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FIGURE 20.6 Representation of chemisorption of a long-chain aliphatic acid. (From Ref. [20.3].)
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produce films of metal phosphide, sulfide, or chloride on the sliding surface. These reactive additives are known as extreme-pressure, or EP, additives. The processes by which modern boundary lubricant additives generate surface films may be very complex. A single additive such as trixylyl phosphate may be initially adsorbed on the metal surface, then react to form a chemisorbed film of organometallic phosphate, and finally, under severe sliding or heating, react to form metal phosphate or phosphide. All these boundary lubricant compounds have corresponding disadvantages. As a general rule, they should be used only where the conditions of use require them. The mild, adsorbed compounds have the least undesirable side effects. They are more readily oxidized than the usual mineral-base oils and, as a result, have a higher tendency to produce corrosive acidic compounds and insoluble gums or lacquers. However, these effects are not serious, and mild antiwear additives are widely used
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Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
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in small quantities where sliding conditions are not severe, such as in hydraulic fluids and turbine oils. The stronger chemisorbed additives such as fatty acids, organic phosphates, and thiophosphates are correspondingly more reactive. They are used in motor oils and gear oils. Finally, the reactive sulfurized olefines and chlorinated compounds are, in fact, controlled corrodents and are used only where the sliding conditions are very severe, such as in hypoid gearboxes and in metalworking processes. Boundary lubrication is a very complex process. Apart from the direct filmforming techniques described earlier, there are several other effects which probably make an important contribution to boundary lubrication: 1. The Rehbinder effect The presence of surface-active molecules adjacent to a metal surface decreases the yield stress. Since many boundary lubricants are more or less surface-active, they can be expected to reduce the stresses developed when asperities interact. 2. Viscosity increase adjacent to a metal surface This effect is controversial, but it seems probable that interaction between adsorbed molecules and the free ambient oil can result in a greaselike thickening or trapping of oil molecules adjacent to the surface. 3. Microelastohydrodynamic effects The interaction between two asperities sliding past each other in a liquid is similar to the interaction between gear teeth, and in the same way it can be expected to generate elastohydrodynamic lubrication on a microscopic scale. The increase in viscosity of the lubricant and the elastic deformation of the asperities will both tend to reduce friction and wear. However, if the Rehbinder effect is also present, then plastic flow of the asperities is also encouraged. The term microrheodynamic lubrication has been used to describe this complex process. 4. Heating Even in well-lubricated sliding there will be transient heating effects at asperity interactions, and these will reduce the modulus and the yield stress at asperity interactions. Boundary lubrication as a whole is not well understood, but the magnitude of its beneficial effects can be easily seen from the significant reductions in friction, wear, and seizure obtained with suitable liquid lubricants in slow metallic sliding.
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20.6 DETERIORATION PROBLEMS
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In theory, if the right viscosity and the right boundary properties have been selected, then the lubrication requirements will be met. In practice, there is one further complication the oil deteriorates. Much of the technology of lubricating oils and additives is concerned with reducing or compensating for deterioration. The three important types of deterioration are oxidation, thermal decomposition, and contamination.A fourth long-term effect is reaction with other materials in the system, which is considered in terms of compatibility. Oxidation is the most important deterioration process because over a long period, even at normal atmospheric temperature, almost all lubricants show some degree of oxidation. Petroleum-base oils produced by mild refining techniques oxidize readily above 120 C to produce acidic compounds, sludges, and lacquers. The total oxygen uptake is not high, and this suggests that the trace compounds, such as aromatics and
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Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
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