EP0663002A1 - Lubricated metal workpiece and method - Google Patents
Lubricated metal workpiece and methodInfo
- Publication number
- EP0663002A1 EP0663002A1 EP93921045A EP93921045A EP0663002A1 EP 0663002 A1 EP0663002 A1 EP 0663002A1 EP 93921045 A EP93921045 A EP 93921045A EP 93921045 A EP93921045 A EP 93921045A EP 0663002 A1 EP0663002 A1 EP 0663002A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant
- metal
- lubricated
- range
- hardness
- 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.)
- Withdrawn
Links
Classifications
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/40—Esters containing free hydroxy or carboxyl groups
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/70—Esters of monocarboxylic acids
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- 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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- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- 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
- C10M2207/126—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 monocarboxylic
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/284—Esters of aromatic monocarboxylic acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/286—Esters of polymerised unsaturated acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/2875—Partial esters used as base material
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/288—Partial esters containing free carboxyl groups
- C10M2207/2885—Partial esters containing free carboxyl groups used as base material
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
- C10M2207/2895—Partial esters containing free hydroxy groups used as base material
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- 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
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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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
- C10N2040/241—Manufacturing joint-less pipes
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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
- C10N2040/242—Hot working
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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
- C10N2040/243—Cold working
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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
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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
- C10N2040/245—Soft metals, e.g. aluminum
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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
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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
- C10N2040/247—Stainless steel
Definitions
- This invention relates to lubricated metal workpieces, particularly of steel and aluminium, and to a method of using such workpieces to make structures of shaped components.
- lubricated metal workpieces particularly of steel and aluminium
- a method of using such workpieces to make structures of shaped components There is current interest in techniques for producing adhesively bonded structures of shaped aluminium components for use in the automotive industry. Such a technique is described for example in EPA 127343.
- the technique of converting a coil of aluminium metal sheet into a structure of shaped components for use in the automotive industry may typically involve the following steps:-
- the metal surface is pre-treated to provide a strongly bonded layer thereon which acts as a base for subsequently applied adhesive.
- a lubricant is applied to the treated metal coil.
- the coil may then be stored or transported, with the lubricant serving to protect the treated metal surface, and is cut up into pieces ready for press-forming.
- the components are assembled into the shape of the desired structure, and may be spot welded or otherwise fixed to hold the structure together until the adhesive is cured.
- the adhesive is cured at elevated temperature.
- the metal surfaces of the structure are subjected to an aqueous alkaline cleaner which removes the lubricant.
- the structure is painted.
- the press-formed components may be secured together to form the structure by mechanical means, e.g. by rivets or spot-welds, either in addition to or instead of adhesive bonding.
- a lubricant for use in such a technique needs to fulfil several requirements: a) The lubricant must, obviously, have suitable lubricating properties for the press-forming operation. b) The lubricant should be solid at likely metal storage temperatures in order to prevent stacked sheets from sticking together. Furthermore, a film of lubricant that is liquid or sticky is prone to smear and to pick up dust and dirt. c) Since it is not practicable in a production line to remove lubricant prior to application of adhesive, the lubricant needs to be compatible with an adhesive if one is to be used. d) After the adhesive has been applied and cured, the lubricant must be readily removable by an aqueous alkaline cleaner of the type conventionally used to prepare metal surfaces for painting.
- the lubricants of EPA 227360 are designed to be useful, not only for the technique described above, but also for other forming and shaping operations performed on a variety of metals.
- EPA 227360 provides a lubricating composition for press forming consisting of a lubricant dissolved or dispersed in a volatile liquid medium, wherein the lubricant comprises at least one ester of a polyhydric alcohol having two or three hydroxyl groups of which one or two are esterified with a long chain carboxylic acid and has a melting point above ambient temperature but low enough to permit removal from a metal surface by an aqueous alkaline cleaner.
- EPA 227360 mentions that mixtures of esters may be used and may be advantageous; and that the lubricant may contain a minor proportion up to 50% of one or more other lubricating compounds such as long- chain carboxylic acids.
- the lubricants exemplified are: diethylene glycol monostearate in solution in xylene; and diethylene glycol distearate in solution in xylene.
- lubricants described in EPA 227360 are generally successful at meeting requirements c) and d) , they are sometimes less successful at meeting requirements a) and b) . It is surprisingly found that lubricants of this kind are ineffective, so far as aluminium forming operations are concerned, at temperatures above their liquidus. For good aluminium lubricating properties, in ester lubricants of this kind, it appears necessary that some component be present in the solid state, so that the lubricant is solid or at least mushy or viscous, at the forming temperature which may be as high as 35'C or 40'C or even higher.
- the invention provides lubricated metal, wherein a surface of the metal carries a film of a lubricant which a) consists essentially of at least one partial ester of a di- or poly-hydroxy compound with a C8 - C18 saturated carboxylic acid optionally in admixture with a minor amount of a long-chain carboxylic acid or ester thereof, and b) has a hardness in the range 0.2 - 10 N/mm at all temperatures in the range 15 - 30'C, preferably in the range 0.1 - 10 N/mm at all temperatures in the range 15 - 35'C.
- the present invention provides a method of making a structure of shaped aluminium components starting from lubricated aluminium metal sheet as defined, comprising the steps: - forming pieces of the sheet into components, bringing the components together in the shape of the desired structure, and securing the components together by mechanical and/or adhesive means.
- Hardness of the lubricant is measured by a technique whereby a block of the uncoated lubricant is equilibrated at a given temperature and is penetrated by a steel needle.
- the load on the needle (in Newtons) is measured as a function of its penetration into the lubricant (in millimetres), and an average gradient in N/mm is derived over a 30mm penetration.
- the test is derived from BS2000 part 59, "penetration of a bituminous materials", with the further adaption that the needle diameter has been increased to 12mm to ensure that the loads are not too small for accurate measurement.
- lubricant films of this invention have specified hardness values at temperatures within the range 15 - 40 * C, in the case of particularly preferred lubricants, within the range 15 - 45 * C. If the lubricant film is too hard, it is likely to be brittle and have poor frictional characteristics during forming e.g. press-forming. If the lubricant film is too soft, then again the lubricating characteristics are inferior.
- the lubricant film has a hardness in the range 0.2 - 5 N/mm at all temperatures within the range specified at which forming e.g. press-forming is likely to take place in different parts of the world. It is surprising that the hardness of the lubricant film has useful predictive value for its lubricating characteristics.
- the major component of the lubricant film is a partial ester of a polyhydric alcohol with a long- chain carboxylic acid.
- Dihydric or trihydric alcohols are suitable, for example ethylene glycol, propylene glycol, diethylene glycol and glycerol.
- the long chain carboxylic acid is preferably a saturated straight- chain monocarboxylic acid having from 12 to 18 carbon atoms in the chain, such as lauric, palmitic or stearic acid. Mixtures of esters may be used and may be advantageous.
- the partial ester or partial esters may be used optionally in admixture with a minor amount of a long-chain carboxylic acid or ester thereof, preferably a saturated straight-chain monocarboxylic acid having from 14 - 20 carbon atoms in the chain, or ester thereof with a saturated monohydric alcohol.
- the optional minor component is present in an amount of less than 50% most usually 5 - 20%, by weight on the weight of the mixture.
- Particularly preferred partial esters are ethylene glycol monolaurate (EGML) and propylene glycol monostearate (PGMS) .
- a particularly preferred fatty acid is stearic acid.
- Suitable lubricants may be achieved in one or both of two ways. The first is by blending two or more components together; thus a mixture of commercial purity EGML with commercial purity PGMS in a weight ratio of 1:3 has the required hardness characteristic.
- EGML is made by partially esterifying ethylene glycol with "lauric acid", which is a fraction of coconut oil fatty acids and contains more than 30% by weight of fatty acid material which is not lauric acid.
- lauric acid is a fraction of coconut oil fatty acids and contains more than 30% by weight of fatty acid material which is not lauric acid.
- EGML from one commercial source had a melting point of 24 * C.
- the "lauric acid” used in its preparation was a mixture of coconut oil fatty acids with an evident high content of unsaturated fatty acids.
- EGML from another commercial source had a melting point of 29'C and was derived from a coconut oil fraction containing more than 30% of fatty acid which was not lauric acid.
- EGML has been prepared specially for us, using lauric acid containing less than 10% of other fatty acid impurities.
- This EGML has a melting point of 43'C. Unlike the two commercial materials noted above, a film of this EGML does have the hardness characteristic of this invention.
- EGML for use as the only ester in the lubricant of this invention preferably has a melting point of at least 35'C.
- such EGML is a mixture, but of a particular kind.
- Partial esters such as EGML can have impurities arising from two main sources:- a)
- the nominal fatty acid, e.g. lauric acid is in fact a mixture of saturated long-chain monocarboxylic acids, typically containing more than 30% of acids other than the nominated one. An effect of these contaminating acids is to depress the melting point of the partial ester.
- partial esters are preferably derived from fatty acids which are at least 80% pure.
- the partial ester was derived from a fatty acid mixture which contained ethylenically unsaturated acids.
- Such impurities make the lubricant less adhesive-compatible and less easy to remove from the metal surface, and are therefore preferably absent or present in amounts below 5% by weight.
- Partial esterification of a polyhydric alcohol having n hydroxyl groups is effected by reacting a mixture of 1 mole of the polyhydric alcohol with less than n moles of a monocarboxylic acid. This typically results in a mixture containing a substantial proportion of the unchanged polyhydric alcohol, substantial proportions of the or each possible partial ester, and a substantial proportion of the full ester.
- the result of reacting a mixture of 1 mole of a glycol with less than 2 moles of a monocarboxylic acid is a mixture containing substantial proportions of the unchanged glycol, the monoester and the diester.
- Solvent and unreacted polyhydric alcohol may be readily removed by volatilisation.
- the remaining material is generally called a partial ester, and the term "partial ester" is herein used in this sense.
- the partial ester has an acid value intermediate that of the corresponding polyhydric alcohol, and that of the corresponding full ester.
- the lubricating characteristics of the lubricant film on lubricated metal according to this invention fall off at both excessively high and excessively low temperature.
- This frictional coefficient is preferably below about 0.1 at all temperatures within the range of interest, that is to say 15'C up to 30'C or 35'C or 40 * C or 45'C.
- the hardness of the lubricant film at any temperature is predictive of its frictional coefficient.
- the lubricant may need to be compatible with subsequently applied adhesive.
- the esters described herein are compatible as a result of being either absorbed or displaced by subsequently applied adhesive without grossly impairing the adhesive bond strength obtainable.
- resinous lubricants and metal soap lubricants are generally not adhesive compatible in this sense.
- the lubricant has a melting point above ambient temperature, preferably of at least 30"C. This ensures that the lubricant is present as a solid film on the metal substrate, which avoids problems with smearing and blocking during coiling, decoiling, slitting and cutting.
- the use of such a lubricant avoids contamination of the metal surface with a possible adhesive-incompatible oil or contaminant and prevents local build up of lubricant to an undesirably thick layer.
- the lubricant melts at a temperature low enough to permit its removal from a metal surface by an aqueous alkaline cleaner, such as is used in automotive production lines to prepare metal parts for painting.
- the highest practicable temperature for aqueous alkaline cleaners in such circumstances is about 70 * C.
- Lubricants melting below 70'C and preferably below 65'C can thus always be removed by aqueous alkaline cleaners.
- Lubricants melting above 70'C may or may not be removable depending on whether they have chemical groups, e.g. hydroxyl groups, which can react with the alkali to assist removal from the metal surface.
- a commercially available wax having a melting point of 85'C and an acid number of 135 to 155 by DIN 53402 was found not to be removable by aqueous alkaline cleaners.
- glycerol mono-stearate having a melting point of 81 'C and two free hydroxyl groups per molecule, is removable by aqueous alkaline cleaners, and falls accordingly within the scope of this invention.
- a lubricant is deemed removable by aqueous alkaline cleaners if it can be removed by treatment for 2 minutes at 70 * C with a 15% by weight aqueous solution of Ridolene 160 (a silicate-based proprietary cleaner marketed by I.C.I, pic.)
- a further preferred aspect of this invention involves applying the lubricant to the metal in the absence of any volatile solvent or diluent. This avoids the need to evaporate volatile liquid from the lubricant film, and avoids the need to include any surface active agent in the lubricant. It is found that the molten lubricants have satisfactory viscosity for spraying or for application by roller coat. To ensure rapid solidification of the lubricant filr, the metal may be pre-cooled. To ensure good adhesion of a uniform film, the metal may be pre-heated.
- the lubricant may be applied to steel or other metals, but is likely to be principally used on aluminium, which term is used to cover the pure metal and alloys in which Al is the major component.
- the aluminium surface may carry a strongly-bonded inorganic layer, on the top of which the lubricant is present.
- inorganic non-metallic layers are well known, and may be provided for example as chemical conversion coatings or deposited coatings of the no-rinse type, based on chromium, titanium or zirconium; or may be an anodic oxide layer or a siloxane layer.
- the metal may be in sheet form.
- lubricant The rate of application of lubricant will depend on the intended use, but may typically be in the range of 1 - 10 g/m 2 , particularly 2 - 4 g/m 2 , for aluminium coil to be formed into adhesively bonded structures.
- Figure 1 is a schematic view of a strip- draw apparatus used for testing lubricated metal
- Figure 2 is a perspective view of a modified strip-draw apparatus,-
- Figure 3 is a graph of hardness against temperature for films of several lubricants.
- Figures 4, 5 and 7 are Bar Charts showing frictional coefficients of three lubricants at different temperatures and different rates of application.
- Figure 6 is a bar chart showing lubricant residues after cleaning.
- a purpose built strip-draw rig was designed and constructed with reference to ASTM 4173-82 for testing sheet metal forming lubricants.
- the apparatus is shown in Figures 1 and 2.
- the die set shown in Figure 1 was designed to simulate material flowing between pressurised binder surfaces containing a draw bead arrangement.
- the die set of Figure 2 was designed to simulate flow between parallel binder surfaces so as to allow conventional frictional values to be obtained.
- one die 10 of each tool set is mounted on a load cell 12.
- the other die 14 of the tool set is mounted on a hydraulic cylinder 16.
- Flat strips 18, hydraulically pressurised between the two dies, can then be pulled through a particular tool set while the clamp load is measured.
- the draw load is also measured using a second load cell 20 mounted between a testing machine gripping jaw 22 and a cross head 24.
- the strip draw rig is designed to be mounted on either a press simulator or a standard tensile testing frame, depending on the variables under investigation.
- Lubricated strips of material 50 mm wide, were placed between the two faces of the flat tool set of Figure 2 and hydraulically pressurised to a particular load. The strips were then drawn through the die set of Figure 1 for a distance of approximately 250 mm, the draw and clamp forces being recorded as a function of time/displacement of the drawn strip. Results presented in the form of a graph (draw force/2) versus clamp load have a slope equal to the conventional friction coefficient.
- EGML c) Stearic acid d) in a weight ratio of 9:1. Two batches were made on separate occasions. The first is shown by filled diamonds connected by a dotted line; the second by filled diamonds connected by a double solid line. Both materials fall within the scope of the invention.
- EGML b) Stearic acid d) in a weight ratio 9:1.
- the hardness is shown by open diamonds connected by a solid line. Because the hardness was relatively low at all temperatures, this material does not fall within the scope of the invention.
- EGML b) Stearic acid d) in a weight ratio of 3:1. This material, which is not shown in Figure 3, did have a hardness within the scope of the invention.
- Lubricants 1 and 5 were further tested in the strip draw rig illustrated in Figures 1 and 2. In each case, tests were performed at four different temperatures, 20'C, 30'C, 40 * C and 50'C; and at five different rates of lubricant application ranging from 1 to 6 g/m 2 . The results of these tests are shown in
- Lubricant 4 from Example 1 was evaluated.
- the lubricant consists of 90 wt% EGML (mp 43 * C) and 10 wt% stearic acid (mp 70 C) .
- Lubricant 5 from Example 1 was used for comparative purposes.
- the procedure for lubricant application consisted of pre-heating a reservoir of the new lubricant to 70 * C, and applying this onto sheets using air-assisted airless spray nozzles. Lubricant was applied to sheets which were held at both room temperature (20'C), and preheated to 60'C. These sheets were then placed in stacks. In the case of the pre-heated material, the sheets were placed in a stack when the lubricant had solidified.
- the standard test method for adhesive compatibility is to assemble standard lap shear joints with a 10 mm overlap, using lubricated 1.6 mm pretreated coupons and a standard adhesive. A string of six such joints are then exposed to combined stress/humidity testing under a constant load. The time to failure of the first three joints in a set of six joints is then noted. Individual lap shear joints are also exposed to salt spray for given periods of time, and then tested for static strength retention.
- Tests were carried out on joints manufactured with the lubricant 4 on their surfaces prior to bonding. Two lubricant weight levels were evaluated, namely 2.0 g/m 2 and 5.5 g/m 2 .
- the Wax Penetration Test was used to determine the softening response as a function of temperature.
- Lubricated sheets were produced with 3 g/m 2 of different lubricants via the pre-heated blank route, as indicated in section 2.1. These sheets were guillotined into strips 50 mm wide and then drawn through the strip draw rig, using the described procedure, to allow friction values to be determined at temperatures of 20, 30, 40 and 50'C. 2.5 Press Forming Evaluation of the Lubricant 4
- lubricated stacks were produced by applying the lubricant to pre-heated blanks, as described in section 2.1.
- pretreated strips of aluminium were lubricated with lubricant 5 (3.4 g/m 2 ) and lubricant 4 (3.8 g/m 2 ), and given the following treatment: a) 20 minutes at 170'C b) 20 minutes at 180'C c) 20 minutes at 190'C d) 20 minutes at 200'C e) No oven bake.
- Table 2 shows the comparative performance of the lubricants 4 and 5 over the measured temperature range for a given lubricant weight of 3 g/m 2 . These figures show an improved performance of the lubricant 4 at temperatures of 30, 40 and 50"C. They also indicate a similar performance at 20'C.
- Salt spray data after 20 weeks exposure shows excellent strength retention at both lubricant weight levels, out performing the lubricant 5.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB929220719A GB9220719D0 (en) | 1992-10-01 | 1992-10-01 | Lubricated metal workpiece and method |
GB9220719 | 1992-10-01 | ||
PCT/GB1993/002050 WO1994007973A1 (en) | 1992-10-01 | 1993-10-01 | Lubricated metal workpiece and method |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0663002A1 true EP0663002A1 (en) | 1995-07-19 |
Family
ID=10722828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93921045A Withdrawn EP0663002A1 (en) | 1992-10-01 | 1993-10-01 | Lubricated metal workpiece and method |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0663002A1 (en) |
JP (1) | JPH08502089A (en) |
KR (1) | KR950703631A (en) |
AU (1) | AU675242B2 (en) |
BR (1) | BR9307166A (en) |
CA (1) | CA2145989A1 (en) |
GB (1) | GB9220719D0 (en) |
NO (1) | NO951257D0 (en) |
WO (1) | WO1994007973A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2727126B1 (en) * | 1994-11-22 | 1997-04-30 | Inst Francais Du Petrole | LUBRICATING COMPOSITION COMPRISING AN ESTER. USE OF THE COMPOSITION AND WELL FLUID COMPRISING THE COMPOSITION |
US8445106B2 (en) | 2005-08-02 | 2013-05-21 | Kobe Steel, Ltd. | Resin-coated metal sheet and resin composition |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3468701A (en) * | 1966-02-09 | 1969-09-23 | Atlas Chem Ind | Method of preventing blocking of aluminum sheet material |
US4113635A (en) * | 1971-12-13 | 1978-09-12 | Nippon Steel Corporation | Rust-proof lubricant compositions |
US4191658A (en) * | 1974-10-10 | 1980-03-04 | The Lubrizol Corporation | Hot melt metal working lubricants and methods for their application |
GB8530146D0 (en) * | 1985-12-06 | 1986-01-15 | Alcan Int Ltd | Lubricating composition |
ZA873747B (en) * | 1986-05-30 | 1987-11-23 | Alcan International Limited | Prelubricated finstock |
GB8630971D0 (en) * | 1986-12-29 | 1987-02-04 | Alcan Int Ltd | Lubricant emulsion |
US5069806A (en) * | 1989-10-27 | 1991-12-03 | Nalco Chemical Company | Solid dry film prelube with low temperature cleanability |
-
1992
- 1992-10-01 GB GB929220719A patent/GB9220719D0/en active Pending
-
1993
- 1993-10-01 BR BR9307166A patent/BR9307166A/en not_active Application Discontinuation
- 1993-10-01 WO PCT/GB1993/002050 patent/WO1994007973A1/en not_active Application Discontinuation
- 1993-10-01 JP JP6508857A patent/JPH08502089A/en active Pending
- 1993-10-01 EP EP93921045A patent/EP0663002A1/en not_active Withdrawn
- 1993-10-01 AU AU48321/93A patent/AU675242B2/en not_active Ceased
- 1993-10-01 CA CA002145989A patent/CA2145989A1/en not_active Abandoned
- 1993-10-01 KR KR1019950701245A patent/KR950703631A/en active IP Right Grant
-
1995
- 1995-03-31 NO NO951257A patent/NO951257D0/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO9407973A1 * |
Also Published As
Publication number | Publication date |
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NO951257L (en) | 1995-03-31 |
KR950703631A (en) | 1995-09-20 |
WO1994007973A1 (en) | 1994-04-14 |
JPH08502089A (en) | 1996-03-05 |
CA2145989A1 (en) | 1994-04-14 |
AU675242B2 (en) | 1997-01-30 |
BR9307166A (en) | 1999-03-30 |
GB9220719D0 (en) | 1992-11-11 |
NO951257D0 (en) | 1995-03-31 |
AU4832193A (en) | 1994-04-26 |
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