D-A122 595 THE DISPLACEMENT OF WATER FROM l STEEL SURFACE(U) NAVAL i/IAIR DEVELOPMENT'CENTER WARMINSTER PR AIRCRAFT AND CREWSYSTEMS TECHNOLOGY DIRECTORATE C R HEGEDUS 08 NOV 82

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REPORT NO. NADC-82194-60

THE DISPLACEMENT OF WATER FROM A STEEL SURFACE

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Charles R. HegedusAircraft and Crew Systems Technology Directorate

NAVAL AIR DEVELOPKWN CENTERWarminster, Pennsylvania 18974

8 November 1982 I.

CCPHASE REPO T

AIRTASK NO. WF61 64-001Work unit .

APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED ""

Prepared forNAVAL AIR SYSTEMS COMMAN!'

La. Department of the Navy * -

m.J Washington, D.C. 20361 i ~ ~u002 ,

NOTICES

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o0 Commander, Naval Air Development Center01 Tedical Director, Naval Air Development Center02 Compoder10 Directorate Command Projects20 Systems Directrate30 Sensor & Avionics Technology Directorate40 Communication & Navigation Technology Directorate50 Software Computer Directorate60 Aircraft & Crew Systems Technology Directorate70 Planning Assessment Resources80 Eneing.Support Group .

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NADC-82194-60 1.___________5_25_4. TITLE (and S bte s. TYPE OF REPORT a PERIOD COVERED

The Displacement of Water from a Steel Surface Phasea. PERFORMING ORg. REPORT NUMBEL

7. AUTNOR(a) S. CONTRACT OR GRANT NUMBER,'e)

C6 R. Hegedus

S. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM CLEMENT. PROJECT. TASK

Naval Air Development Center AREA & WORK UNIT NUMBERS

Aircraft and Crew Systems Technology Directorate PE No. 6276 INWarminster, Pennsylvania 18974 AIRTASK WF61542001____________________________________ Work Unit ZM501

11. CONTROLLING OFFICE NAME AND ADDRESS IL REPOrT DATE

Naval Air Systems Command 8 Nvemer 1982Department of the Navy 13. NUMBER OF PAGESWashington, DC 20361 77

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Unclassified

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Approved for Public Release; Distribution Unlimited

17. DISTRIBUTION STATEMENT (of the abstract eftered in Slock 20. It dlfferent hr Re um.

II. SUPPLEMENTARY NOTES

IS. KEY WORDS (Continue on rovers* oldi f noc€osary and Identify b block number)

Water DisplacementPetroleum Sulfonate

20. \SSTRACT (Continue on rever'se de If necesary and Identify by block number)

A quantitative test to evaluate liquid compounds for their ability todisplace water droplets from a steel surface has been developed and a study ofthe water displacement mechanism has been made. The test method consists ofplacing water droplets onto an inclined steel surface, followed by the appli-cation of a test agent. The agent flows down the surface, contacting the waterdrops. The water may either remain on the specimen or be displaced. Thespecimen is then immersed in methanol which absorbs residual water on thespecimen. The menthanol is then analyzed for water content, yielding a

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O. Abstract (Continued)

r*:: quantitative result for water displacement.

Five materials have been evaluated. Two silicone alkyd compounds werefound to be good water displacers. A third silicone alkvd compound was foundto be a poor displacer at low angles but effective at higher angles. Anacrylic and an epoxy coating were found to be poor water displacers.

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T A BLE O F CON T E NT S

Page No.

LIST OF TABLES ..... . . . . . . . . . . . . . . . . . . . .

LIST OF FIGURES . . . . . . . . . . . . .. .. .. . .. . . . . .

INTRODUCTION . . . .. .. . .* . . . . . .. .. .. .. .. . 1

EXPERIMENTAL PROCEDURE........ . . . . ....... . ... .

RESU.LTS ... . . . . . . . . . . . . . . . . . .*.. .. .. . . 14

DISCUSSION . . . . . . .. .. .. .... . . . . . . . . . . 27

CONCLUSIONS......... .................... 29

REFERENCES .. . .......................... 30

ACKOWEDGEMETS . . . .. .. .. .o. .. .. .. .. .. .. .. 32

APPENDIX B .... .. .. @. . . .. .. .. .. .. . . .B-

APPENDIX C . . . . . .... . .. . . .. * *C-1

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NADC-82194-60

L I ST O F T AB LE S

Table No. Page No.

I Water Displacement Tests . . . ........................ 4

Ii Method of Specimen Preparation. .. ..... ....... 6

III Water Droplet Properties. .. ...... .......... 7

IV Compounds Evaluated for Water Displacement Ability . . . . . 8

V Water Contribution of the Specimen and Test Agents -Controls. .. ....... ............. . . . . 15

VI Water Displacement Test Results . . . . . . . . . . . . . . 16

VII Test Results in Water Displacing Efficiency . . . . . . . . 17

L I ST O F FI G URE S

FiuroN. Page No.

I Mechanism of Water Displacement - Continuous Phase . . . . . 2

2 Water Displacement Test Procedure - Applicationof Water Droplets .. ....... ............... 10

3 Water Displacement Test Procedure - Specimen HolderLowered to Place Specimen at Appropriate Angle (65 0). . . . 10

4 Water Displacement Test Procedure - Test Agent 1Applied to Upper Edge of Specimen ........................

5 Water Displacement Test Procedure - Absorb 1Displaced Water Using a Cotton Swab ............ . .

6 Water Displacement Test Procedure - Specimen 1Immersed in Methanol in an Airtight Container.. .. ....

7 Water Displacement Test Procedure - MethanolTitrated for Water Content Using A Karl-FisherAquameter ................................ . . . . . . 12

* ~8 Water Displacement Test Results for SA-l . .......... .. .. ...... 1

9 Water Displacement Test Results for SA-2 . . ............... 19

*10 Water Displacement Test Results for AC-I. .. .......... 20

NADC-82194-60

L I S T O F F I G U R E S (C O N T 'D)

Figure No. Page No.

11 Water Displacement Test Results for EE-l. . . . . . . . ... 21

12 Water Displacement Test Results for SA-3. . . . . . .*. . . 22

13 Comparison of SA-l, SA-2, AC-i, and EE-l - WaterDisplacement Efficiency ...... . . . . . ....... 23

14 Comparison of SA-2 and SA-3 - Water DisplacementEfficiency ............................ .. 24

15 Collapse of Water Droplet Leading Edge under 5OXMagnification ............................ 26

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THIS PAGE INTENTIONALLY LEFT BLANK

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K NADC-82194-60

I NT R 0DU CTIO 0N

Water displacement is defined as the removal of macroscopic quantities ofwater from a metal surface by the application of a liquid compound. Theobjective of this displacement is to reduce the risk of corrosion. A situationrequiring the displacement of water is the cleaning and preserving of metallicequipment following water immersion. Another example is the painting of metalssusceptible to corrosion in a marine environment.

Early investigations of water displacement were performed to developcleaning and preservation materials for salvaged naval equipment, references (d)through Mi. In these efforts, removal of continuous layers or puddles of waterwas a significant problem and many materials were evaluated for their abilityto displace water, reference (d).

A mechanism for the displacement of a continuous water layer from a surfaceby organic compounds has been described, references (a) and (i). The displacingagent is dropped onto the water layer. Upon impact, a two-dimensionalspreading pressure is formed at the agent-water interface. This pressure causesthe lateral transportation of water from the impact site and allows penetrationof the agent into the water phase. Spreading pressure has been described by thefollowing relationship, reference (f):

Faw Yw a) - aw

where: F spreading pressure (dynes per centimeter)* aw

Yw- surface tension of the water (dynes per centimeter)

y_ - surface tension of the displacing agent (dynes percentimeter)

y aw - interfacial surface tension between water and the agent(dynes per centimeter)

Being slightly soluble in water (usually between 2 and 25 weight percent),Kthe agent diffuses to the metal surface. By preferential adsorption, the agent

adheres to the surface and displaces the water layer from the metal substrate.Figure 1 illustrates this mechanism.

The following properties are required of an agent for it to successfullydisplace a continuous water layer, reference (i):

1. A surface tension which is significantly lower than the water layer.-* 2. Moderate solubility in water.

3. Moderate volatility.* 4. Low viscosity.

NADC-82 194 -60

AGENT%~sprading Pressure

WATER

rn SOLIDA

C

A. Displacing agent applied to water surface, spreading

pressure and mixing with water beginms.

B. -Agent reaches the surface while pushing water aside.

C. Preferential adsorption of the agent onto the surface

causes water to be displaced.

Figure I. Mechanism -)f Water D %placement -Continuous Phase, Reference (i)

9 2

NADC-82 194-60

The alcohols, especially 1-butanol, have been found to facilitate theKabove mechanism because of their conformance with the required properties and

their amphipathic nature. The polar end of the alcohol allows the compound topreferentially adsorb onto the metal by forming secondary bonds with thesurface.

The above efforts were based on the requirement that a continuous phase ofwater, a puddle, had to be displaced. The phenomenon discussed in this report,however, is the displacement of a discontinuous water phase, water droplets,from a metal surface. This is encountered when painting metal surfaces in amarine environment. The metal is readily susceptible to the formation of watercondensates and spray which will form as droplets on the surface. Corrosioncontrol procedures must insure removal of this water. This can be accomplishedusing water displacing compounds.

A mechanism has been proposed for displacing a discontinuous water phasefrom a metal surface, reference (k). This mechanism requires the displacingagent to:

1. Spread over the metal surface upon application, vetting thesubstrate and contacting the water droplets.

2. Be immiscible with water to en-ure no water entrapment inthe displacing agent.

3. Have a higher affinity for the substrate than water in order forthe agent to diffuse under the droplets and thus displace them from the surface.

The difference between the two displacement mechanisms described is thespreading pressure and water miscibility requirements. Impact, dissolution,and diffusion are the only means by which displacing agents can reach themetal surface when displacing a continuous phase. These are unnecessary whendisplacing droplets because the agents can make direct contact with the surfacewithout mixing with the water. In this case, the controlling factors are agentwettability and preferential adsorption on the metal surface.

There are several tests which have been designed to determine the abilityof a material to displace water, references Ca), (d), (1), (in), (n), and (o).Table I lists the tests and a brief desciiption of the methods. Most of thesemethods are qualitative, with the results obtained from an estimated extent ofsubstrate corrosion caused by water remaining on the metal surface. The moreextensive the corrosion, the less efficient the material as a water displacer.These tests do not lend themselves to quantitative evaluation of the waterdisplacing phenomenon. Only one of these tests is quantitative, references (a)and Cd), and it is designed to test the displacement of a continuous waterlayer. It is not applicable to evaluation of discontinuous water layers.

The objective of this effort has been to devise and validate a quantitativetest for the displacement of a discontinuous phase of water on a steel surface.

3

NADC-82 194-;60

Table I.- Water Displacement Tests

TEST METHD

Continuous water layer, A thin continuous layer of water isreferences (a) and (d) placed onto a steel specimen. A

droplet of test agent is droppedonto the water and the circumferenceof the resulting impression in thewater layer which the agent makesupon contact is estimated. Repro-ducibility of this test is claimedto be !10%.

Static water drop, A drop of water is introduced onto areference (1) flat steel specimen containing a

conical depression. The test agent* is applied. The specimen is then

periodically examined for corrosionproducts in the depression.

Partial water immersion, A steel specimen is immersed in thereference (in) displacing agent and then immersed

in water. The specimen is period-ically examined for corrosion.

Water spray test, A steel specimen is immersed in thereference (1) agent for one hour and then suspended

in a humidity cabinet. The specimenis periodically examined for corrosion.

Oil Test, A steel specimen is immersed in areference (n) constantly stirred mixture of 10%

water in oil. The specimen isperiodically examined for corrosion.

*Water droplets, Water droplets are introduced onto areference (o) steel specimen after which a test

agent is applied and allowed to flowover the specimen. The specimen isthen placed in a 100% relativehumidity chamber. The specimen is

* periodically examined for corrosion.

4

NADC-82194-60

The test was designed as a means of evaluating materials for their waterdisplacing ability and as a research tool to assist future investigation ofwater displacement. Also, several compounds were tested and the results willbe discussed in light of the proposed displacement mechanism.

This work was performed under AIRTASK WF61-564-001, Work Unit NumberZM501.

EXPERIMENTAL

The objective of devising a water displacement test is to provide a quanti-tative means of evaluating compounds for this property. The method which hasbeen devised includes the placement of water droplets onto a steel surfacefollowed by the application of the test agent onto that surface. The specimenis then immersed in methanol. The residual water mixes with the methanol andthe solution is quantitatively analyzed for water content. This result willindicate the quantity of water displaced.

MATERIALS

AISI 1010 steel specimens of dimensions 2 x 4 x 0.125 in. (5.1 x 10.2 x0.32 cm) were used for the metallic substrate. The specimen preparationprocedures are listed in Table II.

Distilled water was used for the test. The water droplets applied to thesteel surface were 25 microliters in volume. Various properties of the waterand water droplets are listed in Table 111.

Reagent grade methanol was stored in air-tight containersuntil used. Theinitial water content of the methanol was determined during the procedure andwill be described later in this section.

Table IV lists the test agents evaluated for water displacing ability.Appendix A lists the specific compositions of these compounds. These materialswere investigated because of the wide range of water displacing ability whichthey exhibited in preliminary studies using the water drop test, reference (o).

The silicone alkyd compounds coded SA-l and SA-2 in Table IV are known fortheir water displacing ability, references (k), (o), and (p). SA-3 has the samecomposition as SA-2 but without petroleum sulfonate. The epoxy ester, EE-l, andacrylic, AC-l, formulations are poor water displacers.

TEST APPARATUS

A specimen holder was designed and fabricated to hold specimens at anglesranging from 5 to 85 degrees in increments of 5 degrees. Machining toleranceswere requested to be within 30 minutes. Confirmation of the specimen angleswas performed by measuring the angle with a calibrated protractor. The specimenslots were found to be within one degree of the specified angle.

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NADC-82194-60

Table 11. Method of Specimen Preparation

Specimens used: 5.1 by 10.2 by 0.32 centimeters, AISI 1010 steel

STEP PROCESS

1 Grind the surface of the specimen toa roughness of 0.432 ± 0.127 root meansquare micrometers (a).

2 Immerse the specimen in boilingmineral spirits (b) for ten minutes.

3 Imrse the specimen in a secondcontainer of boiling mineral spirits.

4 Slowly immerse the specimen into aboiling solution of 90% reagent grademethanol and 10% distilled water.

5 Immerse the specimen into boiling1001 reagent grade methanol.

6 Store the specimen in a dry desicatorat room temperature until testing.

(a) The specimens were purchased in this condition from Metaspec Company.The roughness was measured using a profileometer.

(b) Mineral spirits conforming to Federal Specification TT-T-291.

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NADC-82194-60

Table III. Water Drop Properties

Volume: 25.07 + 0.16 microliters

Weight: 25.07 ± 0.16 milligrams

Height of drop on specimen: 2.06 + 0.04 millimeters

Shape of drop on specimen: Due to surface grooves caused bypolishing, the drops on the specimenwere oblong, forming an ellipse. Thelength of the ellipse was in thedirection of the grooves, which werein the length direction of the speci-men. Preliminary studies confirmedthe direction of the grooves had noeffect on the water displacing abilityof a compound.

Length of-Ellipse:5.54 + 0.12 millimeters

Width of Ellipse:4.17 + 0.14 millimeters

Contact angle of the drop on the specimen (a): 85 degrees

Surface tension of the water (b): 72.8 dynes per centimeter

(a) Measured by observing a drop from a side angle at a magnifica-tion of 50x.

(b) Measured according to ASTM method D-1331, which is the ringmethod for measuring surface tension.

7

NADC-82194-60

Table IV. C wpounds Evaluated for Water Displacement Ability

CODE DESCRIPTION

SA-I A silicone alkyd/silicone binder(Silicone Alkyd) coating with barium petroleum sulfonate

and organic solvents.

SA-2 A silicone alkyd binder paint withpetroleum sulfonate, an organo-titanate,pigments, and organic solvents.

SA-3 The same as SA-2 without petroleum

sulfonate.

AC-1 A poly(methylmethacrylate) binder paint(Acrylic) with a commercial plasticizer, pigments,

and organic solvents.

EE-1 An epoxy ester resin thinned with ylene.(Epoxy Ester)

See Appendix A for the specific compositions of these materials.

8

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NADC-82194-60

A microsyringe was used to apply the 25 microliter vater droplets. Thesyringe was calibrated by measuring six droplets individually using an analy-tical balance. The average drop weight was 25.07 milligrams with a standarddeviation of 0.16 milligram, indicating a drop volume of 25.07 + 0.16microliters.

Half-liter jars with an innier diameter of 6.35 centimeters and a height of15.35 centimeters were used to immuerse the specimens during the procedure.Each jar was sealed'by placing aluminum foil between the jar head and the lid.To confirm that the jars were sealed from atmospheric water, 350 millilitersof methanol were placed in each of six sealed jars. The water content of themethanol was determined before and after a 24 hour period using a Karl-Fishertitration technique specified in ASTM method D-890, reference (q), anddescribed later in this report. No significant increase in water content wasfound.

The Karl-Fisher titrations were performed using an Aqutest IV aquametermanufactured by Photovolt Corporation. The instrument was calibrated daily bytitrating 10 microliters of water.

TEST PROCEDURE

The Test Procedures and Equipment are illustrated in Figures 2 through 7.A specimen was placed at the des ired angle in the specimen holder. The holderwas then inclined such that the appropriate surface of the specimen was horizon-tal and facing upward. Using the microsyringe, six 25 microliter drops of waterwere applied to the specimen, Figure 2. Six drops are the maximum amountpossible without the drops interfering with each other during the displacingaction. After application, the specimen holder was slowly lowered until thespecimen was at the desired angle, Figure 3. The drops were applied in, thismanner to maintain consistancy in transferring the drops from the syringe to thesubstrate. When lowered to the appropriate angle, and prior to agent applica-tion, the drops remained on the specimens at all angles for all specimenstested.

It was determined that one milliliter of test agent would be adequate toCover the entire specimen without excess agent. With the drops in place and thespecimen at the correct angle, one milliliter of the test agent was appliedalong the upper edge of the specimen using a standard two milliliter syringe,Figure 4. Minimal pressure was applied to the plunger of the syringe tominimize momentum of the agenit flowing down the specimen. In this manner, theagent could flow down the panel and contact the droplets. The droplets couldthen flow down and off of specimen thus being displaced. During the test,displaced droplets would often gather at the bottom edge of the specimen,therefore a cotton swab was guided along this edge to absorb and remove anydisplaced water which may have gathered, Figure 5.

At this time, the specimen was removed from the holder and placed in an air-tight jar containing 350 milliliters of reagent grade methanol such that thespecimen was completely immersed in the methanol, Figure 2, Part E.

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The specimen was immersed for 24 hours to allow any vater remaining on thespecimen to be dissolved by the methanol. Preliminary studies indicateresidual water on the specimen will be dissolved by the methanol within24 hours.

The methanol was then tested for water content using a Karl-Fisher titra-tion method (ASTM D-890), reference (q), Figure 6. This is a standard methodfor determining the water content of organic compounds. It is a coulometrictitration which is dependent upon the reaction of water with pyridine. Thespecific chemical reactions and mechanisms used to determine water content bythis method are presented in Appendix B. The results of the titration arerecorded in milligrams of water remaining on a specimen.

Six replicates were tested at each angle for all agents. Four 1 mlmethanol samples were extracted and titrated for each replicate. These fourtitrations were averaged to obtain ;., the water content of the methanolfollowing agent application, for replicates Mi 1 through 6. The x's werethen averaged to obtains X ,nE!the mean water content of the methanol followingapplication of agent na ~cmnage0 tnaddvain ,o n6was also calculated.nat~imnagee Astnadditonsf ( )

The water content of the methanol at the time of titration is attributed toseveral factors:

1. The initial water content of the methanol, X.-

2. Water sorbed on the steel specimen prior to the test.

3. Water present in the test agent prior to the test.

4. Water not displaced from the specimen after agent application.

Factors 1, 2, and 3 were accounted for by performing the following. Prior totesting the various agents for water displacement ability, the initial watercontent of the batch of methanol to be used was determined by the Karl-Fishertitration method. Also, controls of the blank specimen inmersed in methanoland of specimens containing just the test agents were performed to determinethe effect of the specimen and the agents on water content. Water remainingon the specimen following agent application, Xf, was then determined by:

Xf (nO) - I. 2

where: X f Water remaining on the specimen

X (ne Water content of the methanol following agent application

X. -Initial water cortent of the methanol

The results can also be expressed in terms of the percentage of waterinitially on a specimen which a test agent has displaced, water displacingefficiency (WDE). This is determined by equation (3):

13

NADC-82194-60

w -Wi fWEx 100% (3)

* where: W. -amount of water initially on a specimen prior to agent1 application (water sorbed on the steel specimen pluswater introduced onto the specimen).

W f amount of water remaining on the specimen after agentapplication.

R ESU L TS

* The detailed data obtained-from the water displacement tests are listed inAppendix C. These results are summarized in Tables V, VI, and VII, andillustrated on Figures 8 through 14.

CONTROL DATA

* Table V lists the water content of the titrated methanol contributed solelyby a steel specimen and the test agents, the controls. From this data, it wasconcluded that the steel specimen contributed 21.3 milligrams of water to themethanol but that the test agents made no significant contribution to watercontent. The control line of Figure 8 through 12, "Water on a Specimen Priorto Agent Application," W., is the summiation of the water contributed by thesteel specimen, 21.3 milligrams, and the water introduced onto the specimen,150.0 milligrams. W.i is equal to 171.3 milligrams of water.

* TEST AGENT DATA

* The test agent displacement data are presented on Tables VI and VII, and

Figures 8 through 12. The 95 percent confidence interval illustrated on thesefigures was determined by reference (r):

X (, + 2.571(s/)

where s is the standard deviation at point X~n ) 2.571 is the Student's Tdistribution value for 95 percent confidence with five degrees of freedom, andN is equal to the number of replicates, 6.

The test results prove that the five test agents all vary in water dis-

placing ability. Figure 8 illustrates SA-l displaces water effectively,confirming previous studies, references (k) and (o). Water displacement isconstant over the entire interval of specimen angles from 5 to 85 degrees withan average of 25.5 milligram of water remaining on a specimen, a water dis-

* placing efficiency (WDE) of 85.1 percent.

14

NADC-82194-60

Table V. Water Contribution by the Specimen and Test Agents -

Controls (no water droplets added).

, ean Water ContentContributed byControls (milligrams Standard Deviation

Control of water)* (milligrams)

Blank Specimen 21.3 5.6

SA-1 on specimen 14.4 3.2

SA-2 on specimen 22.3 3.4

AC-1 on specimen 23.7 2.7

ER-1 on specimen 24.0 4.9

SA-3 on specimen 24.5 2.3

*Based on six replicates.

15" , .

NADC-821 94-60

Table VI *Water Displacement Test Reaults(171.3 milligrama of water on a specimen prior toagent application).

Anl,8 Sk- 1 S - 2 AC-i 11-Ei AC-3(degrees) X'F a X" a- X* a Xf a Xe -a

(milligramn of water)

5 25.9 11.7 47.6 13.4 137.2 12.3 159.4 1.2 161.7 8.8

10 24.7 4.9 18.8 18.8 86.4 8.2 159.8 3.3 144.6 14.6

15 24.1 4.4 23.5 8.6 84.0 17.1 110.5 15.3 52.9 12.4

20 30.9 5.2 23.3 9.5 80.3 3.4 39.5 11.6 15.1 4.2

25 27.1 3.3 27.6 9.5 79.4 14.3 50.9 11.0 15.7 5.2

30 26.3 4.2 31.4 9.4 80.5 6.8 45.8 4.3 19.6 6.1

35 25.4 7.9 24.2 5.6 81.1 9.8 46.8 3.2 23.0 6.4

40 22.8 5.6 27.6 7.2 43.2 1.3 42.9 1.9 25.4 6.1

45 22.1 5.7 28.6 6.4 19.3 3.2 37.8 4.7 24.3 4.4

50 28.4 4.4 28.3 7.4 17.5 2.7 38.5 5.3 28.3 6.2

55 26.4 6.1 23.3 3.6 28.4 6.5 45.2 4.6 27.6 5.0

60 22.9 4.2 26.5 5.3 20.7 4.9 48.6 4.4 29.4 5.6

65 24.5 4.7 25.4 5.5 23.7 5.8 46.9 4.4 25.7 3.7

70 24.7 4.0 25.2 4.9 24.2 4.9 44.7 5.3 27.9 4.6

75 25.5 5.0 27.3 5.3 23.0 6.17 44.7 5.8 27.1 3.5

80 24.8 4.4 24.2 4.7 24.8 20.1 46.3 4.8 23.3 4.1

85 27.9 4.5 26.7 4.2 30.5 22.3 46.9 4.6 24.2 2.4

*Based on six replicates.

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NADC-82194-60

Table VII. Test Results In Water Displacement Efficiency

Specimen Ansle SA-1 SA-2 AC-1 EE-l SA-3

5 84.9 72.2 19.9 6.9 5.6

10 85.6 89.0 49.6 6.7 15.6

15 85.9 86.3 51.0 35.5 69.1

20 82.0 86.4 53.1 76.9 91.2

25 84.2 83.9 53.6 70.3 90.8

30 84.6 81.7 53.0 73.3 88.6

35 85.2 85.9 52.7 72.7 86.6

40 86.7 83.9 74.8 75.0 84.6

45 87.1 83.3 88.7 77.9 85.8

50 83.4 83.5 89.8 77.5 83.5

55 84.6 86.4 83.4 73.6 83.9

60 86.6 84.5 87.9 71.6 82.8

65 85.7 85.2 86.2 72.6 85.0

70 85.6 86.3 85.9 73.9 83.7

75 85.1 84.1 86.6 73.9 83.6

80 85.5 85.9 85.5 73.0 86.4

85 83.7 84.6 82.2 72.6 85.9

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NADC-82194-60

The results for SA-2 also confirm previous studies, references (k) and (p)that proved this compound to be a good water displacer. Figure 9 suggests thatSA-2 is only a fair water displacer at an angle of five degrees, with 47.6milligrams of water remaining on the specimen, a WDE of 72.2 percent. Between10 and 85 degrees, however, SA-2 is a good water displacer. Along thisinterval, the graph on Figure 4 is constant with an average of 25.9 milligramsof water remaining on the specimen, a WDE of 84.9 percent.

Figure 10 shows that AC-1 is a poor water displacer at angles less than45 degrees but a good displacer at higher angles. At five degrees, 137.2milligrams of water remain on the specimen and the WDE is 19.9 percent.Between 5 and 10 degrees, the WDE is increased to 52.1 percent where itremains constant to 35 degrees. From 35 to 45 degrees the WDE undergoes atransition up to 86.2 percent where it remains constant for angles from 45 to85 degrees.

EE-1 is a poor water displacer. At 5 and 10 degrees, the WDE is approxi-mately 5.8 percent. Between 10 and 20 degrees there is a transition in WDE upto 74 percent where it remains constant to 85 degrees. This is illustrated inFigure 11.

SA-3 is a poor water displacer at angles less than 20 degrees. At anglesfrom 20 to 85 degrees, SA-3 is a good displacer with a WDE of 86 percent. Thisis illustrated in Figure 12.

Figure 13 compares SA-1, SA-2, AC-1, and EE-1. As previously mentioned,SA-1 and SA-2 are good water displacers while AC-1 and EE-1 are poor waterdisplacers. This graph illustrates the difference in water displacing abilityof the four compounds.

Figure 14 compares the water displacing ability of SA-2 and SA-3. SA-2 issimilar in compositon to SA-3 except for the addition of petroleum sulfonate toSA-2 (See appendix B for compositions). This comparison was performed toexamine the effect of sulfonates on water displacement. The graph clearlyillustrates a difference in WDE at angles below 20 degrees where SA-2 is signi-ficantly more effective than SA-3. This confirms that sulfonates do assist inwater displacement. This effect will be discussed later in this report.

DISPLACEMENT ACTION

During the test, as the test agents were flowing down the specimen, it wasobserved that when an agent contacted a drop, the contact angle of the waterdroplet rapidly decreased from approximately 85 degrees to less than 45 degrees.A similar effect has been previously reported, reference (k). Figure 15 is aseries of photographs of a water drop on a horizontal steel specimen. The waterdrop is seen as a quarter of an ellipse on the left side of each photograph.A water displacing compound, AML-350 (see Appendix C for composition), was placedon the specimen (right of the droplet in the photographs) and allowed to flowinto the droplet. The photographs were taken at intervals of 2.5 milliseconds.AML-350 contacts the drop at approximately frame 16. The action is completed byframe 27, after approximately 28 milliseconds. A similar action was observedwhen substituting SA-1 and SA-2 for AML-350.

25

NADC-82 194 -60

WATER

rn~.qy 19

1 10

3 12 21 F

METALSURFACE

4

* I14 23

6 15 24

7 I16 25

9 is27

"Nb

FIGURE 15. COLLAPSE OF WATER DROPLET LEADING EDGE UNDER 5OX MAGNIFICATION

REFERENCE (K)

4 26

NADC-82194-60

DI SC U SS 1I ON

The prime objective of thiseffort has been to devise and validate a quan-4titative test for the displacement of a discontinuous phase of water on a steelsurface. The test method which has been presented has yielded results whichagree with previous investigations, references (k), (o), and (p), and pre-liminary studies using the water drop test, reference (o). SA-l and SA-2 havebeen confirmed to be good water displacers while the displacing ability ofAC-l, EE-l, and SA-3 is dependent upon substrate angle and as such, thesecompounds are considered to be poor water displacers.

Unlike previous test methods, the current method yields data which isquantitative, providing a more precise means of evaluating compounds andallowing a better understanding of their displacing ability.

A secondary objective of this effort was to use the test results to discussthe proposed mechanism for displacing a discontinuous water phase. As pre-viously described, the mechanism requires the displacing agent to:

1. Spread over the metal surface upon application, vetting thesubstrate.

2. Be immiscible with water to ensure no water entrapment in thedisplacing agent.

3. Have a higher affinity for the substrate than water in order for theagent to diffuse under the droplets and thus displace them from the surface.

While the test results did not validate the proposed mechanism, they supportthe interpretation of the displacing action.

The first requirement of water displacement is the ability of the agent towet or spread over the substrate. Wettability is a thermodynamic propertydependent upon the surface tension of the agent, the surface energy of thesubstrate, and the surface energy of the interface between these two phases.The agents tested were formulated specifically to be surface coatings and assuch they were designed to wet steel substrates. It can be deduced however,that if the agents did not wet and spread over the substrate, they would notcontact the water droplet. and could not displace them. Therefore, wettability

is required for displacement to occur.[ The second requirement for water displacement is agent - water immuiscibility.All of the test agents are virtually immiscible with water. If an agent wasmiscible, however, mixing could ensue after agent application, entrapping water.This water would be unable to be displaced by the agent and would remain on thespecimen, resulting in a lower water displacing efficiency.

The third requirement of the proposed mechanism is that the agent have ahigh affinity for the substrate. This is accomplished by a large adsorptiondriving force of the agent onto the solid surface. Agent adsorption was

27

-.

NADC-82194-60

designed as a factor in this study by addition of petroleum sulfonate to atest agent. SA-2 is similar in composition to SA-3 except for the additionof petroleum sulfonate to SA-2 (see Appendix A for compositions).

Petroleum sulfonates have heats of adsorpotion on steel of approximately10 kilocalories per mole, reference (s). This is high relative to mostcompounds. For example, alcohols have been found to have heats of adsorptionranging from 3.7 kcals per mole for methanol to 4.8 kcals per mole for octadeca-nol, with the heat of adsorption increasing with molecular weight, reference (t).Fatty acids have been found to have heats of adsorption on steel ranging from2.1 kcals per mole for acetic acid-to 5.3 kcals per mole for stearic acid, alsoincreasing with molecular weight, reference (t). Castor oil, which contains an

ester group, has a heat of adsorption onto steel of 2.3 kcals per mole,reference (u).

Figure 9 compares the water displacement abilities of SA-2 and SA-3. Thegraph clearly illustrates a difference in water displacing efficiency at anglesless than 20 degrees where SA-2 is significantly more effective than SA-3. Atangles above 20 degrees, the water displacing ability of the two compounds iscomparable. With the only difference between SA-2 and SA-3 being the sulfonateaddition to SA-2, the test results suggest that the high affinity requirementof the proposed mechanism is accurate; compounds with high affinities for thesolid surface will perform better than those with less affinity for the surface.

An observation was made while studying the displacing efficiencies of allthe test agents. The test results illustrate poor water displacers are noteffective at low specimen angles. As the angle of inclination increases, theseagents become effective water displacers. Good water displacers perform wellat all angles. With these observations and the proposal of adsorption assistingin water displacement, one can infer that the graphs illustrate two effectsoccurring during the test, an adsorption effect and a gravity effect.

The adsorption effect is observed at low angles with the efficient waterdisplacers. The agent preferentially adsorbs onto the solid surface, thendiffuses between the water phase and the solid phase. At this point, thecontact angle of the water droplet rapidly decreases and the water spreads overthe displacing agent, eventually flowing off of the specimen. This is notobserved with poor water displacers which will not adsorb as strongly and cannotdiffuse under the droplets. Although this adsorption effect is best observedat low angles, it is not dependent upon angle.

The gravity effect is observed at higher angles with the poor water dis-

4 placers. The agent will flow down the specimen and contact a water drop. Theimpact, in conjunction with the force of gravity and the high specimen angle,

will cause the water drop to flow down and off of the specimen. Although this isbest observed with poor water displacers, gravity obviously assists all com-pounds in their ability to displace water. The gravity effect is dependent uponangle in that the force of gravity affecting the water drops' ability to remainon the specimen is controlled by the trigonometric sine of the specimen angle.

28

NADC-82194-60

In summary, the water displacement test will quantitatively differentiatethe ability of compounds to displace water. The data obtained may also be usedto discuss existing theories and assist in further investigation of water dis-placement.

CON C L U SIO NS

A water displacement test method has been devised. The method includes theapplication of water droplets onto a steel surface, followed by the applicationof a test agent. The specimen is immersed in methanol which absorbs residualwater on the specimen. The methanol is then analyzed for water content,yielding a quantitative result for water displacement.

The method can be used to compare the water displacing efficiency ofcompounds. It can also be used to further investigate the phenomenon of waterdisplacement.

Water displacement at low angles is controlled by preferential adsorption ofthe test agent onto the substrate. At high angles, water displacement iscontrolled by the force of gravity acting on the water drop after the agentmakes contact with the drop. The displacing action has been observed to occurwithin several milliseconds.

Petroleum sulfonates assist in the displacement of water by stronglyadsorbing onto the surface, allowing the agent to diffuse between the water dropand the solid surface.

29

NADC-82194-60

[ REFERENCES

* (a) H.R. Baker, C.R. Singleterry, and W.A. Zisman, "Factors Affecting theSurface - Chemical Displacement of Bulk Water from Solid Surfaces," NavalResearch Laboratory Report 6368, February 1966.

(b) H.R. Baker and W.A. Zisman, "Water-Displacing FluidE and their Applicationto Reconditioning and Protecting Equipment," Naval Research LaboratoryReport C-3364, October 1948.

(c) H.W. Fox, E.F. Hare, and W.A. Zisman, J. Phy. Chem., 59, 1097, (1955).

(d) H.R. Baker, P.B. Leach, C.R. Singleterry, and W.A. Zisman, "SurfaceChemical Methods of Displacing Water and/or Oils and Salvaging FloodedEquipment, Part 1 - Practical Applications," Naval Research Laboratory

*Report 5606, February 1961.

(e) H.R. Baker, P.B. Leach, and C.R. Singleterry, "Surface Chemical Methods ofDisplacing Water and/or Oils and Salvaging Flooded Equipment, Part 2 -Field Experience in Recovering Equipment Damage by Fire AboardUSS CONSTELLATION and Equipment Subjected to Salt-Spray Acceptance Test,"Naval Research Laboratory Report 5680, September 1961.

(f) H.R. Baker and P.B. Leach, "Surface Chemical Methods of Displacing Waterand/or Oils and Salvaging Flooded Equipment, Part 3 - Field Experience inRecovering Equipment and Fuselage of HH 52A Helicopter after Submersion atSea," Naval Research Laboratory Report 6158, October 1964.

(g) H.R. Baker and P.B. Leach, "Surface Chemical Methods of Displacing Waterand/or Oils and Salvaging Flooded Equipment, Part 4 - Aggressive CleanerFormulations for Use on Corroded Equipment," Naval Research LaboratoryReport 6291, June 1965.

(h) H.R. Baker and P.B. Leach, "Surface Chemical Methods of Displacing Waterand/or Oils and Salvaging Flooded Equipment, Part 5 - Field Experience inRemoving Sea-Water Salt Residues, Sand, Dust, and Soluble CorrosiveProducts from AN/FPS-16 (XN-1) Missile and Satellite Tracking Radar,"Naval Research Laboratory Report 6334, October 965.

(i) R.N. Bolster, "Removing of Fluid Contaminants by Chemical Displacement,"Surface Contamination, Vol. 1, ED. K.L. Mittal, 1979.

(j) P. Pomerantz, W.C. Clinton, and W.A. Zisman, J. Colloid Interface Sci.,24, 16 (1967).

(k) C.R. Hegedus, "Water Displacing, Corrosion Preventive Compounds,"Corrosion Control by Organic Coatings, ED. Henry Leidheiser, Jr., NationalAssociation of Corrosion Engineers, Houston, 1981.

(I) H.R. Baker, D.T. Jones, and W.A. Zisman, Ind. Eng. Chem., 41, 137 (1949).

30

NADC-82194-60

R E F E R E N C E S (C O N T 'D)

(m) W.A. Zisman and H.R. Baker, Ind. Eng. Chem., 40, 2338 (1948).

(n) ASTM D665-60, Standard Method of Test for Rust Preventing Characteristicsof Steam-Turbine Oil in the Presence of Water.

(o) G.J. Pilla, "The Development of AMLGUARD, A Clear, Water DisplacingCorrosion Preventive Compound," Naval Air Development Center ReportNumber NADC-78220-60, May 1979.

(p) C.R. Hegedus, "Development of a Water Displacing, Touch-up Paint,"Naval Air Development Center Report Number NADC-80207-60, February 1981.

(q) ASTM D890, Standard Method of Test for Water in Liquid Naval Stores.

(r) C. Lipson and N. Sheth, Statistical Design and Analysis of EngineeringExperiments, McGraw-Hill, Inc., New York, 1973.

(s) P.J. Kennedy, ASLE Trans., 23, 370 (1980).

(t) T. Allen and R.M. Patel, "An Investigation into the Mechanism of Adsorptionfrom Solution," A.J. Groszek - Editor, BP Symposium on the Significance ofthe Heats of Adsportion at the Solid/Liquid Interface, March 1971.

(u) A.J. Groszek, ASLE Preprint Paper Number 51 LC-9, Lubrication Conference,October 1961.

31

1I

NADC-b2194-60

ACKNOWLEDGMENTS

The author wishes to acknowledge the efforts of Professor R. D.Corneliussen of Drexel University who assisted in the successful completionof this work.

Dr. John J. De Luccia is also gratefully acknowledged for his enlighteningdiscussions throughout this effort. A special note of gratitude is extendedfor his continued encouragement without which this work would not have beenperformed.

The author also wishes to thank his co-workers in the Aero MaterialsDivision for their support throughout this effort.

32

-

NADC-82194-60

APPENDIX A

A-1

NADC-821 94-60

THIS PAGE INTENTIONALLY LEFT BLANK

A-2

NADC-82194-60

APPENDIX A

COMPOSITION OF SA-lCa)

PERCENT (WEIGHT)

Isopropanol .......... .................... 4.6

Aromatic Hydrocarbon (b) .. ............. ... 21.2

Trichlorotrifluoroethane ....... ............. 28.6

Ethyl Cellulose (c) ... ................ ... 0.4

Barium Sulfonate (d) ... ............... .... 4.0

Alkyl Amonium Organic Phosphate (e) .......... 1.0

Silicone Varnish (f) ........ ............... 5.

Silicone Resin (g) ... ................ ... 5.1

Silicone Alkyd Resin (h) .. ............. ... 30.0

100.0

(a) This material is marketed commercially as AMLGUARD. it

conforms with Military Specification Mi1-C-85054.

(b) Amsco Solvent G (American Mineral Spirits Co.)

(c) T-200 (Hercules Powder)

(d) NaSul BSN (R.T. Vanderbilt Co.)

(e) R.P. No. 2 (E. I. DuPont)

() DF-88 (General Electric)

(g) SR-82 (General Electric)

(h) Varkyd 385-50R (McCloskey Varnish Co.)

A-3

NADC-82194-60

C0MPOSITION OF SA-2

PERCENT (WEIGHT)

Silicone Alkyd Resin (a) ....... .............. 39.1

Ethyl Acetate ................... . . 19.4

Mineral Spirits (b) .. ............... . 11.7

1,1.1 Trichlorotrifluoroethane .. . . . . . 7.7

Sodium Petroleum Sulfonate (c) .. ......... . 2.1

1 Rutile; titanium Dioxide (d) . ........... ... 11.5

Zinc Molybdate (e) .. ........ ......... 6.4

Isopropyl, Tri(N-ethylamino-ethylamino)titanate (f) (4.5% in isopropyl alcohol) . . . . 2.1

100.0

(a) Varkyd 385-50E (McCloskey Varnish Co.)

(b) AMSCO Solvent G (Union Oil of California)

(c) Alox 904 (Alox Corporation)

(d) R-960 (E. I. DuPont)

(e) Moly-White 101 (Sherwin Williams Chemicals)

(f) KR-44S (Kenrich Chemicals)

A-4

1

NADC-82194-60

COMPOSITION OF AC-1 (a)

PERCENT <WEIGHT)

Acrylic Resin (b) .......... . . . . ... 43.6

Acrylic Resin (c) ............. . ... 32.8

Titanium Dioxide ...... .. ................. 18.4

Cellosolve Acetate ............... .... 3.8

Plasticizer (d) .... .................. ... 1.4

100.0

(a) This material conforms with Military Specification Mil-C-81352.

(b) Acryloid A-21 (Rob. and Haas Co.)

(c) Acryloid B-44 (Robn and Haas Co.)

(d) Santicizer 160 (Monsanto Co.)

A-5

NADC-82194 -60

COMPOSITION OF EE-1

PERCENT (WEIGHT)

Epoxy Eater Resin (a). .. ......... ....... 80.0

Xylene . . . . . .. .. .. .. .. .. .. . .. 20.0

100.0

(a) Varkyd 13-50z (McCloskey Varnish Company)

-A-

IL

NADC-821%-60

COMPOSITION OF SA-3

PERCENT (WEIGHT)

Silicone Alkyd Resin (a) ............. 39.9

Ethyl Acetate ................... .. . 19.8

Mineral Spirits (b) ................ 11.9

1,1,1 Trichlorotrifluoroethane ... ........... 7.9

Rutile; titanium dioxide (c) . ........... ... 11.7

Zinc Molybdate (d) ................. 6.5

Isopropyl, Tri(N-ethylmino-ethylamino)Titanate (e) (4.5% in ethyl alcohol) ...... 2.3

100.0

(a) Varkyd 385-50E (McCloskey Varnish Company)

(b) ANSCO Solvent G (Union Oil of California)

(c) 1-960 (E. 1. DuPont)

(d) Moly-White 101 (Sherwin Williams Chemicals)

(e) KR-44S (Kenrich Chemicals)

A-7

NADC-82194-60

COPOSITION OF AH.-350 (a)

PERCENT (WEIGliT)

Barium Petroleum Sulfonate (b) .......... ... 50.0

Mineral Spirits (c) . ......... . . . . . . 50.0

100.0

1 (a) This material conforms with Military Specification Mil-C-81309,

Type I.

(b) Alox 2028 (Alox Corporation)

(c) Mineral Spirits conforming with Federal Specification TT-T-291.

II.

:" A-8

NADC-82194-60

APPENDIX B

B-1

NADC-821 94-60

THIS PAGE INTENTIONALLY LEFT BLANIK

B-2

NADC-82194-60

APPENDIX B

KARL-FISHER METHOD OF DETERMINING WATER CONTENT OF METHANOL

The test was performed using an Aquatest IV Aquameter manufactured

by Photovolt Corporation. The principles of determining water content

are as follows. The methanol is titrated with a Karl-Fisher reagent

which is a mixture of iodine, sulfur dioxide, pyridine, and methanol.

The reagent reacts with water as follows:

c 5 5 -1 2 + C 5 5 -so 2 + C 5 5 + 2o --0

H sos2 so 22CHN + CH5RN" and C5H5N' + CH30H-

C 5H5N,

When water is present, the electrodes of the aquameter which are in

the solution remain polarized. As water reacts with the reagent during

titration, the electrodes become depolarized. Finally, a slight excess

of iodine will totally depolarize the electrodes, allowing a large

increase in current flow through a micrometer. When the micrometer

records a current of 40 microamps for 30 seconds, the titration is

complete. The amount of water initially present is caluclated by:

(ml of KF reagent used) x (mg H20/ml KF reagent) x (1000 g/mg)

(ml of sample titrated) x (SpG of methanol)

- micrograms of water per gram of methanol

B-3

NADC-821 94-60

THIS PAGE INTENTIONALLY LEFT BLANK

B-4

NADC-82194-60

APPENDIX C

C-1

NADC-82194-60

THIS PAGE INTENTIONALLY LEFT BLANK

C-2

NADC-821 94-60

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