US3723314A - Lubricant for metalworking - Google Patents

Lubricant for metalworking Download PDF

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Publication number
US3723314A
US3723314A US00127764A US3723314DA US3723314A US 3723314 A US3723314 A US 3723314A US 00127764 A US00127764 A US 00127764A US 3723314D A US3723314D A US 3723314DA US 3723314 A US3723314 A US 3723314A
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US
United States
Prior art keywords
weight
lubricant
oil
acid
emulsion
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Expired - Lifetime
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US00127764A
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English (en)
Inventor
R Davis
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Mobil Oil AS
ExxonMobil Oil Corp
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Mobil Oil AS
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to emulsifiable lubricants useful in the cold-rolling of metals. More particularly, the invention is concerned with such lubricants which have improved hard water stability properties.
  • the roll oil must also be able to remove metal fines from the metal being rolled, otherwise they would mar the finished surface. Also the metal fines should be easily removed from the oil. If permitted to remain in the oil, they can cause metal surface defects in later rolling operations. Moreover, the known roll oils tend to remain on the surface of the metals during the annealing stage, leaving severe stains thereon.
  • a lubricant might overcome all the abovementioned problems under ideal conditions, it may still be subject to other deficiencies due to conditions en countered in everyday practice.
  • One of these is the formation of insoluble salts in hard Water.
  • the additive of this invention permits the use of hard water by inice creasing the stability of the lubricant emulsion therein. This eliminates the costly step of reducing the hardness level of such water in those areas wherein soft water is not available naturally.
  • US. Pat. No. 3,071,544 describes rolling oil emulsions containing a number of components, including a small amount of an organic acid.
  • the acid is either liquid or oil soluble or is reacted with other components in the formulation to provide oil soluble soaps, such as the soaps of alkanolamines.
  • US. Pat. No. 3,311,557 describes emulsions for the hot rolling of nonferrous metals which contain a fatty acid, a polyol and ethanolamine.
  • the ethanolamine reacts with the acid in suflicient proportion to provide a ratio of base number to acid number of from 0.15 to 0.4.
  • Specific examples of this patent show the use of oil-soluble, liquid fatty acids.
  • U.S. Pat. 3,432,434 teaches a metal rolling lubricant containing an alkylaromatic hydrocarbon which might contain an alkali or alkaline earth metal phosphate or an amine phosphate.
  • This invention provides an emulsifiable lubricant comprising an oil from the group which includes paraflinic and naphthenic mineral oils, synthetic ester lubricants, polyolefin fluids and polyoxyalkylene oxide fluids, a solid aliphatic monocarboxylic acid and an amount suflicient to improve the hard water stability thereof of a mixture of monooleyl and dioleyl phosphates.
  • the lubricant emulsions used in the cold rolling of metal in accordance with this invention broadly consists of about 0.75% to 10% by weight of an oil-solid acid composition in water.
  • the mixed oil-acid neat composition contains from about 20% to about 50%, preferably from about 20% to 40%, by weight of the solid acid.
  • the oil-soluble phase being about to about 50% by weight of the oil-acid composition, includes an oil, such as a mineral oil, i.e. parafiinic or naphthenic oils, emulsifiers and emulsion stabilizers.
  • the oil may constitute from about 20% to about 60% by weight of the neat composition.
  • the typical final lubricant emulsion of this invention consists of water, emulsified oil droplets, and the solid acid closely attached to the droplets.
  • the components include from about 1% to about 15% by weight of the oil phase of an alkanolamine having from about 2 to about 4 carbon atoms per alkanol group and from about 1% to about 15% by weight of the oil phase of an emulsifier preferably having a hydrophilic-lipophilic balance of at least 10.
  • the oil phase may also contain from about 0.05% to about 2% by weight of an aromatic sulfonate and from about 2% to about 15% by weight of a monoor dioleyl phosphate ester.
  • the oil-acid composition contains the components in the following percentages: (1) from about 30% to about 50% by weight of a lubricating oil; (2) from about 20% to about 40% by weight of the solid aliphatic saturated mono-carboxylic acid having from about 14 to about 26 carbon atoms; (3) from about 3% to about 12% by weight of an alkanolamine having from 2 to about 4 carbon atoms; (4) from about 5% to about by weight of a mixture of monoand dioleyl phosphate ester; (5) about 3% to about 12% by weight of an emulsifier having a hydrophilic-lipophilic balance of at least 10; and (6) from about 0.1% to about 1.5% by weight of an aromatic sulfonate.
  • the mixing equipment needed for combining the components of this invention are of a conventional nature, known in the art.
  • the oil, the water, the acid and the other components, with the exception of component (6) are mixed together initially at a temperature of from 50 C. to about 100 C., and preferably 80 to 90 C., for a sufiicient period to obtain a uniform composition.
  • From about 30 minutes to about 7 hours, preferably 1 hour, of mechanical mixing is ordinarily sufficient to obtain the desired emulsion mixture. It may be found necessary to subject the mixture to a particle size reduction step in order to obtain uniformity.
  • Such a step may be carried out by means of suitable equipment for this purpose, such as a colloid mill, homogenizer and the like.
  • the preferred mixing procedure is performed by first using a mechanical mixer and then the homogenizer maintaining the temperature higher than 60 C., preferably from about 80 to about 90 C.
  • the mixture is cooled rapidly to a temperature below 50 C., and the aromatic sulfonate is mixed in.
  • the mixture is thereafter submitted to a final homogenizing treatment.
  • a concentrated emulsion may be initially prepared by the supplier prior to shipment to the mill.
  • emulsion concentrate that is, the compositions which will require the least mixing time in the mill equipment, compositions containing from about to about 60% by weight of the above components (1) to (6) and from about 80% to about 40% by weight of water are preferred. These concentrates are simply diluted in further amounts of water to produce the 0.75% to 10% emulsion for use.
  • the various individual components of the water-free or neat composition are discussed hereinafter.
  • the formulations set forth overcome the disadvantages of some prior art compositions, i.e. they improve the brightness and cleanliness of cold roll steels, both in the operation and following annealing. They also improve the hard water stability of such formulations.
  • the oils used in this invention include both naphthenic and paraflinic mineral oils having a Saybolt viscosity in the range of from about 40 to about 500 S.U.S., preferably cfrom about 60 to about 300 S.U.S. at 100 F. and synthetic lubricants, such as synthetic ester lubricants, polyolefin fluids, alkylene oxide-derived fluids and the like having the same broad and preferred viscosity ranges.
  • the oil is present in amounts ranging from about 20% to 60% by weight of the neat composition, and preferably from about 30% to about 50%.
  • From about 20% to about 50% by weight of neat composition is an aliphatic, saturated monocarboxylic acid having from about 10 to about 30, and preferably from about 14 to 28, carbon atoms.
  • This range includes myristic, palmitic, stearic, arachidic, and behenic acids which are all normally solid, and insoluble in mineral oils and water.
  • stearic acid is employed.
  • acids which may be in a solid and undissolved state, such as a large particle or suspensoid, at any point during the use or storage of the emulsion lubricant.
  • the alkanolamine is used as an emulsifying agent in the lubricant, in amounts ranging from about 1% to 15% and preferably 3% to 12% by weight of neat composition.
  • Primary, secondary, and tertiary alkanolamines may be used.
  • Triethanolamine, isopropanolamine, tri-isopropanolamine, and isobutanolamine are examples of suitable compounds for use in this invention.
  • the phosphate used in the practice of this invention is a mixture of monoand dioleyl phosphates, wherein the concentration of each component is within well defined limits.
  • concentration of mono-oleyl phosphate will range between about 30 and about 45% of the phosphate mixture, and the concentration of dioleyl phosphate [C O P(O) OH] will constitute the remainder, i.e., from about 70 to about 55% of the mixture.
  • the phosphates may be prepared in known ways.
  • the monoand dioleyl phosphates can be made separately by reacting oleyl alcohol and POCl in the usual ratio, followed by forming the acid. The individually made components can then be combined to form the mixture of the invention.
  • the mixed monoand dioleyl phosphates can be made in one step by reacting oleyl alcohol with P 0 usually in the ratio of 3 moles of alcohol to 1 mole of P 0
  • oleyl alcohol as commercially obtainable, is not pure C So, the preferred oleyl alcohol, even one prime commercial grade, is not made up wholly of C18 but is about 60% of unsaturated C with lesser amounts of C C C and C alcohols, which may only be partially unsaturated. Some stearyl alcohol may also be present.
  • the concentration of the emulsifiers or emulsion stabilizers may range from about 1% to about 15% and preferably from about 3% to about 12% by weight.
  • emulsifiers include cationic, anionic and nonionic emulsifiers, such as amines having from 4 to 36 carbon atoms and the C.;C alkyl phenols, and fatty or resin alcohols, fatty acids, esters and partial esters of fatty acids and polyols and fatty acid amides, each having from 4, and preferably from 8, to 36 carbon atoms.
  • a preferred group of emulsifiers are the alkoxylated derivatives of the above-listed organic compounds obtained by reacting them with an alkylene oxide having from about 2 to 4 carbon atoms, such as ethylene oxide (also termed ETO).
  • a preferred group of emulsifiers is the N-acyl-substituted dialkanolamides, the acyl group having 8 to 30 carbon atoms, such as lauroyl diethanolamide.
  • Other emulsifiers include gum arabic, often used in the preparation of wax emulsions.
  • the aromatic sulfonate acts as a control agent of the particle size and viscosity of the emulsion. It is present in relatively minor proportion, ranging from 0.05% to 2.0%, and preferably 0.1% to about 1.5%, by weight of the emulsion concentrate.
  • the aromatic sulfonates include oil soluble metal salts of petroleum sulfonic acids and synthetic alkaryl sulfonic acids, particularly those having a molecular weight of from about 300 to 800.
  • the preferred alkyl substituents on the aromatic ring contain from about 8 to 24 carbon atoms.
  • the aromatic sulfonate used in the lubricants of this invention is an oil-soluble beta-naphthalene sulfonic acid-aldehyde condensate, and particularly useful is the formaldehyde condensate.
  • Preparations for producing such condensates are generally known in the art. They may also be used in the form of an alkali metal salt.
  • emulsion compositions containing additionally a liquid fatty acid, having from about 12 to about 22 carbon atoms, preferably oleic acid or linoleic acid, in combination with an aliphatic fatty acid amide having from about to about 18 carbon atoms, preferably lauroyl amide, possess further improved anti-corrosion properties in the cold-rolling of steel.
  • Oleic acid offers additional oiliness characteristics which aid in the filmforming properties of the lubricant, but it does not provide any anti-corrosion protection by itself. It is known that amides do provide some anti-corrosion properties alone.
  • the fatty acid amide acts in an improved manner evidencing unusual cooperation, as between coagents.
  • the combination of oleic acid and lauroyl amide protects the surface of the metal strip against rust in a very effective manner.
  • the oleic acid is used in minor quantities ranging from 1% to about 5% by Weight of concentrate.
  • the amide is used in amounts ranging from about 4% to about 8% by weight of concentrate.
  • compositions. of this invention are particularly useful in the cold-rolling of steel, as well as in other metalworking operations.
  • the lubricants herein described permit the high speed gauge reduction of the metal in metal rolling operations. They also provide an unusual improvement in removing metal fines caused in the rolling. It is well known that in rolling of metal when the metal billet is fed into rollers, small particles of metal may break off. These particles usually remain in the lubricant. When normal lubricants are used, the smaller particles, or fines, do not always settle out when the lubricant is passed into the reservoir or holding tank at the conclusion of the rolling operation.
  • the emulsion lubricants of this invention is unique in that the presence of the solid acid may act to reject the metal fines from the emulsion and float them to the surface where they are removed in the skimming step.
  • Naphthenic oil havin%a viscosity of 100 S.U.S. at 100 F.
  • Solvent refined para nic oil having 8. 71500811237 of 100 S.U.S. at 100 F.
  • Hydrogenated tallow fatty acids having the COmDOSI'tIOD (wt. percent): 13% C14; 23-33% C10; and 6577% C15.
  • An emulsifiable lubricating composition suitable for the cold-rolling of metals and having increased hard water stability said composition made by mixing from about 20% to about 60% by weight of a lubricating oil selected from the group consisting of naphthenic and parafiinic mineral oils, synthetic ester lubricants, polyolefin fluids, and polyoxyalkylene fluids, from about 20% to about 50% by weight of a saturated solid aliphatic monocarboxylic acid having from 10 to about 30 carbon atoms, from about 1% to about 15% by weight of an alkanolamine having from 2 to about 4 carbon atoms per alkanol group, from about 1% to about 15% by weight of an emulsifier having a hydrophylic-lipophilic balance of at least 10, from about 0.05% to about 2.0% by weight of an aromatic sulfonate having a molecular weight between about 300 and 800 and from about 2% to about 15 by weight of a phosphate, the improvement whereby said phosphate is a
  • composition of claim 1 wherein the mixture of phosphates is present to the extent of from about 5 to about 10% by weight.
  • composition of claim 1 comprising from about 20% to about 40% by weight of acid having from about 10 to about 20 carbon atoms, from about 3% to about 12% by weight of alkanolamine, from about 3% to about 12% by weight of the emulsifier, and from about 0.1% to about 1.5% by weight of aromatic sulfonate.
  • An emulsion lubricant composition comprising from about 0.75% to about 10% by weight of a composition of claim 3 and from about 99.25% to about 90% by weight of water.
  • composition of claim 3 wherein the acid is hydrogenated tallow fatty acid.
  • composition of claim 3 wherein the alkanolamine is triethanolamine.
  • composition of claim 3 wherein the emulsifier is lauroyl diethanolamide.
  • composition of claim 3 wherein the aromatic sulfonate is a naphthalene sulfonate-formaldchyde condensate.
  • composition of claim 8 wherein the said condensate is in the form of an alkali metal salt thereof.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US00127764A 1971-03-24 1971-03-24 Lubricant for metalworking Expired - Lifetime US3723314A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12776371A 1971-03-24 1971-03-24
US12776471A 1971-03-24 1971-03-24

Publications (1)

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US3723314A true US3723314A (en) 1973-03-27

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US00127763A Expired - Lifetime US3723313A (en) 1971-03-24 1971-03-24 Lubricant useful in metal working

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US (2) US3723314A (enExample)
JP (1) JPS5134844B1 (enExample)
AT (1) AT320112B (enExample)
AU (1) AU456255B2 (enExample)
BE (1) BE781017A (enExample)
BR (1) BR7201738D0 (enExample)
CA (2) CA969167A (enExample)
DE (1) DE2207504A1 (enExample)
FI (1) FI53832C (enExample)
FR (1) FR2130714B1 (enExample)
GB (1) GB1366768A (enExample)
IT (1) IT950672B (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4178260A (en) * 1974-10-31 1979-12-11 Exxon Research & Engineering Co. Ester based metal working lubricants
US4749503A (en) * 1986-03-07 1988-06-07 Chemical Exchange Industries, Inc. Method and composition to control microbial growth in metalworking fluids
KR20190028720A (ko) * 2016-07-12 2019-03-19 푸슈 페트롤러브 에스이 윤활제 조성물 및 용도
US20250051676A1 (en) * 2022-03-31 2025-02-13 Dow Global Technologies Llc Water based semi-synthetic metal working fluid composition containing an alkyl alcohol amine

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU531338B2 (en) * 1978-06-30 1983-08-18 Mobil Oil Corp. Metal working lubricants
US4370244A (en) * 1978-12-21 1983-01-25 Akademie Der Wissenschaften Der Ddr Process for cold mechanical working of metallic materials
FR2450275A1 (fr) * 1979-03-01 1980-09-26 Hoechst France Fluides industriels pour le travail des metaux
GB8307975D0 (en) * 1983-03-23 1983-04-27 British Petroleum Co Plc Soluble-oil cutting fluid
AU602422B2 (en) * 1987-08-21 1990-10-11 International Lubricants Inc. Jojoba oil and jojoba oil derivative lubricant compositions
AU4170297A (en) 1996-08-30 1998-03-19 Solutia Inc. Novel water soluble metal working fluids
JP5206622B2 (ja) * 2009-08-07 2013-06-12 三菱瓦斯化学株式会社 金属微細構造体のパターン倒壊抑制用処理液及びこれを用いた金属微細構造体の製造方法
WO2020190915A1 (en) 2019-03-19 2020-09-24 Cryovac, Llc Film support in vertical form-fill-seal systems
CN110257154B (zh) * 2019-05-30 2022-08-02 山西太钢不锈钢股份有限公司 轧制润滑液基础油的制备方法
JP7580211B2 (ja) * 2020-06-16 2024-11-11 株式会社ネオス 金属加工油剤組成物及び金属加工方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4178260A (en) * 1974-10-31 1979-12-11 Exxon Research & Engineering Co. Ester based metal working lubricants
US4749503A (en) * 1986-03-07 1988-06-07 Chemical Exchange Industries, Inc. Method and composition to control microbial growth in metalworking fluids
KR20190028720A (ko) * 2016-07-12 2019-03-19 푸슈 페트롤러브 에스이 윤활제 조성물 및 용도
KR102235348B1 (ko) 2016-07-12 2021-04-06 푸슈 페트롤러브 에스이 윤활제 조성물 및 용도
US20250051676A1 (en) * 2022-03-31 2025-02-13 Dow Global Technologies Llc Water based semi-synthetic metal working fluid composition containing an alkyl alcohol amine
US12410376B2 (en) * 2022-03-31 2025-09-09 Dow Global Technologies Llc Water based semi-synthetic metal working fluid composition containing an alkyl alcohol amine

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FI53832C (fi) 1978-08-10
CA971157A (en) 1975-07-15
AT320112B (de) 1975-01-27
AU3901272A (en) 1973-08-16
US3723313A (en) 1973-03-27
CA969167A (en) 1975-06-10
DE2207504A1 (de) 1972-10-05
FR2130714B1 (enExample) 1978-07-07
FI53832B (fi) 1978-05-02
BE781017A (fr) 1972-09-21
FR2130714A1 (enExample) 1972-11-03
IT950672B (it) 1973-06-20
AU456255B2 (en) 1974-12-12
JPS5134844B1 (enExample) 1976-09-29
GB1366768A (en) 1974-09-11
BR7201738D0 (pt) 1973-05-24

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