1 LUBRIICABING GREASES FATTY ACIDS IMPROVE UNIFORMITY Reducing The Variables If lubricating grease performance is to be con- Soap composition can make or break a lubricating sistent, five or more variables must be kept in line: grease. However, the full effect of the fatty acid com- 1. Variation in the soap cation (metallic component) ponents upon grease performance is not yet scientifi- cally defined. Many practical findings about fats and 2. Variation in the fatty-acid radicals fatty acids guide the greasemaker, but they do not 3. Variation in the petroleum oil show up consistently in purchase specifications for 4. Variation in additives - free alkali, free fatty these materials, even when intended for use in the acids, water, glycerol, anti-oxidants, modifiers, same type of grease. etc. 5. Variation in the processing method and process With the help of the electron microscope, we now control. know that the structural framework of a typical grease So far as base metals for soaps are concerned, is composed of fibrous crysralline aggregates of their relation m structure and performance have been soap, acting as a kind of colloidal sponge upon the explored in great detail (1) and will not be reviewed mineral oil. This must retain its oil-retentive structure here. under shear, temperature change, and time. Still, two greases which appear quite different under the micro- At the same time, the metal cation and the fatty- scope, as well as in their composition, may prove to acid radical are so interrelated in their effects upon be equal in performance. There is no single optimum the soap structure that generalizations as to the soap structure in grease. It is specifically interrelated effect of a particular metal (say, lithium) on perform- to the other constituents, and to the type of service ance also depend on the particular fatty acid combina- into which the grease goes. tion with which it is linked. Some metal soaps are critically affected by the degree of saturation of the Today's grease manufacturer, as he works to acid, others far less so. improve his product in a scientific way, faces he RATIO OF STEARATE task of reducing the variables, so that the effect of TO OLEATE IN SOAP any particular ingredient on performance can be pre- A-IM):o determined. This will direct his choice of materials 8-75: 25 toward more completely purified and uniform composi- C-5030 tion. One of the important milesmnes on the road to APPARENT scientific greasemaking is the increasing availability of fatty acids (and their pre-formed soaps) of well- defined and uniform analysis. Of course, there are many non-critical jobs for which minimumprice greases appear to be "good enough". But the whole trend of industrial design is tending to upgrade grease requirements, and to give enough payoff value to unifonn performance to justify the higher cost of uni- FIG. I - Effect of soap composition on apparent form raw materials. viscosity. (Moses and Pudd ington data) A sodium base grease, for example, may be satis- factory when the ratio of stearate to oleate is, say, 50:50. Aluminum oleate, however, is not a satisfactory grease component, and saturated acids will be pre- ferred when aluminum is the meml base. Two calcium- base grease fonnulations may have similar character- istics, despite wide variations in fatty acid polyun- saturant content or chain-length distribution. But two lithium-base greases will respond vety critically to fatty-acid differences of the same order. In general, metals with a narrower tolerance to variations fatty- acid length and structure are being favored in high- quality greases. Effect of Petroleum Oil Variations Variation in petroleum oil composition, as it affects grease performance, is too broad and basic a matter for review here. Again, an intricate inter relationship with the soap phase exists. Physical characterisacs of the oil, such as viscosity, are important to the strength and length of the soap fibers formed. In fact, the same soap may form an entirely different fiber saucture as oil viscosity changes. Also, the structure of the fibrous soap network is affected by the chemical composition (cyclic vs. chain hydro- carbons) of the oil. C. J. Boner writes, "Until lubri- cating oils of more definite chemical composition are FIG. 2 - Structure of a lithiuwcalcium stearate -. available, it will be difficult to draw rigid conclusions type grease as shown by the electron as to the effect on saucture. .". (2) This, of course, microscope (10,000~) adds to ow difficulty in relating the oil-retention and service of existing greases to their fatty acid com- Srandard grades of tallows and animal greases position, except where petroleum oils of identical are defined only in terms of solidifying point (titer), composition are assured. free fatty acids, M.I.U.*, and color, with no control over the particular combination of fatty acid radicals Variation in Fats except that arising from the simila; tendency of fats of particular animals to hold to the same proportions. Animal fats are estimated to constitute over 80 There is also lack of control over water-soluble per cent of the fatty materials used in the production impurities such as proteins and gelatinous matter. of lubricating greases. In this class, the biggest Even for the buyer of animal fats who limits his single component will be inedible tallow, totalling 40 purchases to a single source to minimize these varia- million pounds or more per year. As a traditional tions, the effect of seasonal and geographical factors material to which the art of the greasemaker has long and the time and temperature changes in movementof accustomed itself, tallow makes upin familiarity what stock to market will still exist. it lacks in uniformity. Particularly in the conventional lime-base and sodium-base greases, it can be "doc- tored" to produce greases of structural uniformity and Will Greater Uniformity Pay? reasonably good performance. But as one supplier was recently quoted: "All my business life I've sup- It would be idle to contend that a grease manu- plied fats to your industry and wondered how you facturer, having built a paying business on his skill could possibly make uniform products. Your specifi- in coping with such variable raw materials, should cations could be met by hundreds of combinations of now abandon tallow and grease "across the board" beef, pork, and sheep fars." (3) for something higher-priced. At the same time, the *Moisture, Insolubles, Unsaponifiable -- a "catch-all" classification of the valueless content of the fat. exploration of the full possibilities of uniform raw fatty acids may require wider use of corrosion-resis- materials on performance is now receiving wider rant tanks and equipment. (5) Moreover, the point has study. One tendency has been to seek some inorganic been raised that the claim of greater uniformity for or synthetic thickener which is inherendy uniform. fatty acids has not always been substantiated in But it is proving even more rewarding to explore practice: Acids meeting the conventional test speci- soaps and soap source materials freed from "un- fications as to titer, saponification value, iodine knowns .' ' value and the lik,e may still produce differences in performance. There are technical as well as economic limita- tions to he degree that natural fats as such, parti- During World War 11, for example, regulations for cularly those of by-product origin, can be supplied glycerine recovery forced a shift to fatty acids on with any assurance of chemical uniformity. But these the part of grease manuhcturers. Many of these limitations are much less severe when glycerides are r r emergency" mixed acids had no more uniformity hydrolized to fatty acids and glycerol. Distillation, than the "bottom-of-the-bauel" type of fat available solvent separation, fractional crysmllization, and at that time. Experience with these mixed fatty acids other processes such as hydrogenation, are more ef- can not be applied to the purified, specialty types fectively applied to the fatty acids than to glycerides available today. to alter or adjust their composition and to eliminate impurities. Source materials of different origin permit Of course, since uniformity and reproducibility enrichment to arrive at a uniform composition of the are obtained at some extra production cost, this desired chain-length distribution, degree of saturation, brings us to a question of which particular fatty acid and - if necessary - molecular anangement. characteristics are worth paying for. Are we measur- ing and specifying the right things to produce a better Even more strictly standardized fatty acids (or product, in terms of actual grease service? their pre-formed soaps) can be expected in the future. Their commercial development is technically possible. What price - composition analysis? As the value of uniformity becomes more widely held, and thus improves the economics of their manufacture, As shown in Table 1, seven conventional tests the grease industry will have a much wider range of used to characterize fatty materials have gained ac- products to choose from to meet specific needs. ceptance, and are reflected in purchasing specifica- tions of the grease industry. Some of these, taken Fatty Acids vs. Glycerides together, establish the average composition of the material. For example; under certain conditions, the Aside from factors of uniformity and controllabi- composition of stearic-palmitic mixtures can be lity of composition, purified fatty acids have been calculated from titer (6). cited as being preferable to raw fats for the following reasons. (4) It may be asked, should not these specifications 1. Greater ease of saponification. be supplemented or replaced by a breakdown such as shown in Table 2? From the standpoint of research 2. More complete saponification. and product development, such composition analysis 3.