2546
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
metastable phase states by appropriate control of concentratioiis, Temperature, and mechanical treatment during processing. The! results of this survey indicate that existing manufacturing conditions do not in general result in a phase state for the grease' greatly difierent from simple dispersion of normal soap crystals in oil, except for modifications due t o additives such as barium neetate, etc. 2. The origin of the varying deyrecs of dispersion or pcrfcction o r crystallization in greases processed in various ways may be traceable to the phase state of the eoap in oil a t more elcvnted rcmperatures. Exploration of this possibility for the system talcium stearate-cetane (24) has shown that such effccts are real in soap-oil systems and such studies could, therefore, probably be profitably exploited. 3. The utility of a soap as a grease former is probably limited at, high temperatures by the formation of solutions of oil in soap in which the soap particles lose their discretr status and become u. ooherent sticky inass rather than a fibious matrix with cnrneslied fluid lubricant. T h a t oil solubility in soap can Iw extensiveIy modified by additives has already been found empirically (see i m i u m acetate). Thc systematic study of such effccts, related to the general fields of salting out and solubilization, seems t o be R useful way of correlating and interpreting such empirical rcsults. 4. The temperatures of formation of oil-swollen sticky masst+ Luther than greases by soaps in oil seem to be associated closelv Kith the temperatures at which the oil-frce soaps exist in mesomorphic rather than crystalline form, so that the polymorphic behavior of a given soap provides a useful indication of its probable performance as a grease former in respect, t o lempcrntm(~ -\ability. ACKNOWLEDLRIENT
The greases were supplied by various manufactui cis, iiicludiiig B~ttenfeldGrease and Oil Company, California Research Company, Shell Development Company, and Union Oil Compaiiy 1\ few samples were taken from a display of petroleum produels furnished by the Texas Company. The authors wish to ~cknow.1edge the cooperation of these companies in furnishing samplcs Together with defining data. This research was carried out part of a project, "Phase Studies of Greases," supported by thf, Office of Naval Research, Contract No. N6-onr-2387'0-2,
XR0.57057.
Vol. 41, No. 11
LITERATURE CITED
(I) Buerger, M. J., Smith, L. B., Ryer, F. V., and Spike, J. E., Jr., Proc. Natl. Acad. Sci. U.S., 31, 226 (1948). (2) Doseher, T. A t . , and Vold, R.D., J. Colloid Sci., 1, 299 (1946). (3) Doscher, T. M., and Vold, It. D., 9.I'hys. h Colloid Chcm., 52,
97 (1948). (4) Verguson, R. H., Oil & Soap, 21,6 (1944). (5) Gallay, W., and Puddington, I. E., Can. J. Reseamh, B26, 166 (1948). (6) Hattiangdi, G. S., Vold. M. J., and &'old, R. D., IKD.Exvm. CHEM.,41, 2320-4 (1949). (7) Kilemgard, E. N., "Lubricating Greases; Their lllanufaoture and Use," pp. 584ff, New York, Reinhold Publishing Corp., 1937. (8) I,awrence, A. S.C., J . Inst, Petroleum, 31,303 (1945). (9) Mvsels. K. J.. and McBain. J. WeeJ. Phus. & Colloid Chem 52, 1471 (1948). 110) Ott, T. F., Clarke, P. 8., and Van Marter, C,TI., U. 8.Patent 2,033,148 (March 10, 1936). (12) Ross, R . , and McBain, J. W., OaL & Soap, 23,214 (1946). (12) Sheffer, H., Can. J . Research, B26, 481 (1948). (13) Smith, G. H., J . Am. Oil Chem. Soc., 24,353 (1947). (14) Smith, G. H., and McRain, J. W,, J. Rhys. & Colloid Chem 51, 1189 (1947). (18) Smith, Go H., Pomeroy, H. H., iMcGee, C.G., and M y s e h , IC J . , J . Am. Chem.Soc., 70,1053 (1948). (16) \'old, M. J., Anal. Chem., 21, 683 (1949)* (17) Vold, M. J., J . Am. Chem. Soc., 63,160 (1941). (18) Vold, M. J., Hattiangdl, C . S., and Vold, R.D., 9.Am, Oil Chernists' Soc,, 26, to be published. it91 Vold. M . J.. Hattiangdi. 0. S,, and Vold, R, ID., J . ColZoid 9cl 4 , 9 3 (1949). ( 2 0 ) T'old, R. D., J. Am. C'hehem. Soc., 63, 2915 (1941).
