EP1230331B1 - Utilisation de cristallites lamellaires en tant qu'additifs extreme-pression dans des lubrifiants aqueux, cristallites lamellaires et leur obtention - Google Patents

Utilisation de cristallites lamellaires en tant qu'additifs extreme-pression dans des lubrifiants aqueux, cristallites lamellaires et leur obtention Download PDF

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Publication number
EP1230331B1
EP1230331B1 EP00971481A EP00971481A EP1230331B1 EP 1230331 B1 EP1230331 B1 EP 1230331B1 EP 00971481 A EP00971481 A EP 00971481A EP 00971481 A EP00971481 A EP 00971481A EP 1230331 B1 EP1230331 B1 EP 1230331B1
Authority
EP
European Patent Office
Prior art keywords
lamellar crystallites
range
carbon atoms
lamellar
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00971481A
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German (de)
English (en)
French (fr)
Other versions
EP1230331A1 (fr
Inventor
Gilles Lorentz
Jean-Marie Georges
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06—Particles of special shape or size
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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

Definitions

  • the present invention relates to the use, as extreme pressure additives in aqueous lubricants, lamellar crystallites. It also concerns these lamellar crystallites and their production.
  • the subject of the present invention is the use in aqueous lubricants, as as extreme pressure additives of lamellar crystallites, of micron size, and comprising a stack of organic phases and aqueous solutions; said crystallites being dispersed within the aqueous lubricant.
  • these lamellar crystallites whose length is less than or equal to 100 ⁇ m, the width less than or equal to 30 ⁇ m and the thickness less than or equal to 200 nm, come into contact with the surface of the metal to be transformed, and that they favor the lubrication, by a slip of the lamellar crystallites the in relation to each other, during the transformation / deformation operation.
  • the attached figure represents a photograph taken by transmission electron microscopy (Cryo-MET, full scale of photography: 2 ⁇ m). It represents lamellar crystallites according to the invention.
  • a second subject of the invention consists of such lamellar crystallites.
  • Another object of the invention consists in obtaining crystallites lamellar.
  • the method comprises contacting a solution or a dispersion comprising the optionally neutralized acid, with the metal occurring under a ionic and / or metallic form.
  • said lamellar crystallites present a length of between 0.1 and 100 ⁇ m.
  • the length of the crystallites lamellar is between 0.5 and 20 ⁇ m.
  • the lamellar crystallites moreover have a width varying between 0.5 and 30 .mu.m. More particularly, the width of the lamellar crystallites is between 0.5 and 10 ⁇ m.
  • the thickness of the lamellar crystallites is between 5 and 200 nm, preferably between 10 and 100 nm.
  • the dimensions of the lamellar crystallites which have just been indicated correspond to average values. In other words, there is a distribution of sizes of lamellar crystallites whose average is in the ranges above.
  • the lamellar crystallites are more particularly constituted of a stack organic phases (O) and aqueous solutions (A) according to the sequence O / [A / O] n, n being an integer different from 0 and such that the stack has a thickness from 5 to 200 nm.
  • n is a positive integer that can be at most 100. preferably, n is an integer between 1 and 20.
  • said acids are optionally in a form neutralized by a organic or mineral base.
  • the carboxylic acids likely to enter the composition of the organic phases of the lamellar crystallites according to the invention are selected from saturated or unsaturated mono- or polycarboxylic acids comprising from 5 to 40 carbon atoms.
  • R 1 - COOH corresponds to the following formula: R 1 - COOH; formula in which R 1 represents an alkyl, alkenyl radical having one or more ethylenic unsaturations, linear or branched, having from 5 to 40 carbon atoms (the carbon atom of the carboxylic group being included), optionally substituted by one or more radicals; hydroxyls and / or at least one carboxylic function.
  • the acid corresponds to the above formula, in which R 1 represents an alkyl radical comprising 7 to 30 carbon atoms, optionally substituted by one or more hydroxyl radicals and / or one or more preferably a carboxylic function.
  • the second carboxylic function if present, can be find end of chain or not.
  • the organic phase i) is derived from at least one fatty acid, comprising more particularly a single carboxylic function.
  • saturated fatty acids mention may be made of stearic acids, palmitic, behenic.
  • unsaturated fatty acids include unsaturated fatty acids having a single double bond such as linderic, myristoleic, palmitoleic, oleic, petroselenic, doeglic, gadoleic, erucic; fatty acids unsaturated having two double bonds such as linoleic acid; fatty acids unsaturated having 3 double bonds such as linolenic acid; fatty acids unsaturated having more than 4 double bonds such as isanic acids, stearodonic, arachidonic, cypranodonic; unsaturated fatty acids carrying hydroxyl group such as ricinoleic acid and mixtures thereof.
  • the acids are preferably used. palmitic, behenic, stearic, palmitoleic, oleic, petroselenic, erucic, linoleic, linolenic, ricinoleic.
  • (RO) x -P ( O) (OH) x ' formula, in which R, identical or not, represent a hydrocarbon radical, optionally polyalkoxylated, x and x 'being equal to 1 or 2, provided that the sum of x and x' is equal to 3.
  • R is an aliphatic, cycloaliphatic hydrocarbon radical or aromatic, saturated or unsaturated, containing 1 to 30 carbon atoms.
  • the radicals R which are identical or different, are alkyl or alkenyl radicals carrying one or more linear or branched ethylenic unsaturations containing 8 to 26 carbon atoms.
  • the radicals R may be aromatic radicals bearing alkyl, arylalkyl substituents, or alkylaryl; these radicals comprising 6 to 30 carbon atoms.
  • such radicals include, inter alia, nonylphenyl, mono-, di- and tristyrylphenyl radicals.
  • the OA group corresponds to an oxyethylenated radical, oxypropylene, oxybutylenated, or mixtures thereof.
  • said grouping corresponds to an oxyethylenated and / or oxypropylenated radical.
  • y average, it is preferably between 0 and 80.
  • the acid used in the composition of organic phases of the lamellar crystallites may be in a form neutralized by a mineral or organic base.
  • the bases that can be used to neutralize the acid, the basic compounds which create monovalent species are suitable.
  • bases used are preferably water-soluble.
  • alkali metal hydroxides hydroxycarbonates, carbonates, bicarbonates, ammonia.
  • Suitable organic bases include, but are not limited to, primary, secondary or tertiary amines comprising 1 to 40 carbon atoms, optionally substituted with one or more hydroxyl radicals, and / or one or several oxyalkylenated groups.
  • Said alkylenated groups are preferably oxyethylenated units.
  • the number of oxyalkylenated units, are present is less than or equal to 100.
  • Suitable amines mention may be made of monoethanolamine, diethanolamine, ethylenediamine, aminoethylethanolamine, aminomethylpropanolamine.
  • Polyoxyalkylenated fatty amines can also be used in as an organic basis, such as those marketed by Rhodia Chemistry under the name Rhodameene® CS20.
  • the lamellar crystallites further comprise at least one metal in the form of a multivalent ion. More particularly, said metal can be in the form of a divalent ion or a trivalent ion. It is likewise not excluded to implement several metals, with identical or different degrees of oxidation.
  • said metal is chosen from columns IIA, VIII, IB, IIB, with the exception of cobalt and nickel.
  • the metals are chosen from calcium, magnesium, copper, zinc, iron, aluminum.
  • the lamellar crystallites may comprise a mixture of at least two metals.
  • the lamellar crystallites comprise a mixture of two metals, which preferably are zinc and copper.
  • the quantity of lamellar crystallites dispersed in the aqueous lubricant during its use usually represents 0.1 to 5% by weight relative to the total weight lubricant when in use.
  • the amount of lamellar crystallites is between 0.1 and 1% by weight relative to the same reference.
  • the lamellar crystallites according to the invention can be used in presence of at least one nonionic surfactant.
  • the number of polyoxyalkylene units, if present, of these nonionic surfactants usually varies from 2 to 100. It should be noted that, by polyoxyalkylenated units, the oxyethylenes, oxypropylene, or mixtures thereof.
  • the surfactant content usually varies between 0 and 5% by weight total amount of lubricant when used.
  • Lamellar crystallites can be obtained by contacting a solution or a dispersion comprising the acids possibly neutralized with the metal presenting in ionic and / or metallic form.
  • dispersion we mean a dispersion of vesicles, droplets or micelles in an aqueous medium.
  • a dispersion comprising at least one nonionic surfactant, such as in particular chosen from the list indicated previously.
  • the surfactant content usually varies, in the case where it is present, between 1 and 30% by total weight of the concentrated dispersion.
  • the latter may indifferently be under its metal form or in the form of a multivalent cation.
  • Said cation can itself be find in the form of a solid, a solution or a dispersion.
  • salts of mineral acids such as halides, with chlorides for example; nitrates, as well as salts organic acids such as formate, acetate, among others.
  • metal in a form oxide, hydroxide, carbonate, or the metal itself.
  • the contacting is carried out in the presence of at least one compound having the effect of buffering the pH.
  • at least one compound having the effect of buffering the pH we choose one or several compounds such that the pH of the medium is between 7 and 9, preferably between 8 and 8.5.
  • the contacting takes place with stirring.
  • the metal under the chosen form in the solution or dispersion of the acids possibly neutralized by the aforementioned mineral or organic base.
  • the operation is advantageously carried out at a temperature below 100 ° C., and preferably at a temperature between 20 and 60 ° C.
  • the lamellar crystallites according to the invention are therefore used, and this constitutes a another object of the present invention, as an extreme-pressure additive in aqueous lubricants used for the deformation or transformation of metals.
  • deformation is understood to mean in particular the drawing, rolling operations. Processing operations refer more specifically to cutting of metals.
  • the metals which can be the subject of such treatments are in particular, and mainly, steels, stainless steels, aluminum, copper, zinc, tin, alloys based on copper (bronze, brass), etc.
  • lubricants aqueous phase comprising the lamellar phases according to the invention are used in the drawing operations of brass-plated steel wires.
  • Aqueous lubricants are generally colloidal dispersions in water. he It should be noted that the dispersions may be emulsions or dispersions solid particles or phases organized in an aqueous medium.
  • Aqueous lubricants generally have a pH of between 7 and 9.
  • They may further include conventional additives in this field, such as preservatives, anti-corrosion agents, anti-foam agents, stabilizing agents.
  • the lamellar crystallites according to the invention can be indifferently introduced in a bath treatment or deformation of the metal, new or worn.
  • the lamellar crystallites according to the invention can be introduced into the bath in the form of precursors. So we can add to the bath, on the one hand the solution of the possibly neutralized acids, and on the other hand, the metal in the form required.
  • the resulting mixture is then diluted 10 times.
  • Brass powder (15 g / l) was then added with stirring at 40 ° C.
  • the mixture is left stirring for 5 days at the temperature indicated above.
  • the figure shows indeed lamellar crystallites of section between 50 and 100 nm and longer than 2-3 ⁇ m (full scale of the figure: 2 ⁇ m).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP00971481A 1999-10-21 2000-10-23 Utilisation de cristallites lamellaires en tant qu'additifs extreme-pression dans des lubrifiants aqueux, cristallites lamellaires et leur obtention Expired - Lifetime EP1230331B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9913139A FR2800091B1 (fr) 1999-10-21 1999-10-21 Utilisation de micro-lamelles en tant qu'additifs extreme-pression dans des lubrifiants aqueux, micro-lamelles et leur obtention
FR9913139 1999-10-21
PCT/FR2000/002944 WO2001029159A1 (fr) 1999-10-21 2000-10-23 Utilisation de cristallites lamellaires en tant qu'additifs extreme-pression dans des lubrifiants aqueux, cristallites lamellaires et leur obtention

Publications (2)

Publication Number Publication Date
EP1230331A1 EP1230331A1 (fr) 2002-08-14
EP1230331B1 true EP1230331B1 (fr) 2005-04-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00971481A Expired - Lifetime EP1230331B1 (fr) 1999-10-21 2000-10-23 Utilisation de cristallites lamellaires en tant qu'additifs extreme-pression dans des lubrifiants aqueux, cristallites lamellaires et leur obtention

Country Status (14)

Country Link
US (1) US6806238B1 (es)
EP (1) EP1230331B1 (es)
JP (2) JP2003528940A (es)
KR (1) KR100523717B1 (es)
CN (1) CN100345950C (es)
AT (1) ATE292668T1 (es)
AU (1) AU772577B2 (es)
BR (1) BR0014935B1 (es)
CA (1) CA2387820C (es)
DE (1) DE60019327T2 (es)
ES (1) ES2235968T3 (es)
FR (1) FR2800091B1 (es)
MX (1) MXPA02003685A (es)
WO (1) WO2001029159A1 (es)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2820431B1 (fr) * 2001-02-06 2007-04-27 Rhodia Chimie Sa Procede de deformation de metaux mettant en oeuvre un lubrifiant aqueux additive permettant d'augmenter la productivite
KR100591778B1 (ko) * 2005-01-19 2006-06-26 몽 필 김 곡물 분쇄기
AT502630B1 (de) * 2005-10-21 2008-01-15 Miba Sinter Austria Gmbh Bauelement, insbesondere formteil, mit einer beschichtung
US7449432B2 (en) * 2006-03-07 2008-11-11 Ashland Licensing And Intellectual Property, Llc (Alip) Gear oil composition containing nanomaterial
CN106350190B (zh) * 2016-08-19 2019-04-30 湖北省化学工业研究设计院 一种高强镀黄铜钢丝拉拔润滑剂及其制备方法
EP4240819A1 (en) 2020-11-05 2023-09-13 Ardagh Metal Packaging USA Corp. Metalworking formulations with corrosion inhibitor formulations
KR102477036B1 (ko) 2022-05-26 2022-12-19 주식회사 에스에이치엘 습식윤활액 조성물

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3036118A (en) * 1957-09-11 1962-05-22 Wyandotte Chemicals Corp Mixtures of novel conjugated polyoxyethylene-polyoxypropylene compounds
US4452711A (en) * 1983-01-20 1984-06-05 Aluminum Company Of America Aqueous metalworking lubricant containing polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers
US5964692A (en) * 1989-08-24 1999-10-12 Albright & Wilson Limited Functional fluids and liquid cleaning compositions and suspending media
GB8926885D0 (en) * 1989-11-28 1990-01-17 Albright & Wilson Drilling fluids
US5807810A (en) * 1989-08-24 1998-09-15 Albright & Wilson Limited Functional fluids and liquid cleaning compositions and suspending media
US6166095A (en) * 1993-12-15 2000-12-26 Albright & Wilson Uk Limited Method of preparing a drilling fluid comprising structured surfactants
MX9606330A (es) * 1994-06-13 1997-03-29 Du Pont Composicion inhibidora de corrosion para acero.
FR2758561B1 (fr) * 1996-11-25 1999-04-23 Rhodia Chimie Sa Compositions d'orthophosphates soufres, leur procede de preparation et leur utilisation
JPH11279581A (ja) * 1998-03-26 1999-10-12 Kyodo Yushi Co Ltd 金属加工用水溶性油剤
FR2777902B1 (fr) * 1998-04-28 2002-03-15 Rhodia Chimie Sa Utilisation dans un lubrifiant de trefilage,d'une suspension d'un sel de cobalt comme agent d'adherence,suspension et son obtention

Also Published As

Publication number Publication date
CN100345950C (zh) 2007-10-31
EP1230331A1 (fr) 2002-08-14
US6806238B1 (en) 2004-10-19
CA2387820C (fr) 2007-05-01
ATE292668T1 (de) 2005-04-15
KR100523717B1 (ko) 2005-10-26
DE60019327T2 (de) 2006-05-04
JP2003528940A (ja) 2003-09-30
MXPA02003685A (es) 2003-10-14
FR2800091B1 (fr) 2005-01-28
BR0014935A (pt) 2002-06-11
BR0014935B1 (pt) 2011-03-22
JP2009287030A (ja) 2009-12-10
KR20020052192A (ko) 2002-07-02
AU772577B2 (en) 2004-04-29
DE60019327D1 (de) 2005-05-12
CN1382203A (zh) 2002-11-27
ES2235968T3 (es) 2005-07-16
AU1033001A (en) 2001-04-30
CA2387820A1 (fr) 2001-04-26
FR2800091A1 (fr) 2001-04-27
WO2001029159A1 (fr) 2001-04-26

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