Classifications

• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
  • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
  • C21D1/58—Oils

Definitions

• Properties of steel can be varied by heat treatment to obtain desired microstructures such as martensitic microstructure. Quenching and tempering is the heat treatment commonly used to obtain such microstructures. It involves heating steel to an austenitizing temperature such as 800°C, and then cooling through the martensite transformation temperature range at a rate rapid enough to minimize transformation at temperatures above the martensite range. This is accomplished by quenching the heated steel. The first requisite of a quenching medium is therefore a sufficient cooling rate to obtain the desired results. The temperature gradient caused by the quenching operation results in relatively high thermal and transformation stresses which may if excessive lead to cracking or distortion. In the prevention of these problems, the maximum quenching rate is limited by the nature of the component being heat treated.
• Quenching media commonly used are water, oil and brine. Brine quenching is the most severe. Water approaches it in severity. Oil quenching is much less drastic. It has been proposed to add to various mineral oils to be used as quench oils an ashless dispersant such as an alkenyl succinimide. See for instance United States Patent Specification No. 3866603.
• quench oil which comprises a major amount of a mineral oil and contains effective amounts of olefinic polymer, ashless antioxidant, and, optionally, alkaline earth metal or alkali metal detergent.
• a preferred embodiment of the invention is a quench oil for use in the heat treatment of ferro-metals, said composition comprising a major amount of mineral oil and (a) about 0.3 to 7.5 weight percent of at least one olefinic polymer of a lower mono-olefin and (b) about .01 to 2.5 weight percent of an ashless antioxidant which is one or more of (i) a sterically hindered phenol, (ii) an alkylated aromatic amine, or (iii) a sulfurized alkylphenol.
• a quench oil for use in the heat treatment of ferro-metals which comprises a major amount of mineral oil and (a) about 0.3 to 7.5 weight percent of at least one olefinic polymer of a lower mono-olefin; (b) about .01 to 2.0 weight percent of an ashless antioxidant which is one or more of (i) a sterically hindered phenol, (ii) an alkylated aromatic amine, or (iii) a sulfurized alkylphenol and (c) about 0.02 to 2.5 weight percent of alkaline earth metal or an alkali metal detergent which is one or more of an alkaline earth metal arylsulfonate, alkali metal arylsulfonate, alkaline earth metal alkylphenate, alkaline earth metal sulfurized alkylphenate or an alkaline earth metal phosphonate phenate.
• the base mineral oil is suitably a liquid hydrocarbon obtained by conventional petroleum refining methods including hydrocracking, hydrotreating and the like.
• a useful viscosity range is about 1.5 to 20cSt at 100°C and more preferably 4 to l2cSt at 100° C .
• Polymers contemplated for use in this invention include homopolymers or copolymers of lower mono-olefins, i.e., a C 2 to C 10 olefin, as for example, ethylene, propylene, n-butylene, isobutylene; copolymers and terpolymers of the lower mono-olefins and higher mono-olefins and diolefins having up to 2,000,000 or higher molecular weight, preferably 200 to 50,000 molecular weight.
• the polymers are those of isobutylene having a molecular weight of up to 10,000 or higher.
• the polymer is polyisobutylene having a molecular weight of about 700 to 5,000 and most preferably from about 900 to 2,000.
• the amount of olefinic polymer can vary from about 0.3 to 7.5 weight percent when present in a mineral oil containing an ashless antioxidant and more preferably from about 0.5 to 5.0 weight percent.
• a very useful class of ashless antioxidants includes the hindered phenols. These are phenolic compounds having at least one tert-alkyl group substituted at a nuclear position ortho to a phenolic hydroxyl group. Representative examples of these are:
• Another useful class of ashless antioxidants are the aromatic amines. Examples of these are N,N'-di- octylphenylenediamine, N-isopropylphenylenediamine and the like.
• alkylated diphenylamines such as
• Sulfurized alkylphenols can also be used as the ashless antioxidant. These can be made by reacting an alkylphenol with elemental sulfur at elevated temperature. This forms sulfur bridging groups between alkylphenol molecules.
• the phenols are preferably para- alkylated. Examples of alkylphenols which make useful sulfurized products are:
• the amount of ashless antioxidant in the quench oil should be an amount that provides the required amount of stabilization.
• a useful range is about .01 to 2.5 weight percent when used in combination with the olefinic polymer only and from about .01 to 2.0 weight percent when used in combination with both olefinic polymer and detergent.
• the more preferred alkaline earth or alkali metal detergents are the alkaline earth or alkali metal arylsulfonates. These include both the so-called natural sulfonates derived by sulfuric extraction of petroleum as well as the synthetic sulfonates made by sulfonating synthetic alkylbenzenes.
• the alkaline earth metal sulfonates include both neutral and over based sulfonates.
• alkaline earth metal as used herein includes calcium, barium and magnesium.
• alkali metal as used herein includes sodium.
• alkaline earth metal arylsulfonates are the calcium salts of alkylbenzene sulfonic acids in which the alkylbenzenes have an average molecular weight of about 300-700.
• alkaline earth metal detergents includes the alkaline earth metal alkyl phenates (e.g. US 2,228,671; US 2,252,663; US 2,280,419; US 2,412,903; US 2,610,982; US 3,779,920; US 3,691,076) and alkaline earth metal sulfurized alkyl phenates. (e.g. US 2,249,626; US 2,331,448; US 2,336,074; US 2,342,887; US 2,346,826; US 2,362,292; US 2,366,874; U S 2,406,564). These are made by reacting alkaline earth metal hydroxide or oxide (e.g. CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 ) with an alkylphenol or sulfurized alkylphenol.
• alkaline earth metal hydroxide or oxide e.g. CaO, Ca(OH) 2 , BaO, Ba(OH) 2
• the alkyl substituent preferably contains about 4-20 carbon atoms such as in isobutylphenol, 2-ethyl- hexylphenol, nonylphenol, 1-ethyldecylphenol and the like.
• the corresponding sulfurized detergent is made by well-known methods such as by heating a mixture of alkylphenol and sulfur and then reacting the sulfurized phenols with an alkaline earth metal base.
• Alkaline earth metal phosphonate phenates are typically made by the coneutralization of a mixture of a phosphosulfurized polyolefin and an alkyl phenol or an alkyl phenol sulfide. Co-neutralization may be carried out using, for example barium oxide, barium hydroxide, calcium oxide or calcium hydroxide or an alkoxide of magnesium or a carbonated alkoxide of magnesium in an alkanol, such as described in British Patent 1303048.
• the alkylphenol sulfide that is to say a compound containing two or more alkylphenol residues linked by one or more sulfur atoms
• the alkylphenol is preferably one which has an aromatic nucleus that is substituted by an alkyl group having from 5 to 20 carbon atoms, especially from 7 to 12 carbon atoms.
• An alkyl group having 9 carbon atoms is often particularly satisfactory.
• alkylphenol sulfide rather than the alkylphenol itself.
• the sulfide can be a monosulfide, but disulfides, trisulfides, tetra- sulfides, pentasulfides and other polysulfides are also very useful.
• a suitable alkylphenol sulfide can in fact be made from an appropriate alkylphenol by reaction with sulfur dichloride, the composition of the product depending on the molar ratio of alkylphenol to sulfur dichloride used and the alkylphenol residues being linked in general by monosulfide links.
• alkylphenol sulfide and alkylphenol starting materials are nonylphenol and dodecylphenol and the product of reacting from three to five moles of an alkylphenol in which the alkyl group has from 7 to 11 carbon atoms with from two to four moles of sulfur dichloride.
• a particularly preferred example is the reaction product of four moles of nonylphenol and three moles of sulfur dichloride.
• the polyolefin that is used in phosphosulfurized form is preferably one of relatively low molecular weight; it can be for example a polypropylene, polybutene or polyisobutylene, for instance one that has an average molecular weight between 500 and 2500, for example 1100. It can for instance have been phosphosulfurized by reacting it with a phosphorus sulfide such as for example P 4 s 3l P 4 S 7 , or more preferably P 2 S 5 .
• the phosphosulfurized polyolefin can be used as such that is to say in the form in which it is produced by phospho- sulfurization.
• alkylphenol sulfide or alkylphenol and the phosphosulfurized polyolefin can be used in any desired relative proportion, but usually it is preferred to employ these in a weight ratio between 1: 12 and 6: 1 especially between 1: 9 and 4: 1 and more preferably between 3: 7 and 1: 1.
• the amount of alkaline earth or alkali metal detergent can vary from about .02 to about 2.5 weight percent. A preferred range is about .05 to 2.0 weight percent and a most preferred range is about 0.1 to 1.0 weight percent.
• the invention also includes a quench oil concentrate cocprising a mineral oil solvent and (a) olefinic polymer and (b) ashless antioxidant, and, optionally, an alkaline earth metal or alkali metal detergent.
• a convenient way to prepare the quench oil is to add a quench oil concentrate to the mineral oil base.
• the concentrate contains the proper amount of each additive such that when blended in the mineral oil base the resultant quench oil will contain the proper amount of each additive.
• a useful concentration range of each class of additive is 25 to 90 weight percent olefinic polymer and 2.0 to 30 weight percent ashless antioxidant.
• a useful concentration range of each additive is 25 to 90 weight percent olefinic polymer, 1.0 to 20 weight percent ashless antioxidant and 2.0 to 15 weight percent alkaline earth or alkali metal detergent.
• Oxidative Stability Test was conducted by bubbling air through a test oil at 150°C for 72 hours at 10 l/hr. A small amount of iron acetylacetonate (40ppm) was added to the test oil to promote oxidation. Test criteria were the increase in total acid number (TAN), percent insolubles and percent viscosity increase measured at 40°C. Results were as follows:

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• 1984
  • 1984-10-17 EP EP84307104A patent/EP0178354A1/de not_active Withdrawn
• 1985
  • 1985-10-17 JP JP23226585A patent/JPS61106710A/ja active Pending

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