AD CCL REPORT NO. 268 C) FINAL REPORT STUDY OF LONG TERM PACKAGING OF ETHYLFNE GLYCOL ANTIFREEZE BY JAMES H. CONLEY JULY 1969 4.1: THIS DOCUMENT HAS BEEN APPROVED FOR PUBLIC RELEASE AND SALE; ITS DISTRIBUTION IS UNLIMITED U.S. ARMY ABERDEEN RESEARCH & DEVELOPMENT CENTEF COATING & CHEMICAL LABORATORY Aberdeen Proving Ground Maryland COLOR ILLUSTRATION'Z RMSPRODUCEDr IN BLACK A, WHITE
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AD
CCL REPORT NO. 268
C) FINAL REPORT
STUDY OF LONG TERM PACKAGING OF ETHYLFNE GLYCOL ANTIFREEZE
BY
JAMES H. CONLEY
JULY 1969 4.1:
THIS DOCUMENT HAS BEEN APPROVED FOR PUBLIC RELEASEAND SALE; ITS DISTRIBUTION IS UNLIMITED
U. S. ARMY ABERDEEN RESEARCH & DEVELOPMENT CENTEFCOATING & CHEMICAL LABORATORY
Aberdeen Proving GroundMaryland
COLOR ILLUSTRATION'Z RMSPRODUCEDrIN BLACK A, WHITE
iUSTIEI' AT :G4
BY
I L
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CCL REPORT NO. 268
FINAL REPORI
STUDY OF LONG TERM PACKAGING OF ETHYLENE GLYCOL ANTIFREEZE
BY
JAMES H. CONLEY
JULY 1969
AMCMS CODE NO. 5025.11.803
DEPARTMENT OF THE ARM) PROJECT NO.IGO62105A109
U.S. ARMY ABERDEEN RESEARCH & DEVELOPMENT CENTERCOATING AND CHEMICAL LABORATORY
ABERDEEN PROVING GROUNDMARYLAND
THIS DOCUMENT HAS BEEN APPROVED FOR PUB' IC RELEASE
AND SALE; ITS DISTRIBUTION IS UNLIMITED
UNCLASS I FIED
i
COLOR ILLUSTRATION 4-1; RCDUCEDIN BLACK AP.D WHITE;
ABSTRACT
The object of this study was to investigate conditions which would
effect long term packaging of ethylene glycol antifreeze. Factors in-vestigated were ph, dilution, different inhibitor systems and differentmetals.
Aluminum and tin-coated steel panels were partially immersed inethylene glycol solutions contained in test jars at room temperaturesfor a period of ten years. Inhibitors used in this study included borax,borax/glycol condensate, mercaptobenzothiazole, and the sodium salt ofmercaptobenzothiazole. pH values ranging from 6 to 10.5 were used.Test solutions contained 0%, 3% and 66-2/3% water.
No system tested was adequate for 10 years storage. All systemsexhibited corrosion in the liquid phase and/or the vapor phase.
II
TABLE OF CONTENTS
Page No.
TITLE PAGE................................................
ABSTIRACT .................................................... I
Coating & Chemical Laboratory was directed by Army Materiel Commandto investigate improved antifreeze compounds.
Federal Specification O-A-548, Type I 3ntifreeze which is specifiedfor Army use in TB-750-651 is composed of undiluted ethylene glycol withborax as an inhibitor. As packaged it has an acidic pH (below 7.0) andtends to cause corrosion of tin containers in long term storage. Thismaterial is used in conjunction with 0-I-490a, Inhibitor, Corrosion,Liquid Cooling System. One of the constituents of 0-I-490a is mercapto-benzothiazole (MBT) which greatly enhances the inhibitive properties ofborax in ethylene glycol mixtures which have been diluted for vehicleuse. However, chemically, MBT is an acid, and was found to rapidlycorrode the tin containers when incorporated directly into undilutedO-A-548 antifreeze packages. The Army, therefore, uses a two packageantifreeze system, which is logistically undesirable.
This study was initiated primarily to study conditions which mightpermit the incorporation of O-A-548 and 0-I-490a into a one packageantifreeze system. Preliminary data on this study were presented inCCL Report Nos. 86 and 100. These data showed that under specifiedconditions ethylene glycol could be packaged with MBT and stored forshort periods in both aluminum and tin coated steel containers.
This present report contains data derived from the study since thetwo year inspection.
II. DETAILS OF TEST
A. Test Panels.
Aluminum (alloy 2024) panels 2-1/2" by 3", were prepared byabrading with 320A carborundum paper and steel wool (00 Grade), rinsingwith hot ethyl alcohol and drying in an oven at 210°F.
Tin coated steel panels, 2-1/2" x 3" were prepared by lightlyabrading with steel wool (00 Grade), rinsing in hot ethyl alcohol anddrying in an oven at 210F. The edges of these panels were then dippedin an non-crystalline hydrocarbon wax so that steel edges would not beexposed.
B. Test Jars.
The glass jars used in the test were 14-1/2 ounce screw captype, approximately 3" in diameter and 4" deep. The jars were closedwith screw caps containing lacquered paper pulp liners.
I
C. Ethylene Glycol.
Ethylene glycol used in the tests was "purified" grade, FisherScientific Company. This glycol contained less than 0.5% water.
D. Inhibitors.
1. Borax - The borax used was sodium tetraborate, decahydrate,C.P. It analyzed 101%, calculated as borax, the excess percentage beingdue to the loss of water of hydration.
2. Borax-glycol condensate - This material was prepared inaccordance with the procedure outlined in CCL Report No. 81. It analyzed14.0 + 1.0% sodium tetraborate (by weight).
3. Mercaptobenzothiazole - Eastman Kodak 2-mercaptobenzothiazole"practical" grade, was used.
4. Sodium salt of mercaptobenzothiazole - R. T. Vanderbilt's
"NACAP", which is a 50% water solution of sodium mercaptobenzothiazole,was used in the tests in amounts corresponding to the quantity of MBTused.
E. Tests Conducted.
1. Test solutions - Thirty-five test solutions used in this
study are listed in Tables I and II. A pH of 10.5 was attained by the
addition of 5.ON aqueous sodium hydroxide.
2. Test procedures - Approximately 200 ml. of solution was
placed in each jar. The metal test panel was approximately one halfimmersed. This permitted inspection of panels exposed to both theliquid phase and the vapor phase. The screw caps were firmly tightenedand the jars stored on a shelf at room temperature.
3. Inspection - One set of duplicate panels were removed intwo month intervals up to 8 months for inspections. The duplicate setof panels were left undisturbed for a total of 24 months storage andinspected. The panels were then placed back in the test jars and leftundisturbed for a total of 10 years. The final inspection Included inthis study was made after 10 years storage.
III. RESULTS OF TEST
A. Effect of dilution on tin-coated steel.
Results of inspections up to 8 months and 2 years are includedin CCL Report Nos. 86 and 100, respectively. Results in Table I and thephotographs show all undiluted samples exhibit heavy corrosion both inthe vapor phase and liquid phase. Tests with 97% glycol and 3% water
2
(Test Nos. 6 and 11) were better than the undiluted samples but were notas good as the tests with 66-2/3% water (Test Nos. 12 to 23A). Thisshows that dilution decrea.es corrosion on tin-coated steel.
B. Effect of dilution on aluminum.
Results of the effect of dilution on aluminum in Table II and
the photographs show that dilution increased corrosion in nearly everycase. One exception was noted with 2-1/4% borax-glycol condensate, 1/2%NACAP at pH 10.5.
C. Effect of pH.
Increasing the pH of undiluted glycol to 10.5 increased thevapor phase corrosion of aluminum in every caje with only a slight differ-
ence in the liquid phase corrosion. Increasirg the pH to 10.5 at 3%dilution decreased the corrosion of tin-coated steel but at 66-2/3% dilu-
tion the increased pH increased corrosion.
D. Comparison of borax-glycol condensate.
Borax-glycol condensate was slightly better than borax in
66-2/3% dilution low pH tests in the liquid phase and in the high pH
tests with tin-coated steel. Borax was better than the condensate in thehigh pH test with 1/2% NACAP at 3% dilution (Table II, Test Nos. 27 and28).
E. Comparison of MBT and its sodium salt.
The sodium salt of MBT (NACAP) was better than MBT in almostevery case. In Test Nos. 8 and 11 with 97% glycol, 2-1/4% borax and3% water at pH 10.5 the MBT was better than the sodium salt.
F. Best ove-all inhibitor combination.
In choosing a single inhibitor combination from this groupwhich would be best on both metals, borax, MBT, and 3% water at pH 10.5would be the best. At 66-2/3% dilution the condensate with NACAP at pH10.5 is the best. Even these would not be considered satisfactory forlong term storage due to the presence of some corrosion either in thevapor phase or the liquid phase. All corrosion is more severe after 10years storage and in the same order as reported after 2 years storage.
IV. REFERENCES
1. Authority, AMC Program Directive.
2. Federal Specification 0-1-490, Inhibitor, Corrosion, Liquid CoolingSystem.
3
3. Federal Secification O-A-548a, Antifreeze, Ethylene Glycol, Inhibited.
4. CCL Report No. 81, Development of an Operational Preservative HydraulicBrake Fluid, August 1959.
5. CCL Report No. 86, Study of a Newly Developed Inhibitor for EthyleneGlycol in Storage, October 1959.
6. CCL Report No. 100, Storage of Ethylene Glycol with Various Inhibitors,14 March 1961.
4
DISTRIBUTION LIST FOR AMCMS CODE NO. 5025.11.803
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Defense Documentation CenterCameron Station 20Alexandria, Virginia 22314
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Commanding GeneralU. S. Army Materiel CommandATTN: AMCRD-GFWashington, D. C. 20315
Continental Army CommandDepartment of the Army 3Fort Monroe, Virginia 23351
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9 2-1/4% 3 Very heavy vapor phase corrosion. Very rustyBorax-Glycol Excessive pitting in liquid phase. (black)
Condensate1/4% MBT,pH 5.75
7
TABLE I - (Continued)
Photo Inhibitor Dilution, Solution
No. Combination % water Results Appearance
10 2-1/4% 3 Vapor phase stained. Tin com- Very slightBorax-Glycol pletely removed in liquid phase. yellowCondensate, Steel shows intergranular corro- sediment.1/4% MBT, sion.pH 10.5
11 2-1/2% 3 Moderate vapor phase corrosion. Very slightBorax Liquid phase coated with crystals sediment.Condensate but no evidence of pits.1/2% NACAP,pH 10.5
12 None 66-2/3 Very heavy vapor phase corrosion. Very rustypH 4.55 Panel completely dissolved except
17 2-1/4% 66-2/3 Very heavy vapor phase corrosion. RustyBorax, Heavy pitting and rusting in1/4% MBT, liquid phase.pH 10.5
17A 2-1/4% 66-2/3 Very slight vapor phase corrosion. SlightBorax Tin completely removed in liquid sediment1/4% MBT phase. Steel show intergranularpH 10.5 corrosion.
8
TABLE I - (Continued)
Photo Inhibitor Dilution, Solution
No.. Combination % water Results Appearance
18 2-1/4% 66-2/3 Very slight vapor phase corrosion. SlightBorax-Glycol Tin completely removed in liquid yellowCondensate phase. Steel shows intergranular sediment1/4% MBT, corrosion.pH 7.55
19 2-1/4% 66-2/3 Vapor phase okay. Tin partly SlightBorax-Glycol removed in liquid phase. Some sedimentCondensate intergranular corrosion. (white)1/4% MBT
20 2-1/4% 66-2/3 Slight vapor phase corrosion. Heavy whiteBorax, Slight corrosion and stains in sediment1/2% NACAP liquid phase.pH 7.88
21 2-1/4% 66-2/3 Slight vapor phase corrosion. Very slightBorax, Light etching with tin removed sediment1/2% NACAP, in one spot.pH 10.5
22 2-1/4% 66-2/3 Very slight vapor phase corrosion. Heavy lightBorax-Glycol Moderate-heavy stain in liquid yellowCondensate, phase. sediment1/2% NACAP,pH 7.88
22A 2-1/4% 66-2/3 Slight vapor phase corrosion. Moderate-Borax-Glycol, Heavy corrosion at interface on Heavy yellowCondensate, one side. Liquid phase okay. sediment1/2% NACAP,pH 7.88
23 2-1/4% 66-2/3 Slight vapor phase corrosion. Very slightBorax-Glycol, Light yellow stain in liquid sedimentCondensate, phase. No pitting.1/2% NACAP,pH 10.5
23A 2-1/4% 66-2/3 Very slight vapor phase corrosion SlightBorax-Glycol, pitting in liquid phase sedimentCondensate,1/2% NACAP,pH 10.5
9
TABLE I I
Results of 10 Year Inspection Aluminum Panels
Photo Inhibitor Dilution, SolutionNo. Combination % water Results Appearance
24 2-1/4% 3 Heavy vapor phase corrosion. ModerateBorax, Moderate-heavy corrosion in white1/4% MBT, liquid phase. sedimentpH 10.5
25 2-1/4% 3 Moderate vapor phase corrosion. Very slightBorax-Glycol, Moderate corrosion in liquid sedimentCondensate, phase.1/4% MBT,pH 10.5
35 2-1/4% 66-2/3 Slight vapor phase corrosion. Very slightBorax-Glycol, Moderate pitting In liquid phase. sedimentCondensate,1/2% NACAP,pH 10.5
1
APPENDIX B
12
TIN COATED SjCEt i 'ELS
irCbCin Undfluted Lut lent: tAi)I with v31 Icu,3 H.hibhci
T IN COATED STLEL A~
JI )f ',/ene GICj i cu.
15 ittt
TIN COATED SICEL t-nhLiLS
:c if 3 - 13*;. £ttylene G~C I 1l, tC 1/3, watct, wiLto vat hk~us irhib~
Ilt M0s4Z S7ELt PANELS
ci.-tt.inrnet t~iL' 3- IP. iy !:t Gly~vlf, :6-2/3% water, wit h vorious nb
a,
Powl.s Inmmrsed In 33-1/n gthylww g1y.Io, 4"-2/3flterp wIt various Inhibitors,
fAA
.... .. ....
7p
DOCUMENT CONTROL DATA • R&D(SC Ce ,. C V IAIS itt i-rt, iii . i te ., hody of aha nere and inet ing an oit atton miait h. ntered whep lite o v llt put tI, rie IIteii'tedi)
U.S. Army Aberdeen Research & Development Center UnclassifiedCoating & Chemical Laboratory 2h GnOup
Aberdeen Proving Ground, Maryland 210053 nEPORT TITLE
STUDY OF LONG TERM PACKAGING OF ETHYLENE GLYCOL ANTIFREEZE
4 DESCRIPTIVE NO'ES (Type of report and inciteaeve dalete)
Final Report5 AUTHOR(S) (Last name., first name. initial)
Conley, James H.
6 REPORT DATE 74. TOTAL NO. OF PAG6S 7b. NO. Or REFI
July 1969 24 6Ba CONTRACT OR GRANT NO. 98. ORIGINATOR'S REPORT NUMBER(S)
AMCMS Code No. 5025.11.803 CCL #268b PROJECT NO
G062105A109 Ob. OTHER REPORT NO(S) (Any oternumbers thatmay be as.ai*idthise report)
10 AVA IL ABILITY.'LIMITATION NOTICES
This document has been approved for public release and sale; its distribution isunlimited. Qualified requesters may obtain copies of this report from DefenseDocumentation Center.
11 SUPPLEMENTARY NOTES 12. SPONSORING MILITARY ACTIVITY
U.S. Army Materiel CommandWashington, D. C. 20315
13 ABSTRACT
The object of this study was to investigate conditions which would effect longterm packaging of ethylene glycol antifreeze. Factors investigated were pH,dilution, different inhibitor systems and different metals.
Aluminum and tin-coated steel panels were partially immersed in ethylene glycolsolutions contained in test jars at room temperatures for a period of ten years.Inhibitors used in this study included borax, borax-glycol condensate,mercaptobenzothiazole, and the sodium salt of mercaptobenzothlazole. pH valuesranging from 6 to 10.6 were used. Test solutions contained 0%, 3% and 66-2/3%water.
No system was adequate for 10 years storage. All systems exhibited corrosion inthe liquid phase and/or the vapor phase.
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