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:. **!/> STLCOPCB4095674 MONSANTO CHEMICAL COMPANY Organic Chemicals Division St. Louis Research Department St. Louis Research Report No* 2176 . FINAL REPORT ON -- F--UN-- C--TIO--NA-- L--FL--UI--DS-- --- A-- P--PL--ICA--TI--ON-- R^ES--EA--RC--H-- (1--95-- 6---57--) JOB NO. 2-02-750.01-5152 October 14, 1958 Reported by; J.D. Sullivan Work done by; R. E. Hatton J. D. Sullivan DSW 621644 STLCOPCB4095675 DISTRIBUTION FOR REPORT NO. 2176 1. 2. 3. 4. 5. 6. f-1T 8. 9. v^Co. File T. M. Patrick - R. E. Hatton J. H. Lum - F. B. Zienty - file Duplicate file Res. and Dev. file - C.C. J. D. Sullivan T. P. Sands - Organic Development Department R. Davis - Organic Sales Department Extra Extra - This report contains confidential Information which is the property of the Monsanto Chemical Company which shall be disclosed only to duly authorized persons. The recipient Is held accountable for the filing and safe custody of this report which must be returned on demand. DSW 621645 STLCOPCB4095676 INTRODUCTION TABLE OF CONTENTS PAGE NO. SUMMARY REFERENCES EXPERIMENTAL WORK AND DISCUSSION I. Formulations (1) Thickening Agents for Tricresyl Phosphate (TCP) 2 a. TCP Formulations as Transition Fluid b. Compatibility with Hydrocarbon Oils c. Shear stabilities of TCP Formulations d. Hydrolytic Stabilities of TCP Formulations 2 2 3 3 (2) Utilization of OS-70 in Pydraul Fluids. '4" a. Preparation of FH-127, FH-128 and FH-129 4- (3) Pilot Plant Production of OS-90 and OS-91 5 (4) Pydraul 150 Defoamer Concentrate (5) Production of Fluid OS-16 (Pydraul 6o) a. Screening of Blue Dyes b. Storage Stability of OS-16 (6) Production of Fluid OS-83 (Pydraul 625) (7) Viscosity Spread of Pydraul AC 5 5 6 6 6 6 (8) Blending of Aroclor 1248RI 7 II. Applications 7 (1) Heat Stabilities of MCDP and Santiclzer 141 7 (2) Heat Stabilities of Pydraul F-9 and FH-127 7 (3) Compatibility of Pydraul AC with Fluorochemical 101 8 (a) Aroclor 1254 with Fluorochemical 101 8 DSW 621646 STLCOPCB4095677 TABLE OF CONTENTS (Cont'd) (4) Coefficients of Thermal Expansion PAGE NO. 8 a. Of Pydraul 150, Pydraul 600, Pydraul AC and OS-79 8 (5) Ice-Box Storage Stability Tests 10 (6) Applications of Pydraul Fluids 10 a. Pydraul 600 in Dept. A-9 (St. L.) b. Pydraul F-9 in W-Bldg. (St. L.) c. Pydraul AC at Nltro d. Pydraul F-9 at Mobay 10 11 11 11 III. Evaluations 15 (1) Various Substituted Biphenyls 15 a. Isopropyl Biphenyls and Alkylated Aroclors 15 (2) Polyester Permanent-Type Plasticizers a. Santicizer 4o4 and Santicizer 4o8 (5) 'Viscosities of Various Phosphonates 12 15 14 a. D1 2-Ethylhexylchloromethyl phosphonate b. Dibutylchloromethyl Phosphonate 14 14 (4) Viscosity of Trl(o-Benzylphenyl) Phosphate 14 (5) Dayton Fluids 14 a. Octyl 5-(0ctyloxy) Propionate b. (2-Ethylbutoxy) Propionate 14 14 (6) Various Phosphates from Carbide Coal Xylenols 14 ACKNOWLEDGMENT 15 APPENDIX DSW 621647 \ / STLCOPCB4095678 INTRODUCTION 1. Since Monsanto's entry into the field of functional fluids in 1948, their marketed fluids have been divided into two lines. One group consists of Skydrol fire-resistant aircraft hydraulic fluids, the other includes the Pydraul fire-resistant industrial hydraulic fluids. This report covers work on functional fluid application research for 1956 1957, principally in the industrial field, including the formulations and property determinations of new fluids, a study of extended applica tions for current Pydrauls, evaluation of potential base stocks and production of new fluids. SUMMARY Since consistency of viscosity is considered more important than low change of viscosity with temperature, the current trend in func tional fluids is toward shear stable formulations. For this reason, shear stable Pydraul 625 replaced Pydraul 600, Fluid OS-16 was marketed as Pydraul 6o and Pilot Plant blends of OS-90 and OS-91, as well as Aroclor 1248RI, were submitted to potential customers for large scale evaluations. Further formulation problems, brought under study, were the selection of a shear stable thickening agent for trlcresyl phosphate and the utilization of OS-70 (a trlaryl phosphate) in Pydraul fluids. In a search for new base stocks, viscosity evaluations were made on various substituted biphenyls, polyesters, phosphonates, propionates and phosphates. Heat stabilities and storage tests were run on the more promising base stocks and formulations. Coefficients of thermal expansion and compatibilities were determined on a series of Pydrauls fluids in an effort to meet the requirements of new industrial applica tions . REFERENCES 1. Final Report No. 620 "Hydraulic Fluids and Synthetic Lubricants", 117-2080 by R.E. Hatton, May 15, 1952. 2. Final Report No. 728, "Functional Fluids", 117-2580 by R.E. Hatton, May 21, 1955. 5. Final Report No. 988, "Functional Fluids - Application Research 1952-54", 117-2508 by R.E. Hatton, L.W. Bannister, W.E. Koerner and O.B. Cecil, August 4, 1954. 4. Final Report No. 1562, "Functional Fluids - Application Research for 1954-55", Job No. 2-02-750.01-2815 by R.E. Hatton, July 6, 1956. 5. Tentative Process, Report No. P-707 "Preparation of 0S-16", Job No. 2-02-750.01-5132 by J.D. Sullivan, July 15, 1956. 6. Tentative Process, Report No. P-74q, "Blending of OS-83, Job No. 2-02-750.01-3132 by J.D. Sullivan, December 27, 1956. 7. Tentative Process, Report No. P-810, "Blending of Aroclor 1248RI, Job No. 2-02-750.01-3132 by R.E. Hatton, November 19, 1957- DSW 621648 STLCOPCB4095679 2. FX PERIfltF.NTAL WORK AND DISCUSSION I. Formulations 1. Thickening Agents for Trlcresyl Phosphate (TCP) a , TCP Formulations as Transition Fluid The purposes of this Investigation were: - functional fluid. General - To market a new phosphate ester based Specific - Formulate a transition fluid for "changing over" from hydrocarbon oil to Pydraul F-9 without closing down a large hydraulic installation, since some hydrocarbon oils are insoluble in phosphate esters. Since Pydraul F-9 is soluble in naphthenic and paraffinic base oils, various Acryloids were tested as a thickening agent for trlcresyl phosphate in an effort to formulate a transition fluid for "changing over" from hydrocarbon oil to Pydraul F-9 without closing down a large hydraulic installation. The following table lists the various Acryloids and polyacrylates tested along with the amounts, required to attain the desired viscosity of the transition fluid. Additive Code in TCP Required Amount Reference 70/50 2EHAc/EAc 50$ in OS-69* Skydrol 500 Acryloid Oil Free N-5262A N-5262A-pure quill Skydrol 7000 Acryloid duPont's V.I. Improver Special Acryloid P-72 50020 L-1501 PC-1544 754 PL-172 G-5575X insoluble soluble insoluble insoluble Insoluble soluble soluble 5.9$ -- -- -- 4.2$ 4.5$ A-99268 A-99266. A-99268 A-99267 A-99266 A-99266 A-99266 x OS-69 = 10 TCP in Aroclor 1242 b. Compatibility with Hydrocarbon Oils The more promising additives, as well as several Ucon fluids, were formulated with trlcresyl phosphate (TCP) to a desired viscosity and each formulation was mixed with an equal volume of paraffinic oil, as well as an equal volume of naphthenic oil. The mixtures were allowed to settle before careful separation and analysis of each layer. Table I identifies the TCP formulations in combination with the hydrocarbon oils and lists some of the physical properties of each component before mixing, along with the corresponding changes in these properties as a result of the mixing operation. PL-272 is an experimental duPont additive, 50020 is the Acryloid used in Skydrol 500 and 50-HB-660, as well as 75-H-90,000, are water soluble Ucons. DSW 621649 STLCOPCB4095680 & t- I I . "jI ft M o UT4 CM N, Di w in CM m <7\ cu H l/> CM CVJ in m tK\ ci ft ft m CO o coco CM CM rt H t1 o (ft 0 (ft ift (ft (ft 00 m o m mm l cvi cm ++ H+ C+M Pt Oft(ft 00 (0ft (ft pmo o oo ' CIM CIM CIM ?VO CMxfCO H CM rC Jtl<N 3 i I I I +++ 3 * N -# m * m CM tnvo i o m VO crv ci CO t- CMm* C-CO fve*jm-.sc mm in m in CO i s o fOI CMCO c- * El SS*nPm&-tffce- mo\ in $ H voH inIS.c*M*m CO o jM-vo CSrM inOVQ cm mm#-in 1ft(l (ft S(ft -jT-oy w .(KRTft * *t < OVCT\ O .USS 1S& isR USSftM SUm $(ft(ft RK (ft 3 h invoco $u\33- m o cm 5 * r *m 3 mm** h m*c m voc- cooto*^ o|m#j ***** ~******%i s*********** DSW 621650 STLCOPCB4095681 3. Essentially no interchange of layer volume resulted in mixing the phosphate ester formulations with paraffinic oil, whereas measurable amounts of naphthenic oil was dissolved in the phosphate ester layers. Cellulube 220 experienced the largest take-up of naphthenic oil. All of the additives tested were essentially retained ' ih the TCP layer after the mixing operation. The phosphate ester extracted colored material from both of the hydrocarbon oils. The paraffinic oil caused the TCP layer, containing Ucon's 75-H-90,000, to turn coal black upon mixing. The TCP extracted additives from the paraffinic oil which resulted in increased viscosities and viscosity indices of all of the TCP formulations tested but the mixing caused a decrease in the specific gravities of the phosphate ester layers due to equally mutual solubilities. The specific gravities of the paraffin base oil layers were correspondingly increased. On the other hand, the naphthenic oil caused a decrease in the specific gravities, the viscosities and the viscosity Indices of all of the phosphate ester layers by straight dilution, which in turn caused a substantial increase In the specific gravities of the naphthenic oil layers. c. Shear Stabilities of TCP Formulations The shear stability of various tricresyl phosphate" (TCP) formulations were evaluated in the Functional Fluid Testing Laboratories. Ucon 75-H-90,000 was shear resistant at a 1.58# concentration of TCP. The following table lists the shear characteristics along with the concentration of various polymers required to convert TCP into fluids with viscosities comparable to Cellulube 220. # Polymer in TCP 5.9# 50020 io# hb-66o 8# 75H-90,000 1.58# 75H-90,000 4# PL-272 Cellulube 220 TCP ## Initial Sheared36 Shear Initial Sheared36 Shear 49.36 44.38 105.60 47.80 48.00 47.02 33.30 41.40 43.62 101.71 47.80 4o .20. 46.52 -- 16.1 1.7 3.7 0 16.3 1.1 -- 6.84 5.75 5.38 6.26 4.77 4.34 5.41 5.39 12.40 5.38 4.98 4.70 20.9 0.6 -- 0 20.4 1.5 x 12 passes through a Diesel Injector Shear machine d. Hydrolytic Stabilities of TCP Formulations Continuing, the investigation of thickening agents for tricresyl phosphate, the following formulations were submitted by the Functional Fluid Application Research Laboratories for hydrolytic stability determinations. Formulation #1 Formulation #2 Formulation #3 Formulation #4 1.55# Ucon 75-H-90,000; 200 ppm RI-150 1.55# Ucon 75-H-90,000; 0.2# RI-150 4# HF-825 1.55# Ucon 75-H-90,000; 50 ppm Tretolite AD-9 DSW 621651 STLCOPCB4095682 !4 . The following results were obtained from the standard "coke-bottle" method for hydrolytic stability on these formulations: Formulation #1 Formulation #2 Formulation #3 Formulation #4 Weight Loss (Cu) mg./sq. cm. 0.39 0.69 0.71 0.29 Appearance of Copper Test Strips brown w/ black streaks reddish-bronze color gray-black cast It. tan w/ gray cast The appearance of the copper strips #1 and #4 are border line and all of the above copper strips show more copper staining than a similar test on Cellulube 220. The maximum allowable copper weight loss in this te3t is 0.30 mg. per sq. cm .^according to military specifications MIL-H-19^57 and Cellulube 220 ranges between 0.06 and 0.12 mg. per sq. cm. These formulations are not considered satisfactory for submission to the Navy under the above specification. 2. Utilization of OS-70 In Fydraul Fluids a. Preparation of FH-127, FH-128 and PH-129 -- 0S-70, a triaryl phosphate from Productol's "Special-B Grade" cresylic acid, proved to be ^isatisfactory for use as a substi tute for tricresyl phosphate (TCP) in Pydraul F-9 (A-79808), Pydraul 600 (A-79809) and Pydraul AC (A-79807). As a result of viscosity, pour point and specific gravity determinations, 45$ Santicizer 140 in OS -70 proved to be a suitable substitute for the 45$ TCP component of Pydraul F-9 (A-79821). Substituting a mixture of 0S-70 and triphenyl phosphate (D-ll) (70$ to 30$) for the TCP component of Pydraul F-9 gave a comparable fluid from the standpoint of physical properties (A-79822) . Table II shows the scope of this study. Varying the amounts of Acryloid 710 used in conjunction with OS-70 in the Pydraul F-9 formulation gave poor Vi's. Substituting 0S-70 for TCP In the regular Pydraul AC formulation gave high viscosities and pour points. Using OS-70 in the Pydraul 600 formulation and reducing the concentration of Acryloid 710 gave a fluid with satisfactory viscosities but high pour points. The formulations for Pydraul F-9 and Pydraul AC in which 55$ 0S-70 and 45$ Santicizer l4o were substituted for the TCP component were designed as FH-127 and FH-128 respectively (A-79850). A sample representing a mixture of fifty percent regular Pydraul F-9 In FH-127 was labeled FH-129. Table III lists the physical properties of these fluids which were sent to Douglas Aircraft Company for evaluation and for approval of formulation changes. DSW 621652 STLCOPCB4095683 o > in o try CM P.4* 00 co^00 r-t Orl 'O'P vp in M0 ON rH OH vO VO st O CO st CO *H O r-i mo O ON CM OK o\o O rH vp m FNVO ao in CQ rH O r-i K\ st CM Oi 1 O lA^St K\ cost CO H O rH 0 m1 ON 1 0 St St 00 CO 0 in vO {m co 00 ON 00 O0 c*st st ON O > z o M H * O a# a H w o CM CQ o > 1 O O H in in 00 f- ++ 0 CM -t * VO a 0 VO O VO O0 K> st OO Ol sf st St st 0 Os 1 l f iH 1 l 1 ++ aa 00 m c-- 0 VO 1 1 I I l 1 t- VO 0OOOO mt- ON CM St on O m VO H on St CM O m St St St rH iH rH 1 m st 1 11 a (0 CM 1 K\ 1 st a 0 K\ CM st 1 1 1 1 0OO0 iH ON VO st m St m ON K\ CM VO K"\ K\ -t J 1 1 1 O ON st O Jt b & aa3 iH a O > 0a 00 00 in in 00 00 rH Ol -=* in 00 00 00 in m 00 00 m in #H CO st in a0 00 H (7l lAst OO OO mt-st m OO OO OO in m 00 00 VO St st m e0 00 rH ON lAst OO OO #H On st in OO OO OO m in OO OO t-- m KNvO DSW 621653 STLCOPCB4095684 V 5. TABLE III Sample Acidity, NN Moisture, # Sp. Gr. at 25/25C. Pour Point, F. Viscosity, cs . at 210F. Viscosity, cs. at 100F. FH-127 0.05 0.06 1.289 0 5.5^ 49.0 FH-128 0.03 0.05 1.355 +20 4.78 75.2 FH-129 0.05 0.05 1.282 0 5.66 51.0 The Douglas Aircraft test results on these fluids are listed In the Appendix of this report. 5. Pilot Plant Production of 0S-90 and OS-91 Fifteen gallons of 0S-90 and 15 gallons of OS-91, high viscosity Aroclor formulations, were prepared in the pilot plant for shipment to the Chrysler Corporation. OS-90 contains 55# Aroclor 1254 and 45# Aroclor 1248, whereas OS-91 contains 20# Aroclor 1260 and 80# Aroclor 1254. These formulations will be tested as high density torque converter fluids. The following table lists the analyses of these formulations. Viscosity at 100F. at 210F. Acidity Moisture Sp. Gr. at 25/25C. Pour Point 118.3 cs. 4.32 cs. 6.11 cps. 0.02 NN 0.01# 1.499^ +35 F. 4. Pydraul 150 Defoamer Concentrate 917.7 cs. 7.11 cs. 0.02 NN 0.03# 1.5659 +60F. A supply of Pydraul 150 defoamer concentrate (A-79828) containing 50 ppm D.C. 200 was prepared for the U.S. Steel Gary Plant. 5. Production of Fluid OS-16 (Pydraul 60) . OS-16 is 2-ethylhexyl diphenyl phosphate (Santiclzer l4l) containing a sufficient amount of dye to Impart to the fluid a characteristic blue color. OS-16 was Introduced by Monsanto in 1949 as a low viscosity, non-toxic, fire-resistant hydraulic fluid and underwent extensive testing in various applications of the coal mining industry. This product was very satisfactory as a hydraulic fluid for coal mining machinery but a demand for OS-16 did not materialize because the price was considered prohibitive. In 1955* the Aluminum Company of America found OS-16 to be an excellent hydraulic fluid in a. control mechanism because of its shear stable viscosity index in addition to its fire-resistant characteristics. The Increased demand for OS-16 in this application warranted the large scale production of this fluid. A tentative process for the production of OS-16 was pub lished In Report No. P-707, July 13, 1956 by J.D. Sullivan under Job No. 2-02-750.01-3132. This fluid is being marketed under the name of Pydraul 60. _ ___ ' ____ DSW 621654 STLCOPCB4095685 6. a. Screening of Blue Dyea Because the production of "Blue Mist" dye was dis continued, a search for a suitable substitute wa3 undertaken to provide the characteristic color for OS-16. Traffic Blue, Blue 3, Blue 2, Blue TX from the Patent .^Chemical Co. (A-79810) and duPont oil Blue A (A-79805) were- evaluated for this application. DuPont Blue A was far superior from the standpoint of solubility and concentration. A color comparable to 28 ppm Blue Mist dye in Santicizer 141 was obtained with a similar solution containing 7 ppm duPont Oil Blue A and the resulting dye concentrate did not require filtration before formulation when the latter was used. Thus, duPont Oil Blue A was adopted for the OS-16 formulation and sufficient dye concentrate was prepared in the laboratory to supply the production requirements of OS-16 in Department 50 (A-79810-ll) . b. Storage Stability of 0S-16 A sample of OS-16 (Lot R-3156) was removed from the Packing Room after five years of drum storage. The blue dye had faded to a light purple and the acidity increased to 0.85 NN (A-79837). 6. Production of Fluid OS-85 (Pydraul 625) __ OS-85* a shear-stable version of Pydraul 600, is the most recent addition to the Pydraul line of fire-resistant industrial fluids. Several gallons of OS-83 were prepared in the laboratory and submitted for customer evaluations in particular applications where consistency of viscosity appears to be more important than low change of viscosity with temperature. This new functional fluid has a specific gravity of 1.3566 at 25/25C. (A-89452) and a viscosity of about 625 SUS at 100P. The viscosity of OS-83 varied from 6.0 cs. at .210 F. to 6800 cs. at 50P. Temperature Viscosity in cs. 210 F. 130P. 100F. 75P. 50P. 6.02 36.65 135.5 644. 6810. A tentative process for the production of OS-83 was pub lished in Report No. P-74o, December 27, 1956 by J.D. Sullivan under Job No. 2-02-750.01-3132. 0S-83 has been officially transferred to the Sales Department and this fluid is being marketed under the name of Pydraul 625. 7 Viscosity Spread of Pydraul AC Proposed applications of Pydraul AC required determining viscosities of Pydraul AC in order to predict the pumpabillty of the fluid at various temperatures. The viscosity of Pydraul AC varied from 5.00 cs. at 210F. to 3200 cs. at 50F. DSW 621655 STLCOPCB4095686 7. Temperature Viscosity In cs. 210F. 150F. 108P. 75P. 58 F. 8. Blending of Aroclor 1248RI 5.00 26.7 84.5 556.0 5210 Aroclor 1248RI Is a rust Inhibited version of Aroclor 1248 proposed for use as a fire resistant hydraulic fluid. Some trouble has been experienced with deposits and rust in certain hydraulic systems using Aroclor fluid. The addition of a small amount of rust inhibitor, Santolube 70, should decrease this tendency. A tentative process for the blending of Aroclor 1248RI was published in Report No. P-810, November 19, 1957 "by R.E. Hatton under the Job No. 2-02-750.01-5152. II. Applications 1. Heat Stabilities of MCDP and Santicizer 141 1-Methylcyclohexylmethyl diphenyl phosphate (MCDP)" was prepared for comparison in thermal stability with Santicizer 141 (2ethylhexyldiphenyl phosphate). The former compound was considerably more stable at 150C. but about equivalent at 175C. Viscosity characteristics were poorer than those of Santicizer l4l. The following table lists the weight losses and acid formations at various temperatures for Santicizer l4l and MCDP. Material Temp. Hours Wt. Loss NN Santicizer 141 MCDP Santicizer 141 . fcf&F Santicizer 141 MCDP 150 150 150 150 175 175 12 12 24 24 24 24 0.25# 0.15 1.16 0.16 51.4 26.2 1.25 0.27 7.0 0.56 215 209 In the evaluation as plasticizers, 1-methylcyclohexylmethyl diphenyl phosphate was considerably poorer in flex but slightly better' in volatility and kerosene extraction than Santicizer 141. 2. Heat Stabilities of Pydraul F-9 and PH-127 Samples of Pydraul F-9 and FH-127 were heated in beakers in a 150C. oven for 52 day3. Samples were taken at intervals and examined. Little difference was noted. FH-127 is a pydraul type fluid made from 0S-70. The following table lists the results of these tests. DSW 621656 STLCOPCB4095687 3. Time in Oven 150C. 0 27 hr . 74 hr. 1 wk. 11 da. 18 da. 25 da. 52 da. Acidity, (NN) PF9 .082 .082 .112 .122 .245 .467 .841 1.12 FH-127 .082 .082 .112 .122 ,245 .467 .841 1 .12 Weight _Lossx PF9 FH-127 s g- 1.6 3-9 6.1 9.2 14 .4 19.4 25.5 1.8 4.2 5.9 8.8 14 .9 19.9 25.5 Sp. Gr. at 25/25C PF9 1.275 1.275 1.275 1.275 1.275 1.269 1.261 1.272 FH-127 1.289 1.290 1.289 1.291 1.288 1.284 1.277 1.285 x 900 grams of each fluid was used in this test. *, 0 O --r 1 CM Time in Oven 150C. Viscosity 100F. PF9 FH-127 cs. cs. Viscosity PF9 cs. FH-127 CS . .0 27 hr. 74 hr. 1 wk. 11 da. 18 da. 25 da. 52 da. 52.9 51.7 51.6 51.0 51.2 52.1 54.4 53.6 48.5 50.0 50.0 51.1 51.0 52.0 54.0 54.$ 5.91 5.50 5.37 5.30 5.32 5.40 5.51 5.32 5.54 5.35 5.61 5.65 5.67 5.82 6.07 6.01 ' 5. Compatibility of Pydraul AC with Fluorochemical 101 A liquid was required having a higher specific gravj than,and incompatible with Pydraul AC for use in certain air compressor lubricating devices. Shaking equal amounts of Pydraul AC or tricresyl phosphate in Fluorochemical 101 formed a white liquid which Immediately separated into two phases. Aroclor 1254 - Fluorochemical 101 mixtures did not entirely separate after standing for several days. 4. Coefficients of Thermal Expansion (WEK and WDW) A Vycor pyconometer was used to measure the densities of the four Pydraul samples over the temperature range 0-200C. These data are tabulated below: Pydraul 150 . Temperature (C.) 0.1 24.9 60.I 88.8 117.5 149.9 Density (g./ml.) 1.1428 1.1225 1.0935 1.0707 1.0467 1.0198 Volume (ml./g.) 0.8752 0.8910 0.9145 0.9340 0.9554 0.9805 DSW 621657 STLCOPCB4095688 9. Pydraul AC-OS-67 Temperature (C.) 24.9 64.4 100.3 133.0 162.0 191.6 Density (g./ml.) 1.3475 1.3119 1.2813 1.2472 1.2230 1.1958 Volume (ml./g.) 0 .7421 0.7623 0.7805 0.8017 0.8176 0.8363 Fluid OS-79 24.9 69.3 98.0 128.5 165.0 198.5 1.3598 1.3181 1.2936 1.2631 1.2317 1.2015 0.7354 0.7587 0.7730 0.7917 0.8119 0.8323 0.2 24.9 59.9 98.6 145.3 191.0 1.4231 1.3992 1.3655 1.3289 1.2836 1.2392 0.7027 0.7147 0.7323 0.7525 0.7791 0.8070 The equations of the straight lines which result when density is plotted as a function of temperature are: Pydraul 150 -- dt = 1.1428 - Pydraul AC-OS-67 -- dt - 1.3703 - Pydraul 600 -- d - 1.3823 - Fluid OS-79 -- d* = 1.4232 - (8.17 x 10-4)t (9.07 x lO-4)*. (9.12 x 10"4Jt (9.67 x 10-4)t Where d-^ is the density in g./ml. at tC. These equations can be used to calculate exact densities within the experimental range, and may also be used to obtain approximate densities outside the experi mental range. Calculated values differ from experimentally observed values by less than 0.1$. To obtain volumes in ml./g. at any tempera ture, calculate the density at that temperature and then take the reciprocal of thi3 value. The coefficients of thermal expansion were calculated from the equation; coefficient 2 (Va - Vi) (v2 + Vi) (Ta - Ti) DSW 621658 STLCOPCB4095689 10. Where V2 is the volume at temperature T2 and Vi is the volume at temperature Ti. These coefficients, as calculated from the experimental points of widest separation, are listed below: Pydraul 150 --- 7-576 x 10~*/c. Pydraul AC-OS-67 7.160 x 10"4/C. Pydraul 600 ----- 7-121 x 10~VC. Fluid OS-79 --- 7-242 x 10"VC - These values may be converted to engineering units (value/F.) by dividing by 1.8. 5- Ice-Box Storage Stability Tests The following table lists the results of ice-box stability tests on various formulations along with the date on which these test3 were started. a. Pydraul F-9 in which the TCP (tricresyl phosphate) component of the fluid was substituted by 50$ triphenyl phosphate and 70$ 0S-70 was compatible (5-15-56 to 2-57). b. Pydraul F-9 in which the TCP component of the fluid was substituted by 45$ Santicizer 140 and 55$ 0S-70 was . compatible (5-15-56 to 2-57). c. Aroclor 1242 (70.2 grams) and Acrylold 794 (22.5 grams) was compatible (7-2-54 to 2-57). (7-9-5^)- d. Pydraul 150, Batch #2, W-Bldg., was compatible e. Santicizer l4l (90 grams) and 10 grams HF-855 was compatible (7-9-54 to 2-57). f. FH-87 (90 grams) and 10 grams of R-5876X was compatible (7-6-5^ to 2-57). g. Santicizer l4l (90 grams) and Acryloid 710 (10 grams) separated on storage (7-6-54). h. Santicizer l4l (69.1 grams) and Acryloid 794 (7-5 grams) separated on storage (7-2-54). 6. Applications of Pydraul Fluids (a) Pydraul 600 in Dept. A-9 (St. Louis) An earlier analysis of Pydraul 600 used as a bearing lubricant in a speed reducer of Department A-9 showed a moisture content of 0.02^, but the acidity had increased to 18 NN. The system was cleaned out and recharged with fresh Pydraul 600 (A-71050). The following table lists the acid build-up at the Indicated operating temperatures during the second run. DSW 621659 STLCOPCB4095690 11. Operating Temperature Acidity After 4 days After 5 days 138.2F. 147.2P. 2.47 NN 2.75 NN It would appear that conditions experienced in this unit are too severe for Pydraul 600. (b) Pydraul F-9 in W-Bldg. (St. Louis) . Pydraul P-9 was successfully demonstrated as a gear lubricant in an Oilgear Hydraulic Pump in the W-Bldg. The following table lists the analytical results of this used Pydraul F-9. Z-898 Specifications Viscosity at 100F. at 210P. Moisture Acidity Sp. Or. at 25/25C. 4o.o6 cs. 4.54 cs. 0.30$ 0.1 NN 1.2711 45-60 cs. 5.2-6.1 cs. 0.25$, max. Q.15> max. 1.275-1.295 The drop in viscosities of the fluid indica-tes the usual shear experienced in the operation but is quite satisfactory for used fluid. The moisture content is a little above specification but the acidity is excellent for used fluid. (c) Pydraul AC at Nltro An oil found in Instrument air line drops at Monsanto (Nitro) was shown to contain chlorine and phosphorus in approximately the same tfatio these occur In Pydraul AC. Therefore, it appears certain that leakage of Pydraul AC from the air compressor had occurred. (d) Pydraul F-9 at Mobay Two samples of Pydraul F-9 containing phosgene and isocyanate along with varied percentages of orthene were prepared to test the resulting formulations for lubricity. The following table identifies these formula tions and lists the corresponding physical properties (A-75727). DSW 621660 STLCOPCB4095691 12. FH-125 FH-126 Pydraul F-9 containing: 0.05$ (wt.) phosgene 0.10$ (wt.J Isocyanate 6.5$ orthene Pydraul F-9 containing: 0.05$ (wt.) phosgene 0.10$ (wt.) Isocyanate 20.0$ (wt.) orthene Sp. Gr. at 25/25C. Acidity Viscosity at 100F. at 210F. 1.2764 0.49 nn 51.51 cs. 4.70 cs. 1.2802 0.49 NN 15.29 cs. 5.08 cs. The following table lists viscosity data on Pydraul F-9 con taining varying percentages of orthene. Formulations 95$ F-9 + 5$ orthene 90$ F-9 + 10$ orthene 80$ F-9 + .20$ orthene Viscosities at 100"F. at 210"'F. 35.85 cs. 47W "cs. 24.75 cs. 4.25 cs. 15.57 cs. 5.24 cs. Samples of these contaminated fluids and of the original pydraul F-9 were sent to Douglas Aircraft Co. for Shell Four-Ball Wear Tests. Results are as follows: Wear Scar Diameters in mm. Steel on Steel Steel on Bronze Loadings: 1 kg. i.Q. kg. 40 kg. 1 kg. 10 kg. 40 kg FH-125 FH-126 Pydraul F-9, Lot Y-76 Previous Samples of Pydraul F-9 .39 .53 .42 .53 .14 .24 .20 _ . .88 .87 .70 .70 .62 1.00 1.23 .63 1.10 1.32 .55 1.18 1.27 .40 _ _ _ _ 1.27 Notes: Bronze balls tarnished in FH-125 and FH-126. Bronze balls did not tarnish in Pydraul F-9. Steel balls were also slightly discolored in FH-125 and FH-126 but not in Pydraul F-9 Although the bronze balls tarnl3hed with the contaminated samples, the wear values in our opinion do not reflect any significant change . In the case of the steel balls, the wear values do reflect a somewhat significant difference, perhaps even more so for the 4o Kg. load than for the somewhat larger spread by lower reproduci bility results obtained at one Kg. We think it would be safe to say that some increase in chemical wear attack could be expected for the two contaminated samples run under boundary layer conditions with steel bearing on steel. DSW 621661 STLCOPCB4095692 13. All the data seem to indicate that the contamination expected In this application degrades the Pydraul P-9. It is impossible to relate exactly 3uch results to actual experience in a vacuum pump in terras of life of equipment, satisfactory operation, and so on. Only an actual test can provide such Information. If Pydraul P-9 as such is satisfactory, then these results indicate that contaminated Pydraul P-9 will not be as good a lubricant and that corrosive attack is possible. III. Evaluations (1) Various Substituted Biphenyls The unexpected viscosity properties of various Isopropylated triphenyl phosphates prompted viscosity evaluations cf Isopropyl biphenyl, isopropyl Aroclors and butyl Aroclors. These results were compared with viscosity determinations on TCP formula tions containing these compounds. The following table Indicates that the various substituents lowers the viscosity index of the resulting biphenyls and that the Isopropyl group is no exception. Viscosities (c3,) Viscosity - at 100P. at 210F. Index Isopropyl biphenyl 5.26 (Aroclor 123.2) -Dichlorobiphenyl 6.75 Isopropyl Dichlorobiphenyl 19.14 Butyl Dichlorobiphenyl 278.26 (Aroclor 1242)-Trichlorobiphenyl 15.58 Isopropyl Trichlorobiphenyl 131.35 1.57 1.58 2.65 9.20 2.26 5.54 --- -203 -224 -250 -447 The viscosity effects resulting from formulating these substituted biphenyls in TCP are additive and the isopropyl derivatives In contact with the phosphate ester grouping shows no improvement In viscosity properties. 50^ Isopropylbiphenyl 50$ Dichlorobiphenyl 50$ Isopropyl Dichlorophenyl 50$ Butyl Dichlorobiphenyl 50$ Isopropyl Trichlorobiphenyl 9.99 15.06 25.65 72.65 56.39 2.21 2.6l 3-38 5.60 4.76 -8 - 76 -123 -101 -173 (2) Polyester Permanent-Type Plasticizers Viscosities were determined on polyester permanenttype plasticizers submitted by Dr. T.M. Patrick. The sample labeled Santicizer 4o4 had viscosities of 785 cs. at 130 and 113 cs. at 210F. The viscosities for Santicizer 4o8 were 730 cs. at 130F. and 123 cs. at 210F. DSW 621662 STLCOPCB4095693 14. (3) Viscosities of Various Phosphonatea . The following table Hats the viscosity characteristics of dl-2-ethylhexyl chloromethyl phosphonate and dibutylchloromethyl phosphonate which are currently being tested as additives and/or base stocks for functional fluids. Viscosity 100F. at 210F. Di 2-ethylhexylchloromethyl phosphonate 9.56 cs. Dibutylchloromethyl phosphonate 4.11 cs. 2.28 cs. 1.32 cs. . (4) Viscosity of Tri (o-Benzylphenyl) Phosphate Continuing the study of structural effects on the viscosity indices of phosphate esters, tri (o-benzylphenyl) phosphate (RSM-A96232) has a viscosity at 100 F. of 681.6 cs. and 18.47 cs. at 210 F. to give a viscosity index of -80. Viscosity determinations on the above compound illustrates the reduction in viscosity index resulting from the addition of aromatic side chains on the phenyl groups of triphenyl phosphate even through the media of methylene linkages . --. (5) Dayton1s Fluids . Octyl 3-(octyloxy)propionate (CP-15074) and 2-ethylbutyl 3-(2-ethylbutoxy)propionate (CP-15075) were submitted for primary evaluations as functional fluids by Central Research, Dayton, Ohio. The following table lists various physical properties of these compounds. Viscosity at 100F. at 210F. Pour Point Flash Point Fire Point CP-15074 6.25 cs. 1.93 cs. -78 F. 335F. 355F. CP-15075 2.94 cs. 1.17 cs. -90 F. 290F. 305F. These compounds are not promising as high temperature functional fluid base stocks. (6) Various Phosphates from Carbide Coal Xylenols Various trlxylenyl phosphates were evaluated as possible functional fluids. The triaryl phosphate prepared from Carbide Coal Hydrogenation xylenols gave a higher viscosity index than similar phosphate esters made from other xylenols. DSW 621663 STLCOPCB4095694 15. Source of Raw Material Viscosity (cs.) V.I. at 100JF. at 210"F. Notebook Productol's D-2 Xylenol Productol* s D-3 Xylenol Carbide Coal Hydrogenation Xylenol -34 -3 +17 69.ll 64.50 41.34 5.97 6.07 5.06 A-79802 A-79803 A-84116 ACKNOWLEDGMENT We appreciate the work of the production departments in the successful large scale formulating of Pydraul 60 and Pydraul 625 The assistance rendered by the Functional Fluids Application Labora tories, the Research Physical Chemical Group, the JFQ Analytical Section, the Pilot Plant personnel, and Douglas Aircraft Physical Testing Laboratories is gratefully acknowledged. de 1-30-59 J. D. Sullivan R. E. Hatton DSW 621664 STLCOPCB4095695 APPENDIX The following table lists the Shell 4-Ball scar diameters In mm. for Pydraul 600, PH-127 and FH-128 as reported by Douglas Aircraft Company. Fluid Pydraul 600 Pydraul 600 FH-127 FH-127 FH-128 FH-128 Lot Number Y-54l Y-541 Z-2457 Z-2457 Z-2458 Z-2458 Steel On Steel 1 Kg. 10 Kg. 40Kg. 0.13 0.14 0.17 0.17 0.13 0.23 0.39;0.46 0.55 0.49 0.55 0.22 0.26 0.77 0.75 0.24 0.23 0.75 0.75 Steel On Bronze 1 Kg. 0.43 0.50 lOKg. 0.92 0.70 40 Kg. 1.15;1.49 1.48;1.39 0.56 0.52 0.47 0.60 1.06 0.92 1.17 1.09 1.23 1.17 1.18 1.18 The following table lists the results of the oxidation-corrosion tests on FH-127* Pydraul F-9 and Pydraul 600 as reported by Douglas Aircraft Company. Viscosity at 130F.(cs.) Neut. No. mg.KOH/gm. Fluid Lot No. % Initial Final Change Initial Final Change FH- 127 Z2457 20.5 20.8 +1.5 .00 .06 -- FH- 127 Z2457 20.5 21.1 +2.9 .00 .04 ' -- Pyd . F-9 -- 20.2 20.2 0.0 .00 .06 -- Pyd . 600 Y-541 43.9 44.0 +0.2 .00 .03 -- Pyd . 600 Y-541 43.9 45.8 +4.1 .00 .00 -- Fluid FH-127 FH-127 Pyd. F-9 Pyd. 600 Pyd. 600 Cu -.09 - .16 -.09 -.13 -.07 Wt. Change mg./cm.2 Fe A1 Mg + .01 .00 + .03 + .02 + .08 + .08 -.03 + .09 +. 06 + .02 + .05 -.01 + .05 -.01 + .10 Cd/Fe + .04 + .04 + .08 + .07 + .05 DSW 621665 STLCOPCB4095696 Further tests run on FH-127, Lot Z-2457 at Douglas Aircraft Company are as follows: KVCs at 210F. KVCS at 100F. Pour Point 5.^8 49.2 -1F. Hot Manifold Flammability - No ignition at 1410, maximum attainable temperature. High Pressure Spray Flammability - No ignition. AIT (Quartz in iron) 1-1150 -5 (Drops - F. - Secs.) Foaming Tendency - Sequence: Ml. of foam at end of 5 min. blowing period Ml. foam after 10 min. settling period Foam half life In secs. Foam life In secs. 75P. 200F. 75F. (After 200 F . test) 60 15 90 None None None 20 80' 5 25 35 160 Rubber Swell (7 days at 158F.) Material % Swell Hardness Int. Final Butyl (P & RP Compd. 805-70) Nitrile (P 8s RP Cmpd. 479-70) t 13.1 109.3 81 69 70 48 On the Pydraul 600, Lot Y-541 , the following results were obtained: High Pressure Spray Flammability - No ignition. Hot Manifold Flammability - No Ignition at 1445, the highest attainable temperature. AIT (Quartz in iron) 1-1158 -5 (drops - F. - Secs.) (continued on next page) DSW 621666 STLCOPCB4095697 Foaming tendency - Sequence: Ml. of foam at end of 5 min. blowing period 75F. 200F. 75F. (after 200F. teat) 270 140 l4o Ml. foam after 10 min . settling period 70 None 50 Foam half life in secs. 560 25 200 Foam life in secs. 600 50 600 Rubber Swell Material Butyl (P & RP Cmpd. 805-70) Nitrile (P & RP Cmpd. 479-70) <$> Swell 59.2 121.8 Hardness Int. Final 81 52 68 45 DSW 621667 STLCOPCB4095698 STLCOPCB4095699