Extreme pressure additives

The base lubricant is usually a petroleum oil while the thickener usually consists of a soap or soap mixture. In addition they may contain small amounts of free alkali, free fatty acid, glycerine, anti-oxidant, extreme-pressure agent, graphite or molybdenum disulphide. 

Anti-wear and extreme pressure additives phosphoric esters, dithiophosphates, sulfur-containing products such as fatty esters and sulfided terpenes or chlorinated products such as chlorinated paraffins. 

The role of anti-wear and extreme-pressure additives is to create a solid lubricant at the interface of the metal by chemical reaction. 

In the other market areas, lead naphthenates are used on a limited basis in extreme pressure additives for lubricating oils and greases. Sodium and potassium naphthenates are used in emulsiftable oils, where they have the advantage over fatty acid soaps of having improved disinfectant properties. Catalyst uses include cobalt naphthenate as a cross-linking catalyst in adhesives (52) and manganese naphthenate as an oxidation catalyst (35). Metal naphthenates are also being used in the hydroconversion of heavy petroleum fractions (53,54) and bitumens (55). 

Sulfurized olefins (S2CI2 plus isobutene) are further reacted with S and Na2S to give products useful as extreme pressure lubricant additives (144,145). The reaction of unsaturated natural oils with sulfur monochloride gives resinous products known as Factice, which are useful as art-gum erasers and mbber additives (146,147). The addition reaction of sulfur monochloride with unsaturated polymers, eg, natural mbber, produces cross-links and thus serves as a means for vulcanizing mbber at moderate temperatures. The photochemical cross-linking of polyethylene has also been reported (148). 

Sulfuiized and sulfurchlorinated unsaturated compounds and meicaptans are used as lubricant additives (antiwear, friction modification, load-carrying, extreme pressure and temperature, corrosion inhibition, and antioxidants), refinery catalyst regeneration compounds, steel processing (annealing) aids, and vulcanization catalysts (see Lubrication and lubricants). 

In the lightening of petroleum hydrocarbon oil, esters of mercaptocarboxyhc acids can modify radical behavior during the distillation step (58). Thioesters of dialkanol and trialkanolamine have been found to be effective multihinctional antiwear additives for lubricants and fuels (59). Alkanolamine salts of dithiodipropionic acid [1119-62-6] are available as water-soluble extreme pressure additives in lubricants (60). 

Minor and potential new uses include flue-gas desulfurization (44,45), silver-cleaning formulations (46), thermal-energy storage (47), cyanide antidote (48), cement additive (49), aluminum-etching solutions (50), removal of nitrogen dioxide from flue gas (51), concrete-set accelerator (52), stabilizer for acrylamide polymers (53), extreme pressure additives for lubricants (54), multiple-use heating pads (55), in soap and shampoo compositions (56), and as a flame retardant in polycarbonate compositions (57). Moreover, precious metals can be recovered from difficult ores using thiosulfates (58). Use of thiosulfates avoids the environmentally hazardous cyanides. 

Lubrication Additive. Cerium fluoride, CeF, can be used as an additive to lubricant formulations to improve extreme pressure and antiwear behavior (43). The white soHd has a crystal stmcture that can be pictured as [CeF] layers separated by [F] atom sheets, a layer stmcture analogous to that of M0S2, a material that CeF resembles in properties. 

Chlorinated paraffins with the general molecular formula x 2x-y+2) have been manufactured on a commercial basis for over 50 years. The early products were based on paraffin wax feedstocks and were used as fine retardants and plasticizers in surface coatings and textile treatments and as extreme pressure—antiwear additives in lubricants. The development of chlorinated paraffins into new and emerging technologies was constrained principally because of the limitations of grades based on paraffin wax and the lack of suitable alternative feedstocks to meet the demands of the new potential markets. 

Chlorinated paraffins are versatile materials and are used in widely differing appHcations. As cost-effective plasticizers, they are employed in plastics particularly PVC, mbbers, surface coatings, adhesives, and sealants. Where required they impart the additional features of fire retardance, and chemical and water resistance. In conjunction with antimony trioxide, they constitute one of the most cost-effective fire-retardant systems for polymeric materials, textiles, surface coatings, and paper products. Chlorinated paraffins are also employed as components in fat Hquors used in the leather industry, as extreme pressure additives in metal-working lubricants, and as solvents in carbonless copying paper. 

Ethers, esters, amides and imidazolidines containing an epithio group are said to be effective in enhancing the antiwear and extreme pressure peiformance of lubricants. Other uses of thiiranes are as follows fuel gas odorant (2-methylthiirane), improvement of antistatic and wetting properties of fibers and films [poly(ethyleneglycol) ethers of 2-hydroxymethyl thiirane], inhibition of alkene metathesis (2-methylthiirane), stabilizers for poly(thiirane) (halogen adducts of thiiranes), enhancement of respiration of tobacco leaves (thiirane), tobacco additives to reduce nicotine and to reduce phenol levels in smoke [2-(methoxymethyl)thiirane], stabilizers for trichloroethylene and 1,1,1-trichloroethane (2-methylthiirane, 2-hydroxymethylthiirane) and stabilizers for organic compounds (0,0-dialkyldithiophosphate esters of 2-mercaptomethylthiirane). The product of the reaction of aniline with thiirane is reported to be useful in the flotation of zinc sulfide. 

METALWORKING FLUID Fluid applied to a tool and workpieee to eool, lubrieate, earry away partieles of waste and provide eoiTosion proteetion. Generally eomprising neat mineral oils, or water-based materials, or a mixture of the two. Fluids may also eontain emulsifiers, stabilizers, bioeides, eoiTosion inhibitors, fragranees and extreme pressure additives. 

Metalworking fluids contain mineral oils (refer to p. 80) or synthetic lubricants they are used neat or in admixture with water. They may contain small amounts of biocides, stabilizers, emulsifiers, coiTosion inhibitors, fragrances and extreme pressure additives. The formulations render them suitable for application to metal being worked, generally from a recirculatory system, to provide lubrication, corrosion protection, swarf removal and cooling of the tool and machined surface. 

The zinc. salts of these acids are extensively used as additives to lubricating oils to improve their extreme-pressure properties. The compounds also act as antioxidants, corrosion inhibitors and detergents. Short-chain dialkyl dithiophosphates and their sodium and ammonium salts are used as flotation agents for zinc and lead sulfide ores. The methyl and ethyl derivatives (RO)2P(S)SH and (RO)2P(S)CI are of particular interest in the large-scale manufacture of pesticides such as parathion, malathion, dimethylparathion, etc. For example parathion. which first went into production as an insecticide in Germany in 1947. is made by the following reaction sequence ... 

Plain slideways are preferred in the majority of applications. Only a thin film of lubricant is present, so its properties - especially its viscosity, adhesion and extreme-pressure characteristics - are of vital importance. If lubrication breaks down intermittently, a condition is created known as stick-slip , which affects surface finish, causes vibration and chatter and makes close limits difficult to hold. Special adhesive additives are incorporated into the lubricant to provide good bonding of the oil film to the sliding surfaces, which helps to overcome the problems of table and slideway lubrication. On long traverses, oil may be fed through grooves in the underside of the slideway. 

The performance of soluble oils is made possible not only by their high specific heat and thermal conductivity but by their low viscosity, which permits good penetration into the very fine clearances around the cutting zone. Consequently, these fluids are used mainly where cooling is the primary requirement. Lubricating properties can be improved by polar additives, which are agents that enhance the oiliness or anti-friction characteristics. Further improvements can be effected by EP (extreme-pressure) additives, which are usually compounds of sulfur or chlorine. 

For the more difficult operations, neat oils containing EP (extreme-pressure) additives have to be used. The EP cutting oils usually contain additives based on sulfur or chlorine, or combinations of them. The sulfur in EP oil can be present in two forms. In the inactive fluid, it is chemically combined with a fatty-oil additive, which is blended with mineral oil to produce sulfured fatty oil. The active version, on the other hand, contains sulfur in elemental form, dissolved in mineral oil the fluid is known as sulfured mineral oil. Chlorine is usually present only as chlorinated paraffin, which is blended sometimes singly with mineral oils and sometimes in combination with fatty oils and sulfured additives. 

These are usually mineral oils or synthetic basestocks containing a complex mixture of additives including corrosion inhibitors, extreme pressure additives and emulsifiers. They are almost exclusively oil-in-water emulsions, although in rare instances, invert emulsions may be used. They are normally used between l%-20% emulsions depending on the application. As these products are water extendible, they are subject to attack by micro-organisms. As a consequence, they are often formulated with one or more preservatives. 

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