llj However, the identification and understanding offactors governing energetics in these reactions is not achieved as ofyet. This problem in our opinion can be understood in terms of themicrostructure of these materials. This report focuses on the studyof microstructure of energetic materials using novel non-destructive,non-intrusive x-ray diffraction techniques developed at Brimrose.

The term "micro-structure" is used in the metallurgical sensemeaning "the study of the perfection/imperfection in the crystallattice." Conventional as well as novel x-ray diffraction techniqueshave been used to quantity the '"micro-structure." The materials onwhich these studies have been carried out include RDX/HMX caoposites.Ammonium Perclorate (AP), Aluminum (Al), RDX/Al in PBX, AP/Al in PBXand AP in HTPB elastareric binders. Work on other materials is alsoincluded for the sake of completeness.

The reported study is divided into three major categories:

1) Measurement of micro-lattice strains (single crystal)

2) Micro-structural study of various mixtures of energeticmaterials a-d/or simulants (polycrystalline aggregates)

3) Evaluation of process induced damage.

The current effort has its major emphasis on the use of real timeguantitative x-ray diffraction techniques for rapid quality controlof crystalline solid propellants. These techniques are non-destructive and non-contacting in nature. Presently, the speed ofanalysis is limited by the intensity of the x-ray source and thecomputing machinery utilized. All the x-ray techniques discussed inthis report have been successfully implemented in real time (30ms) ornear real time (few seconds). This study has resulted in thedevelopment of an x-ray quality control tool for productionapplications and much needed quantitative tool for advanced researchenvironments.

The Phase I effort has shown the effect of processing damage onRDX. Process induced damage modifies the microstructure and hencethe properties of propellants. The Phase I effort has also clearlyhighlighted the importance of the incident signal intensity.Currently this factor predominantly limits the on-line capability ofthe system. The Phase II study will overcome this barrier byincorporating a high intensity x-ray source in the system. Incombination with monochromators, 2-D x-ray image detectorspowerful computing machinery. These techniques can then beimplemented in on-line production applications.

¶ MCAL APP X

X-ray diffraction (refs 1 througli 11) has been successfully usedas a Quality Control/Quality Assurance tool for several d& "desnow. Historically, photographic film was used to record x-raydiffraction events. These techniques are caunbersome and tedious touse. Using nuclear track plates (photographic emulsions on glassplates) the spatial resolution limit of the photographic technique isin the vicinity of i-3pm Digitization of photographic data is verytime consuming. Typically, this is done using photo densitometers tomeasure the gray shades in the film. Data thus collected isdigitized by cci1puters.

The use of electronic detectors to directly record x-raydiffraction phenomena has become an increasingly attractivealternative. These detectors range fromit point counters to2-dimensional x-ray array detectors. The current emphasis is on the2-dimensional real time x-ray imaging system that was pioneered byGreen et. al. (refs 13 through 14) at Johns Hopkins University. Thisgroup of investigators has been successfully utilizing the x-rayimage tube to register real time x-ray diffraction events (ref 15).Rosemeier et. al. (ref 16) have used the x-ray image tube to studylaser induced microstructural damage. Ananthanarayanan et. al.,(ref 17, have successfully integrated the x-ray image tube with animage processor to obtain digital real time x-ray images. Figure 1shows a three stage, first generation x-ray image intensifier used bythe above mentioned investigator. Figure 2 depicts the DIXIE(Digital Intensity X-ray Image Enhancer).

X-ray Diffractcmetry, Powder Diffraction

T1here are two distinct x-ray diffractometric techniques:

a. Conventional x-ray diffractometry

b. Double crystal x-ray diffrac•ometiry (rockingcurve analysis)

Figure 3 shows the x-ray optics and geometry of the conventionaldiffractcmeter. Here the essential principle is that the specimenand detector rotate about the diffract-cmeter axis with 6-2e angularvelocity relationship. This coupled rotation minimizes errors due tochange in absorption factors with incidence angle.

The first crystal being the monochromnator and the secondcrystal (of the "double") is the crystal to be analyzed. In contrastto conventional diffractometry, here the detector is fixed as thesample is rocked (oscillated) about the diffractometer axis. Alsoknown as rocking curve diffractometry, this technique has been usedby several investigators (ref 18) with point counters (ref 19) andlinear position sensitive detectors (ref 20) to study materials andmicrostructural morphologies. 7he detector can be positioned (fixed)at any to-theta value and the diffraction domain probed by rockingthe specimen about the diffractcme ter axis.

2

Rocking Curve 7opography

Rocking curve topography is the implementation of double crystald.ffractoinetry in 2-dimensions i.e., the incident beam is2-dimensional and the detector used is a 2-dimensional arraydetector. Typical incident beam size and diffraction geometry areillustrated in Figure 4. This technique can be used with:

a. White incident beam

b. Monochromated incident beam (n, -n or n, +n setting)

This study utilizes the former and is called White Rocking CurveTopography. No attempt is made to monoctiramate the incident beam. A0.6 kW conventional Cu x-ray source containing K.3 , K•2 andK components along with some fraction of the Brehmstrahlung wasused as an incident beam. A line source was used to maximizesampling area. Grazing incidence angle of (1-50) was used toirradiate the entire specimen area. The specimen was mounted on ahigh precision multi-axis, computer controlled goniometer. Thissample manipulation system allows the probing of the entirereciprocal space volume to determine and optimize the requireddiffraction topographs. There are typically 6 degrees of freedom onthe specimen gonicmeter. The translation resolution of the actuatorsis O.lum and the angular resolution of the rotary stages is 0.1 arcsec. The individual actuators are equipped with optical encoders tominimize, if not eliminate, backlash and other related errors. Adetailed schematic of the entire rocking curve topography system isdepicted in Figure 5a-c.

Some of the pioneering work on rocking curve analysis was doneby Weissmann (ref 21) et. al. at Rutgers University using a linearposition sensitive detector (ref 22). Ananthanarayanan (ref 23) et.al. at Brimrose Laboratories have significantly enhanced thistechnique by successfully integrating a 2-dimensional detector in thesystem. Thus, it is now feasible to obtain 2-dimensional rockingcurve topographs (maps), integrated intensity maps and peak shiftmaps of 1.5" diameter area in less than 3 secs. The spatialresolution of this technique is currently 100-150pm and the angularresolution is fractions of arc seconds. With CCD's (charge coupledevices) the spatial resolution is improved to 20-251 m. The dynamicrange of the existing CCD's is about 16,000:1. The use of qualitycontrol techniques as discussed here will perhaps some day lead toCCD's with resolution comparable to those obtainable with nucleartrack plates.

Rocking curve analysis involves the measurement of the FWM(full width at half maxima) of individual Bragg diffraction spots.By oscillating the analyzed crystal about the diffractometer axisthrough its diffracting domain, the entire reciprocal volume can berecorded. The FWHM measured thus is a function of the localdislocatiun Pensity. Hersch et. al. (ref 24) showed this relation tobe p w 0 /2b where, 0 - NWHM, P - dislocation density, b -Bergers vector. Dinan et. al. (ref 25) have clearly shown the utilityof the rocking curve technique for the characterization of var±,ssubstrates and epitAxial films used in micro-electronicsapplications. These investigators used a point counter in theirexperiments.

3

1PP9

In the present study both 1-D and 2-D x-ray sources were used.Topographic images were obtained by scanning the specimen surfacewith the I-D x-ray beam while no such translation was required in thecase of the 2-D x-ray beamn and 2-D detector combination.

RESULTS AND DIS(XCSIO]NS

Micro-lattice Strain Measurements

Figure 6 shows the (222) rocking curve analysis from a NaCIcrystal with a Brinel hardness indentation. This indentation wasmade with a 20kg preload. The Bragg peak broadening (perspectiveview) shown in Figure 7 clearly depicts the -.:slocation morphologyaround the indentaticn. The strain anisotropy along the (110)directions can also be seen. In contrast to the rocking curve halfwidth map, the peak shift map has little correlation with thehardness indentation. This is reasonable because the effect of theindentation on the lattice parameter map (Bragg peak shift map) isminimal.

Figure 8 depicts the rocking curve topograph fram a ZnCdTeepitaxy/InSb substrate grown by MBE. This topograph shows dislocationstriations formed either by the growth process and/or by twinning inthe substrate. These striations have definite crystallographicorientation. Further analysis is required to accurately determine theorigin of this morphology.

The Cd 9 5 Zn. 0 5 Te layers were grown by MBE on t100} InSbsubstrate. CcTmosition of the alloy layers was set by adjusting theterperatures of two effusion cells, one containing polycrystallineCdTe, other, elemental Zn. Additional details of substrate surfacepreparation and growth conditions are given elsewhere (ref 26).

In conclusion DARC topography technique providesquantitative information about the micro-lattice straininhcmogeneities in various crystalline materials. These maps of theBragg peak shift, Bragg peak broadening can be translated toappropriate micro-lattice strain maps. The integrated intensity undereach pixel can also be used to determine epitaxial film thickness.The DARC technique is highly amenable to automation and on-lineproduction applications.

Prcpellant Mixing & Distribution

Solid Propellant Characterizatior. During the preliminaryphases of the investigations of pure RDX and HMX, x-ray diffractionspectra were acquired. Examples of the x-ray spectra of both pureRDX and pure HMX are shown in Figure 9 along with a typicalproduction grade sample of RDX. These spectra are unique to thephases and the relative intensity of each spectum is indicative ofthe amount o. the constituent phases.

The method presented here can provide a point by pointdetermination of several important parameters of a solid propellantcasing cross seci.on. These include:

a.) relative amounts of RDX, HMX and Al powder-b.) particle size.

4

By comparison of adjacent regions, this informationcan be used to study agglomeration of the individual phasesthroughout the cross-section. This information will permit athorough analysis of the effect of particle size on the non-uniformdistribution of the solids and their tendency to agglomerate.

The method utilized here is based on the ability tocollect x-ray diffraction spectra on a point by point basisthroughout a large specimen area and then to be able to correlatethis spectra to the contituents within the small volume giving riseto the diffraction event. Thus, there are two main concerns whichthis study addresses:

a.) the ability to scan the x-ray probe over a largespecimen area with a spot size in the range ofImm diameter and

b.) the ability to correlate the collected diffractedspectra with the properties of interest, namelyvolume fraction and particle size of theconstituents.

This x-ray method employs a conventional x-raydiffraction unit modified in several important ways for the currentapplication. These include the use of a position sensitive detector(PSD) and 2-D detectors. The use of digital detectors and thewrputer permits a much more rapid analysis than would ordinarily be

expected. The use of a small incident beam and scanning of thesample would permit mapping of the important material parametersthroughout the sample with high spatial resolution.

Constituent Phase Analysis

The operating principle of the method is based on thediffraction spectra of pure RDX and pure HMX shown in Figure 9. Asmentioned previously, these spectra are unique to each phase and theintensity of the spectra is roughly proportional to the amount cf theindividual phase. Thus, in a sample representing a mixture of thetwo phases, the measurement of the relative intensities of the ur idquepeaks permits a calculation of the volume fraction. This is shown inFigure 10, which is a region of the two unique spectra, enlarged forclarity. Also, shown in this figure are two regions of interest (orwindows). Note that in the first window, centered at about 220 thatthe diffraction peak for HMX is quite strong while the peak for RDXis absent. Similarly, in the second window, centered at about 380,the RDX peak is strong while the HMX peak is absent.

The windows cited aove can be easily followed with the aidof a Position Sensitive Detector (PSD) as the detector element. Sucha device permits the simultaneous observation, of a large angularrange. Thus, two windows mentioned above can be easily monitored andthe total diffracted intensity within that window can be determined.Moreover, there is no fundamental restriction as to hcw many windowscan be created. Thus, it is possible to create a large nutmber ofwindows which can be used to monitor the unique signals coming frcMany additional phase, such as prwdered alumintm.

5

The operating sequence for the above method is shown inFigure 11. The sample is held stationary while a small, wellcollimated x-ray beam impinges on a region Inmm diameter. Theresulting x-ray diffraction profile is collected over the fullangular range of the position sensitive detector. When thediffracted intensity is sufficient for a reliable analysis, theprofiles are transmitted to the dedicated microcarputer for analysis.While the data is undergoing analysis, the sanple is translated immso that the next region is brought into the incident x-ray beam Theprocess is then repeated until all of the sample surface has beenexamined.

Real Time Particle Size and Phase Analysis

Laue X-ray diffraction technique has been successfullyused to study thin discs of propellant coaposites. Using a 2-D x-raydetector several discs of propellant composites containing RDX, Al,AP, HMX in elastomeric binders (PBX, HTPB) were examined.

1t.ese discs were typically 3-5am in diameter and 0.1-0.5rmthick. Figures 12 & 13 show the Laue diffraction irmages obtainedfram various grain size of simulants and actual propellant powder.These images show the effect of partirle size on Laue diffractionspots (size, distribution and density). Software will be madeavailable to analyze these images for particle size measurement.

Figure 14 shows the Laue transmission hiage from an Al foil(Reynold's wrap). Preferred orientation can be observed due to themechanical rolling that the Al foil was subjected to. Figure 15depicts the x-ray pattern from a Al, Cu, Brass & Ni foils. Thesepatterns are characteristic of each material and clearly show thepczlycrystalline nature with preferred orientation or texture due tomechanical rolling in the case of Al. In a sense, they are themicrostructural "finger prints" of the individual material(constituent phase). A! & Ni were chosen for this study due to thehigh signal/noise ratio available with existing x-ray optics forthese materials. The limitation for actual propellant was in theintensity of the x-ray source itself. This limitation can beovercome by utilizing higher intensity x-ray source (rotating anode,synchrotron or pulsed x-ray generator).

Process Induced Microstructural Damage

Several samples of production grade RDX/UMX mixtures wereexam'ned using conventional diffrartometry. These results aredepicted in Figure 16a-e and were obtained with Cr radiationmonochramated by a bent crystal graphite mionochramator. Productiongrade material had similar x-ray diffraction profiles as pure RDXsubjected to mechanical grinding (with a mortor & pestle). Onesample (lot 78), however, was an exception. These "deformationpeaks" have been attributed to stress/strain induced phasetransformation products. Further studies have to be conducted withotter cmplimerntary techniques to establish this hypothesis and willbe a part of continuing investigations.

6

PBASE I CONCLUSION

Real time x-ray quantitative techniques have been successfullyutilized to characterize single crystals, powder aggregates andparacrystalline ccomposites.

Single Crystal Characterization - using DARC x-ray topography,the surTface/sub-sur face micro-latticl strain state has beenquantified. These topographs yield valuable information about themicro-structure of energetic materials.

Poly-crystalline Aggregates - using real time 2-D x-raydetectors and high speed computers conventional x-ray diffractiontechniques can be phenomenally accellerated. With appropriate x-raysignal intensity, these tecnniques can easily be adapted toproduction oriented environments. Experiments on "free falling"sugar particles have been very successfull and promising.

The current limitation in the analytical tool developed duringthe Phase I effort is the incident source energy (0.8kW x-raygenerator). This limitation reduces the signal to noise ratio. Anobvious solution to this impediment is the use of high intensityrotating anode x-ray generator. This type of a generator typicallycan produce an order of magnitude highez signal, thLs allowingmonochromation and consequently improving the overall resolution(both temporal as well as spatial) of the techniques.

MIMRE DIREL'TINS: NDMEL CONCEPT IN X-RAY POWER ANALYSIS

Conventional x-ray powder cameras (Deby-Scherrer) comprise of apoint x-ray source and cylindrical film to record the x-ray patterns.Additionally, the powder sample is rotated about the camera axisthroughout the exposure time. The rotation is required to bringvarious grains into Bragg condition. This film technique inherentlyintegrates all the diffraction events over the exposure time(typically 1-3 hours). The diffraction geometry involved in theabove case is shown in Figure 17.

The availability of 2-D real time x-ray detector systemscolemented by enormous computing power has facilitated a unique andnovel concept in powder analysis. This involves the integration ofreal time Laue transmission patterns in polar coordinates. Thisintegration is tantamount to rotating the specimen about thetransmitted beam direction. However, this integration will requireonly one 2-D image (33ms exposure time) as opposed to the severalhours of exposure in the conventional powder technique. A schematicillustration of this concept is depicted in Figure 18. In addition,the 2-D detector system will allow the recording and storing ofstandard 2-D diffraction patterns in digital or video foriat. Thisopens up a whole new concept in materials data bank. Currently,standard diffraction patterns of various crystalline materials arestored by the JCPDS (Joint Committee for Powder Diffraction Studies,Swarthmore, PA). These data are stored in a tabular form and requireenormous storage space for interactive search/match schemes. Withthe concept of 2-D diffraction spectra, the storage can beaccorplished in the video format on a high speed laser disk recorder.It will also allow the customization and periodic updating of thedata bank according to user specifications and demands.

7

1. Bowden, F. P., Proc. Roy. Soc. (London) A264 (1958) 146.

2. Elban, W. L. and Armstrong, R. W., 7th Intern. Syrp. onDetonation, 1981.

3. Jach, J. S., Nature 196 (1962) 827.

4. Singh, K., Trans. Faraday Soc. 52 (1956) 1623.

5. Bowden, F. P., Stone, M. A. and Tudor, G. K., Proc. Roy. Soc.(London) A188 (1947) 329.

6. Bowden, F. P., Mulcahy, M. F. R., Vines, R. G., and Yoffe, A. D.,Proc. Roy. Soc. (London) A188 (1947) 291.

7. Bowden, F. P., Proc. Roy. Soc. (London) A246 (1958) 146.

8. Dick, J. J., J. Appl. Phys. 53 (1982) 6165.

9. Elban W. L., Coffey C. S., Yoo K. C., and Rosemeier R. G.,"Microstructural Origins of Hot Spots in RDX Explosive and aReference Inert Material," NSWC MP 84-200, 1984.

10. Coffey C. S., Elban W. L., and Jacobs S. J., "Detection of LocalHeating and Reaction Induces by Impact," in Proceedings of theSixteenth JANNAF Combustion Meeting, Vol. I, 1014 Sep 1979,CPIA Publ. 308, pp. 205-219.

11. Elban W. L., and Armstrong R. W., "Microhardness Study of RDX toAssess Localized Deformation and Its Role in Hot Spot Formation,"in Proceedings of the Seventh Symposium (International) onDetonation, 16-19 Jun 1981, NSSW MP 82-334, pp. 976-985.

12. Guinier, A., X-ray Diffraction, W. H. Freeman & Co., 1963 ed.,San Francisco.

13. Reifsnider, K. and Green Jr., R. E., An Image Intensifier Systemfor Dynamic X-ra Diffraction Studies, Rev. Sci. Instr. 39,1651, (1968).

14. Green Jr., R. E., Adv. X-ray Anal., 20 (1977) 221.

15. Green Jr., R. E., Boettinger, W. J., Burdette, H. E. andKuriyama, M, "Asymmetric Crystal Topographic Camera," Rev. Sci.Instrum., Vol. 47, No. 8, August 1976.

16. Rosemeier, R. G. and Allik, T. H., "(1aracterization of LaserMaterials by Real-Time X-ray Topography," The InternationalConference on Lasers '84 Proceedings, (1984) p. 112.

17. Ananthanarayanan, T. S., Rosemeier, R. G. , Mayo, W. E. andSacks, S., "Novel Non-destxuctive X-ray Techn'que for Near RealTime Defect Mapping," submitted at the 2nd International Sqp•siumon the Nondestructive Characterization of Materials, Montreal,Canada (1986).

8

18. Ananthanarayanan, T. S., Rosemeier, R. G.. Mayo W. E. andBecla, P., "Micro Lattice Strain Mapping," Materials ResearchSociety yo Proceedings Series, Vol. 90.

19. Halliwell, M. A. G., Lyons, M. H., Tanner, B. K. and Ilczyszyn,P., "Assessment of Epitaxial Layers by Automated Scanning DoubleAxis Diffractometry," Journal of Crystal Growth 65 (1983)p. 672-678.

20. Mayo, W., Yazici, R., Takemoto, T. and Weissmann, S., XII Congressof Int. Union of Crystallography, 1981, Ottawa, Canada.

21. Reis, A., Slade, J. J. and Weissmann, S., J. Appl. Phys. Vol. 22,p. 655 (1951) Slade Jr., J. J. and Weissmann, S., J. Appl. Phys.Vol. 23, p. 323 (1952).

22. Yazici, R., Mayo, W. E., Takenotcq T. and Weissmann, S., J. Appl.Cryst., 16 (1983) 89.

23. Ananthanarayanan, T. S., Mayo, W. E. and Roseneier, R. G., "HighResolution Digital X-ray Rocking Curve Topography," submitted atthe 35th Annual Denver Conference on Applications of X-rayAnalysis, Denver, Colorado (1986).

24. Hersch, P. B., Partridge. P. G. and Segall, R. L., Phil. Mag.Vol. 4, p. 721 (1959).

25. Dinan, J. H., Qadri, S. B., "Evaluation of Substrates of Growtho• HgCdTe by Molecular Beam Epitaxy," J. Vac. Sci. Technol.A4 (4), Jul/Aug 1986.

26. Dinan, J. H. and Qadri, S. B., "Thin Solid Films," 131 (1985) 267.

9

--- w -- -- I - -- - -..-- -- ,---- - il?--- - --

ELECTRON

X-RAY PHOTOCATHODE LENS FIBER OPTIC COUPLINGSCINTILLATION PHOSPHOR

WEAK X-RAY IMAGE STRONG VISIBLE IMAGE

Figure 1 PIXI Portable Image X-ray Intensifier.

SCamera •_ IMAGE IIBM -(192k)I PC, XT, AT

.B.RIMROSE I- Processor

DIXIE---- VIDEO

System MONITOR

Schematic

Ext./Aux. Monitors,

VCR, etc.

Figure 2 DIXIE Digital Intensity X-ray Image Enhancer.

10

DiffractometerCircle

II-

Figure 3 Gearmetry of Conventional X-ray Diffractcxreter franCullity, B. D., "Elements of X-ray Diffraction,"Addison-Wesley Publishing Co. Inc., Reading MA.

RocKing A, IS

SIncideni x-ray Be-am

K ~le0111roctea X-ray

licage

Figure 4 Diffraction Geametry for Whtite Beam Rocking CurveTopography.

:¢ii

rt

DIGITAL AUTOMATED ROCKING CURVE TOPOGRAPHY

DIXIE OPTION I MAGE. .. RS170 VIDEO

MNONCI4ROMATOR(Si or 6*1

SLITS

PRINTER ULTI-AXI

SSPECIMEN

[ [ GONIOMETER IEEE488

SCOMPATABLE14G CONTROL REfMOTE -

D ISPLAY TERWNAL CONT"ROLM'ONJTOR NXIE" DIGITAL INTENSITY X-RAY IMAGE ENHANCER

Figure 5a Schematic of a Digital Rocking Curve Analyzer.

12

DARC TOPOGRAPHY

(DIGITAL AUTOMATED ROCKING CURVE)

rocking axis (-I*)sample

7 IS,

subsrat

x-ray beam

epi- layer

Figure 5b

rocking axis sml

x-ray beam

Figure 5cphsA

13

ty, ,** -

Ný010

)41N I4

Figue 6 A.i~t Rocking Curve Topogrtaph CRaito(222)Rfeto

~~~~22ReflectionSraeOinain(0)2-1et 5.25

Incidence Angle $= 30 - 40j, ae (Angular Increment)between Pranies a 0.100.

14

aa 5

Figure 7 NaC2. Hardness Indentation (222) ReflectionPerspective of Rocking Curve Topograph.

I Oiwn

A. Bragg Peak Shift M4ap B. Bragg Peak, Broadening map

Figure 8 ZnCdTe Epi/InSb (111), 010) Reflection, Cu Radiation(white).

MAX

i1'1\J. SillF

700 C1(CW RAIT3A ] ON)I

N (.C, 'TEN 4001

S IT 20 - --- --------

20 30 40 50 60 70 SO 90Bw-,GC- ANVGI-E (DEGFELS)

600 {PURE RDX

I 500| (CR RADIATION)

N.T 400

N 300s

SII 20U ITY 100

20 30 40 50 60 70 s0 90

BRAGG ANGLE (DEGREES)

1200 RDX PRODUCTIONLOT 78

N 1000 (CR RADIATION)T

S.E Booi'i NSs 600

T 400

SY 200

20 30 40 50 60 70 80 90

BRAGG ANGLE (DEGREES)

Figure 9 Rapid X-ray Diffraction Pattern of BIX and RDX.

16

%V11N1)0W WNO

I J~ I ___L____ d

BRAGG ANGLE (deptee&)

Figure 10 Showing Partial X-ray Diffraction Profiles toRDX & BMX wit~h Appropriate Windows for ConstituentPhase identification and Ccnposition Analysis.

DIRETIONSOURCE

PSD

HmxWINDOY) , DX

WINDOW

Figure 11 Schaniatic of Proposed System.

U 17

3-D Perspective

Pseudo QColr

1'lgure 1 2a Real Tim~ La~ue 1) (rali.1 1oi Pa~ttern~ frrcii al,)Ati 1)\iiclttl

3-D Perspective

Pseudo Color

Figure 12b Real Time Laue Diffraction Pattern fran Sugar Particles44-74111.

10

P~euidc, Color

f i i.Sja d~ce

POXsts 4mnRX ~ n A cicie inU RDXA-ýe

10%, A4r'P Cai ait A

PE -,T M AJ

Q brimrose

FIgure eTP 13 'YEsfSeer Pcpll

A2? in

PROPELLANT

HOPPER +" " DEBYE-SCHERRER

ARC

•, --- 2--- - :-- ----

Figure 13c REAL TIME TRANSMISSION LAUE

23

Figure iL iC~t3 S& ,n IrE- frjiT aT, PL Foil (Reynolds

Figure~t~c 5 C<fof th~e X-ray; Pattern f1rcxm an Al, Cu, Brass

2.1

03 '---

-e -

CL)

(Ur

U* LU

U-)

jzoc

-~IF-

LA.-

IDL

(0 cu -C 00

co

I• .".- r- ~~LLJ

LId

CDD

Co,

! •

z:• -- '0--)

C.,

--I -

. ., . . •. •

LP .- 'v 4w

i I i i

C.).

26 !

0[

r S)00

LUJ

0c:

Q-00

Lrr

05

C-

in CL

M CD CD CF

%V. S!D

(D 0u0 wN

'y-X

CL

L n

CIOCY)

UCt)

CC

CF,

rLI ru'V4

28)

CL

clz

crC)

CL

Ajz

CIDCD~ Q S

29

TM -

* II!r

* I

•, /

/ \/ \

\ S . _ -"

S.

Figure 17 Formation of X-ray (Debye-Scherrer) Powder Pattern in aCylindrical Camera.

1(281=I~r xk~,-JO d -t

22

r2

r -radius of diffraction cone 2 I 0

6 = Bragg angle

d specimen to detector distance

d

Figure 18 Inproved Real Time Powder Diffraction Technique.

30

[ --... .- '-- -

ComanderArmament Research, Development

and Engineering CenterU.S. Army Armaent, Munitions

And Chemical CommandATI'N.: SWAP.-MSI (5) (Bldg 59)S.R-AEE-W { 5)Picatinny Arsenal, NJ 07806-5000

Ccim.nderU.S. Army Armament, Munitions

and Chemical ComandATTN: AM -.GCL (D)Picatinny Arsenal, WJ 07806-5000

AdministratorDefense Technical Information CenterATTN: Accessions Division (12)Cameron StationAlexandria, VA 22304-6145

DirectorU.S. Army Material Systems

Analysis ActivityATIT: AMXSY-MPAberdeen Proving Ground, MD 21005-5066

CommanderChemical Research, Development

and Engineering CenterU.S. Army Armament, Munitions

and Chemical CommndAqTIN- SMOCCR-MSIAberdeen Proving Ground, MD 21010-5423

CcmmanderChemical Research, Development

and Engineering CenterU.S. Army Armament, Munitions

and Chemical CaimandATIN: SMCR-RqP-AAberdeen Proving Ground, MD 21010-5423

DirectorBallistic Research LaboratoryATTN: A.MX8R-OD-STAberdeen Proving Ground, MD 21005-5066

ChiefBenet Weapons Laboratory, CCACArmament Research, Development

and Engineering CenterU.S. Army Armament, Munitions

and Chemcial CommandATI: CM-CA-CB-TL

Watervliet, NY 12189-5000

31

CcmmanderU.S. Army Arnament, Munitions

and Chemical CIamandATM: SMC-R-ESP-LRock Island, IL 61299-6000

DirectorU.S. Army TRAOc Systems

Analysis ActivityATM: ATAA-SLWhite Sands Missile Range, NM 88002

32

32