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STLCOPCB4094648 fa. `. tmif lai fUi S3 DISTRIBUTION .v % ' ' HEET " T--------- fl f Ten copies of the Pinal Report entitled, "Functional Fluids -- AddII- n& pnuR^earCl1' Jot No* 117-250Q dated August 4, 1954 by been distributed Was* foalnlonwl3?t:er w- E. Koerner, and 0. B. Cecil h.mavvec 1. Pile 2- R. E. Hatton 3. H. K. Nason -Pile 4. Duplicate Pile 5. Circulate: Asst, and Ass. Res. Dlrs. - Pile 6. H. R. Qanrath 7. 0. R. Buchanan. , 6. Extra .4 e $ * 9. Extra 1C. Extra v - oe1rhIert cnt*lns confidential information which is the property 'to !duivMauth^?75e:alCaL Co:ripany ^ whlch iahalll be disclosed only7 ` ` ? theSii!! H J persons. The recipient lslheld accountable for on de^J.d? custody of the report, which.must be returned 11 DSW 620622 Tf (j STLCOPCB4094649 I. INTRODUCTION. i. *-*/ */- i kf- II. SUMMARY . . III. REFERENCES. IV. EXPERIMENTAL WORK AND DISCUSSION................................................ A. Pydraul F9.......................................................................................... 1. Formulation Change.............................................................. 2. Use of Petroleum Derived Trlcresyl Phosphate. 3. Solubility of Water in Pydraul F9 ..... . 4. Hydrolytic Stability......................................................... 5. Compatibility with Skydrol........................................... 6. Flammability In Contact with Molten Nitrate . 7. Flammability on Spraying Into Open Flames . . 6. Relative Evaporation Rates........................................... 9. Screening New Components............................................... 10. Testing System Accessories........................................... 11. Competitive Fluids.............................................................. 12. Customer Service Samples................................................ 15. Physical Measurements .................................................... 3. Skydrol 7000..................................................................................... 1. Compatibility Studies .................................................... 2. Hydrolytic Stability......................................................... 3. Solubility of Water In Skydrol 7000 ................... 4. Customer Service Samples............................................... f f* 5. Physical Measurements . . . . ................................. C. Skydrol 500 (Pluld CS-40) .................................................... 4s 1. 2. 34. 5. 6. 7. Q. 9v 10/ Formulation of Skydrol 500. ......... Oxidation and Corrosion Tests ........ Selection of Dye.................................................................. New Formulation of Skydrol 500. ............................. Screening Inhibitors................... ..................................... Thin Film Corrosion Tests................... ....................... Hydrolytic Stability......................................................... Solubility of Water In Skydrol 500. ................... Skydrol 500 from WADC Packing Test........................ PhyaicalTMeasurecents .................................................. Fluid OS-45 and OS-45-1, iMoin................... 13 IS: MFf \ i DSW 620623 f iff * STLCOPCB4094650 H. Steam Turbine Lubricants, (Fluid OS-58) I. Low Temperature Industrial Fluids (Fluid OS-57) J. Preparation of Esters 1. Azelate Eaters 2. Plnate Esters Succinate Esters a. Di-isodecyl Succinate b. Dl-trldecyl Succinate c. D1 (Sterox AH) Succinate. Phosphate Eaters a. r.-Heptyl Diphenyl Phosphate b. Alphanyl 79 Diphenyl Phosphate. 5. Adipate Eaters Preliminary'Screening . 1. Viscoeity Index Improvers 2. Base Stocks............................ STLCOPCB4094651 ; f |*f'V? ? l? 3^ * Eiectrical Properties. 5* +:- 76 f 7 ,* V /, , a. Apparatus and Methods........................................................76 b. Results....................................................................... 76 4. Thermal Conductivity.............................................................78 a. Apparatus and Methods........................................................ 78 b. Results....................................................................................... 80 V. CONCLUSIONS.......................................................................................................8} 1. Pydraul F9........................................................................................ 83 2. Skydrol 7000 .........................................................................................84 3. Skydrol 500..................................................i- . ................................. 84 4. Pluid 0S-41................................................................................................. 86 5. Fluid OS-54................................................................................................. 86 6. Steam Turbine Lubricants.................................................................86 7. Fluid OS-57.................................................................................... * - 87 3. Miscellaneous Fluids ...................................................................... 87 9. Preliminary Screening. ............................................................... 67 10. Physical Measurements.......................................................................... 87 VI. APPENDIX........................................................... .... 87 STLCOPCB4094652 9?o "MSnsanto7bectune 'iftteresWd In' the"field5 of' func tional'fluids and with-the Introduction,of Skydrol and the signing of a Joint agreement With 'the1 Douglas Aircraft Co., Inc., started research^in the ^general1 field of fluids which were principally synthetic In nature. Functional fluids have been defined as fluids without which a machine cannot perform its designed function -- for example, hydraulic fluids, lubricants, heat transfer fluids, etc. Ear.iy work resulted in Pydraul F-9, a non-flammable type industrial hydraulic fluid and the development of background information. Many other fluids have been proposed and are in various stages of development. This report convers the period of August, 1952 through July, 1952*. The scope of the work was large Including formulation studies, property determinations, application research, sample preparation, and sales service. SUMMARY Pydraul P-9 and Skydrol 7000 are Monsanto's commercial fluids In the functional fluid field. Skydrol 7000 Is a non flammable type hydraulic fluid for aircraft and Pydrual F-9 is a non-flasmable type fluid especially designed for station ary hydruallc machinery. Both fluids have enjoyed consider able success In,sales. Efforts were expended to Improve the competitive position of Pydraul p-9 by a change in formulation to reduce raw material costs, by examination of r.cmpetltlve fluids and by investi gation of new sources of raw materials. Many properties were determined for Pydraul P-9. These Included such things as compatabllity with other materials, hydrolytic.stability, solubility of water In the fluid,' specific heat, electrical properties, thermal conductivity, variation of density with temperature, and fl&mnablllty cliaracterlstlcs under specified conditions. As a customer service, samples of used Pydraul F-9 were examined for condition and reusability. Similar tut less extensive work was done with Skydrol 7000. Several samples were examined as a customer service and properties such a3 compatabllity with various materials and hydrolytic stability studied. Skydrol 500 was developed to meet the low temperature require ments of military specifications forjnon-flamaable-type air craft hydraulic fluids. It waa necessary to charge certain additives and a satisfactory formulation was developed with Douglas. Test procedures for*examination! of* |hi jflvjidswepe fed jand aus43 - * - .............. - ' |re: m the lea J ' i. :# DSW 620626 * m STLCOPCB4094653 fl\H^P|^f^<^l^dl^rSe?K^ais51ytic stability of fgkydro] 500^waa*studled.t`*It;Has shown. that results of the recommended test doinot correlate ^with actual use data. The overall , result-of such work has been a strengthening of the competi tive position of Skydrol 500. ' Further work on Fluid OS-41, which was designed as a torque converter fluid, has shown that corrosion is not a problem. Various properties were determined to aid in evaluation of the fluid by prospective ouStooers. Leakage in hydraulic steering systems on automobiles led to fires. A non-flammable type fluid (Fluid OS-54) was developed for this use and is under test. The same fluid is of interest for shipboard use and is under consideration by the Navy. A definite need exists for a fire resistant, steam turbine lubricant. A fluid (Fluid OS-58) has been developed and after examination by the Engine Teat Laboratory for rusting characteristics and the addition of anti-rust additives it was sent to various groups for further evaluation. A formulation for a lower temperature industrial fire resistant hydraulic fluid was devised (Fluid OS-57). Such a fluid has been reported as needed in applications where Fydraul F-9 is too viscous at low temperatures. Tests on this fluid are in progess by several Interested people. Heat stability studies were smarted and indicated the fluid to be similar to Skydrol in this characteristic. Samples of many compounds were given preliminary screening for evaluation as functional fluids. Certain materials were of sufficient Interest to warrant further testing. III. REFERENCES 1. Pinal Report, ''Hydrualic Fluids and Synthetic Lubricants", 117-2050, by R. E. Hatton, May 15, 1552.2 2. Final Report, "Functional Fluids", 117-2560, May 21, 1553, by R. E. Hatton. Iti*i * 3. Pinal Report, "Formulation of 0S-40 and OS-45", 117-2534, by L. J. Breuklander. M iff : 4. Final Report, '"Dibutyl phenyl Phosphate -- Pilot Plant Preparation", <117-2555. , DSW 620627 a g f * yv - ft ''` STLCOPCB4094654 Pydraul F-9 1. Formulation Change In an effort to reduce the raw mater!al* costs of ' Pydraul F-9. Mr. H. K. Nason suggested that the Aroclor 1248 concentration be increased about five per cent. The effects of such changes were Investi gated. Formulations were prepared using the following proportions: Regular: 47.9* 47.9 4.2* tricresyl phosphate Aroclor 12 48 Santodex Special: 44.2* 51.6* 4.2* tricresyl phosphate Aroclor 12*" Santodex Raw materials vary somewhat In properties and there fore two formulations of the regular and special type were made. Those numbered one were from one set of raw materials and those numbered two were from another set. Therefore, the properties of the "ones" should be compared and those of the "twos" should be compared to determine the effects of formulation changes. The data are as follows: Regular Special Regular Special Vlscoslty,cs,210*F. 5.68 100*F. 50.60 Viscosity Index 29 Sp. Or., 25/25*C. 1.2659 Pour Point, *P. -5 Flash Point, *?. 410 Plre Point, fp. 680 5.7'1i"ff 5.67 52.25 50.20 23 30 1.2760 1.2661 00 405 405 680 s8? j %.77 52.56 27 1.2763 +5 410 680 ' i f- Our specifications for Pydraul P-9 include a 0*F. maximum pour point, 15 minimum viscosity index, and specific gravity of 1.26 to 1.20 at 25/25*C. <Other specification properties such as appearance, color, moisture, and acidity would be uncharigfed|by fsbclf a i formulation change as that proposed. Not included ir. our formal specifications but listed4in the^general STLCOPCB4094655 tun i ^TOperty|wnlcl^doesinot pass] Epr^iff^dwpoiSt^be'irig about?? 5P. higher for *th"special formulation, j ? j| , ! ; Before such a change in formulation could be adopted, approval by Douglas Aircraft Co. of its utility was required. Five gallons of the formulation were prepared in the laboratory. The properties of this batch were as follows: Viscosity, 210F. 100F. Viscosity Index Specific Oravity,25/25',C. Four Poir.t Flash Point Fire Point Acidity 5.72 cs. 51.91 cs. +26 1.2756 +5F. 405F. 680F. 0.06 NN The sample was sent to Douglas under the code number PH-98 for their evaluation. Tests by the personal at Douglas Indicated that the new formulation was essentially functionally equi valent to regular Pydraul P-9. The formulation of Pydraul P-9 was changed In June, 1954 by amendment to the manufacturing process. The formulation for Pydraul F-9 Is therefore 44.2# trlcre9yl phosphate, 51.6# Aroclcr 1248, 4.2# Santodex, and 50 ppm of silicone defoaaer, DC 200 - 350 cs. at 25C. Use of Petroleum Derived Trlcresyl Phosphate tt Only trlcresyl phosphate (TCP) derived from coal tar cresols had been used in Pydraul P-9 production. In view of the increased use of TCP and the shortage of coal tar cresols, TCP has been made from petroleum cresols In the plant. Samples of Pydraul P9 were prepared using TCP frcm petroleum cresols and using a purchased TCP (Kronitex AA from Chlo-Apex). The physical properties of these samples as compared to specifications for pydraul P9 are as follows: i ' iff 1; * ri Petroleum Kronitex AA Specifications Viscosity,C3,210*pjh ' 5.64 100*Fr 51.9 Viscosity index 1 ; 18 s* 4.51-6.51 40 - 60 15 minimum MH*2? fc DSW 620629 STLCOPCB4094656 , w.... ,, , used for the TCP was Productoli' 210 out I" ~ Samples of these Pydrauls were sent to Douglas, for lubricity^ f * 1 testa.^ It was reported by Douglas (that no significant * difference was found In the Shell Pour Ball Wear Test. " f The use of Productol derived TCP or "Kronltex AA" TCP alone for Pydraul P9 was approved, thus Increasing the types of TCP available for this use to three. Solubility of Water In Pydraul F9 The solubility cf water in various functional fluids was determined at room temperature and at 210P. by the following procedures. In the determination at room temperature, a sample of the fluid was stirred from 1-1/2 to 2 hours with an equal volume of water by bubbling an air stream through the mixture to insure intimate contact. The layers were allowed to separate about one hour. The ester layer was then centrifuged for one hour at 1500 rpn to free from occluded water. Samples of the ester were weighed In duplicate into tared stoppered flasks cpntalnlng a mixture of benzene and methanol blanked with Karl Fischer reagent. In the determination at 210P. a sample of the fluid was stirred from 1-1/2 to 2 hours with a large main tained excess of water by bubbling an air stream through the mixture contained In a large tube placed in a 210*F. constant temperature bath. The layers were then allowed to separate for four hours at 210P.. The ester layer was clear showing no occluded water to be present in It. Using a warmed plpet, samples of the fluid layer were weighed in duplicate tared stoppered flasks containing a mixture o- ; ..n . . and methanol blanked with Karl Plsher reagent. The samples were then titrated with Karl Fisher reagent. The results using Pydraul P9 were as follows: Solubility of water at 75*P. 0.17J6; 0.l8f6 Solubility of water at 210`F. 0.5^56; 0.55 Hydrolytic Stability ' f i* ti A regular*"coke bottle" hydrolytic stability test (fro 5001 fectlon ofith DSW 620630 STLCOPCB4094657 Some interest had been expressed In the compatibility of Skydrol and Pydraul F9 by various customers. Mixtures were prepared using ratios of 75:25, 50:50, and 25:75. After several days at room temperature. * no evidence;0f*separation'was*noted*T Storage at 0*C. for 24 hours did not result In separation. It can be concluded that Skydrol and Pydraul F9 are mutually compatible at temperatures to 0C. 6. Flammability in Contact with Molten Nitrates A series of experiments wereperformed in an attempt to determine the flammability characteristics of Pydraul P9 ir contact with molten metal nitrates. A 50:50 mixture of sodium and potassium nitrates was heated to at least 1000*P. Iron, porcelain, and l nickel crucibles were used. lOnjl^eating ,the mixture - nitrates/ gas Was'evolved after?therma8s had melted. Pydraul`F9>was dropped and sprayed onto the surface ' `ten*nitrates at temperaturesiofi1000*- ~ STLCOPCB4094658 f f ff :PydrauW8^dTe^twEjWt|fuM^Wt4p05i2at ^ the molten titrate'jmd'these fumes couldtoef Ignd a spark or a flame. The experiment using the nickel . crucible was r epeated several days later with the | same mixture of nitrates. The evolution of gas was I much less at 1000P. and spontaneous Ignition did not occur. It appears from these data that pydraul - will not spontaneously ignite in contact with a 50:50 mixture of sodium and potassium nitrates at 1000F. except under certain specialized conditions, that is a rapid evolution of gas and in the presence of nickel. The vapors of Pydraul can be ignited. These results are similar to those previously obtained for Pydraul F9 and molten aluminum. The work with the molten nitrates was undertaken to answer questions concerning the use of Pydraul as the hydraulic fluid In machinery used to heat treat aluminum by immersion of the aluminum in a molten nitrate bath. 7. Flammability on Spraying into Open Flames The behavior of Pydraul F9 on spraying into open flames in an incinerator was examined. This work was done to provide data for Insurance personnel as requested by the Sales Department. The 3Dray outfit supplied by Douglas Aircraft Company was used. The equipment was designed so that nitrogen pressure could be placed upon a resevoir containing the fluid under test and the fluid forced through a small orfice and formed into a fine spray. The pres sure used in the tests was 1000 psl. The fluid was drawn up into the resevoir by the use of a suction pump. This equipment was set up in front of the plant'incinerator in which a wood fire had been built and after the entire incinerator had become hot because of the burning of waste paper. Temperatures of 1100 to 1^00`F. were measured In the incinerator by means of optical pyrometry. Three fluids were used, Pydraul F9, DTE Medium (mineral oil),_and Houghto-Safe 271 (water base fluid). Spraying the DTE Medium into the incinerator resulted in vigorous burning as the fluid contacted the flames and hot surfaces. Spraying Pydraul F9 tended to increase the flame slightly, the fluid vaporizing and burning. There was no flash back. SDraying Houghto-Safe 271 resulted in no_ increase in flames. These resul.ts ^ Ienfc>strat& IPydraui F9',oifilre resistant jpropertke " ' l*thd ilstldofioltioiis^ > The|4o$ :resul^ |tft ** ''' " * " `j-e'oofcLv iilXyap. 'or* STLCOPCB4094659 late ................ -. - . . ,, * .The relative,evaporation of several fluids was deter- *^i;imlned|lS^sponse to a Sales5Department requests The ; . ' ?jjrboQdvfi^efused is as follows: 250 ml. beakers were > . fllledSapproxlmately 3/4 full with the fluid under ' study,^weighed, covered with ribbed type watch glasses'/ and allowed to stand In the laboratory at room temperature. The fluids examined were Pydraul F9, DTE; Medium (mineral oil) and Houghto-Safe 271 (water base fluid). A similar volume was used in each case, being about 180-190 ml. The fluid weights were about 230, 160, and 185 grams, respectively. The beakers were weighed periodically and the weight losses observed were as follows: Total Loss in Weight, Grams Total Days Pydraul F9 DTE Medium Houghto-Safe 271 0.0 0.0 0.1 23.1 0.1 50.1 0.1 69.6 0.1 80.4 These data show that the Pydraul F9 and the mineral oil, DTE Medium had lost no appreciable amount while the water base fluid, Houghto-Safe 271, had lost about 40jC by weight in 65 days. Both Pydraul F9 and DTE Medium were unchanged in appearance. The Houghto- Safe 27.1 sample decreased greatly in volume and the solids .which are normally present seemed to increase ' ^8 lighttypin' amount. These data point up the problems involved in maintaining the proper concentration of water in water base fluids and the greater permanence of Pydraul F9. 9. Screening New Components A Monsanto defoamer, N5262A from Nitro was examined in Pydraul F9 and in Skydrol. No foam suppression was found in Pydraul F9 at a concentration of 0.0l. A slight tendency toward more stable foam was noted. The material*appeared to set a3 a defoamer in Skydrol * 4 . but .wag^jab .moi^e effective than the presently tused^ rr inmaterit 1SeverajLdifferent types 4of,cresyllc. acid.had ibee .dreg luct ;*ata -"g^sflei f: iLiulk!. DSW 620633 STLCOPCB4094660 regular* plant; |?Shell' iel fcgLirarl^pho'apl:. . , B,?from.. `,, , ,, petroleum oresylic aolW(*wCAA g.'ade) and Midi refers to the ester made from Midland Tar's cresylio * i 'acid; ' v *y % s ' ' ' f ' ? .i Sample Shell 2000AA Midland Viscosity, cs. 21C"F. 100*P. Viscosity index Sp. Or., 25/25*' Plash Point Fire Point Pour Point 5.28 55.6 -50 1.1555 455F. 700*F. +10F. 4.76 4.57 59.2 55.1 -10 -42 1.1459 1.161 4659F. 465F. 665*F. 655P. 0F. -15F. The data reflect the higher content of xylenols in the cresyllc acid, In specific gravity, viscosity, and pour point of the esters. The tricresyl phosphate from Midland Tar cresyllc acid was converted to Pydraul F9 (called sample M-F9). Tricresyl phosphate (regular plant A-ll) was used to prepare Pydraul F9 using the same other Ingredients (called sample A-11-F9). The data are as follows: %f* Sample Viscosity, cs., 210F. 100*F. Viscosity index Sp. Gr., 25/25*C. Flash point Fire point - Pour point A-11-F9 5.76 52.2 +28 1.2654 405F. over' 675F. +5F. M-F9 ' 6.11 58.6 +26 1.2545 405F. over 675F. +10F. The data for the two samples reflect the higher content of xylenols in the Midland Tar cresyllc acid, the F9 type fluid made from the triaryl phosphate having higher viscosity and pour point and lower specific gravity. It does not appear that such tricresyl phos phate would be of value for Pydraul F9 production. 1. Testing System Accessories f ii , i Samples of "0" rings made, pf butyl and Neoprene^rubber^ ? \ were?soaked In Pydraul F9 for 7 days at ISO0?.* -Visual' observation showed that the "0" ring immersed in ' t i Pydraul>F9. became larger in diameter, thicker, and; -------- *-1^ble?.. ffhesf efiti^ie'dlaa ys ` DSW 620634 ire-*'- * * -\V. .'V *, STLCOPCB4094661 of asbestos and some kind'of binder. Has Immersed" la S' Skydrol and PydrauliP9-'and *he fluid held at 150p; for'fifteen days., No visible changes In. fluid or gasket occurred. ' ' ^ ; ; . 11. Competitive Fluids Competitive fluids for Pydraul F9 are Llndol HF and Houghto-Safe 271. Samples of these fluids were obtained and comparative tests have been run. Llndol HF is reported to be tricresyl phosphate. HoughtoSafe 271 is reported to be a water base type fluid. Data obtained thus far and compared to Pydraul F9 specifications as typical properties are as follows: Property Pydraul F9 Lindol HF Houghl Viscosity,cs,210 F. 4.51-6.51 1}0F. 100'F. 40.0-60.0 Viscosity Index 15 min. Sp. 0r.f 25/25F. 1.26-1.28 Flash point, 6F- 420 - 450 Fire point, F. 650 - 725 Pour point, #F. +5 max. 4.20 14.60 51.0 -25 1.169 450 645 -10 8, 43. 154 1 280 280 +5 The Houghto-Safe 271 fluid was medium yellow in color and a flocculent material separated on standing. Shaking dispersed the solid temporarily. Considerable boiling was found while running the flash point. The volume had decreased aboutt50^per cent before a flash was obtained. The Lindol HF fluid appears to have ' properties similar to tricresyl phosphate a3 normally prepared. STLCOPCB4094662 in ^~ fe&tnidy j * .W 12. fCustomer ServicefSamples r ' '' , .-.-fs. . s '. : ~> ' '} f - ' 5 ' ' During part of the time covered by this report samples of Pydraul P9 were submitted by various customers for study. Each sample will be handled separately in this section of the report. The work was continued under job number 117-2635 which covers the second year of this report. A sample of Pydraul F9 removed from a pump test by the Hydraulic Press Manufacturing Co. was submitted for analysis. The sample contained a so-called "scum". Examination of the fluid indicated no change in physical properties except for loss of viscosity index. Thi3 is normal for Pydraul F9. Analysis of the fluid Indicated less than O.OI56 copper and no water soluble chlorides. The amount of zinc present was estimated to be about 0.0556. It might be surmised that the zinc came from the brass bearings in the pump, the copper being effectively removed by plating on the steel parts. Some copper plating was reported by H.P.M. The scum layer showed freedom from more than traces of the' common metals but more than one per cent silica. It had the appearance and behavior nn heating of a silicone grease or rubber. Pydraul F9 in use at the Trico Products Company had become emulsified with water and was separated by centrifugation. An examination of the separated, used Pydraul indicated that fluid was within specification limits on moisture and foaming characteristics. Viscosities were as expected for used Pydraul. The acidity was 0.34 NN, considerably above our specifi cation maximum of 0.15 NN. Thl3 high acidity was probably due to hydrolysis during emulsification. *i A sample of used Pydraul F9 wa3 received from Alloy Die Casting Company who Indicated that the fluid had been used for over a year. Analysis showed that the fluid was quite dark and had the following physical properties: viscosity, 4.26 cs. at 210*F., 37-91 cs. at 100?. for a viscosity index of -105; and acidity of 0.13 NN;;and^a specific gravity ati25/25C. of 1.256. TheVlsc'osity was a3 would be expected for used Pydraul F9-'' The very low acidity was somewhat unexpected and indicates the long service .life of. M\ was] reltrfb DSW 620636 1 x **#? i] STLCOPCB4094663 , __ _ ... . _ ,, . I The iresulting y|ear|ln-|^ . v^y^hirifls^ei^fwiljlt n<f visifire 'tftisp^de'd'natter (. (Sample A). A .small, amount of dirt.was present on the filter paper. Part of thl3 liquid wasf then filtered through a layer, of Attapulgus earth. The resulting material (Sample.B) was dark: yellow in color and completely clear. No trouble was experienced in the filtration. However, as would be exptected, the filtration through Attapulgus earth was somewhat slower than through paper alone. The physical data for these two samples as compared - to specifications for new Pydraul F9 are as follows: Pydraul F9 Sample A Sample B Specifications Viscosity,cs.,210F. 100F. Viscosity index Acidity, NN Sp. Gr., 25/25C. 4.27 37.60 -98 0.15 1.2521 4.25 36.91 -94 0.04 1.2525 4.51-6.51 40.0 -50.0 15 min. 0.15 max. 1.26-1.28 These physical properties indicate that the Attapulgus earth does remove acidic materials as well as colored bodies. The"viscosity data show normal wear and are as expected for used Pydraul F9. The material should be satisfactory for use after filtration, especially if Attapulgus earth is used. Two samples of Pydraul P9 were received which had been submitted by the Eaton Manufacturing Co. of Battle |J|eek, Michigan and have been examined. The first sample wa3 marked as follows: "Put in pump H-l-51. Sample taken 2-16-53." This sample (called No. 1) was dark in color and had dark colored particles floating in it. It was allowed to stand several days and the solids tended to accumulate on the surface. The entire mixture wa3 filtered using filter paper only and a dark yellow very slightly hazy filtrate resulted. The residue on the paper was black-in color. This filtration was very slow. The filtrate,was examined for physical properties with the results shown (sample No. 1): . $ ? I ? I I'M Ml ! i - flfis Sample J No. 1 No. T2 Specifications >10^ i 4.50. i4.57i Mi51-6^5l 6< fie DSW 620637 WWfP f g i* STLCOPCB4094664 wW'i ! -I t These'-data: indifdlteFthafg^ff P^drl Uatiafaofor3ftc^|<lirftie^a5^p^ov| removed. * The-filtered material raeetaTspeol on acidity and specific gravity and viscosity data are as would be expected for used Pydraul F9. '' * ; ? The second sample was marked as follows: "Put In machine 11-28-51. Pydraul added February. 1953. Sample withdrawn 4-2-53. Machine No. 246481." This sample (called No. 2) was quite milky and full of solids. Some of the solids tended to accumulate in an upper layer on standing. However, the fluid still appeared milky. This sample was filtered through filter paper only and the filtration was extremely slow. The resulting filtrate was dark yellow and clear with no evidence of separation of layers. The residue on the filter paper was black and slightly sticky. The physical data for the filtrate are given above under sample No. 2. It appears that the Pydraul F9 has been contaminated as evidenced by the low specific gravity. ; /. w- -i '*$% 11 v A i I Two samples of Pydraul F9 were submitted by the Trico Products Corp. These samples represented used Pydraul F9 that had been centrifuged to remove water. Questions-concerning its reuse and flammability were raised. Both samples contained a certain amount of sludge which could be removed by filtration through filter paper. Both samples were al30 dark in color and this color and sludge could be completely removed by filtration through Attapulgus earth. Analytical data for the two samples as received are as follows: (Viscosity was determined on a filtered sample). Sample Trico #1 Trico #2 Specs. Viscosity,cs.,210F. 100F. Viscosity index Sp. Or., 25/25*C. Acidity, NN Moisture, % Flash point, F. Fire point, F. 4.46 39.7 -79 1.2ol 0.15 0.45 445 730 4.41 39.1 -84 1.260 0.12 0.46 435 760 4.51-6.51 40-60 15 min. 1.26-1.28 0.15 max. 0.20 max. The viscosity data are as would be expected for used, , Pydraul F9 and indicate'normal shear. - The'specific gravity is high and indicates negligible contamination. The rioisture content is quite high ant represents t | tenfraideda|*wa tejr < robe -l3 lused rjul isludg "*e| Pi isaidggi Thi I ' ` MLy De reus sba Sir it| DSW 620638 STLCOPCB4094665 in^thls inve^eL|a^lorf because of the Plaited a&otint' ; ' off sample#|ff^|,fxioot.4 Since the accuracy of this , micro, techhic^tfl fibout 15F* it would appear that * all samples aj^app>xlniately equivalent in these properties. ' Samples .of fresh Pydraul F9 and the Trico samples placed in watch glasses would flash when matches were laid at the edge of the liquid. Undoubtedly the-small amount of liquid involved was raised to the flash point. This test was used by the customer and reported by him only for the used Pydraul F9. Trico Products oorp. have been recovering used Pydraul F9 which has been contaminated with water. A sample was received and found to have the following properties: Viscosity, 210 F. 100F. Viscosity index Acidity Specific Gravity, 25/25C. Flash point Fire.point Moisture 4.65 cs. 41.62 cs. -56 0.42 NN 1.2591 415F. 690F. 0.20g The sample appears to be somewhat high in acidity (specification maximum is 0.15 NN). The specific gravity is slightly low indicating some contamination probably with petroleum oils. The moisture content is satisfactorily low. t - * ** * - Two samples of Pydraul F9 were received from Delco Radio Division of General Motors Corporation for analysis to determine if they were contaminated with petroleum oils. The regular tests were run on these materials and the following data obtained: Sample Reed Prentice 1 No. 5 Cleveland No. Viscosity,cs.,210F. ' 4.56 100F. t 36.97 Viscosity index i Acidity; *HNI * K- f I f J 0.'09 Sp. Gr., 25/25C. Flash point" j . 1.257 ! ' 420 , , 'ireipoii "145 ` * 5.84 57.46 -215. ? f ' Of 15? * ' 1.247 400 let Jnt m *f DSW 620639 STLCOPCB4094666 ,..__sbfreflej5 te 4iah?polht?^Ali othei^&araete1 [expected for used*'pydraul F9. -4' m- ` ^ > *:*i4 f< 15V ^Physical Measurements iforsi Data concerning specific heat, variation of density with temperature, electrical properties and thermal conductivity of Pydraul F9 are given in section M of this report. " B. Skydrcl 7000 1. Compatibility Studies American Airlines had requested data concerning compatibility of Skydrol 7000 and aviation gasoline. Five samples were prepared using Grade 100/130 gaso line. These samples contained 0.1#, 0.3#, 1.0#, 10# and 25# Skydrol. There was no evidence of separation of liquids or sediment at room temperature or at temperatures as low as -15F. Evaporation cf the gasoline from the 1#, 10#, and 25# solutions mentioned above left a clear residue which appeared to be Skydrol. Skydrol is completely compatible with Grade 100/130 gasoline under the conditions tested. The compatibility of Skydrol 7000 and Skydrol 500 in the ratio of 1:9 was examined at room temperature and at 32F. At both temperatures there was evidence of separation into liquid layers, the upper layer being less than one per cent of the mixture. There was no *-* ' evidence of separation of viscosity index^improver at these temperatures. However storage of the mixture at -4oF. resulted in the separation of a resinous material. This material went back into solution cn warming. Because of the wide differences between specific ' gravity of Skydrol and hydraulic fluid MIL-0-5606 (petroleum fluid), it should be possible to determine the approximate amount of contamination of Skydrol by this fluid. The specific gravity of various mixtures of Skydrol and MIL-O-5606 fluid was deter M mined.; Results are as follows: , ; - * ' f ? t 9 i - f | ` - S . 4 f I l * Composition Sp. Or.; 25/25C. >6061 36m i|o8;^ '10610I DSW 620640 STLCOPCB4094667 rolytlic Stability Mi tv. _ ,, - .. During an extensive study of the nyarolybia; ItaMllI of Skydrol 500, Skydrol 7000 was used as a reference fluid. The data for these various tests are best presented with the work on Skydrol 500 and can be found in the appropriate section of this report. 3. Solubility of Water in Skydrol 7000 The procedures given in the section on Pydraul F9 were used to determine the solubility of water in Skydrol 7000. The results were as follows: Solubility of water at 75*F. 0.5*+$; 0.5*+$ Solubility of water at 210F. 1.73$; 1.75$ The acidity of the fluid was measured before and after exposure to conditions similar to the water solubility determination at 2108F. for an extended period. The initial acidity was 0.12 NN; after 4-1/2 hours exposure, 0.13 NN; and after 7-1/2 hours, 0.22 NN. 4. Customer Service Samples Vickers Incorporated had run a pump test at 225*F. using Skydrol and had reported extremely high corrosion and fluid decomposition. It was suspected that these phenomena were caused by local overheating from the electric heaters used in the reservoir of their system to maintain a fluid temperature of 225?. resulting in thermal decomposition of the Skydrol with subsequent corrosion of metal parts.by the decompo sition products (principally organic phosphoric acids). A sample of Skydrol from the pump test was found to have an acidity of 114 NN while other samples of Skydrol maintained at 250*F. in an oven for 7 days had acidities ranging from 3.0 NN to 7.1 NN. These data indicate that the Skydrcl in the pump test had been exposed to unusually high temperatures. A sample of Skydrol-water mixture from Pan American Airways wa3 examined. It was freed from rust by filtration and separated into two layers. The oil layer was examined and found to contain'0.69$ moisture and 0.05 NN acidity. Shaking ithe Skydrol layer with Drier!te and allowing to stand followed^by filtration ff gave a product analyzing 0.24$ moisture]and meeting new material specifications iThg ,dat Indicated that. l [water can b`e r^povd Joy djyl jdangers clue fLccf In''cbm` ' ` m [recdgnized. m m e hydra; ?ik- '? nf'di or 3tra DSW 620641 ki STLCOPCB4094668 f * raii jments : . '* s t; Data concerning the thermal conductivity of Skydrol 7000 are^given in section M of this report. C. Skydrol 500 (Fluid 0S-40) A fluid was developed in cooperation with Douglas Air craft to meet military specification MIL-F-7100 for a non-flammable type aircraft hydraulic fluid. This fluid was called Fluid 0S-40 and was based on dibutyl phenyl phosphate. Work leading to this fluid is described in the final reports on Job numbers 117-2080 and 117-2380. It was decided during the period covered by this report to call this fluid Skydrol 500. Therefore, all references in this report will be to Skydrol 500. 1. Formulation of Skydrol 500 Skydrol 500 formulation first used consisted of 87. dibutyl phenyl phosphate, 12.056 Acryloid U, 0.956 phenyl glycldyl ether (PGE) and 0.1# wax disulfide (WDS). Several batches were made up using this formulation. Since the PGE-WDS combination was added as inhibitor and copper deactivator and since new lots of these additives had been received preparatory to making a pilot plant run, oxidation and corrosion tests were run at 250F. using the standard procedure. Data are as follows: Sample -t Viscosity, cs., Initial Final 130 F. Acidity, NN Initial Finali . Effect on metals, wt. change, mg./cm.2 Copper Iron 1 > Alumlpuml | | s * Magnesium Cadmium plated 7.33 7.16 0.15 0.21 7.33 7.21 O.15 0.21 .55 ,01 BB 7.79 7.79 8.20 8.15 0.03 1.5 0.C3 1.4 STLCOPCB4094669 ib* ?! I! leaefvariations appear to .befno* 3a sec dat& off Sky< rin `the PilotfPlant-under Job wita%i -2458. fluid had properties similar to th03e of the labora tory prepared material. : Several different lots of Acryloid had been supplied by Rohm and Haas as viscosity index improver for Skydrol 500. In order to suggest specifications for this additive solutions of their material were prepared in dibutyl phenyl phosphate at 12 weight per cent concentration. The data are as follows: Sample U R3825X5 R3876X Viscosity,cs. ,210.-. 100F. -40P. 5-59 10.68 580 3.96 11.67 520 3.92 11.54 530 The latter two samples would give Skydrol 500 of satisfactory properties. Spec Iflcatlons were suggested based on these latter twc samples. Oxidation and Corrosion Tests Skydrol 500 consisted ol dibutyl phenyl phosphate (FH-87), a viscosity index improver, and an Inhibitor pair which Included a copper deactivator. The formu lation first studied contained wax disulfide (WD3) from Shell as the copper deactivator and was cloudy because of the limited solubility of the WDS. Work at Douglas had indicated that ethylene bis tolyl sulfide (EBT3) was more satisfactory as a copper deactivator from the standpoint of less copper attack and complete solubility. A larger amount of the EBTS was prepared by Shell and sent to Monsanto for use in preparing Skydrol 500. This particular sample was not checked by Douglas; therefore a sample of Skydrol 500 was prepared and placed in the Oxidation and Corrosion Test at 250F. The results are as follows: Sample Viscosity,cs.,130F Initial Final Acidity, N'N Initial ; tFinal i |ffect|c&i ale {char1 Skydrol 500 EBTS ^153^ FH-87 S8.01 8.01 7.79 7.90 2 93 8.33 3.33 8.06 8.08 2.95 0.02 0.02 10.01 .0.01 Oj. 03t |0.fl3 1' tfii DSW 620643 if- STLCOPCB4094670 ( t : t - t f t i I i&J-SViaX _,,..i-* v-g-'-m1?I t . _ ,, ,, 3$iS||!.I^P?5^Miterialv which was/fcade i|^. \ ICrdm' tHelliS'laMaaaqjla^pf' copper deactivatozCS -Coppe^ j | loaaelt^e^au^ _0i^fc%0.6 ,ng. per sq.r craw ls * * fcontrastedbo' %he loaflea- reported by Douglas of about *0.2. A sample of the EBTS they used was requested and further testing was to be done to determine, if possible, reasons for<the different results obtained. Two samples of Skydrol 500 from wax disulfide (Skydrol 500 WDS) were also run, one clarified by filtration and one used as Is (very cloudy, solids present). The latter material gave a greater viscosity increase and acidity increase than the filtered material. Attack on metals was similar. A sample of FH-87 was also Included in the test as a standard. Normal results were obtained. The formulation used for the Skydrol 500 was 86.75$ dibutyl phenyl phosphate, 11.75^ Acryloid R3876X, 1.0$ phenyl glycidyl ether, and 0.5$ ethylene bis (tolyl sulfide ). A sample of EBTS was obtained from Douglas (labeled WVJ, lot LR-1864-40) and samples of Skydrol 500 were prepared from our lot of EBTS (lot P-4221) and from the Douglas sample. Both lots of EBTS came originally from the Shell Chemical Company. Results of an Oxidation and Corrosion 'rest at 250F. are as follows: Sample EBTS Skydrol 500 EBTS EBTS W'wJ WWJ FH-57 Wt. change, mg. /cm.2 Copper -0.573 -0.542 -0.612 -0.488 -0.427 -2.85 Cadmium/ -0.031 -0.039 -0.008 -0.008 -0.008 -0.016 steel Iron 0 0 -0.023 -0.023 -0.008 0 Magnesium 0 -0.008 -0.016 e 0 0 Aluminum 0 +0.008 +0.008 0 0 0 Initial NN 0.05 0.04 0.04 C.C4 0.04 0.02 Final NN 0.20 0.16 0.19 0.19 0.15 0.86 The identity of samples is as follows: Skydrol 500EBTS was made using our sample of EBTS (lot P-4221), Skydrol 500-WWJ,was -madei using Douglas sample of EBTS (lot LR-1846-40) and FH-87 was the standard dibutyl phenyl phosphate. Two separate preparations of Skydrol 500-EBTS j^er,e made .J -.The results indicated i ` ` | Dbuglsts resuits land :on| is tent IfrCnl tqs't * fote fthaft; th'e' re si mi tray DSW 620644 * ftt 1vy L f 1 t\ STLCOPCB4094671 lifrur *.... wtl % | 80;M j r-i 4 , . j,.sample ?bi^ffl1SS^hpgil^hefe|j6ppex.,. ,, tndke*UBing the tJduglisfsainple f t I)ou^lalr,rr!e?<3?fe'd^ copper losses of 0.14'to 0.19 mg. per sq. cm. with ' their sample of EBTS and 0.23 with our sample. ? The results shown for dibutyl phenyl phosphate (FH-87) are normal. Work was continued to determine the causes of different results in the Oxidation and Corrosion Test obtained by the two laboratories. As a part of this investigation the two samples of EBTS were comparatively evaluated. Results are as follows: 25 Sp.Qr. at % %C $H 25/25C. Calculated for ethy lene bis (tolvl sul fide) (Cl6Hl8S2) 23.37 70.04 6.61 -- Ethylene bis(tolyl sulfide) Lot No. P-4221, Shell Develop ment Co. Emeryville, Calif. - 23.71 69.57 6.53 1.6196 1.121 WWJ-Base Lot Bt. 23.53 69.48 6.50 LR-1846-10,Douglas Aircraft Cc., Inc. Santa Monica 22.90 69.66 6.49 1.6192 1.122 22.97 69.85 6.44 Because of the differences in copper attack in the oxidation and corrosion test with Skydrol 500 experi enced by our laboratory and by the Douglas laboratory, further work was undertaken to study the test. It wa3 found that moisture in the air used for the test was at least partially responsible for the differences. The air used came from the regular plant compressors and passed through a commercial drier and pressure reducer before use. However, it appears that this equipment did not sufficiently remove moisture. The data obtained in two tests using Skydrol 500 are as tabulated on the following page. f. The Skydrol 500 samples are as follows: V-2178 wasi t the oldest sample of Skydrol 500 available containing ethylene bis tolyl sulfide as a copper deactivator, WWJ was made from Douglas' sample of ethylenetbic ` tolyL sulfide, EBTS was jnade. Skydilbl feOO wasi bade dr ess Wap flOfppn | mpianniif*thhaltt { vf >1 - m the DSW 620645 STLCOPCB4094672 height chan#ge ,? Sample? CuT Pe -* rpaV^aqt_A- cclmd.ftj JK Cd/Pe Initial final V-2178 (Reg) V-2178 (Reg) + dye WWJ (Reg) WWJ (Dry) EBTS EBTS P.P. P.P. P.P. P.P. dye /-2176 (Dry) + dye P.P. (Wet) - 0.92 -0.01 1.15 0 -0.66 0 0.19 +0.01 - 0.91 o - 0.25 +0.01 - 0.54 o 0.40 -0.02 - 0.44 -0.02 0.49 -0.02 0.53 0 11.6d 0 0 +0.01 -0.02 0.05 0 0 -0.01 0.04 0 +0.01 -0.01 0.03 -0.01 +0.01 -0.02 0.03 0 -0.02 -0.02 0.03 0 0 -0.02 0.03 -0.01 -0.02 0 0.04 -0.01 0 -0.01 0.04 -0.02 0.04 -0.01 0.03 -0.02 0.04 +2.40* 0.04 0.29 0.30 0.35 0.28 0.35 0.29 0.28 0.05 0.08 0.06 0.04 4.64 *Cd actually stripped In spots, weight gain due to surface coating. the air was speclal_y dried by passage through Drlerite, and (Wet) means that the air was saturated with water at 25-30*0. by bubbling the air through water. These data definitely Indicate that the moisture content of the air influences the corrosive effects of Skydrol 500, the (Wet) sample showing extreme copper, magnesium, and cadmium attack. In all cases drying the air lessened the corrosive action. Two tests are represented In these data, the first six samples being from the first test ar.d the remainder from the second. The results In the second test are still somewhat high even with drying and further work will be required to elucidate all factors involved in the test. All future tests will be run using bottled air to be sure of freedom from.contamination and the air will be thoroughly dry. These results again indicate the relatively poor hydrolytic sta bility of dlbutyi phenyl phosphate, the base stock used for Skydrol 500. . Selection of Dye * For identification purposes, it wa3 proposed to dye Skydrol 500 a distinctive purple. Several oil soluble purple; dyes as well as mixtures of red and blue dyes > M were added5to Skydrol 500. The resulting solutions containing 10 ppm dye were heated at 150*C. for various perilods o time, jOnly ,Alizarine Irisol N1 , , , f no; nei'dli Pye iffs. tfasido.lqri-stable!.fc^rif*lyeifcayfe I pri :X; I m DSW 620646 V . - , m? yt + ---* ItT? ? 1 * " ~ r 'S.t - STLCOPCB4094673 $ ,i * _ m :s of?AlizairIne?Irl3oifN cmrtiie? and corrosion test results were studied as Indicated in the previous section. The data indicated that the presence of the dye resulted in slightly greater * copper attack. However, it was felt that this ? increase la not significant. Therefore, the addition of 10 parts per million of Alizarine Irisol N was used as the colorant in Skydrol 500- New Formulation of Skydrol 500 The formulation of Skydrol 500 was finalized as follows: 86.75# dibutyl phenyl phosphate 11.75# Acryloid R3876X 1.00# phenyl glycldyl ether ' 0.50# ethylene bls(tolyl sulfide) 10 parts per million Alizarine Irisol N' Several batches of Skydrol 500 were prepared in r.he Pilot Plant. The physical data for these are ts follows and give some Indication of ranges expected in formulation: - Property: Viscosity,cs.,21C*F. 100F. -40F. -65F. Acidity, NN Sp. Gr., 25/25C. 3.98 3-96 3.97 3.95 11.84 11.70 11.73 11.69 550 550 530 530 2600 2270 2230 2230 0.04 0.06 0.08 0.07 I.O63 1.063 1.062 1.063, Based upon these data and similar data from laboratory batches, the following tentative specifications were proposed for Skydrol 500: Appearance Viscosity at 2I0*F. 100*F. Sp. Gr. at 25/25C. Acidity Moisture f t' it - , 5. Screening Inhibitors Clear, purple, oily liquid, free of sediment 3-95 + 0.05 cs. i 11.7 + 0.5 cs. 1.063 + 0.003 0.15 Nf5 maximum 0.25# maximum ` *4 ' * I-I ff STLCOPCB4094674 - t 11 __ _ ?1 i sfjferle3 foT;|Sp^5|toe re prepared an< examined in|thl Oxi*datl on &.h<3F <jorrosion Test at 250P.* Results are follows: ' jample No. * k1 Vi3cosity,cs,i30*F. Initial Pinal Acidity, NN 2.91 8.16 8.33 8.09 8.09 7.79 2.93 8.36 8.53 8.57 8.29 8.20 Initial 0.03 0.04 0.96 0.08 0.07 0.03 Final O.63 0.85 1.76 2.83 0.26 1.50 Wt. change,mg/cm^ Copper Iron -3.27 -3.00 -2.66 -7.08 -1.86 -0.69 +0.01 +0.02 0.00 +0.02 +0.02 0.00 Aluminum Magnesium +0.01 +0.02 +0.02 +0.02 +0.05 0.00 +0.02 +0.01 +0.02 +0.01 +0.01 +0.01 Cadmium plated +0.02 +0.02 +0.02 +0.02 +0.05 +0.03 steel These samples are as follows: No. 1 is dlbutyl pher.vl phosphate (FH-87); No. 2 is FH-87 and 12$ Acryloid R-3576X; No. 3 is sample No. 2 and 0.5/6 dimer acid; No. 4 is sample No. 2 and 0.1$ sulfurized terpene and ~ 0.9$ phenyl glycidyl ether; No. 5 is sample No. 2 and 0.5$ dibenzyl sulfide and 1.0$ phenyl glycidyl ether; and No. 6 is Skydrol 500. Several conclusions may be drawn. None of the Inhibitors studied performed as well as those used in Skydrol 500. The Acryloid viscosity index improver used for Skydrol 500 had little effect on the oxidation and corrosion character istics of the base stock. Douglas Aircraft personnel found that ethylene bis (tolyl sulfide) functioned very satisfactorily in Skydrol 500 and the search for other new materials was not pressed. However, the ethylene bls(tolyl sulfide) was not readily available and was quite expensive. A number of materials were screened by Douglas and by our laboratory but none were found to be nearly as satisfactory as that presently used. Samples of sulfur containing materials were requested from Nitro and together with several others were used to prepare Sky drol 500 like, formulations which were run in the . . regular Oxidation*and Corrosion Test (MIL-F-710C' * specification). The data obtained may be summarized Me Slyfcrc andex Imp inmCrOrnSf3lC.il. m DSW 620648 I_J "ft Vf-f f W v ft STLCOPCB4094675 f - SamDle 1 S9 - i i r . v i Fluid Effectfon' metals* w t change- J Acidit:Vi HN Loss in mg.'per sq . cm. Initial Pinal f> Cu Cd/Fe Pe Mg A1 l.Skydrol 50C Base 2.Skydrol 500 3.Base + J-1362 i 4.Base + J-I363 i 5.Base + M-2 b.Base + N-4713 7.Base + N-3337 ; B.Base + N-5520 ! 9*Base + N-125 llO.Base + Rosin 1 Amine D 0.04 0.07 0.09 0.09 0.06 0.10 0.07 0.09 0.08 0.20 0.85 0.09 0.68 0.73 2.42 2.40 0.21 3.98 0.5 0.9 0.9 0.9 1.1 1.1 0.9 1.1 0.15 2.25 1.1 0.8 \ - 3.00 +0.02 +0.02 +0.01 +0.02 - 0.30. 0 +0.01 -0.01 0 - 0.72 -0.03 -0.02 -0.01 -0.02 - O.96 -0.01 -0.02 0 0 - 9.89 -0.16 -0.01 0 -0.66 -13.7 0 -0.01 0 +0.01 - 0.92 -0.16 + 0.02 -0.02 0 -18.3 0 0 -0.21 0 - O.52 0 0 +0.05 +0.02 -21.0 1-0.12 +0.04 -1.45 1+0.02 1l contains the regularly used copper deactivator (0.5$) and inhibitor (phenyl glycidyl ether, 1.0%). Materials J-1362 (l,2-di(t-butylmercapto)ethylene) and J-1363 (1,2-dif t-octy lmercapto )ethyle.ne ) from Dayton and N-4713 (di-o-ethylphenylthiourea), N-3337 (P, 6'-truc-dlproplonltrile), N-5520 (diphenylthiourea) and N-125 (bis/2-(2-benzothiazolyl:nercapto)ethyl:/ether'i from Nitro were examined as copper deactivatcrs at 0.5$ concentra tion with 1% phenyl glycidyl ether and 98.5% Skydrol 500 Base. Materials M-2 (benzo( c )cinr.oline 5 oxide) and Rosin Amine D were examined as combination deactivatorinhibitor additives at 0.5% concentration in Skydrol 500 Base. None of the materials examined appear to be as effective as the presently used additives. Copper attack and acidity development were greater in all cases, copper attack actually being increased by the additives in somes cases. A series of inhibitors and metal deactivators were studied previously lr. Skydrci 500 type formulations the Oxidation and Corrosion Test. In an effort to shorten and simplify such screening, a heat test was run on the same samples. Samples were held at 150C. for 46 hours and examined for weight loss, acidity development, and color development. Results are as follows: > * . - - i* i ** ' Weight Acidity Color, Gardner^ Sample Lcss,% Initial! Final Initial! Final 1 29 u7' 9.5 P .;7 ij t-f a DSW 620649 Hfff tlSEL fj] STLCOPCB4094676 Ft ll t li IiHWtyrffmenyi f . phosphate B2 Skydrol-500 B3 J-1363 ; B4 J-1362 B5 N-3337 : \'' f - .. y- V s frlf I f0.02' 22.7 If iln 24.3 0.04 12.8 2 5 29.2 0.09 18.9 2 14 25.9 0.09 23.9 2 8 21.4 0.07 23.0 2 12 The identity of samples is as follows: Skydrol 500 is regular material, M-2 is Skydrol 500 Base with 0.5# benzo(c)cinnoline 5 oxide, and all other samples con tained Skydrol Base with 1.0# phenyl glycidyl ether and 0.5# inhibitor. These are as follows: N-4713 is dl-oethylphenylthiourea, N-125 is bis/5-(2-benzothlazolylmercapto)ethyl7ether, N-5520 is dlphenylthiourea, N-3337 is (3,vv-thiodiprcprionitrile, J-1363 is 1,2-di(t-octylmercapto)ethylene and J-1362 Is 1,2-di(t-butylnercapto)ethylene. None of the materials appeared successful in surpressing acldlty development. It was concluded that a simple heat test was insufficient for selecting inhibitors and copper deactivators for Skydrol 500. In an effort to improve the heat stability of Skydrol 500, sample's of dlbutyl phenyl phosphate (FH-87) containing various materials were heated in an oven at 150C. for 24 hours. Results are r.s follows: Weight Sample Loss A. FH-87 1.7# B. FH-87 + 0.5# Phenyl -naphthylamlne (PAN) 1.5# C. FH-87 12# Acrylold R3876X 1.8# D. FH-87 + 12# Acrylold R3876X + 0.5# PAN 1.9# E. FH-87 + 12# Acrylold R3876X + 0.5# Oronite 250 2.6# F. Skydrol 500 l.S# These data Indicate that neither phenyl c^-naphthylamir.e nor Oronite 250 (a dialkyl sellnide) are effective in reducing weight loss at 150C. due to decomposition in either Skydrol 500 or its components. 6. Thin Film Corrosion Tests The Naval Air Experiment Station had been testing: Skydrol 500 and reported considerable corrosion in the thin film corrosion test at 225 To help correlate our data .with; theirs! and ,, sipci we. .had never, run this particular tdsfcoft fj|re^ca!r?iecl >ojut. j Mejtill | t i I clfl Sr j Ln< T Ld: DSW 620650 STLCOPCB4094677 rtfi. fI Konlnflammahl! _ aejTXircraifi , W using_ Skydrol* 500; * sets fof samples we: 225*F., and one set at 200#F. The specification calls for a temperature of 200*P. ` $ ! The procedure used can be summarized as follows: metal panels (provided for this test by the Navy and polished by them) were cleaned by boiling one minute in isopropyl alcohol, one minute In C.P. benzene, wiped with filter paper, and then boiled one minute In C.P. benzene. Each panel was weighed and the following pairs were placed In six ounce screw cap bottles containing 150 ml. of Skydrol 500: steel and copper, steel and 24ST aluminum, and steel and 6lS aluminum. The metal panels were completely immersed In the fluid and allowed to soak for five minutes. The thoroughly wetted surfaces were then put together so that the steel was uppermost in the couple. The bottle was sealed with the cap, an aluminum liner being used to prevent contact between the vapors and the regular plastic cap liner. The Jars were then placed in an oven held at the desired temperature for 14 days. The samples were identified a3 follows: 1. Steel and Copper at 225F. 2. Steel and Aluminum 24ST at 225F. 5. Steel and Aluminum 6lS at 225 r. 4. Steel and Copper at 225F. 5. Steel and Aluminum 24ST at 225F. 6. Steel and Aluminum 6lS at 225F. 7. Control, Skydrol 500 only, at 225F. 8. Steel and Copper at 200F. 9. Steel and Aluminum 24ST at 200F. 10. Steel and Aluminum 6lS at 200F. 11. Control, Skydrol 500 only, at 200F. The following observations were made during the test: At no time were the bottles removed from the oven or the metal specimens disturbed in any way. At the end of seven days, all bottles containing copper specimens had some precipitate. Bottle 1, at 225F., had some solids but the fluid was clear while the fluid in bottle 4, also at 225F., was cloudy. The precipitate was white to blue in both cases. The fluid in bottle 8 at 200F. was also clear and therejwas some precipi tate present. All other bottles were free*of precipi tate and cloudiness. After ten, twelve, and fourteen days, the same reaultsswere observedtexcept ithat the amoun.t. ;o* -f precipita* t-e' *n thei bottledicpitiairtLnl jt( * III. . . . . . . . . . .pper ^increased tsjj 1 ? I I i Ii ' "At the end of exai iViitii [ou ................ imcfoec* frof ' '' .. I DSW 620651 *11 STLCOPCB4094678 Mi,... ,...,_ , 1 their made f, aerie.s-i"f run at 225 --a - - If f 3 v^will be describee first. The fluid in bottles 1 and 4 (copper) was darker than the control (bottle 7) that in bottle X being clear and that in bottle 4 teing cloudy. There was some precipitate in both bottles 1 and 4. The fluid in bottles 2, 3, 5 6, and 7 was perfectly clear and of the same color. The metal specimens were removed from the fluid. The small amount of solids on the copper drained with the fluid from the specimen. In all cases the metals slid apart easily, there being no tendency to stick. The metal specimens were cleaned in the same manner as before the test. The copper specimens were changed in color and appeared to be lightly eoched with the contact surfaces being stained. A very few small pits were observed in the contacting surface of the copper from bottle 4. The steel appeared unchanged from bottles 1 and 4. The aluminum-steel specimens appeared unchanged. However, on cleaning, a small amount of white solids was noted on the contacting surfaces. No precipitate was present in bottles 2, 3, 5, and 6 and none forned cn standing for several days or on cooling to about 8C. The following observations were made on the 2C0F. series: There was less precipitate in the bottle containing the copper (bottle 8) than in those run at 223F. and the precipitate was more gelatinous and less dense. Again, the fluid from bottle 6 was darker than the control but not as dark as the 225F. fluid. Bottles S, 10, and 11 were all the same color and no precipitate was present. The metal specimens slid apart easily. The copper had changed color and was stained on the contacting surface. Only a minute amount of precipi tate was found between the steel-aluminum 24ST couple and none between the steel-aluminum 6lS couple. No precipitate formed in bottles 9 and 10 cn standing for several days. The weight changes for the various specimens are tabulated on page 29. s A series of photographs were taken of the various specimens and fluid after the test. These are listed as follows: A. Test Results At 225F. '- Bottles 1, 2, 3, 4, 5, b, and 7. if? Mill!ti B. Te,st *Rpsiilt4 &t. CC iBottles 8, 9, 10 and 11. i mklie! i- i I emo\ aa .ill tit ?! DSW 620652 STLCOPCB4094679 ftunlmJaUisT -fSteel fi lores flaaediat _ Removal from Fluid. If sa * t" Aluminum 6lS - Steel Couples ImaeCj-utely after Removal from Fluid. ' v Copper and Steel Specimens after Cleaning - Contact Surfaces. H. Copper and Steel Specimens after Cleaning contact Surfaces. Non- 1. Various Fluids after Test. (From left to right) Capper-steel test at 225F. - clear Copper-3teel test at 225F. - cloudy Copper-steel test at 200F. Aluminum 6lS-steel test cooled to 8.5C. with specimens present. Aluminum 6lS-steel test cooled to 8.5C. Control at 225F. Our results differed from those of the Navy in showing much les3 corrosion on copper and less precipitate and in showing' no changes with aluminum. After discussion with Naval personnel, it was decided to repeat these tests at both laboratories. An Important point to be noted In this test was the decreased attack on copper at 200F. as compared to 225F. This emphasizes that Skydrol 500 is satis factory for the temperatures for which it was designed but will attack metals and decompose at higher tempera tures . A second test was carried out to help correlate the results with the Naval Air Experiment Station. A detailed report of the procedure and the results obtained follows: A "thin film corrosion test" as outlined in military specification, MIL-F-7085A (Aer), Fluid; Hydraulic, Noninflammable, Hydrolube. Aircraft was carried out using Skydrol 500, Skydrol, and Hydrolube H-2. The purpose of the test was to confirm results obtained, in the previous test and to obtain comparative *data\ Skydrol 500 and Skydrol were run at test temperatures 225F. and 200*F.; Sk^dr )1 ,500,, Skydrol r dr o-i run. at|. 1( VEhe Isfretjlftcf perature Ml i ,`: inm t H DSW 620653 STLCOPCB4094680 ill $ VO CD ON VJl ., . | f" fO t/j > ro ro ro ro oo oo OO OO ro ro ro ro ro ro ro ro ro ro ro ro ro ro vjivji ro ro VJl VJl ro ro VJl VJl ro ro vji on VrJo1VrJo1 rVoJ1VroJ1 ro m ro i-- ro vji ro m ro m roui ro m ro m ro ui mo oj cr\ Vrl OS ro 04 04 \J1 ro On 04 04 VjJVJl as O* 04 * ^ ^s ro om cxj ro VO 4=- -Cr 04 ^JVO M VJl VJl CM I-* rr<M X3 VJl -S ro o ro -tr -frVD -s crs Ov ON Ql -tT -trCO ro a- h- so ro as ova ro *r CO-tr 04 01 ro -fr so 03 -a o on as cd 1- -s -eroo -S CO Vji rsj VJl \J1 M -Cr M p [M I-1 3 P ct (U9 d D PPO> f # I *I II ^o vji as II oo sos 1 V--1 * ro vji O vji ii I-* O CD--s ii MO vo -er ii ~>3 H Co vji oo 11 Po l-b 1+ OO -nJ M 11 t--' hCO04 vo ' >:) P- o 3 a p M ct O if OrtT) *i lJ'vJJl\sAxJ o o i ii ii oo i oo <o_iv i4ro mr xftpv CO $3 IS M DSW 620654 Htf i H tn STLCOPCB4094681 m I by them) were cleaned by boiling one minute in iso- ' propyl alcohol, one minute in C.P. benzene, wiped with filter paper, and then boiled one minute in C.P. benzene. Each panel was weighed and the following pairs were placed in six ounce screw cap bottles containing 150 ml. of test fluid: steel and copper, steel and 24ST aluminum, and steel and 6lST aluminum. The metal panels were completely immersed in the fluid and allowed to soak for five minutes. The thoroughly wetted surfaces were then put together so that the steel was uppermost in the couple. The bottle was sealed with the cap, an aluminum liner being used to prevent contact between the vapors and the regular plastic cap liner. The Jars were then placed in an oven held at the desired temperature for 14 days. The Jars were examined daily for visual changes. At no time were the Jars removed from the oven or the metal specimens disturbed in any way. The samples are identified in Table 1. The numbers are used to identify the samples throughout the test and in the photographs taken at the end of the test. The observations made during and after the test will be reported by grouping the samples according to test temperature. The results of the 225F. test will be reported first. During the first four days darkening of the copper was observed. On the fifth day a small amount of fuzz was noted on the steel in the copper-, steel couples in Skydrol 500 and the fluid was hazy.** The steel in the copper-steel couple in Skydrol (Jar 7) appeared to have rust spots although the fluid was clear. On the sixth day the fluid in Jar 1 was clear and that in Jar 4 was hazy and the amount of fuzz on the steel had increased (Skydrol 500). Sediment was forcing in the bottom of both Jars. These phenomena became more marked on the seventh and eighth days and on the eighth day the fluid (Skydrol) in Jar 7 became hazy. By the tenth day the fluid in Jar 4 was clear and considerable brown sediment was noted in both 1 and 4. On the eleventh day a haze was noted in Jar 9 for the first time. (Skydrol with aluminum 6lST-steel , couple). Little change was noted from the eleventh day to the end of the test. At no time wa3 any sediment or ^noticeable change observed in Jars 2, 3, 5,, and 6 ythlch '- ` ` " iOQ I fM m rjr^ti&ris ;1' 4rid gil *1* DSW 620655 STLCOPCB4094682 1.1 v % perfectly clear and of the same color. No precipi' tate formed In these even after several days at room temperature. The fluid (Skydrol) in bottles 7, 8, and 9 was cloudy and considerable fluffy solid was present in all Jars. None was observed in the control (Jar 11). On standing several days at room tempera ture no sediment was noted in Jar 11 while some material settled in Jars 7, 8, and 9. The metal specimens were removed from the fluid. In all cases the specimens slid apart easily, there being no tendency to stick. The metal specimens were cleaned in the same manner as before the test. The copper specimers were changed in color and non contact surfaces appeared to be lightly etched with the contact surfaces being stained. The steel from the copper-steel couples appeared to be lightly stained. On cleaning the aluminum-steel samples, a snail amount of white solids was noted on the contacting surfaces. Removal of these solids by cleaning left some small stains. The steel from the aluminum-steel couples In Skydrol appear to be etched and was discolored. The weight changes of the metal specimens are given in Table 2. Photograph 1 shows the fluids in the Jars after the test had been completed. Photographs 2 and 3 show the metal surfaces after cleaning, contact and non-contact surfaces, respectively. , t The weight loss data for a previous thin film corrosion test on Skydrol 500 at 225F. and at 200F. are given in Table 3 for comparative purposes. All weight losses are calculated on a total surface area of 40 sq. cm. since the specimens are fairly uniform. The observations made cn the test at 200F. are as follows: During the first five days no changes were noted except for a slight darkening of the copper. The fluid in jars 13 and 16 (copper-steel in Skydrol 500) appeared to be slightly hazy on the sixth and seventh days but no deposit was noted on the metal specimens until the eighth day. The amount of deposit f . I Increased slightly from day to day until5 the end of ]the test in Jars 13 and 16 and a small amount settled to the bottom of the Jar. The solid material was blufsh-whfte and f luffy as^ compareditp Jthe.sidarikl itainei jars. DSW 620656 STLCOPCB4094683 f- | 1115 At the end of the fourteen-day period, the Jars were r - removed from the oven. The fluid (Skydrol 500) in ? Jars 15 and 16 was darker than in Jar 22, the control, and a fluffy bluish-white sediment was present. The fluid (Skydrol 500) in bottles 14, 15, 17, 18, and 22 was perfectly clear and of the same color. The fluid (Skydrol) in Jars 19, 20, 21, and 25 was perfectly clear and of varying shades of green. No precipitate formed in any of the Jars from this test (except 15 and 16 where it was already present) on cooling to room temperature and allowing to stand for several days. The metal specimens were removed from the fluid. In all cases the specimens slid apart easily, there being no tendency to stick. The copper specimens were changed in color and the steel specimens from the copper-steel couples were covered with a small amount of solid which was readily removed by the cleaning procedure. All other metal specimens appeared to be essentially unchanged. The weight changes of the metal specimens are given in Table 4. The fluids in the Jars areshown in Photograph 4 and the metal specimens are shown in Photographs 5 and 6, contact and non contact surfaces, respectively. The weight loss data from a previous thin film corrosion test on Skydrol 500 at 200F. are given in Table 5 for comparative purposes. During the l60F. test the following observations were made: There were no changes observable in any of the Jars during the entire test except for a slight darkening of the copper specimens. At the end of the fourteen-day period, the Jars were removed from the oven. No change was noted. However, on cooling the fluid (Hydrolube H-2) in jars 24. 25, and 26 to room temperature after removal of the specimens, a slight cloudiness was noted and a black sediment settled to the bottom. The fluid (Skydrol 500 and Skydrol) in all other Jars was clear after several days at room temperature. Colors were quite similar to those of the control samples. On removing the metal specimens from the Jars, it was i * found that they slid apart easily, there being no tendency to stick. The metals from the Hydrolube Hr2 test, wllj (described first. jT1 'ighj | Mid (shi jtajr^s on the c.ont |th| ' csxeelffrj (Saif 24)f e^-gteelj cc^ip] fed U hJsk * m DSW 620657 m t- K f* STLCOPCB4094684 rift 33. * f '* ? f < . * k ' ' the cleaning leaving stains. The copper specimens from the Skydrol 500 (jar 27) and the Skydrol (Jar 50) were darkened and stained slightly on the con tact surfaces. None of the other metal specimens from Jars containing these two fluids were changed in any way. The weight changes of the metal speci mens are given in Table 5. Photograph 7 shows the fluids after the test. Photographs 8 and 9 show the metal specimens after cleaning, contact and non contact surfaces, respectively. The test data given in this report point up the variations that can occur in such a test method as the thin film oxidation test. Skydrol and Skydrol 500 exhibit 3ome corrosion to copper at any tempera ture studied but are entirely satisfactory toward aluminum and steel. It is of interest to note chat Skydrol 500 at 200F. exhibits similar copper attack to that of Hydrolube H-2 at l6oF. with lesser steel attack. The results of the tests may be summarized as follows: Results from test to test and even among samples in the same test do not appear to be reproducible depending greatly upon the surface condition of the metal specimens and other factors. This has also been observed by the NAES testing. Skydrol 500 and Skydrol exhibit some corrosion to copper at any temperature studied, the amount of corrosion increasing with increasing temperature. These results have also been observed in the oxida tion and corrosion tests as normally run. Skydrol 500 and Skydrol are entirely satisfactory toward aluminum and steel. It is of interest to note that Skydrol 500 at; 200?. exhibits similar copper attack to that of Hydrolube H-2 at l60F. with lesser steel attack.. p% I: DSW 620658 STLCOPCB4094685 STLCOPCB4094686 riff i ' 35. TABLE 2 METAL SPECIMEN WEIQHT CHANGES -- 225F. TEST Metal Fluid Original Weight,g. Total change in weight,mg. Change in weight,: per sq. Ccpper Steel Skydrol 500 53-4356 23.5722 -57.5 + 2.2 -1.44 +0.00 A luminui. 24ST Steel 16.6033 236590 + 0.2 - 0.8 + 0.01 -0.02 Aluminum 6lST Steel 15.7954 23.1940 - 0.8 - 1.2 -0.02 -0.03 Copper Steel 53.1519 15.6254 -40.4 + 5.9 -1.01 +0.15 Aluminum 24ST Steel 16.7029 ? 23.0874 - 0.4 - 0.8 -0.01 -0.02 Aluminum 61ST Steel 15.5560 20.0069 + 1.2 + 0.1 +0.03 0 Copper Steel Skydrol Aluminum 24ST Steel Aluminum 6lST Steel , 53.3210 21.2964 17.0472 18.9982 15.4622 } f2^. 3686 ,, - 6.6 -12.2 +1.4 -18.8 + 2.2 -20.1 -0.17 -0.31 +0.04 -0.47 +0.06 . {|0.50 I t: ; : DSW 620660 STLCOPCB4094687 m 3P 36. TABLE 3 METAL SPECIMEN WEIGHT CHANGES -- SKYDROL 500 Metal Original Temperature Weight,g. Copper Steel Alumlnum 24ST Steel Aluminum 6lST Steel Copper Steel Aluminum 24ST Steel 225F. ti 1 l |! - ft 53.5261 23.5494 16.1641 23.7427 15.9475 23.7635 53.3652 23.4633 16.4648 22.9787 Alumlnum 61ST Steel *1 If 15.3948 23.7424 Copper Steel Aluminum 24ST Steel 200p. II It 53.2497 22.6201 16.1068 23.0226 Aluminum 9?Tt * * f% *,.| Steel r ' 16.2795 23.7570 Total change in weight, mg. -61.9 - 1.3 + 0.1 - 0.7 - 0.7 - 1.1 -78.8 - 1.5 - 0.4 - 1.9 - 0.7 - 1.6 -15.5 - 2.0 - 0.6 - 0.7 - 0.6 - 1.5 Change in weight, mg, per aq. cm, -2.05 -0.03 0 -0.02 -0.02 -0.03 -1.97 -0.04 -0.01 -0.05 -0.02 -0.05 -0.39 -0.05 -0.02 -0.02 -0.02 -0.04 I? DSW 620661 i* rf f fff i t f fl I l STLCOPCB4094688  I. i %V TABLE 4 METAL SPECIMEN WEIGHT CHANGES -- 200F. TEST Jar No. Metal Fluid 13 14 15 16 5 ; t 18 Copper Steel Aluminum 24ST Steel Aluminum 61ST Steel Copper Steel ^^umlnum 24ST * * Steel Aluminum 61ST Steel Sky(d( rol 50i 0 ti II V 11 " 11 ft n If 11 II It tl 11 11 It 19 Copper Steel Sky1d1 rol 20 Aluminum 24ST Steel - 11 ii 21 Aluminum 61ST f f Steel * 11 11 4 5 Original Weight,g. Total change in weight. 53.0064 21.9960 -13.4 - 1.6 17.0990 19.0333 - 1.7 - 0.8 15.8269 23.4393 - 2.0 - 1.6 52.4116 23.0129 -25.6 + 0.1 16.7492 23.7303 - 1.2 - 1.2 15.7112 21.5281 53.0931 23.9586 - 0.2 - 1.3 -65.1 - 1.1 17.3663 22.7990 - 0.3 - 1.0 16.1604 - 0.5 21.5514 * : - 0.9 Change m weight,mg per 3q.C:.; -0.34 -0.04 -0.04 -0.02 -0.05 -0.04 -0.64 0 -0.03 -0.03 -0. 01 -0.03 -1.65 -0.03 -0.01 -0.03 -0.01 -0.02 hl| nil l'`tilt* DSW 620662 :M U Htl STLCOPCB4094689 I TABLE 5 METAL SPECIMEN WEIGHT CHANGES -- 160F. TEST Metal 24 Copper Steel Fluid 25 Aluminum 24ST Steel 2b Aluminum 61ST Steel 27 Copper Steel Skydrol 500 2o Aluminum 24ST Steel 29 Alumlnum 61ST Steel 30 Copper Skydrol Steel 31 Aluminum 24ST Steel 32 Aluminum 6lc-T Steel Original Weight,g. 52.3658 22.1810 16.8112 21.7205 16.2667 23.9669 54.6217 24.3267 16.9318 24.4910 16.1940 22.9145 54.2995 23.9531 16.6345 19-4128 15.9833 23.6478 Total change in weight,g. -18.1 - 2.0 - 0.7 - 3.6 - 1.5 - 5.2 - 6.1 - 1.7 - 1.5 - 1.7 - 2.0 - 0.9 -20.5 - 1.5 - 2.1 - 1.2 - 1.0 . i - 1.1 Change weight,! per sq. -0.45 -0.05 -0.02 -0.10 -0.04 -0.13 -0.15 -0.04 -0.04 -0.04 -0.05 -0.02 -0.51 -0.05 -0.05 -0.03 -0.03 -0.03 ! 1 t* t I DSW 620663 STLCOPCB4094690 m- f | : i' 2f A list,of?the captions for photographs 1 through 9 are as follows: ' '* * :i f. f # ' ' ' if Photograph 1 - Fluids From 225F. Test v Copper-steel Aluminum 24ST-steel Aluminum 6lST-steel Controls 1,4-Skydrol 500 2,5-Skydrol 500 7 - Skydrol 8 - Skydrol 3,6-Skydrol 500 10-Skydrol 500 9 - Skydrol 11-Skydrol Photograph 2 - Metals From 225*F. Test - Contact Surfaces Copper-steel Aluminum 24ST-steel 1,4-Skydrol 500 2,5-Skydrol 500 7 - Skydrol 8 - Skydrol Aluminum 6lST-steel 3,6-Skydrol 500 9 - Skydrol Photograph 3 - Metals From 225F. Test - Non-Contact Surfaces .. , Copper-steel Aluminum 24ST-steel 1,4-Skydrol 500 2,5-Skydrol 500 7 - Skydrol - Skydrol Aluminum 6lST-steel 3,6-Skydrol 500 9 - Skydrol Photograph 4 - Fluids From 200F. Test Copper-steel Aluminum 24ST-steel Aluminum 6lST-steel Controls 33,16-Skydrol 500 14,17-Skydrol 500 15, lG-Skydrol 500 22-Skyarcl 500 19- Skydrol ' 20 - Skydrol 21 - Skydrol 23-Skydrol Photograph 5 - Metals From 200F. Test - Contact Surfaces Copper-steel l3,i6-Skydro] 19 - Skydrol Aluminum 24ST-steel Aluminum 6lST-steel 14,17-Skydrol 500 ' 15,l8-Skydrol 500 20 - Skydrol 21 - Skydrol Photograph 6 - Metals From 200F. Test - Non-Contact Surfaces Copper-steel 13,16-Skydrol 500 19 - Skydrol ' Aluminum 243T-steel 14,17-Skydrol 500 20 - Skydrol Aluminum 6lST-steel 15,13-Skydrcl 500 21 - Skydrol Photograph 7 - Fluids From lb00F. Test Copper-steel. * 24-HydrO lul>^ H-2 27-Skydrol 500 30-Skydrol Aluminum 24ST-steel Aluminum 6lST-steel Controls l^5-$ydfoiuhe H-2 26'-Hydro*lube H-2" 35-Hydrolube H-2 '28-Skydrol 500 il-Skydrol 29-Skydrol 500 32-Skydrol 34-Skydrol 500 35-Skydrol X it-li I |i| i I If-f cel t'Pv- i HI % If. M iitv iP DSW 620664 STLCOPCB4094691 iI f M t M 1 Hydrolytlc: Stability *' | ^ '' Considerable concern had been expressed by potential users of Skydrol 500 concerning its hydrolytic stability. Tests were, therefore, started to study Skydrol 500 in the hydrolytic stability test, to compare Skydrol 500 and regular Skydrol (7000) in the test and to examine the test procedure. Data for the first two runs are given in Table 6. * v - V ) I The data were obtained by a modified Hydrolytic Stability Test from military specification MIL-F-7100, the so-called "coke bottle" test. The general procedure calls for sealing 75 grams of test oil, 25 grams of water, and a copper test strip in a coke bottle" and rotating end over end in an oven maintained at 95*C. (200*F.). After 48 hours the bottles are removed and the contents examined. Certain modifications in the test procedure were made. These modifications nay be described as follows: The time, temperature, rate of rotation, apparatus, and charges are the same as for MIL-F-7100. The copper specimen is cleaned by the technics used for Oxidation and Corrosion Tests -- including both benzene and acetone washes and not scrubbing with a stiff brush as recommended in the specification method. After the test has been completed, the procedure calls for centri fugation to remove the sludge and weighing of the centrifuge tube after drying to obtain sludge weight. This procedure may be satisfactory for fluids with low specific gravity but is not too feasible for our fluids. We do not centrifuge but obtain sludge by filtration through tared fritted glass filter crucibles, washing the sludge with water. Drying and reweighing gives the sludge weight. * f- In the tests described, we did not wash the fluids until the wash water was neutral to litmus as called for in the specification. The fluid was given one water wash jand >then^ dried. * Vie then determined total * acidity by'titration of both the water and the oil layers. Our total acidity results would probably have been^the same if weihad removed the water soluble m a bcocedur^ is . lddg; iiderabie fcarellt&filrfeke S41 ill1 > m cie LmJ a? > 111*? feai I DSW 620665 STLCOPCB4094692 mould shaI|$fkS.t ibe greater than 0.5: NN and the acid content of water .layer and washes shall not eosnseed By our calculation method tfttis means that the increase in acidity shall not be greater than 0*63 NN. Our acidity values are calcu- lasfced as neutralization number for the oil layer as xlt stands. - Aoidity values for the water layer are caUculated on the basis of 75 grams of fluid charged, the entire water layer and wash being titrated. The viscosity change shall not be more than -5 to +15 per- cent from the original viscosity at 130F. The amount of material (sludge) shall not be greater than 0,5 per cent, or 0.375 grams. Our data indicate that Skydrol 500 fails on acidity development and copper attack. Skydrol 7000 fails on "the same properties but is closer to specification li.-mlts. As is expected with copper losses of greater than 2 mg. per sq. cm., such losses are not too reproducible from test to test, and we have varia tions of from 2.96 to 5.01 in our tests on Skydrol 5CC-. Test 8, bottles 2 and 4, were run without copper. It appears that acidity development is greater without copper. The test seems fairly reproducible except for high copper attack fluids. We slave previously run this test on the base stock used! for Skydrol 500. Copper weight changes of-3.8 to -5.2 mg. per sq. cm. and total acidities of 2.06 to 2.15 jNNtKei^fo|und. These data are in line with thce obtained on the finished fluid. The= -significance of the test described here in regard to service of the fluid is not known. Obviously Skydtrol 7000 does not pass the test and yet has shown re.-c^arkabie servicei life. Skydrol 500 is poorer on hydrolytic stqbillity.both by this test and others. Further test work was undertaken on Skydrols 7000 and 500- using the ."coke bottle" hydrolytic stability test. The: results are|summarized in Table 6. The method used! is the^ same as ^described .except that drying of* the 3 1* in rurfe and 13 was accomplished by evacuation. Resu#tsi |r4%ie iskm^^i^|qd- I1U: ft m f* 111 !l! STLCOPCB4094693 STLCOPCB4094694 .; .. . 42. - i, i s i ' t The data of test 8 show that copper seems to affect; the test using Skydrol 500 only In that less acidity is found when copper has been used. Attention is called to the better performance of Skydrol 7000 as compared to Skydrol 500 (test 9) and the fact that neither are within the MIL-F-7100 specification limits. Since 25% water seemed too great from practical standpoints and since various discussions indicated that 2% water might be a better figure, tests were run usJng various concentrations of water. Test 10 results indicated lessened copper attack and acidity development for Skydrol 500 and Increased for Skydrol 7000 using 2% water. With both fluids, excess water was present at the end of the test. However, during the tests all the water was in solution in the Skydrol 500 samples but not in the Skydrol 7000 samples. Test 12 was run since it was thought that undissolved water might be necessary to get copper attack. Both 1% and 2% water were used. It appears from the results that our assumption was incorrect since with Skydrol 7000, similar results were obtained at 1% and--25# water. Furthermore, using less water with Skydrol 500 (1% compared to 2%) gave increased copper attack and decreased acidity. A series was also run (test 13) increasing the water content. The best results were obtained with 2%. It should be noted that results are comparable from test to test at the same water concentration. .. . ?| ' Based on these data, it appears that Skydrol 500 is within specification limits only in test 12, bottle 2, in which 1%, water was used. Copper attack is just at the upper limit. It is interesting to compare the performance of Skydrols 7000 and 500 at low water concentrations, 2% or less, where copper attack is less for Skydrol 500 and acidity development is about the same. Based on service life of Skydrol 7000, these phenomena might be interpreted to mean that Skydrol 500 would be satisfactory from a.hydrolytic stability standpoint. ,. : . ^ | If I : ` Hydrolytic stability tests using the' Vcoke bottle" technic had shown that the results wlthjSkydrol type fluids depend atloni (fofet< iesired |tb 'cfe jfpe |es teplba! conducted it k1 ui DSW 620668 rut'' '7 T - - ' t STLCOPCB4094695 * ' * *** If Test Number 1 :i Fluid charged,g. Water charged,g. 18-3 ww 18-4 Acidity, NN Initial Oil layer Water layer Total 0.13 0.01 0.28 0.29 0.13 0.02 0.23 0.25 0.13 0.02 0.25 0.27 0.13 0.02 0.24 0.26 Viscosity,cs.,130F. Initial Final 8.78 8.71 8.78 8.75 8.78 8.74 6.78 8.76 Effect on copper, wt. change, mg./cm.2 0.00 0.00 0.00 0.00 Sludge weight, g. 0.023 0.056 0.01s 0.012 Solubility of Water in :Skydrol 500 The procedures given in the section on Pydraul F9 were used to determine the solubility of water in Skydrol 500. The results were as follows; Solubility of water at 75F. Solubility of water at 210^. ' * * trerage: 2.1756, 4.2256, 3-9956 4.1# 2.2956 5-9956, 4.1956, . The acidity of the Skydrol 500 was measured before and after exposure to conditions similar to the water solubility determination at 210F. for an extended period. The initial acidity was 0.05 NN; after about 4-5 hours, 0.24 NN; and after 10 hours, 0.3& NN. Skydrol 500 from WADC Packing Test A sample of Skydrol 500 from a packing test at Wright Field wa~s examined. The fluid was quite dark but was easily clarified by filtration through Attapulgus earth. This ^reduced the acid number from 0.21 NN to * 0.12 NN. Spectrographic analysis showed the presence of silicon. It Is apparent that the fluid had become contaminated Mulling ihSi test. ien f the b DSW 620669 M*\ STLCOPCB4094696 m Hr Fluids OS-H? and OS-45-1 j. ,. Fluids OS-45 and OS-45-1 are derived from a tetraalkyl silicate base stock. These fluids have found considerable use as dielectric coolants and high temperature hydraulic fluids. Most of the work concerned with these fluids is reported In final reports on Job numbers 117-2380 and 117 2507. However, certain of their characteristics were studied under this job number following routines establish ed in the study of other fluids. The data are given in this report under section M in order that both method and results may be in one place. Fluid OS-41 1. Inhibitor Studies Fluid OS-41 was developed as a high specific gravity synthetic torque converter fluid. It consists cf Aroclor 1248, Santlcizer 141, Acryloid HF-855 and a defoamer. The fluid was of interest to several potential users and several five-gallon lots were prepared. -- It was reported that Fluid OS 4l attacks steel at high temperatures in the presence of asbestos clutch plates. A regular oxidation and corrosion test was run at 250F. for 168 hours using Fluid OS-41 and OS-41 with inhibitors. The data are as follows: Sample 1 * 12 ! f ^ It '4 < * -5 Initial Final 130F. 13.81 15.22 14.26 15.86 14.05 14.08 14.19 14.91 13.99 15.44 14, Acidity, NN Initial Final 0.04 0.31 1.86 2.36 0.03 0.30 0.05 0.10 0.06 0.31 2.05 Fluid evap.,56 1.2 1.1 0.9 1.2 1.7 1.5 Effect on metals, wfc. change,:mg./cm.2 Copper -1.49 -0.04 , Steel? -0.02 +0.01 Luml^um| | V 0. i^nesium | -d. - |dmidnf 11 ~(t. pfate< s"teeft 1 '* h QS-i ? -fM.-tt- f -0.12 -0.43 -0.8: 0.0Q i jQ.OQ -0.25 0.00 DSW 620670 it -i.rr < * > * * * * * > 'TV * XV STLCOPCB4094697 IS ; ' fevi contain various additives. These are: sample 2, 1.0# Emery's dimer acid; sample No. 3, 1.0# phenyl glycidyl ether; sample No. 4, 0.9# phenyl flycldyl ether and 0.1# Shell's WDS; sample No. 5, 1.0# phenyl alphanaphthylamlne; and sample No. 6, 1.0# Santolube 394c. The data show that under the conditions of this test, steel was not attacked. However, copper, magnesium, and cadmium plated steel were corroded. All addi tives except phenyl alpha-naphthylamine suppressed magnesium and cadmium plated steel attack and decreased copper attack, dimer acid and phenyl glycidyl ether being most effective. 2. Hydrolytic Stability A regular "coke bottle" hydrolytic stability test was run on Fluid OS-41 and several other fluids for comparative purposes. Results are as follows: Fluid Pydraul F9 OS-41 OS-54 Acidity, NN Initial Water layer Oil layer Total 0.08 0.03 0. Oo 0.11 0.17 0.16 0.12 0.28 0.16 0.19 0.11 0.30 Viscosity,cs.,130*F. Initial . Final - , # Change . 20.91 20.13 -3.7 13.94 13.75 -1.4 22.05 21.93 -0.5 Effect on copper,wt. change, mg./cm.2 Sludge, weight, g. -0.05 0.002 -0.22 -0.20 0.014 0.021 These results indicate that all three fluids would pass MIL-F-7100 requirements, the military specifica tion from which the test was taken. 3. Physical Measurements I | : f i I- ; 5 * Data 'Concerning* specific heat and thermal conduc- ' : ' -i tlvity for Fluid OS-41 are given in Section K of this report. ,i - fell a w 3a STLCOPCB4094698 Viscosity,cs210 F. 100*F. Viscosity Index Acidity, NN Sp. Or., 25/25C. Flash Point, F. Fire Point, F. Pour Point, F. 3.25 15.68 72 0.20 1.0644 385 445 -45 3.15 15.53 65 0.21 1.0649 340 425 -55 The final formulations seem quite similar except for somewhat higher flash, fire, and pour points when Ucon DLB-50E is used. A sample of the Ucon DL3-50E was suDmltted to Douglas and was approved by them for use in Fluid L-3A. Data concerning specific heat and thermal conductivity are given in Section M of this report. Fluid OS-54 i% * Formulation Data STLCOPCB4094699 mi -ft | f*f * f f | I : ?' - * | lit was felt that a fluid base'd on equal protlons of ^Santicizer 141 and Aroolor 1248 with a viscosity index improver might be satisfactory. A series of "samples were made up from a base stock (equal weights of Santicizer 141 and Aroclor 1248) and various amounts of Acryloid HF855. The data for these samples as well as the properties desired are as follows: Specific Viscosity at: Vis. Gravity Pour 216^. lOff^FT Index 25/25C Point Base stock 2.65 14.8 -52 Base stock + 5!^ Acryloid H?855 5.53 29.5 135 Base stock + 6% . Acryloid HF855 6.20 33.2 140 Base stock + 7% Acryloid HFe55 Base stock + 8$6 5.95 37.3 144 Acryloid HF855 7.72 41.7 145 Base stock + 9% Acryloid HF855 8.50 46.2 146 Desired properties 7.44 41.6 140 -- -35F. Fluid OS-54 7.64 41.2 145 1.209 -30F. From these data it seemed that the fluid containing 8jC Acryloid HF855 was most suitable. A larger batch was prepared using this formula and sent to Saginaw t?^Steering Gear for evaluation as Fluid OS-54. 2. Preparation of Larger Amounts Since preliminary tests on Fluid OS-54, proposed as a non-flammable type power steering fluid were promising, the prospective customer asked for more v material. A twelve-gallon batch was prepared in the laboratory consisting of Santicizer 141, 46$6 Aroclor 1248, and 8% Acryloid HF855. This lot of OS-54 had a viscosity of 7.41 cs. at 210F., 40.3 " cs. at 100F., and a specific gravity of 1.210 at itiioK C.. These properties are quite similar, to of previous samples! The material was sent :to the prospective customers for evaluation. Lstj the ide\ itiiii ud 'An lc m i p m i STLCOPCB4094700 ___________ Fluid OS-54 W Building Prep. Typical Properties Acidity, NN Moisture Sp. Gr., 25/25C. Viscosity,cs.,+210*P. +100P. Viscosity Index Pour Point Lot V-1277 0.10 0.19* 1.211 7.34 39.46 + 144 -35F. ,04 - .10 1.209 - 1.210 7.26 - 7.72 39.20 - 41.72 +145 -30*F. Fluid OS-54 became of interest to the Navy for shipbeard use and 200 gallons were ordered. It was felt that a defearner would be necessary for this use, there fore four drums of the OS-54 batch were individually defoamed in the Pilot Plant facilities bv the addition of 50 ppm of DC Fluid 200, 330 cs. at 25 grade. The analysis of a composite samples from these four drums, identified as Lot K-250, is as follows: Appearance Moisture Acidity, NN Sp. Gr., 25/25C. Viscosity,cs.,+210F. , , +100F. Viscosity Index Pour Point Pale yellow, slightly opales cent viscous liquid 0.10* 0.11 1.2109 7.24 39.46 +142.7 - 40F. t *- s Twenty gallons of defoamed OS-54 were furnished to Douglas Aircraft Company for testing purposes. Four five-gallon cans of 03-54 were individually defoamed lr. the Pilot Plant. This material was sent under the same analyses as the preceedlng. Hydrolytic Stability The hydrolytic stability of Fluid OS-54 was determined . by the regular "coke bottle" technic. ' The data are * f given in Section E of this report. Fluid OS-54 passes the test. , . HluiJ OJ 1 I II 4 earipli m lot fdi fl i i6 {iwasliptreipaj 4 improue ` 1 W&B !i|: Lne I1#? DSW 620674 STLCOPCB4094701 S' t- - -. i ^ The analysis of this formulation isras follows: ' 5c . 47* - -- - - - Viscosity, 100P. ' 210'F. Specific Gravity,25/25*0. Acidity Moisture Pour Point 44.37 cs. 7.34 cs. 1.2323 0.27 NN 0.12# -25*F. This sample was prepared with the oil-free Acrylold because it is believed that the oil in the Acrylold usually used in formulating this Fluid is the cause of high values obtained in Navy's oxygen demand test and Diesel ignition test. H. Steam Turbine Lubricants Considerable Interest was expressed In a non-flammable type steam turbine lubricant. It was suggested that fluids based on tricresyl phosphate and Aroclor 1242 be studied. A base stock consisting of 25# tricresyl phos phate and 75# Aroclor 1242 was prepared (called ST Ease) and mixtures containing 3 weight per cent (called ST-3) and 4 weight per cent (called ST-4) of Acrylold 794 were also prepared. Data for these mixtures as well as specifications for a steam turbine lubricant are as follows: - > f j f Viscosity,cs,2l0 F. SUS Viscosity,cs,100F. SUS Viscosity Index Four Point,8?. Sp. Or., 25/25C. Acidity, NN Flash Point,F. Fire Point,F. Specifi cations t ** 40 - 50 140 -170 +20 max. ST Base ST-3 f f >' 2.81 1.3044 35.7 21.50 104 -212 43.8 37.74 176 +74 -5 -5 1.3044 0.02 355 665 ST-4 6.42 47.2 44.30 206 + 103 -5 The sample ^labeled ST-3 appeared to be satisfactory from a viscbsit^ and, pcftirfpoint standpoint.! fTwo gallons of fluid were "prepared and submitted to the Engine Test Laboratory jfor demulsification and rust^tests. One 82 tered through Jllterfcpap( ?iy The othei Lit' saiki rbsf Hr 6*2? 1 DSW 620675 l- i STLCOPCB4094702 m- Sample Pydrual F9 Fluid ST-3 Acidity, NN Initial Oil layer Water layer Total 0.08 0.03 0.08 0.11 0.03 0.02 0.05 0.07 Viscosity,cs., 150F. Initial Final % Change 20.91 20.13 -3.7 17.43 17.31 -0.7 Effect on copper, wt change, mg./sq. cm. Sludge weight, grams -0.05 0.002 -0.06 0.009 Comparative data are given for Pydraul F9. Both fluids are quite satisfactory In this test and give similar results. The two samples were"examinea by Mr. D. W. Dinsmore and Mr. E. P. Cunningham In the Engine Test Laboratory. Results are as follows quoting from memos dated 6-22-54 and 7-3-54. "The following physical data have been obtained on two samples of proposed turbine oils: Sample ST-3 Sample ST-3& Viscosity at 100*F.f SUS Viscosity at 210F., SUS Viscosity Index Demulslbility Charac teristies, Minutes to break ASTM D-665* Turbine Oil Rust 10 = perfect Based on these data. It*13 concluded that either lubricant is quite satisfactory with regard to demulsiblllty characteristics, however, the rusting characteristics are very? poo STLCOPCB4094703 - mi -Blend**'.1 ' %. ASTO D-665 Rust* With Without Water W-ish Water Wash ST-Ja 5.5, 3.5 ST-3a + 0.2# (w) Santolube 70 5.0, 5.0 50'ppm Santolene C ST-3a + 0.2# (w) Armeen 10D 50 ppm Santolene C 5.0, 5.0 ST-3a + 50 ppm Santolene C 3.0, 2.0 ST-3a + 500 ppm Santolene C Pydrual F-9, w-62 2.5, 2.5 3.0, 2.0 TCP, V-594 3.5, 3.0 Aroclor 1248, A-614 Aroclor 1242," #194 3.5, 2.5 4.0 *18 hour3 U3ing salt water. Pydrual ?9 has been reported to have borderline rust inhibiting properties, however, our results do not con firm this. The use of distilled water in place of salt water might^be *the answer. A definite improvement over Pydraul P9`Is"shown by the addition of Santolube 70 or Armeen l6D to the ST-3a base fluid." 6 Reasoning from chese data it was concluded that samples containing rust inhibitors should be submitted to interested groups for evaluation. t -. About five gallons of Fluid ST-3a, called Fluid OS-58 for sampling purposes, was prepared. This material consists of 356 Acryloid 794, 24.2535 tricresyl phosphate, 72.75% Aroclor 1242 and 50 parts per million silicone defoamer (DC200 --350'; os.).. Part of the fluid was convertedto Fluid 'OS-58411-tfy? the addition' of 50 parts per million Santolene C fend 0.1# Santolube 70. The rest, was converted to Fluid pS^8-;2; by^ the;addition of 50 parts per million S&rtoleQ 11. lie i ter 5 aim ft 3$ is lea: Him, [Sf m DSW 620677 STLCOPCB4094704 14 Fluid OS-58-1 os-58-2 Visoosity,C3.,210F. . 100F. Viscosity Index Pour Point, F. Acidity, NN Sp. Or., 25/25`C. 5.28 56.39 +84 -5 0.07 1.301 5.32 36.64 +79 -5 0.09 1.301 Low Temperature Industrial Fluids (Fluid OS-57) There are many applications for non-flammable type Indus trial hydraulic fluids that cannot be filled by Pydrual F9 because of Its low temperature properties. It was suggested that other fluids of the phosphate esterAroclor type, in addition to those already studied, be examined. It was felt that the mixture of 30# 2-ethylhexyl diphenyl phosphate (FH41) and 70# Aroclor offered promise as a base stock. Fluids were examined starting with those containing Aroclors 1248 and 1242 in equal mixture and finally ending with those containing only Aroclor 1242.as the Aroclor portion of the base stock. The following system of naming was used: LT-1 Base consisted of 30# FH4l, 35# Aroclor 1248, and 3556 Aroclor 1242. The amount of Acryloid 794 added as viscosity index Improver was indicated by the use of a second number. For exaple, LT-1-5 means 5# Acryloid 794 in LT-1 Base. LT-2 Base consisted of 30# FH41, 51-5% Aroclor 1242, and 17.5% Aroclor 1248. LT-3 Base consisted of 30# FH-41 and 70# Aroclor 1242. The data for these series of fluids are as follows: Fluid Viscosity, cs 2lO"F. 10CTF. Viscosity Pour Index Point LT-1 Base 2.60 LT-1-5 7.32 LT-1-8 11.74 LT-2 Base 2.50 , LT-2-5 7.06 i 1I LT-2-8 I l* :11.43 LT-3 Base 2.42 J.Trl-2*.! 4.7J- 16.13 42.11 67.03 14.63 38.63 61.50 ft 13.40 25.pl Jcfcps 2810 ;i }Ss; rorf s :5si -117 +137 + 144 - 99 + 142 +149 - 81 +120 4i;4i -25 -25 -20 -25 -25 -25 4 rth is jtypfe a.i DSW 620678 STLCOPCB4094705 i -i! 53. 8-ii that.Fluid LT-3-4.4 meets|the 100'F. requirement but is too viscous at 0F; JThe; specific gravity at 25/25C. of this fluid was 1.257 withfa,flash point of 36CtF. and a fire point of 495F. ' . f ' r. Because of the high 0#F. viscosity of the LT-3 fluids, the ratio of FH41 to Aroclor 1242 was changed to 70:30 for the LT-4 Base. This base did not appear to give the necessary viscosity properties and hence LT-5 Base was prepared consisting of 25# Aroclor 1242 and 7556 FH41. A satisfactory fluid based on viscosity characteristics was prepared in LT-5-7.5. The series was also extended to Include LT-6 Base which consisted of 20 Aroclor 1242 and 8o FH4l. The physical properties of these fluids are as follows: Fluid Viscosity, 1C8 . 2lOuF. IOCtF. Viscosity Sp.Gr. Pour Index 25/25C. Point,*F. LT-4 Base 2.44 10.98 560 LT-4-4.7 5.45 22.53 850 LT-4-6 6.57 26.78 930 + 23 + 174 + 174 1.165 1.148 1.143 -60 -55 -55 LT-5 Base LT-5-6 LT-5-7.5 LT-5-9 2.44 6.41 7.90 9.47 10.77 25.28 30.87 36.66 490 630 650 640 + 31 + 176 +172 +169 ] .152 1.131 1.126 1.121 -55 -55 -55 -55 LT-6 Base LT-6-6 lt-6-8 2.45 10.59 420 4 36 6.22- 23.75# .490 4 ; - +180 8.28 30.97" 510 9 4174 1.138 1.119 ' 1.116 -60 * -55 -55 point of LT-5 -7.5 was found to be 380F. and )olnt. 470F. The fluid was called Fluid OS-57. Two batches were prepared in the Interim Production facilities for testing in an Askanla Regulator by U.S. Steel Co. This material.had the following properties: Batch 12 Viscosity,cs.,210*F. * s 7.76 it ` : Acidity, NN ,Sp. Gr., 2|/| r. I *, - `i 01<.1;i825 7.73 30.45 , 650 * * 0.08 1.124* Q.23 ff ^3 ?: & :& s .ri DSW 620679 STLCOPCB4094706 M ;5rf8 tovert and weight loss, acidity, appearance, and in some cases viscosity were determined. The data for a test run at 175C. (>'I7F.) are as follows: Time In Hours Wt. Loss, Acidity, NN Appearance 0 0.0 0.08 Light yellow 6 0.8 5.1 Deep yellow 12 18.1 -- Black, 2 layers 18 20.3 -- Black, 2 layers 24 21.0 133 Black, 2 layers A similar test was carried tut at 150C , (302F.). The * data are as follows: Time In Hours Wt. Loss, 1 Acidity, NN Appearance 0 0.0 25 1.0 49 2.9 72 19.2 96 ' 21.7 168 23.0 512 28.3 0.08 1.51 12.4 -- -- -_ -- Light yellow Medium yellow Orange Black, 2 layers Black, 2 layers Black, 2 layers Black, 2 layers The data for the thermal stability test at 125C. (257F.) are as follows: Time Wt.?los8. Acidity, Viscosity, cs. Viscosity Hours Days X NN 210 F. 100 F. Index Appearance 00 24 1 4o 2 72 3 120 5 l5C 7 240 10 312 13 3o0 15 0.0 0.08 0.4 0.33 0.6 0.57 1.6 0.82 1.6 1.42 1.6 1.85 3.3 6.12 4.6 -15.6 8.0 -- 7.73 7.48 7.47 7.44 7.43 7.43 7.53 7.79 -- 30.45 29.47 29.33 29.44 29.45 29.54 30.00 30.92 -- 172 Light yellow 172 Yellow 172 Yellow 172 Medium yellov; 172 Deep yellow 172 Light orange 171 Deep orange 171 Brown -- Black,2 layers Tlfelthermal stability of "Fluid OS-57 is* compared to that of Pydraul F9 and Skydrol 7000 In the graph on the fcllowihgjpage., ^t;.would appear that Fluid OS-57 Is similar In >sabllityitoisksdrol and will equitable for. use I f ft STLCOPCB4094707 STLCOPCB4094708 5 &. '3J Rft:; *v *& tr ft; J. Preparation of Esters (Prepared by L. W. Bannister) 1. Azelate Esters Raw Materials Used: 1. Azelalc acid 2. 2-Ethylhexanol 3. Iso-octanol 4. n-Butariol 5. Sulfuric acid 6. Sodium carbonate 7. Potassium permanganate 8. Sodium mettDisulfite 9. Attapulgus earth Emery Industries,Inc. #597 Enjay Co., Inc. #540 #213 #512 #516 #522 #608 a. Dialkyl Azelates (symmetrical) R0C(CH2 )^.C0R; R = n-butyl, 2-ethylhexyl, and lsooctyl Azelalc acid has recently become commercially available from Emery Industries, Inc. and it was of Interest to prepare some of its esters for evaluation as functional fluids (specifically for utility in Jet turbine lubri cants) and as plasticizers. The esters indicated above were all prepared by the same standard procedure: 1 mole of the acid or acid anhydride was stirred and heated with 2.2-2.3 moles of the alcohol at 100-110 in the presence of a catalytic amount of sulfuric acid. The water formed during the reaction was distilled out under reduced pressure, azeotroplng with some of the excess of alcohol used. When esterification was complete (2-6 hours) the solution was cooled to 60-80* and washed first with sodium carbonate solution and then with water. Steamdistillation wa3 used to remove the excess of alcohol, following which another carbonate wash was applied, excess carbonate being washed out with water. Permanganation was carried out at 70-80 for four hoursV (Decolonization with sodium metabisulfite was ' followed by washing with: (1) water, (2) carbonate solution, (3) more water. Dehydration at 90-100 (20 mm. filiratiom through Attapulgus .earth afforded 111.; Brc DSW 620682 mn STLCOPCB4094709 Molecular Weight Yield, % Viscosity,cs.,210*P. 130F. 100F. -40F. -65 Acidity, NN Sg$gr., 25/25C. pBur Point Viscosity Index Plnate Esters Raw Mater-ia^fl Used: Plnlc ac'ld (95) Southern Regional Research 2. n-Octanol Laboratories duPont Co. 5. Iso-octanol Enjay Co., Inc. 4. n-Hexanol Carbide and Carbon 56.. Sulfuric acid Sodium carbonate #213 #512 78.. Potassium permanganate Sodium metablsulflte #518 #522 190.. Attapulgus earth Norlt #608 a. Dialkyl Plnates (symmetrical) CH3 ch3 0 \/ li ^ C R0C-CH- CHCH2COR; R = n-hexyl, n-octyl, and isooctyl vch2 j Although plnlc acid from pinene is stili-^iih priced,' work being conducted at the Southern Regional Research Laboratories on the oxidation of pinene. may, lead .to an attractively/priced: plnlo acid ' - ~ `` a alreapy fbeenfanowri iy; ^ 5c|i|aif h|ee Jn4e|e mrnai yf scare-- i^epai^a bfrtifei STLCOPCB4094710  ' f : if ,,. . .. . .: 4 $j W MBipH9 * ' * * * * * _. ..... |e^ees8eMo^^^iother| twojalcohols) of the alcohol ^nj Tthe''presencef ofFcatalytic* amounts of sulfuric acid,1 During the esterification the pressure of the system was gradually reduced in order to remove water of esterification, pressure being maintained at JO mm. during the last hour of the 3-hour esterification period. After being washed with carbonate solution and with water the crude esters were steamed free of unreacted alcohol, re-washed with carbonate solution and water, permanganated at 70-80, re-washed (water, carbonate solution, water) and dehydrated. The esters were then stirreu with 2^ each of Norit- and Attapulgus earth before filtering through Attapulgus earth. Yields and properties are summarized below: n-Hexyl Plnate n-Octyl Plnate Isooctyl Pinate Color Molecular Weight Yield, % Viscosity,cs.,210F. 150F. 100F, -40F. -65F. Viscosity Index Acidity, NN Sb, Gr., 25/25* nfib W- Point Very slightly yellow 354.51 -- 2.76 6.73 ' 10.54 1420 9190 +116 0.12 0.948J 1.4498 5. Succinate Esters Very slightly yellow 410.62 91 3.63 8.90 15.06 2220 13100 + 145 0.07 0.9522 1.4524 Below -85F. Medium yel 410.62 97 4.07 11.13 19.44 11150 -- + 126 0.56 0.9579 1.4540 -55F Raw Materials Used: Succinic anhydride Maleic anhydride Diethyl succinate Isodecanol Trldecanol Stercx AH Sulfuric acid Sodiuii methoxlde ' ' Sodium carbonate Potassium permanganate Sodiur :itel At&4' m Monsanto ti 49 F_. B. Zier.ty Enjay Co., Inc. Enjay Co., Inc. Monsanto (Anniston) #215 . ,, W-Bldg. ` #512 #516 If?t i i#522 jner sli- htrfl DSW 620684 , Til f f mil STLCOPCB4094711 $ f 1i Nf isfrdecyll Suc'c T < C10H210CCHaCHa^0C10H2i ^1(^21 = branche^ decyl { The "iaodecyl" alcohol used in this preparation is made by Enjay via the oxo process on Cg olefins. 1. From Succinic Anhydride A mixture of 200.1 g. (2.00 moles) of succinic anhydride, 697 g. (4.41 moles) of Enjay's isodecy1 (l.e., branched chain) alcohol, and 3 ml. of 98$ sulfuric acid was stirred and heated at 100-110 as the pressure on the system was gradually reduced to 20 mm. When no more water distilled through the straight take-over still head attached to the reactor, the reaction was stopped (6 hours). The crude ester was washed with carbonate solu tion and water at 50-60 and was then steamed at 110 until 5 liters of distillate had been collected. After a re-washing with carbonate solution and water the ester was dehydrated at'95* (20 mm.) for an hour and filtered ..... through Attapulgus earth. There was thu3' obtained 749 g. (94j6) of light yellow dilsodecyl succinate, nfP 1.4477, sp. gr. 25/ 25 0.9201, N.N. 0.03. Other properties of this material are listed in tabular form at the end of this section. From Dl-lsodecyl Maleate ; Dl-lsodecyl maleate, prepared frc.m Enjay's lsodecyl (l.e., branched chain) alcohol and maleic anhydride as described in the final report on Job No. 117-2221, was hydrogenated over nickel formate catalyst at 80 and 700 psl by D. B. Merrlfleld. Interestingly, the up-take of hydrogen was 1275b of theory. The quantitative yield of crude di-lsodecyl succinate, after filtration through Attapulgus earth, was medium-yellow and opalescent, n5 > * ; 1.4477, sp.gr. 25/25's0.9197, N.N. 0.064. | f It was permanganted for 4 hours at 75-85, ; ;taking up a considerable quantity of perman-, 'gana,te. .After decolorlzataon with *rvriii/r ' ` trabtaTbisulflte jthe es,ti| {manner j ljt|wa| 4a] DSW 620685 STLCOPCB4094712 iI t- til ^ * -sh ingi tto ip. ulg_us earth.; The :.pro~, is thenf "J*(ow, h;55 11.4.4''8` 1, spTgr'. f25/25 0.9225, N.nJo.42, |? ; *t## Dl-trldecyl Succinate (MW < 482.75) m? C15H270CCH2CH2cl0C15H27 (C H = branched tridecyl groups from Enjay's C alcohol) Enjay's tridecyl alcohol used in this preparation Is made from propylene tetramer via the oxo pro cess . The procedure for the preparation of this ester was the same as that given in (1) above for the conversion of succinic anhydride to di-isodecyl succinate except that 827.1 g. (4.13 moles) of Enjay's tridecyl alcohol was substituted for the isodecyl alcohol. Time of esterificaticii was only 1.75 hours, however, and the work-up included permanganatlon at 70-80. The deydrated ester, 909 g. (94.256), was filtered through Attapulgus earth aa a medium-yellow oil. The properties are listed in the table at the end of this section. c. Di-(Sterox AH) Succinate (MW = 1143.5) 00 C13H27^0CH2CH2^7 50CCH2CHado(CH2CH20)7 ' Sterox AH is one of a series of compounds prepared at Anniston by alkylation of n-trldecar.cl with ethylene oxide, Sterox AH having an average mole cular formula of C15H27(0CH2CH2)? cOH. It was of interest to prepare^tn4 succinate'of this compound for screening as a functional fluid. \ *| * | ( * It ~ Thl3 succinate was prepared by alcoholysis of ethyl succinate by either basic or acidic catalysis. When Sterox AH and an equivalent amount of ethyl .succinate were heated at 100-110 under reduced |pre3sure without a catalyst no alcoholysis took t When Q.b% of sodium methoxlde was added |ana Heating resumed under'reduced pressure alcohol jwas evolved; the reaction mixture was maintained |at *100^110j (15 mm,) pyerijlght, ji,ts itotal loss in {equips life! irbhri ire DSW 620686 f STLCOPCB4094713 wm m / * >lbo|liq|( 15 ''>)fan! fthe product (quantitliSLyl | yield) vaa filtered through a Buchner funnel* Properties if this Sterox AH succinate are given in the table at the end of this section. f When 3/6 of p-toluenesulfonlc acid was used as the catalyst an 8756 of the theoretical alcohol was evolved at 100-110 (40 mm.) over a period of 36 hours. The crude ester was washed at 50-60 with an equal volume of a solution of sodium carbonate and salt. Pour layers were obtained, of which the lower two apparently aqueous layers were discarded. The organic layers were stirred with another volume of more dilute salt solution at 50-60 and the slight middle layer was discarded with the aqueous layer. The organic layer was washed once again with salt solution, dehydrated at 100 (10 mm.) and filtered. A 61.1^6 yield of Stoerox AH 3ucclnate was thus obtained; its properties are Mated below. Dl-(Stercx AH) Succinate Dl-lsodecyl Di-trldecyl (by NaOMe (by TsOH succinate succinate catalysis) catalysis) Vise c-slty, cs .,210 ?. 3.21 5.17 130F. 100F. 8.09 13.46 15.39 30.16 -40F. 5650 >20000 -65F. Viscosity Index Acidity, NN + 117 0.03 *112 0.18 + 13; 0.13 Snpp^gr., 25/25C. 0.9201 1.4477 0.9123 1.4545 1.0224 Four Point -60F. - 45F. + 55F. Color It. yellow It. yellow dark red 13.07 76.78 *143 0.50 1.0152 + I5F. dark red 4. Phosphate Esters Raw Materials Used: Phosphorus oxychloride n-Heptanol "Alphanol 79 ' Phenol Plant lye* 5 ' Potassium permanganate Sodium metabisulflte #244 Eastman Kodak Shell Chem. Co. U3P Monsanto #229 #516 ' #522 i ; #213 S3 Ltd i lid li #! i DSW 620687 V It f t ni 1 lift STLCOPCB4094714 T _ iitiifeii i-Heptyl*Dlphenyl Phosphate (Mw'= 348.41) 62, CHaCCHaJeOPOtOC^Ja This compound was made by the Santicizer 141 Tentative Process to extend Monsanto's series of alkyl diphenyl phosphates. The yield of unpermanganated, slightly yellow n-heptyl diphenyl phosphate was 87.4#. Its properties are listed in the table at the end of this section. "Alphanol 79" Diphenyl Phosphate (MW = 359.2) Late in 1952 there became available from Shell Chemical Co. Ltd., a supply of mixed Cj, Cp, and Co primary alcohols designated by the trade'name ' "Alphanol 79". Interest In this alcohol prompted preliminary process studies and sample prepara tions. Among the esters prepared ana testea as plasticizers and functional fluids was "Alphar.o 79' diohenyl phosphate. This compound was prepared according to the Santi cizer 141 Tentative Process in 84# yield. The properties of this light yellow fluid are tabulated below. n-Heptyl Diphenyl Phosphate 'Alpnanol 79 Diphenyl Phosphate Viscosity,cs.,210P. 130*F. 100F. -4DP. -65*F. Viscosity Index Acidity, NN Sp.gr., 25/25C. n<y> ; Pour Point . Adipate Esters 2.32 8.72 212D. + 84 0.06 1.0976 1.5086 2.52 6.09 9.73 5710. + 93 0.18 1.0536 1.5082 - 70F. Raw Materials Used: t hi 'Mpl?c acid * ' * 27 Ethoxy dethoxy propanol A i 34 p.-Toluene3ulfonic acid. h 1 l^J(^L^bo|^t| W duPont Carbide and Carbon DSW 620688 STLCOPCB4094715 _____ T. . . ? . Ift-la. $ Dl-( et&oxyethagroropy1)1Adipate i(|irf 1.430) * Main] it r t( * ' % JCaEtQCHCHpCCHaCHa CH^H ^ 'ill. Ilfcilps 4 `U s- * Ethoxy ethoxy propanol, presumably prepared by interaction of Ethyl Cellosolve and proplene oxide has recently come on the market. The average molecular weight (160) of the commercial product indicates some higher molecular weight impurities, probably mainly ethoxy ethoxy propoxy propanol. It was of interest to examine derivatives of this relatively cheap new alcohol with regard to their utility as plasticizers and/or functional fluids. To this end the adipate ester was prepared and screened to these uses. Adipic acid (1 mole) and ethoxyethoxypropanol (Carbide and Carbon) (2.25 mole, calculated on the basis of an average molecular weight of l6o for this alcohol) were stirred and heated at 100 120 under vacuum in the/pf^gS^ce of a catalytic amount of p-toluenesulfonlc acid. After twenty hours, titration of an aliquot of the reaction mixture indicated that esterification had taken place with only 90)6 of the original carboxylic acid groups; therefore, another 0.25 mole of ethoxyethoxypropanol was added to the reaction mixture and the reaction was continued for another eighteen hours at 110-120. At this point titration of an aliquot indicated that 97/6 of the original carboxylic groups had been esterified. The mixture was then washed with sodium carbonate solution and twice with water, all at 50-60, and was then steamed at 105-110 until five volumes of distillate had been collected. After another wash with carbonate solution and two washes with water, the batch was dehydrated at 100-110 (10 mm.), stirred with 1% each of Norlt and Attapulgus earth, and filtered through Attapulgus earth. The yield and properties of this di(ethoxyethoxypropyl) adipate are as follows: Yield 91% * Color * ^ s yellow n25 1.4420 Specific Gravity,25/25` 1.0238 Acidity,_ NN jcdsit' liofp.l t 0.04 l I 5425 IOO?P. 111? .56 |40|K. 059 f yii A DSW 620689 Vt*> i -f * t STLCOPCB4094716 Er.v ' M 4; t H - * if i: net '? ^VlSC08ii srovei f ' ? ' h <. ft*" sf fif'*** * -* . *; \ A sample Of Acrylate VI Imprt.er (A) was received from Dr. Palmer land waafpart of his Pilot Plant preparation. This material-was examined in various functional fluid base stocks. Results are as follows : Sample Pydraul Base + 156 A + 3* A + 5% A + 1C# A Viscosity in C3 . 216uf. 160 F. -"Wf. 3.85 3.97 5.45 6.81 11.07 39.80 44.10 54.56 63.47 101.3 .. -- ---- 2-Ethylhexyl diphenyl phosphate 2.45 + 5% A 4.10 9.68 16.46 5804 25000 Viscosity Index -252 -285 - 19 + 53 + 102 + 78 + 174 Dibutyl phenyl phosphate + 5% A + 10* A 1.44 2.47 3.96 Tetraoctyl 'silicate 2.28 + 5* A 3.36 4. 17 b.95 11.37 6.75 9.80 194 Sepn. Sepn. 235 373 -- + 190 +244 + 164 +222 These data indicate that the Acrylate VI Improver functions satisfactorily in Pydraul Base (a 50:50 mixture of Aroclor 1248 and trlcresyl phosphate) and in tetraoctyl silicate resulting in the expected increase in viscosity and in viscosity index. In the only example of alkyl diaryl phosphate studied, the viscosity index is improved but an unusually high viscosity was found at -40F. With the example of dialkyl aryl phosphate studied, actual separation of polymer occurred at -40P. It appears that thi3 VI improver may have value as a replacement for Sar.tcdex in Pydraul F9 and further work is planned. Work at Central Research by Dr. Joseph Fields has resulted in three variations of 2-ethylhexyl acrylate/ ethyl acrylate, copolymers for use as viscosity index improvers in dibutyl phenyl phosphate to prepare , Skydrol 50O|ty|5e Jflui'ds / ?Samples of the* polymer solutions, which were labeled J-1072, J-1073, and J-1074 and a samp^ of Acrylold R3876X, the regularly , :500f were l3soli ha; the DSW 620690 urns : STLCOPCB4094717 S 4*>i# #: i' ^ fSampiel l^uty pho 9 ph6 te* + Acryloid R3876X + J-1072 i + J-1073 : + J-1074 4.03 4.01 4.03 11.06 11.65 11.88 11.67 11.53 501 507 470 426 2640 1870 1800 1720 All three samples from Dr. Fields were soluble at -65F. and gave good viscosity index improvement. Shear sta bility is a very important characteristic of this type material and was determined. These samples and the base stock, dibutyl phenyl phosphate, were put through the G.M.-71 Diesel Injector Shear Test by Dr. Palmer's group and samples taken after five and ten passes were returned to us for analysis. The data are as follows: Sample No. of ViscosityIf- C3 % los: passes 2106F.. 100DF. -p . -65F. VI of VI Dibutyl phenyl phosphate (FH87) 0 1.45 4.18 -- 5 10 1.46 1.46 4.18 4.1S -- -- 89 -- ---- ---- FH87 + Acryloid R3876X ?H87 + J-1072 FH87 + J-1073 FH87 + J-1074 0 '5 10 0 5 10 0 5 10 0 5 10 4.03 3.44 3.31 11.85 10.18 9.79 4.01 3.33 3.17 11.88 9.88 9.44 4.03 3.07 2.89 11.67 8.98 8.52 4.06 2.88 2.72 11.53 8.38 7.97 501 -- 500 507 -- 495 470 -- 426 426 -- 379 2640 -- 2220 1870 -- 1810 1800 -- 1540 1720 -- 1390 2'U 221 217 239 217 209 243 200 265 202 192 -- 13.2 15.5 ___ _ 14.7 20.0 -__ 22.1 27.9 ____ 35.s 41.5 The % loss in VI Wcl 5 'calculated as the decrease in vi: cosity index improvement caused by shear. It appears that the copolymer designated J-1072 is somewhat similar in shear characteristics to the Acryloid R3876X showing slightly more shear after both 5 and 10 passes. Both i *J-1073 'and J-1`074 are much les^ shear "stable. The y ' $ I viscosity `of the J-1072 blend at -65F. is considerably .lower than that o the R3876X blend. - Q DSW 620691 ,1:1 lift STLCOPCB4094718 % ? |Bae_ .-D--u--s--t---- fhisfreport/ a liquids Vere submitted'by other* groups for soreeningy aa functional fluid,, base stocks. The results of the preliminary screening given these materials are ' summarized in the following paragraphs. * |* A sample of butyl 9 (10) carbobutoxystearate was sub mitted by Central Research for evaluation as a func tional fluid. The data obtained are as follows: Viscosity, 210F. 130F. 100*F. Viscosity Index Specific Qravity, Flash Point Fire Point Pour Point 25/25C. 3.72 cs. 9.42 cs. 15.14 cs, + 155 0.9093 520SF. 520F. +35F. This material has low volatility and satisfactorily high flash and fire points. The viscosity Index Is excellent but the product Is deficient in low tempera ture properties for most uses. A sample`of 'hydrogenated toluene pyrolysate" was examined for the Phosphate Division. The viscosities were 1.47 cs. at 210F.. 2.92 cs. at 130F., 4.14 cs. at 100F., 348 cs. at -40F., and 3730 cs. at -65?. The flash point was 240F. and the fire point was 250F. These data indicated that the product would be of value merely as a base for petroleum type fluids and offers no advantages in either flammability or viscosity. Several samples of derivatives of unsaturated fatty acids (UFA) which had been prepared at Dayton were examined for pour point properties. Results are as follows: Compound Lot No. Pour Point N,N-Dibutyl UFA amide N,li-Dlmethyl epoxy UFA amide 2-Ethylhexyl epoxy UFA . - Butyl .ester; off UFA|+ approx. 11* mole butyl fumarate \ Butyl ester of UFA + approx. 1 butyl irate j-609 j-456 j-455 j-510 '-k j-511 i cate tea if DSW 620692 *i 1 STLCOPCB4094719 screlrp&f 4Wpa^Dayton wer4 prelfifiLhfijiriiy'; Pninctlonar fluids use. The datia are as followss Sample No. : J-843 J-844 J-863 J-1436 J-1256 Viscosity,cs, 210F. 100F. -40F. -65F. Viscosity index Sp.gr.,25/25C. Flash point.F. Fire point, F. 8.99 17.45 Solid -- >00 1.034 595 +55 21.23 150.4 3.52 16.46 Solid 9140 -- 136 -- 101 0.919 0.893 395 320 450 355 2.58 8.44 Solid 1.13 2.85 72 - - 270 153 99 0.886 0.886 395 285 465 300 These samples may be identified as follows: J-S43 is dl(2-ethylhexyl)-q,^-dlphenylglutarate, J-844 is trldecyl trldecyloxypropionate (crude), J-863 is tridecyl trldecyloxypropionate (distilled), J-1436 is n-decyl P'-n-decyloxypropionate, and J-1256 is 2-ethylhexyl P-trimethylsilylpropionate. The first four materials are deficient in low temperature properties. However, because of their high viscosity indexes, work will be done to determine high temperature stability. Further testing is also planned for the sllylpropionate. A number of samples received from Central Research and the Phosphate Division were examined. The data are as tabulated in the table on the following page. In general, these products, except for the trimethyladipate ester and the nonyl r-nonyloxypropionate, do not exhibit properties that make them of interest as functional fluids, particularly because of low tempera ture characteristics. The two compounds mentioned will be further examined. The unusually high flash and fire points of the silicon fluoride derivative are of interest. Five samples were preliminary screened as functional fluids. The data are as follows: Sample No. ' Viscosity,cs.,210F. 100F., v f * : I -4of.I -65P. Viscosity Indexi = 25/ ` ` k N-26 N-27 2.41 2.13 9.71 3.08 1500 * I lloO 8800 .+66 ' 8350 '^ 1.151 N-28 N-38 1.48 1.05 4.48 2.38 320 Solid* 1710 Solid +37 + 133 029, 020 J-1706 9.56 107.6 Solid Solid +6.40`, 05 I? DSW 620693 STLCOPCB4094720 STLCOPCB4094721 I it m h < f: __ I i 1M f < I - $ Samples N-26, N-27, N-28, and N-?8 were submitted from Anniston and sample J-1706 from Central Research. The identity of these materials is as follows: N-26 N-27 N-28 N-58 J-1706 bis(2-ethylhexyl)2-ethylhexanephosphonate tetraethyl ethane-1 2-diphosphonate dibutyl << -acetoxyethanephosphonate bis(dimethylamldo)methaneph03phonate di(tridecyl)trldecanote, the high boiler from the Querbet reaction on tridecyl alcohol. Samples N-26, N-27, and N-28 have sufficiently inter esting properties to warrant stability testing. This will be done. Sample N-}8 la deficient in low temp erature properties and no further studies are planned. Sample J-1706 is deficient in low temperature proper ties. However, such a viscous fluid may be of value for high temperature work. Stability studies will be carried on when further quantities of sample are obtained. Preliminary screening data were completed for a number of samples submitted by Central Research personnel. The data are given in the following table (see next page): The identity of the samples are as follows: K-141 n-Butyl P-n-butoxyproplonate K-1^2 Tridecyl p-trldecyloxyproplonate K-149 2-Butyl-2-ethylprcpanediol-l,3-dllaurate K-150 2-Butyl-2-ethylpropanediol-l,J-dipelargonate K-151 Ester Mixture (esterification of 2-butyl-2- ethylpropanedlol-1,3 with laurlc and pelargonlc acids). K-152 2,2-Dlmethylpropanedicl-l,J-pelargonate laurate. K-153 Ester Mixture (esterification of 2,2-dlrr.ethyl propanedlol-1,3 with pelargonlc ar.d laurlc acids). K-3&4 - Nonyl P-tridecyloxypropionate . K-365 Decyl P-decyloxyproplonate K-366 2-Ethylhexyl (3-trldecylpropionate K-387 Decyl fi-nonyloxyproplonate J-1711 l,4-Bis(2-ethylhexoxy)-2,3,5 ,6-tetrachloro benzene J-1713 1,2,4-Iri( 2-ethy.lhexpxy.) V5, 5,6-trichIcro- i]| U-.l bQn?erfe | i-4-17 12 * | fcltit 11 fcl i t # f * ` iBISnl A"i 15 DSW 620694.01 STLCOPCB4094722 S pecif G ravlt 2 5 /2 5 hli ir a-fi ll-M 70, H CO a> c in Q in *CLl4, COl, 0ft. CVi O m m m SZ +J <aHJ & -0hCO-< oCl, oOJ eg oo m vo =t O "H > m CrHTi o' t--i OoN o' o in o^ in in o in o in m in -=* ^r o ^}- O,-HJ CTs VO CoT\ oo 8 o\ d CoO -3- in m in -=r o (7\ a> rOrHnJ mo ++ Vr--Oi H H ++ nmr--I + lA I O -S' i m < i+ mmo -ii=nn* mmin o vO in VOOJ m o mo min c^d t---4- cino ft. CO 888 o in oP 4oJ CTi o a I *n 04 CM m oo 00 o\ m in t f* 8 CM CMi CM `-fc DSW 620695 STLCOPCB4094723 f |: : |4 (i Si it** ''*( - 4 j|vri>;: " r#| The general class of aikOxypropionateVhave' previously examined. (Samples K-141, K-142, and K-3Q4 through K-387). The n-butylP-n-butoxyproplonate Is too volatile for most fluid uses. All these'alkoxyproplonatea are somewhat deficient in low temperature properties (K-384 through h-387). However, the mixed esters are better In this characteristic than the symmetrical esters previously examined. The most Important consideration is the thermal stability of these esters. This will be determined at a future date. The series of dlol esters (K-149 through K-153) are deficient In low temperature properties. However, it Is expected "hat these esters may have unusual thermal stability. This will be studied at a future date. The chlorine containing aromatic ethers (J-17H through1^-1715) are interesting having fair viscosity properties (especially J-1711, J-1712, and J-1713) and lower pour points as compared to the Aroclors. Such products may be of value in certain industrial applications. However, stability to heat and corro sive action must be determined. Preliminary tests have shown little breakdown of J-1712 or J-1715 at 350F. for 75 hours. Further tests will be conducted. Data on viscosity and cloud points on a series of orga-.ic phosphorus )mpounds were requested by Dr. Chadwick. The res :s are as follows: Compound Vlscosity.cs. viscosltv Cloud 210F. 100?. Index Point,F. ch3po/n(ch3)272 (CH30)2P0H CH3?o(och3)2 1.05 0.53 0.66 2.38 0.92 1.40 133 -163 Below -70 90 Below -70 ch3po/och(ch3)272 0.70 1.46 102 Below -70 C*HgP0(0C4H9)2 CH2=CHP0(0CH2CH2C1)2 1.10 ji . 2.20 2.87 s 8.26 78 ?* f 72' Below -70 Hi 'Below -70 Viscosity data were requested (by an .operating ideDart-j eject on 24ethylheptariol f dIIoIjs : f fl. 15 6 s?.; att it i IP OSW 620696 f fi STLCOPCB4094724 Ifilif 72. " 'it-l L. Miscellaneous Investigations 1. Trlcresyl Phosphate In connection with an inquiry from the Development Department, It was found that 0.05% (by volume) tricresyl phosphate (TCP) will not dissolve in a 1:1, methanol:water solution at 25C. Attempts to prepare the requested solution by dissolv ing the TCP first in methanol and then adding the required amount of water, under otherwise Identical conditions, proved unsuccessful. The solubility of trlphenyl phosphate (TPP) in tricresyl phosphate (TCP) was examined In an attempt to elucidate the composition of cresyl diphenyl phos phate (Santlcizer 140). Samples containing 10, 20, 30, 40, and 50 weight percent TTP in TCP were prepared. Seeded samples at room temperature indicated that about 30 is saturation concentration at about 25C. At 5C. considerable material separated from the 30$ solution while none separated from the 20$ solution of TTP in TCP. Santicizer 140 separates into a solid and a liquid phase on cooling, the solid phase having been identified by the Analytical Laboratory as tri phenyl phosphate. Our data merely indicate that TTP is quite soluble in TCP and do not indicate the amount present in Santlcizer 140 since the solubility ' of TTP in all triaryl phosphates possible in Santi cizer 140 is not known. The heat stability of trlcresyl phosphate (A-ll) was studied. Previous work had shown that in 24 hours, A-ll developed acidity e-uivaler.t to 7 ml. N/2 NaOH at 150C. and 26 ml. N/2 NaOH at 175C. per mole of e3ter charged. The present work Indicated that the acidity developed at 200C. in 24 hours was equivalent to 38 ml. N/2 NaOH per mole of ester. It was also found that 316 stainless steel was discolored but was not corroded by trlcresyl phosphate at 200C. (after 24 hours exposure). The A-ll darkened appreciably. - \ I in the absence and presence of stainless steel. *f ird ,to i certain jfuncti ins >fi These*data lira Is 5 n't DSW 620697 STLCOPCB4094725 : Ml ' Sample ' ; i * t tM Vl3C08lty 73- 1. 50# trlcresyl phosphate 50# dl (2-ethylhexyl)adipate 12,300 os. at -40F. 2. 50# trlcresyl phosphate 50# di(2-ethylhexyl)sebacate 17,400 cs. at -40F. 3. 50# trlcresyl phosphate 50# diamyl adipate 3,400 cs. at -40F. 4. 50# trlcresyl phosphate 50# dl(n-butyl)adipate 125 cs. at 08F. 5. 90# trlcresyl pnosphate 10# diamyl adipate Solid at -40F. 6. 95# di(2-ethylhexyl) phenyl phosphate 5# Acrylold HF855 2,880 cs. at -40F. M. Physical Measurements Section (Prepared by W. E. Koerner and 0. B. Cecil) 1. Specific Heat a. Apparatus and Methods a 1/2 pint narrow-mouth Dewar flask was used as the calorimeter. The energy added to the calorimeter was calculated from observations of the voltage drop across the resistance heater in the calori meter and the current flowing in th ; heating cir cuit for a measured time Interval. A six volt storage battery was used as the source of power. The voltage drop across the heater was about five volts, and the current was about one ampere. A five to seven minute heating period was used. This, quantity of heat resulted in a 2.5C. tempera ture rise when the calorimeter contained water and a' 4 to 5C. temperature rise when .the calorimeter . | i -Contained as sample of functionalffuufd. t )v raercury: in-glass thermometer with 0.2C. or 0.1C. ? divisions was used to measure ^the .temperature, " temperature rise was .detarmirfedLlgripi ' ' * ' ' laylifegd pfi fchJ mi I' f!-:-|i ;v' 7 9i '' . * ` *vt *\7 DSW 620698 I STLCOPCB4094726 H I'M calculations. The best literature value for the Increase In the specific heat of glass with increasing temperature was 0.0S6 Increase per C. This value was used in calculating the calori meter heat capacity at temperatures above 25C. An error of 7% in the heat capacity of the calori meter will result in an error of only 1* In the specific heat since only about lci% of the total heat input is used to heat the calorimeter itself. Results A summary of our experimental data is shown in Table 7 below. Each value is the mean of at least two determinations. TABLE 7 Sample Description Tempierature(C) Specific 1 0S-40 (composite) dated 12/6/52 (same as Skydrol 500) 24 63 101 0.38 0.41 0.44 OS-41 dated 10/1/52 24 6l 99 0.32 0.35 0.3S OS-45 (Batch L) dated 10/1/52 25 60 100 0.45 0.48 0.54 L-JA dated 10/6/52 24 60 100 0.36 0.41 0.42 Pydraul F-9 dated 6/11/55 23 d9 107 0.31 0.33 0.36 These values are the same as heat capacities measured, as cal.^g.^C. or Btu/lb./F. , , The experimentally determined specific heats for each fluid were plotted as a function of tempera ' ` "' ' Istraight line ^was drawn|thrc Agi* STLCOPCB4094727 m Specific Heat - 0.4i8 + 1.17 x 10`s t Specific Heat = 0.582 f 5.05 x 10~4 t Pydraul P-9: Specific Heat 0.296 + 6.28 x 10' where t is In 6C. These equations provide a means for calculating approximate specific heat values outside the range of experimental measurements. Density Variation with Temperature a. Apparatus and Methods A Vycor pycnometer was used for the density measurements. Appropriate corrections for the variation In volume of the pycnometer with tempera ture were made. The. temperatures were measured with calibrated thermometers. b. Results A summary of the experimental data are shown in Table 8. TABLE 8 Tempera?t&re(*C.) Penalty(g./ml.) Volume (ml./g.) Pydraul F-9 (Lot s-1010) dated 1/29/55 25.0 60.0 95.6 130.8 164,6 198.4 1.2576 1.2277 1.1972 1.1671 1.1575 1.1074 0.7952 0.8146 0.8553 O.8568 0.8791 0.9050 Sfafdrol 50C (5/20/55) dated 6/11/55 ii 1 1.1104 ' * 0.9006 ! ; io.cr * ' 8 0.9255 1.0592 .0.9441 iioi83. 182 DSW 620700 STLCOPCB4094728 A straight line resulted when the density of each functional fluid was plotted as a fuction of temp erature. The equations for these straight lines are shown below: Pydraul P-9: dt = 1.2796 - 8.64 x 10' Skydrol 500: 1.0806 OS-45: dt = 0.9106 - 7.22 x 10' Oronite 250: = 0.9381 - 7.16 x 10' where d^. is the density In g./r.il. at tC. Considering OS-45-1 to consist of 99.556 03-45 and 0.556 Oronite 250 and assuming* that the density of the mixture is directly proportional to the per centages of the components, the following equation for OS-45-1 can be calculated: dt = 0.9107 - 7.22 x 10 3. Electrical Properties a. Apparatus and Methods A General Radio megohm bridge was used for the resistivity measurements. sThe dissipation factor and dielectric constant measurements were made on a'General Radio capacitance bridge. The DC resisti vity readingswas made 60 seconds after the initial, the.measuring* STLCOPCB4094729 Pydraul ?-9 (Lot 3-1010) dated 1/29/53 ; <# - - n 60*v Dissipation Factor 32.9# ?' 1000~~- Dissipation Factor 2.2# Specific Resistivity 0.15 X 105 megohm-cm. Dielectric Constant(1000-^) 6.25 OS-45-1 (dated 6/9/53) 6o~ Dissipation Factor 71.8# lOOO'-u Dissipation Factor 5.2# Specific resistivity 0.20 X 10^ megohm-cm. Dielectric Constant( 1000^-) 2.84 Skydrol 500 Specific Resistivity of sample dated 5-20-53 36 megohm-cm. Specific Resistivity of sample dated 7-22-53 46 megohiu-cm. The very low resistivity of Skydrol 500 prompted us to measure the electrical properties of the base 3tock for this functional fluid and several other alkyl-aryl phosphates. Our results are summarized in Table 9 below. TABLE 9 Sample Description Dibutyl phenyl phosphate (Skydrol 500 base) Specific Resistivity (megohm-cm.) 25 Dibutyl phenyl phosphate (from PC13 N3P A-41472) 152 Tri-2-ethylhexyl phosphate " (Flexol TOF) 1520 STLCOPCB4094730 4; 78. it if.! Thermal Conductivity a. Apparatus and Methods Thermal conductivity measurements were made utilizing a method and an adaptation of a cell described by Hutchinson in the 1945 Transactions of the Faraday Society (p. 87). The cell used In making the earlier measurements consisted essentially of a Pyrex tube with a coiled tungsten filament located at the axis of the tube The experimental technique consisted of filling the cell with the liquid in question and passing a measured current through the filament while the entire cell was immersed in a thermostat. The filament was also utilized as one arm in a Wheatstone bridge in which the filament heating current also served as the bridge current. This measurement of the resistance combined with the current measurement enabled one to calculate the, _ heat dissipation In the filament, and from previous calibration of the resistance value could be used to calculate the temperature of the filament. A knowledge of the thermostat temperature permitted a value for AT to be obtained. These values are all related to the thermal conductivity of the liquid in the cell by the following equation: AT Q B where: - AT = T filament - ^ thermostat in C. Q = heat dissipated in the filament in calories/sec. K = thermal conductivity of the liquid In the cell measured in cal./cm. *C. sec. A and B I t' I ' I \ I ' - 11 = constants depending on the geo- ` nietry of the apparatus and the thermal conductivity of Pyrex glass. iBecause m Hi georaeti of the imrftl " Lcsjlcvllkte )ifa tm'eAt i th : 11, was tcoW jcea^ Sonfedc! not gifiKf an r1 I DSW 620703 STLCOPCB4094731 9 However, closer examination of the literature existing on the thermal (conductivities of liquids revealed a rather large spread in the values for some liquids and even a major discrepancy In one of the liquids used as one of our calibration liquids. This led us to design and use a new type cell. Whereas the former cell used a coiled tungsten filament, the new cell used a straight wire platinum filament. Another added feature was a four-lead type of arrangement designed to eliminate end effects. These improve ments enabled the direct calculation of the cell constants A and B. Using these calculated con stants, several liquids whose thermal conductivi ties have been reported in the literature were measured. Table 10 shows the agreement between our values and the literature values. TABLE 10 1 K X 10* (cal/ 0. cm.sec.) . Observed Literature Material (25C.) Value t( c.) Source R20 :h3oh SHCla C2H5Br CC14 148 50.5 52.0 23.6 25.2 143 50.3 33.0 28.6 r24.6 126 .'3 138.0 20 30 12 30 20 ' 0: 20 Riedel Bridgman ICT (Weber) Bridgman Riedel ICT (Goldschmidt) Bates The dimensions of the call and the calculation of the constants A and B are given below: The complete equation relating the measured values and the thermal conductivity is: - _^_T _ l In r2 , 1 Q SfrlKi r1 2tTlKs where: - i- - t *! t f ? ./ i $'4 |I * tf - = thermal conductivity of ulquid in the cell measured In cal./cm. 8C.! sec, ihs&js STLCOPCB4094732 if:* . constant A - 1 In i . -iH-i , : I .ST7TT m 2.503 : log 1, (2)(3.i41b)(B'.4'B)' O.r - ' ?>' - A 0.0978 cm -1 constant B 1 In a 7H ra 2.303 (TJ O. 1415) f OH R'6! oo2) B * 1.53 cm -1 log 1.26 TT07 The experimental procedure was the same as that discussed earlier except that the straight wire filament had a much smaller resistance and necessitated the use of a Mueller bridge for the resistance measurements. The thermostatted bath was maintained within + 0.01C. Currents up to 73 milliamperes were used with resuicing^maximum temperature differentials of approximately 0.5C. Resistance values of the straight wire filament were determined at various power inputs. The temperatures were determined from a previous cali bration of the resistance value of the filament. The slope of the straight line obtained from a plot of temperature of the filament (ordinate) vs. power input (abscissa) gave T which was used directly to calculate the Q thermal conductivi ty of the liquid in the cell. b. {Results t* ' Thermal conductlvltes for six functional fluids and sixteen component materials were measured at two temperatures, 28 and 8iC. Ine results are given in Table 11, page 8l. The mean deviation from, the mean of duplicate runs made on the same sample in the cell was + 0.4# at 28C. and + 0.?# at 8lC. Greater difficulty in ' controlling the thermostat temperature at the higher temperature accounted for this difference. t* i' i t- u s I i 1 f : t H analysis offthe data showed that thermal conduc- tlvltles of functional fluids could be calculated from-the thermal conductivities of theiricomponent< 138. & eaS' rl w DSW 620705 STLCOPCB4094733 fMtaiikfes? fin u 0. B % A " * component a present in p * B " * con>Ponent B present in p Table 1l2)d &d observed values agree within J,% (see TABLE 11 Subs cance Skydrol 7000 OS-41 ^Skydro1 500) OS-45 L-3A Pydraul F-9 Arcelor 1248 Oioctyl phthalate Dj.butyl phthalate Ph03Phate ^Hester 12 Tetraethyl silicate 11ll ?ni"e Unicon(oDLB-50r hnGeXxyy1l ^1 asezbealacatete Parapiex AP-52 San toaex Acrylold HF355 TABLE 12 K x^O5 (Cal./cm. -- C. sec. 1* 2F*cT^----- L81*1 29.9 32.1 27.5 33.1 31.6 27.5 24.0 32.4 32.5 31.3 30.0 31.2 31.7 32.9 30.3 31.9 35.6 36.0 33.0 37.2 30.5 33.6 29.6 32.2 27.3 32.9 31.6 26.6 23.5 30.1 30.9 29.9 30.7 28.5 31.1 32.4 34.4 30.7 33.6 35.1 30.9 36.7 30.2 33.7 Functional Fluid Slcydrol OS-41 OS-45 L-3A Pydraul PQ . 29.9 27.5 33.1 31.6 21. 30; 8 27.8 33.4 -3112 , cal./cm. sec. *CT er"or oFsT calc. error 29 *6 t3bM t ; +'2.7 '26;s 52. V !;fe ?' DSW 620706 STLCOPCB4094734 i fdlfflQ\5.f^liKtheiinethQd, appears Iffane . ft- never a new silicate <or phos~ 5 phate esterlia ^employed In preparing a new fluid, the thermal "conductivity of that ester must be measured. This!difficulty could be alleviated Kith only a alight decrease in accuracy by assigning values to classes of compounds such as silicate esters, phosphate esters, etc. Using this method results could be calculated to agree within of the observed results (see Table 13). TABLE 13 K x 105 (cal./cm. 0 C. sec .1 Functional 28DC. Fluid obs. calc. % error obs. calc. % erro] Skydrol OS-41 OS-45 L-3A 29.9 27.5 33.1 31.6 27.5 31.1 27.6 32.4 31.8 27.6 +4.0 +0.4 +2.1 +0.6 + 0.4 29.6 27.3 32.9 31.6 26.6 30.2 27.0 33.0 33.4 26.9 +2.0 -1.1 + 0.3 -3.8 + 1.1 <t * Listed below In Table 14 are the values assigned to the different classes studied. Assigned values were average values of all measurements made on various members of a giver, class. Since little variation between members of a class was observed, it appeared to be desirable to use the data in this form. Exceptions to the above were the viscosity index improvers. A relatively large variation between these compounds was observed and It would appear advisable to use the reported value for each compound. An asterisk denotes classes of which only one compound was measured, but the values are probably representative of the class. TABLE 14 Substance K x 1(P (cal./cm. C. 28C. ' *Areciers *Azelates t Phthalates si ` Phosphates i * I fc I > I ; ( f #Sebacatea| t iff Silicates `' +Ucon DLB-50 +Paraplexj * Itodexl ryfc 24.0 55.6 32.5 ii -51.. | 06 .'O' >- >31.7 03.0, 23.5 33.6 30.5 30.1 35.1 32.5 30.Q 3.6; 7* 30U. . R 1= aliq| ^,1 1t f DSW 620707 STLCOPCB4094735 m V:.jCOWCL' JIOJ i f* I, ?1. *Pydrai Pydraul1 F9 has found considerable utility as a non flammable type industrial hydraulic fluid. Principal areas of use have been in the die-casting industry. The field of industrial fire resistant fluids is highly com petitive and much of the work was done with the aim of reducing coats and providing data for further uses of the fluid. In an effort to reduce costs, the effects of increasing the Aroclor to trlcresyl phosphate ratio were investigated. Such a change resulted in somewhat higher pour point. Samples were submitted to Douglas for approval and a formulation change was adopted for manufacture which resulted in about one-half oent per pound savings. The trlcresyl phosphate used in Pydraul F9 wa3 always made from coal tar cresols. Increased use of this ester made It desirable to use material made from petroleum cresols or from purchased trlcresyl phosphate. No significant differences in physical properties were found in Pydraul F9 made from each of the three types of tricresyl phos phate. Douglas examined these samples for lubricity in the 4-Ball Wear Test and found them to.,be approximately equivalent. Hence, used alone/ each type4was approved for Pydraul F9 manufacture. Two competitive fluids to Pydraul F9 were given a prelim inary screening. Llndol H? has properties similar to regular trlcresyl phosphate. Houghto Safe 271 is a water based fluid and this is reflected in its properties which in preliminary screening are inferior to those of Pydraul F9. Relative evaporation of Pydraul F9 and Houghto-Safe 271 at room temperature was found to be essentially zero and about 40$, respectively, in 65 days. A great many properties of Pydraul F9 were determined at the request of various groups. These may be summarized as follows: Skydrol 7000 and Pydraul F9 are compatible to 0C. or lower. The solubility of water was shown to be small In Pydraul F9 ranging from O.I856 at 75F. to 0.55^ at 210F. Pydraul F9 is quite hydrolytically stable as demonstrated by the regular "coke bottle" test. | Specific i t heat/ variation of density with temperature, electrical properties, and thermal conductivity were determined, for, Pydraul F9. s i . i i L, . * l - i ' ifti Ichtrac terls^t] navlorfqh spW dFe't?nri. Lne DSW 620708 STLCOPCB4094736 lere" was!no flash back;during s :aat iithturever.* theiPydrafijfcfrq 'burned In the flames. lu^PPwa^l'decideaiyT better the A mineral oil. Pydraul F9*s flammability in contact with molten nitrates was examined in Iron, porcelain, andlnickel cruoibles. Using the iron and porcelain crucibles, dropping or spraying Pydraul F9 onto the surface of the molten nitrates did not cause ignition. In the nickel crucible no ignition occurred at low volatilization rates, but at high rates, intermittent combustion occurred. 1 Several new types of triaryl phosphates were examined as base stocks for Pydraul F9 but none offered any advantage. Several defoamers were screened but were found to be less effective than the presently used silicone. A number of used Pydraul F9 samples were examined as a sales service to various customers. Evaluations were made based on physical properties as to the usuability and condition of the fluid. Also several hydraulic system components were examined for resistance to Pydraul F9. 2. Skydrol 7000 Skydrol 7000 is used as a non-flammable type aircraft hydraulic fluid and is receiving .ontinually widening acceptance. Various properties were determined to aid the saies effort and to learn more about the fluid. Complete compatibility of 25# Skydrol 7000 in aviation gasoline, 1C# Skydrol 7000 in Skydrol 500 and 1556 MIL-0 5606 mineral oil hydraulic fluid in Skydrol 7000 was found under the conditions studied. Water solubility in Skydrol 7000 was shown to be about 0.556 at 75F. and 1.7556 at 210F. The hydrolytic stability of Skydrol 7000 was studied in detail in conjunction with Skydrol 500. In general, the fluid will not pass the military specifications for hydrolytic stability. However, no evidence of hydrolytic instability has ever been reported in actual use. Several used samples of Skydrol 7000 were examined a3 a customer service and recommendations made. Thermal i conductivity wa3 determined. Skydrol 5001 ' f f r r I ijj \ Skydrol 500 was developed in cooperatloniwith the Douglado ^ / geet .military! lsehfclk|ly|df| lf DSW 620709 STLCOPCB4094737 ______________lex^ iwpMv^ilufidl a?cbpper rdeaotSVt j&A^|t^r|i|rife^onslQ^^elefQr^wa8le3cgeT "tTeiting^the' various materials - for suitability Tqv _ plant and larger scale production of fluid. | |^: i The effectiveness and utility of the copper deadtivatorinhibitor pair can only be demonstrated by Oxidation and Corrosion Tests. At first, results obtained by our laboratory and by the Douglas laboratory did not agree. After many runs it was demonstrated that most of the differences were caused by the use of Insufficiently dry air. The first copper deactivator proposed by Douglas was unsatisfactory because of insolubility and efforts were made by both groups to find better materials. Our search resulted in no better compounds than the second one proposed by Douglas. This material, ethylene bis tolvl sulfide, is used in the formulation as it now stands. Specifications were proposed for the fluid and large amounts were formulated in the Interim Production facilities and Pilot Plant. In order that the two Skydrols may be readily identifi able, a search was made for a purple dye for Skydrol 500 (Skydrol 7000 is green). A relatively heat stable purple dye (Alizarine Irisol N) was found and has been adopted for use in Skydrol 500. The* results reported by the Naval Air Experiment Station on a thin film corrosion test at 225F. using Skydrol 50C Indicated rather severe corrosion and a series of tests were run in our laboratory to attempt to check their results. The data from the first series did not show the same results as reported by the Navy, corrosion being less severe. After discussion with Navy personnel, cooperative testing on Skydrol 500 In the* thin film corrosion test was continued. Results for a second series of tests Indicated that the test is not reproduc ible, results depending greatly upon the surface condi tion of the metal test specimens. Comparative tests were run using Skydrol 500, Skydrol 7000, and Hydrolube H-2 at three temperatures. Our results were similar to those obtained by the Navy who also found erratic, nonreproducible test data. The hydrolytic stability of Skydrol 500 was studied by ;the "cokeibottle" technic since some concern.about thisf ; f `property was1 expressed by potential users. SkySrol;500 does not pass the test (as defined by military specifica tion MIL-F-7100) and d.s; somewhat pqorer thaniSl *`J"" ' ' * vdoes,. 9ot|oas| th&stfecifll * ' 1 e.aiMrt.Qlf re up . cop DSW 620710 tff STLCOPCB4094738 'Ixiid ^Ltadefinite water j i. ; . ion?Wuyeran??fth^tea tfdoe s hot appear to * with actual "use experience. le^solubility of water in Skydrol 500 was shown to be i appreciable, being about 2.2# at 75*F. and 4.1# at 210F. ; The specific heat, variation of density with temperature, ' electrical properties, and thermal conductivity of Skydrol 500 were determined. 4. Fluid OS-41 Fluid OS-41 was previously developed as a high specific gravity fluid for use in torque converters. Since some corrosive action toward iron was reported, an oxidation and corrosion test was run using various additives. In no case was iron corroded. However, the additives reduced attack on copper, magnesium, and cadmium-plated steel. The fluid was hydrolytically stable in the "coke bottle" test. Specific heat and thermal conductivity were determined for Fluid OS-41. 5. Fluid OS-54 A series of fires resulting from leakage in hydraulic power steering- systems in automobiles aroused considerable interest in a non-flammable type fluid for this use. Fluid OS-54 was formulated to meet the physical require ments and samples submitted for testing. Such tests for utility in power steering units are continuing. Fluid OS-54 has properties that appear to make it poten tially useable in catapult systems. Fluid in a four-drum quantity was supplied to the Navy for tests aftei a cata pult fire and explosion. These tests are still underway. Since the fluid contains a small amount of oil which is used as a carrier for the viscosity index Improver and since performance in the oxygen demand test is borderline, a sample called OS-54-1 of oil-free material was prepared for the Navy. , . i 51 o. Steam Turbine Lubricants A definite need exists for a fire resistant steam turbine lubricant. A fluid meeting the physical property specifi- I caftlans .was madcap from Aroclor 1242`sand trlcresyl pr.03- ~pHf lt# Wit_h'various ad...d...i.t..ives (' Fluid OS-5"3). Tests by the Engine;Test Laboratory indicated that the fluid passed dejnulj3ificatipn testa and wLth ithe additlofr^qfj. certain, Mi a| is^fo.uj it1 If DSW 620711 STLCOPCB4094739 1 j Pormulatiorf, jeirature Jus illior lie* type hydiravflie flv5d was devised*(Fluid?OS"57)il "it Is felt that such a fluid la needed to fit Into certain applications where the puur point of pydraul F9 makes the latter inoperable. Two batches were prepared In the Interim Production facilities and the fluid Is under test by prospective customers. Thermal stability tests Indi cated that Fluid OS-57 is similar to Skydrol 7000 in this characteristic and much poorer than Pydraul F9- 8. Miscellaneous Fluids Physical measurements of specific heat, electrical proper ties, variation of density with temperature, and thermal conductivity were made on the silicate ester base high temperature fluids (OS-45 and OS-45-1). Alternate raw materials were examined for use in formu lating Fluid L-3A and larger samples prepared for test work by prospective customers. 9. Preliminary Screening Preliminary screening on many liquids was carried out. These materials were either synthesized in our labora tories or submitted by other groups. Azelates, pinates, succinates, adipates, and phosphates were prepared by our group. Certain of these esters as well as some of the materials submitted by other groups will be given further evaluation. 10. Physical Measurements The physical properties of specific heat, variation of density with temperature, electrical characteristics, and thermal conductivity were determined for many of the fluids discussed in this report. A method of calculating thermal conductivity of a fluid from the thermal conduc tivity of the various components was developed and shown to be sufficiently accurate for most work. VI. APPENDIX During the period of this work, other studies in the field of fuctional fluids were in progress. A listing of,Job numbers , | other 'than giveri under references is as follows: 4 Tetraalkyl Silicates iFunctloha: lulds* ~ MinoriPla I vtl, " l i nv! viatic "* ' * ` DSW 620712 STLCOPCB4094740 tit p*H|Iaraf^ivads .... p# |.ifa- tlg1. a. tifIri-5f.'4IA-^aCciiaxiltations 1] [oratory Research for 1954. . . Synthetic Lubricants *' - 117-2720' . Adipate and Azelate Esters, Pilot Plant Prepa ration. The work covered by this report is recorded on the following notebook pages: A30502, 4, 5, 9, 11-13, 15-23, 25, 26, 29-34, 38, 42-^5, (REH) A-30464, 65, 75, 80-82, 84, 85-89 47"5 A36062"06' 8' l8' 19' 21> 2j5' 25' 31, 3T-- 58 A48863, 76, 900 A51001, 32 A45645, 46, 49, 50 A37252, 54, 56, 59, 60, 62-3, 66, 69-79, 81-2, 84-90 A52203-5, 07-12, 14-18, 21-29 9>4' 96'3CO Specific Heats (WEK, OBC) A-32670-6 A-34055-64; 34065-67; 34070-79 A-41320-28 Densities (WEK, OBC) 'A-41251-3 " A-41255 A-36753-4 Electrical Properties (WEK, OBC) (REH) (REH) STLCOPCB4094741 STLCOPCB4094742 STLCOPCB4094743 STLCOPCB4094744 STLCOPCB4094746 STLCOPCB4094749 STLCOPCB4094750 STLCOPCB4094751 STLCOPCB4094754 STLCOPCB4094755 STLCOPCB4094756 STLCOPCB4094758