CN1149311A - Lubricated metal workpiece and method - Google Patents

Lubricated metal workpiece and method Download PDF

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Publication number
CN1149311A
CN1149311A CN95193350A CN95193350A CN1149311A CN 1149311 A CN1149311 A CN 1149311A CN 95193350 A CN95193350 A CN 95193350A CN 95193350 A CN95193350 A CN 95193350A CN 1149311 A CN1149311 A CN 1149311A
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Prior art keywords
lubricant
metal
lubricated
temperature
ester
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CN1044003C (en
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A·R·卡尔
P·G·希斯比
W·F·马维克
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Rio Tinto Alcan International Ltd
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Alcan International Ltd Canada
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/06Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/08Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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Abstract

A lubricant is provided which has a hardness in the range 0.1-10 N/mm at all temperatures in the range 15-40 DEG C. The lubricant consists of at least one full ester of a glycol with a fatty acid, e.g. ethylene glycol dilaurate, optionally mixed with a minor amount of a fatty acid such as stearic acid, and/or a minor amount of a partial ester of a glycol with a fatty acid. The lubricant is useful in the production of press-formed components, and particularly in techniques for converting aluminium sheet to adhesively bonded aluminium structures.

Description

Lubricated metal works and method
The present invention relates to be used to make the lubricated metal works of compression moulding parts, is steel and aluminium especially, the invention particularly relates to the method for using this workpiece to make the moulding block construction.
It is interested that people are used for the method for tackiness agent adherent shaping aluminium part structure of automotive industry to manufacturing usually.This technology is for example being described among the EP127343.The method that aluminum metal thin plate coiled material is machined for the profiled part structure of automotive industry generally includes following steps:
-metal pretreated surface forms strong bonding coat on its surface, and it is as the bottom of the tackiness agent that is coated with subsequently.
-on pretreated metal coiled material, coat lubricant, so described coiled material can be stored or transport, wherein said lubricant is used to protect the metallic surface of having handled; Described coiled material is cut into the section of preparing to be used for compression moulding.
-be the parts of desired shape with the section compression moulding of metal.This and operation are subsequently all carried out on auto production line.
-in the selection area coated with adhesive of profiled part, and need not at first to remove lubricant.
-parts are assembled into the desired structure shape, and can solidify until tackiness agent by spot welding or other fixed form integrated structure.
-tackiness agent solidifies at elevated temperatures.
-with the metallic surface of alkalis aqueous solution Processing Structure to remove lubricant.
-the structure of spraying paint.
In addition, the parts of compression moulding can be mechanically, and for example rivet or spot welding adds tackiness agent or bonding without tackiness agent in addition, is fixed together to form structure.
The lubricant that uses in these class methods need satisfy following requirement:
A) lubricant obviously must have the lubricating quality of the compression moulding of being applicable to operation.
B) lubricant should be a solid under possible metal storage temperature, sticks together with the thin plate of avoiding stacking.In addition, liquid or gluing lubricant film are easy to be defiled and adhere dust and dirt.
C) owing to can not remove lubricant before the coating adhesive on production line, lubricant need be with compatible as if the tackiness agent that will use.
D) in coated with adhesive and after solidifying, lubricant must be easy to remove by the alkalis aqueous solution that routine is used, with the metallic surface that obtains being used to spray paint.
The lubricant of EPA227360 not only is used for aforesaid method, and is used for the operation that other carries out various metal formings and shaping.
In one aspect, the lubricant compositions that EPA227360 provides a kind of lubricant by being dissolved or dispersed in volatile liquid medium that is used for compression moulding to form, wherein lubricant contains at least a ester with polyvalent alcohol of two or three hydroxyls, one of them or two hydroxyls are by long-chain carboxylic acid's esterification, and lubricant has and is higher than envrionment temperature but enough low fusing point, so that can remove from the metallic surface by the alkalis aqueous solution.
EPA227360 proposes to use the mixture of ester, and it is favourable; And lubricant can contain one or more other lubricant compound, for example long-chain carboxylic acids of 50% at the most of small part.Cited lubricant is: the diglycol stearate solution in dimethylbenzene; With the diethylene glycol distearate in dimethylbenzene.
Require c although the lubricant of describing has successfully satisfied usually in EPA227360) and d), they not too be satisfied with sometimes requirement a) and b).People find uncannily, and when carrying out under the aluminium forming operation is being higher than the temperature of lubricant, this lubricant is invalid.In order to obtain good aluminium lubricant effect, the obvious component that in this ester lubricant, needs some to exist with solid state, thereby make lubricant may be up to 35 ℃ or 40 ℃ or higher mold temperature under be solid, be at least pasty state or heavy-gravity.
Obviously, the simple method that solves this isolated problem is to use the different ester with higher melt.Adopt the difficulty of this strategy to be, the ester of higher melt is harder under low temperature and envrionment temperature, so that comes off from employed metallic surface easily and peel off.The metal forming of carrying out under 15 or 20 ℃ is unsafty, because lubricant peels off from metal works under this condition.In order to be used for the different areas in the world, people need a kind of single lubricant system that satisfies high and low temperature standards simultaneously.An object of the present invention is to address that need.
On the one hand, the invention provides lubricated metal, wherein metallic surface has the film of lubricant, lubricant
A) mainly by at least a two or polyol and C 8-C 18The full ester of saturated carboxylic acid form, and at random with a spot of at least a long-chain carboxylic acid and/or a spot of at least a two or polyol and C 8-C 18The partial ester of saturated carboxylic acid mix and
B) under all temperature of 15-30 ℃, have the hardness of 0.2-10N/mm, preferably under all temperature of 15-35 ℃, have the hardness of 0.1-10N/mm.
On the other hand, the invention provides the method for being made the structure of shaping aluminium part by lubricated aluminum metal thin plate defined above, it comprises the steps:
-section of thin plate is shaped to parts,
-parts are assembled into the structure of desired shape,
-and by machinery and/or adherent mode fixing part.
The hardness of lubricant is measured by the following method, wherein, makes a bulk of uncoated lubricant even under given temperature, and thrusts with draw point.Employed testing method comprises that mainly the pin with the 12mm diameter of point thrusts in the lubricant with 20mm/ minute speed, and aforesaid operations materials used test set for example Instron obtains; Conduct is needled into the load of the function of the degree of depth in the lubricant with record.Under different temperature, carry out independent test to obtain entire curve.Subsequently, the slope by the curve that thrusts load and the distance of thrusting draws hardness value.
Though the moulding of metal sheet, for example compression moulding is usually carried out under the temperature of 15-30 ℃ or 35 ℃, and the temperature of some local location can rise to 40 ℃ or even 45 ℃ in pressing process.Thereby lubricant film of the present invention preferably under 15-40 ℃ temperature, under the situation of especially preferred lubricant, has specific hardness value under 15-45 ℃.
If lubricant film is too hard, it is likely brittle, in moulding, has poor frictional behaviour in for example compression moulding process.If lubricant is too soft, lubricity is poor.The moulding of carrying out all over the world, under all temperature of for example compression moulding process, lubricant film preferably has the hardness of 0.1-5N/mm.Surprisingly, the hardness of lubricant film has useful predictive value for its lubricant properties.
The main ingredient of lubricant film is the full ester of the carboxylic acid of polyvalent alcohol and long-chain.Binary or trivalent alcohol with 2-6 carbon atom are fit to, for example, and ethylene glycol, propylene glycol, glycol ether and glycerine.The long-chain carboxylic acid preferably has the saturated long-chain monocarboxylic acid of 12-18 carbon atom in chain, for example, and lauric acid, palmitinic acid or hard ester acid.Can use the mixture of ester class, and this is favourable.Especially preferred ester is ethylene glycol dilaurate (EGDL) and propylene glycol SUNSOFT Q-182S.
Full ester or its mixture can be at random and a spot of at least a long-chain carboxylic acid, and the saturated long-chain monocarboxylic acid that preferably has 14-20 carbon atom in its chain mixes use.Should optional a small amount of component be less than 50% in the weight by mixture, modal is the amount existence of 5-20%, and especially preferred lipid acid is stearic acid.
Full ester or its mixture preferably mix with long-chain carboxylic acid's partial ester with a spot of at least a polyvalent alcohol.Binary or trivalent alcohol are fit to, for example, and ethylene glycol, propylene glycol, glycol ether and glycerine.The long-chain carboxylic acid preferably has the saturated long-chain monocarboxylic acid of 12-18 carbon atom in chain, for example, and lauric acid, palmitinic acid or hard ester acid.Can use the mixture of partial ester, and this is favourable.Especially preferred partial ester is ethylene glycol monolaurate (EGML) and propylene glycol monostearate.
In lubricant mixture, partial ester should exist with the concentration of 40-100% by weight.Lubricant is preferably by the full ester of 50-85% by weight, for example EGDL, the partial ester of 10-30% by weight, and EGML and at the most by weight 20% for example, the lipid acid of 5-20% for example, for example stearic acid is formed.In storage process, lubricant composition may change, and causes the slightly different component on lubricated metallic surface, and these numerical value are meant the lubricant of prepared fresh.Ratio herein is by analyzing, by for example standard method, as vapor-phase chromatography, mass spectrum and infrared absorption spectrometry: in commercial available batching, needn't be in full accord with manufacturers described ratio.
We believe, do not satisfy the single ester of the technical purity that above-mentioned hardness requires, and one or both that examples of suitable lubricants can be as follows obtain.First kind of mode is that two or more components are mixed, and the second way is to use purer material.
These esters are not easy to purify, but we know and believe that EGDL has about 50 ℃ fusing point; EGML has 23-25 ℃ fusing point; Both mixtures have the fusing point between two numerical value.
Full ester and partial ester, for example EGDL and EGML can have by following two impurity that main source obtains;-
A) nominal lipid acid, for example, lauric acid in fact is the mixture of saturated long-chain monocarboxylic acid, contains the acid except that the above-mentioned acid of mentioning more than 30% usually.The influence of these impurity acids is the fusing points that reduced ester.
B) this ester is obtained by the fatty acid mixt that contains ethylenic unsaturated acid.This impurity makes that lubricant and tackiness agent are not too compatible and removes from the metallic surface not too easily, thereby preferably do not exist or 5% amount exists to be lower than by weight.
As mentioned above, under the too high and low excessively temperature on lubricated metal of the present invention the lubricity of lubricant film descend.We have developed a kind of testing method that is used for measuring the lubricity of representing with frictional coefficient (mu) as described below.Frictional coefficient preferably at all interested temperature range Inner less than about 0.1, that is to say 15 ℃ to 30 ℃ or 35 ℃ or 40 ℃ or 45 ℃.As mentioned above, the hardness of the lubricant film under any temperature is the predictor of its frictional coefficient.
According to its required purposes, lubricant must be compatible with the tackiness agent that uses subsequently, and usually, ester as herein described is compatible, thereby the tackiness agent that can be used subsequently absorbs or displacement, and can the available bond strength of obvious damage tackiness agent.In contrast, resin type lubricant and metallic soap lubricant are not compatible with tackiness agent usually in this respect.
Lubricant has the envrionment temperature of being higher than, and preferably at least 30 ℃, more preferably at least 40 ℃ fusing point.This has guaranteed that lubricant exists with solid film on metal matrix, it has avoided erasing in coiling, expansion, rip cutting and cutting process and the problem of piecemeal.Use this lubricant avoided the metallic surface by may with the problem of inconsistent oil of tackiness agent or contaminating impurity, avoided the lubricant local accumulation to become undesirable thick-layer.
Lubricant melts being enough to can the enough alkalis aqueous solution to remove from the metallic surface under the low temperature of lubricant, and for example, it is used for the metal parts that auto production line is used to spray paint with manufacturing.The exercisable top temperature that is used for the alkalis aqueous solution under this environment is about 70 ℃, and therefore, fusing point is lower than 70 ℃, and the lubricant that preferably is lower than 65 ℃ can be removed by the alkalis aqueous solution.Fusing point is higher than 70 ℃ lubricant and whether contains chemical group according to lubricant, and for example hydroxyl can maybe can not be removed, thereby described hydroxyl can help to remove from the metallic surface with alkali reaction.So fusing point is that 85 ℃ and acid number are that 135 to 155 commercial available wax DIN53402 is found and can not removes with the alkalis aqueous solution.If lubricant is by handling at 70 ℃ and can be removed in 2 minutes with 15% Ridolene160 by weight (the proprietary washing composition of the silicate-base of being sold by the I.C.I.plc.) aqueous solution, then it is considered to available alkaline water-detergent solution and removes.
Another aspect of the present invention is included in not exist under any volatile solvent or the thinner lubricant is used for metal, and this does not just need from lubricant film the evaporating volatile solvent and need not comprise any tensio-active agent in lubricant.We find that the lubricant of fusing has the gratifying viscosity of sprinkling of being applicable to or roller coat.For guaranteeing the rapid curing of lubricant film, can pre-cooled metal, for guaranteeing the film of good adhesion, thermometal in advance.
In addition, lubricant is dissolvable in water in the volatile solvent to be used for metal.In fact, very thin film is only obtained by solution, by use solution can sight-feed lubricator agent film thickness to less than 0.5g/m 2
Lubricant can be used for steel or other metal, but may be mainly used in aluminium, all pure metals of term used covering and wherein aluminium be the alloy of main ingredient.The metallic surface can have the inorganic and/or organosilicon prepolymer of strong cohesive property handles or prime coat, has lubricant on its surface.This non-metallic layer is known, can be the chemical conversion coating or the deposited coatings based on chromium, titanium or zirconium of for example non-resinous; Maybe can be cathode oxide layer (on aluminium or titanium) or siloxane layer.Metal can be a sheet form.The usage quantity of lubricant will depend on required purposes, but for the aluminium coiled material that is shaped to tackiness agent adherent structure, be generally 0.1-10g/m 2, for example, 0.25-8g/m 2, especially be 1-4g/m 2
With reference to accompanying drawing, wherein:
-accompanying drawing 1 is the synoptic diagram that is used to test the band stretcher of lubricated metal;
-accompanying drawing 2 is skeleton views of improved band stretcher;
-accompanying drawing 3 is the graphic representations for the hardness and the temperature of various lubricants;
-accompanying drawing 4 and 6 is the bar graphs that show the frictional coefficient of two kinds of lubricants under different temperature and different usage quantity, and accompanying drawing 4 is used for lubricant 2, and accompanying drawing 6 is used for lubricant 1.
-accompanying drawing 5 is to be presented at washing after the bar graph of the lubricant residual volume after the different oven dry.
With reference to ASTM4173-82 design with make the special-purpose band stretching device that is used to test the sheet metal forming lubricant, equipment is shown among attached Fig. 1 and 2.Mould shown in the accompanying drawing 1 is used for the material that simulation is slided between the adhesive surface of the pressurization that has the stretching bellow means.Mould shown in the accompanying drawing 2 is used for the slip of simulation between parallel adhesive surface, to obtain conventional friction co-efficient value.
With reference to attached Fig. 1 and 2, a mould 10 of each tool set is installed on the load cell 12, and another mould 14 is installed on the hydro-cylinder 16.The band 18 that hydraulic is flat between two moulds can be pulled out by a special tool set, during measure to clamp load.Also measure tensile loading with second load cell 20 that is installed between test mechanical Hubei Province clevis pawl 22 and the pinblock 24.Therefore, when using jointly, obtain conventional friction co-efficient value with the parallel plate device shown in the accompanying drawing 2.
According to the variable of required research, the band stretching device can be installed in pressing die like on the device or standard tension test system.
The wide lubricated band of 50mm is placed between two planes of the tool set shown in the accompanying drawing 2, and hydraulic pressure is to required load.Band draws the distance of about 250mm subsequently by the mould of accompanying drawing 1, as time/the function record of distance of stretching band stretches and clamping force.The result who obtains from curve (drawing force/2) form as the function that clamps load has the slope that equals conventional frictional coefficient.
Embodiment 1
Lubricant formulations of the present invention has following component by weight:
61% ethylene glycol dilaurate (EGDL)
19% ethylene glycol monolaurate (EGML)
11% stearic acid
9% other ester class
Determine component through standard gas chromatograph method/mass spectroscopy, this preparation is lubricant 1 hereinafter referred to as.
Another lubricant formulations of the present invention has following component by weight:
70% ethylene glycol dilaurate
21.5% ethylene glycol monolaurate
8.5% other ester class
Determine component through standard gas chromatograph method/mass spectroscopy, this preparation is lubricant 3 hereinafter referred to as.
The preparation of lubricant 2 is used for comparison.Lubricant 2 contains commercial available EGML90% and stearic acid 10%.This lubricant is not at scope Inner of the present invention, only with making comparisons.
We have analyzed commercial available ethylene glycol monolaurate, find to contain seven kinds of different acid, and its ratio is as follows: sad (C 8) 3.9%; Capric acid (C 10) 5.8%; Lauric acid (C 12) 33%; Tetradecanoic acid (C 14) 16.8%; Palmitinic acid (C 16) 11.9%; Oleic acid and stearic acid (C 18) 28%.
Lubricant 1,2 and 3 uses by being sprayed on the Aluminium Alloy Plate that is preheated to 50 ℃, thus, and uniform thin film that can controlled thickness.Measure the hardness (adopting method mentioned above) of lubricant, outcome record is in accompanying drawing 3.
Lubricant 1 and 2 is further tested in the band stretching device shown in attached Fig. 1 and 2.In each case, test is under 0-50 ℃ differing temps; At 1-6g/m 2Between five different lubricant usage quantitys under carry out.These test results are shown in accompanying drawing 4 (lubricant 2) and the accompanying drawing 6 (the 2nd group of lubricant 1 sees below).
Embodiment 2
Estimate the lubricant 1 and 3 of embodiment 1, the lubricant 2 of embodiment 1 is used for contrast.
Experimental technique
Carry out hereinafter described experimental implementation with 1.6mm thickness 5754 materials.
2.1 the use of lubricant on aluminium sheet
The using method of lubricant comprises new lubricant basin is preheated to 70 ℃, uses air-driven vacuum nozzle that lubricant is sprayed at thin sheet surface.Remain on room temperature (20 ℃) and be preheated under 60 ℃ at lubricant and be applied to thin plate.Subsequently thin plate is stacked.Under the situation of preheated material, when solidifying, just thin plate is stacked lubricant.
2.2 compatible ability with tackiness agent
Be used for standard method of test with the compatible ability of tackiness agent and be the standard that tackiness agent assembling with lubricated pretreated sample of 1.6mm and standard has the 10mm overlap and shear overlap joint.This being overlapped on of hexad carried out bonded stress/humid test under the constant load, be recorded in to fall down in the hexad overlap joint junior three time that overlaps.One shearing is overlapped on specific time Inner and carries out the salt sprinkling, and tested static intensity keeps.
Be used in bonding before with lubricator 1 on the surface of overlap joint the overlap joint made test.Estimate the weight grade of two kinds of lubricants, i.e. 2.0g/m 2And 5.5g/m 2
2.3 softening as the lubricant of temperature function
Wax puncture test is used to measure the softening properties as temperature function.Employed testing method comprises that mainly the pin with the 12mm diameter of point thrusts in the lubricant with 20mm/ minute speed, and above-mentioned speed materials used test set for example Instron obtains and writes down as the load that is needled into the depth function in the lubricant.Under different temperature, carry out independent test to obtain entire curve.Subsequently, draw hardness value by curve that thrusts load and the slope that thrusts distance.
2.4 stretching, band estimates
Use 3g/m 2Different lubricants blocks into the wide band of 50mm through the lubricated thin plate of method preparation of the preheated charge described in 2.1 parts with shear, adopt aforesaid method to pass through the band stretching device subsequently and stretch, under 10,20,30,40 and 50 ℃ temperature, measure friction valve.
2.5 the compression moulding evaluation of lubricant 1
The compression moulding test is carried out to estimate lubricant with the compacting simulator.Adopt two kinds of different tests, that is:
(a) the inaccessiable square plate degree of depth.
(b) inaccessiable compacting dome height.
The square instrument of 275mm with the corrugated portion that do not stretch carries out above-mentioned test under standard conditions.
Use 3g/m 2Lubricant 1 and 2 compacting AA5754-0 thin plates, with assess performance relatively.
2.6 the simulation of the possible thermal cycling of prelubricated thin plate heap
For simulating the possible thermal cycling that prelubricated material may experience, by described in 2.1 parts, lubricant being applied to the lubricated lamination of blank manufacturing of preheating.
Use nominal 3g/m 2The manufacturing of lubricant weight contains 30 layers of thin plate, four laminations of each 500 * 500mm.These laminations are heated to four different temperature, 30,35,40 and 45 ℃ respectively in baking oven.After taking out from baking oven, each lamination cools off under the weight of the 18.1kg that applies with the center.After destacking, in many adjacent sheet, take out sample and shift with quantitatively viewed any lubricant.
2.7 washing, baking oven evaporation and resistates
In this part, carry out two kinds of different tests, i.e. different oven for drying after the washing stage comprises not oven dry and typically has the glued construction method of tackiness agent curing cycle.
For first group of test, pretreated aluminum strip is 2 (3.4g/m with lubricator 2) and lubricant 1 (3.8g/m 2) lubricated, carry out following processing:
A) following 20 minutes at 170 ℃
B) following 20 minutes at 180 ℃
C) following 20 minutes at 190 ℃
D) following 20 minutes at 200 ℃
E) do not carry out oven for drying
All bands rise in the Chemkleen CK165 solution at the 20g/ that stirs and washed 3 minutes down at 60 ℃.After drying,, measure as the organic impurity on the band of carbon through analyzing down at 600 ℃.
For second group of test, the thin plate after the washing is with about 4.5g/m 2Coat weight apply lubricant 1 and lubricant 2.Then, thin plate is carried out additional oven for drying and alkali wash period, it comprises:
A) following 10 minutes at 145 ℃
B) following 20 minutes at 190 ℃
C) following 20 minutes at 190 ℃
D) 30 seconds of alkali cleaning, (at 60 ℃, with the Ridolene 336 of the 2.5%w/w that stirs)
In the washing stage, operating weight assay determination method is measured final coat weight.
3. result
3.1 the use of lubricant on aluminium sheet
Remain on room temperature by lubricant 1 is sprayed at, obtain gratifying result on about 20 ℃ thin plate and being preheated on 60 ℃ the thin plate.Lubricant one contacts i.e. curing with keeping thin plate at room temperature.Yet back one condition makes lubricant keep liquid at short period of time Inner on thin plate.
Lubricant this in by spreading nozzle the time without any the other problem that is run into as lubricant 2.
3.2 compatible ability with tackiness agent
In its surface with lubricator stress-the humidity of 1 overlap joint that obtains and salt spray test the results are shown in Table 1, this table is presented at the good intensity that salt sprays after 20 weeks and keeps, test duration was above 100 days in stress/humidity of using 5MPa stress.
3.3 the lubricant as temperature function is softening
With lubricator 1, the 2 and 3 wax puncture tests of carrying out the results are shown among Fig. 3.
At independent two batches of lubricants 1 of occasion preparation.The 1st batch of rhombus with the filling that solid line connects represents that the shaded square of the 2nd batch of with dashed lines connection represents that two batch of materials are all at scope Inner of the present invention, and lubricant 3 usefulness asterisks are represented.
3.4 stretching, band estimates
Table 2 has shown for the 3g/m that determines 2Lubricant weight in the comparison performance of measuring temperature range Inner lubricant 1,2 and 3.These numerical tabulars are understood the performance of the improvement of the 1st batch of under 30,40 and 50 ℃ temperature lubricant 1.They have also shown similar performance at 20 ℃.
3.5 the compression moulding evaluation of lubricant 1
The results are shown in the table 3 of compression moulding test.This form shows, all obtains similar performance at two kinds of lubricants in the drawing and forming process, but 1 carries out in the square plate moulding process with lubricator, improved performance, and the numerical value that obtains is the mean value of five tests in each case.Advance copy carries out under about 22-24 ℃ room temperature condition.
3.6 the simulation of the possible thermal cycling of prelubricated thin plate heap
The lubricated thin plate lamination that has lubricant 1 from the teeth outwards is heated to 30,35 and 40 ℃, cools off under the weight of using at the center subsequently, do not demonstrate the problem of destacking or lubricant shifts between adjacent sheet sign.The corresponding lamination that is heated to 45 ℃ more is difficult to separate, and shows significantly " patchy " outward appearance, and a spot of lubricant between adjacent sheet shifts.For lubricant 2, under 35 ℃ temperature, observe similar effects.
3.7 washing, baking oven evaporation and resistates
After the washing stage, different oven for drying, being included in does not have after the washing stage result of oven dry to show in accompanying drawing 5.This accompanying drawing shows that high oven for drying helps the degree of cleaning on surface.
The result of baking oven evaporation test shows that lubricant 1 is compared with lubricant 2, and almost all evaporations are respectively 0.03g/m 2And 0.35g/m 2Resistates.Behind final neutralizing treatment, operating weight assay determination method is measured final coat weight.The result of two kinds of lubricants drop to-0.01 and-0.03g/m 2Between, show that the washing stage removed all resistatess.
4. discuss
4.1 the use of lubricant on thin plate
The sprinkling of lubricant 1 is used without any difficulty, and metal obtains gratifying result under the room temperature though adopt, and has improved adhesion with the metallic surface by pre-thermometal.
4.2 compatible ability with tackiness agent
The result of stress/humid test shows, uses 2g/m 2The overlap joint that lubricant 1 is made is for the stress of all tests, and test is still underway in the time of 190 days.
Salt after 20 weeks exposed sprays data presentation fabulous intensity under two lubricant weight and keeps, and lubricant 2 is tested.
4.3 softening as the lubricant of temperature function
The hardness that the result of the wax puncture test shown in the accompanying drawing 3 is presented in the temperature range of being measured is improved, and early stage research proposal hardness value on vertical logarithmic axis should remain between the 0.1-1.0N/mm.Obviously exceed the higher hardness value at a lower temperature and will obtain wax, it is brittle, limited value aspect the compacting tool set moulding.Under comparatively high temps, corresponding to the melting range of wax, hardness value is less than 0.1N/mm.Accompanying drawing 3 shows that the hardness of lubricant 1 drops to 0.1N/mm corresponding to its melting range at about 41-42 ℃, and this is than about 10-12 ℃ of lubricant 2 height.So, increased the high melt point scope significantly, and do not produced brittle wax at a lower temperature.And the hardness of lubricant 3 is obviously temperature independent.
4.4 stretching, band estimates
Working as lubricant weight in table 2 explanation is 3.0g/m 2The time, with respect to the frictional behaviour of temperature, lubricant 1 demonstrates 30,40 and 50 ℃ of improvement of tangible frictional coefficient down, and has similar performance in the time of 20 ℃.
4.5 the compression moulding evaluation of lubricant 1
The result of compression moulding evaluation shows that lubricant 1 has suitable performance in the drawing and forming process, but obtains good slightly performance when the square plate moulding.This is to parts, and for example knocker and door Inner pressing are favourable, at this moment, need have the dark angle character of less angular oscillation radius.So improved performance is favourable.
4.6 the simulation of the possible thermal cycling of prelubricated thin plate heap
The result who is applied to the thermal cycling of prelubricated lamination shows, at 40 ℃ of signs that do not have lubricant to shift, only works as lamination and is heated to 45 ℃, has a spot of lubricant to shift during with postcooling.Therefore, between 40-45 ℃ of temperature, the lubricant branch problem of lubricant 1 begins to become obvious.This performance is more much better than lubricant 2, and lubricant 2 is not observed the transfer sign when lamination is heated to 30 ℃, but when lamination is heated to 35 ℃, can observe the transfer sign.Therefore, aspect hardness performance, can obtain the improvement of 10 ℃ of temperature.
4.7 washing, baking oven evaporation and resistates
In accompanying drawing 5, show that in the various oven for drying or the evaluation test of not drying rear surface washing Chemklene solution is washing surface effectively.Under the situation of lubricant 1, high oven for drying condition, 190 ℃ and 200 ℃, help surface clearness really, it is very neatly from the aluminium surface evaporation.
Mensuration shows that with respect to the relative evaporation of the lubricant 1 of lubricant 2 and the test of retain residues lubricant 1 is almost completely evaporation before the washing stage.In addition, obtain lower carbon residue content.
Table 1: the stress/humidity of lubricant 1 and salt spray data
Lubricant weight g/m 2 Stress/humidity is ended fate Salt sprays result (MPa)
3Mpa????4Mpa????5MPa 8 all 20 weeks of 0 week
????2.0 190+????190+????190+ 27.8??25.5(92%)??25.1(90%)
????5.5 190+????190+????137 28.4??25.2(89%)??23.6(83%)
Table 2
Friction valve under following temperature ℃
Lubricant ????10℃ ????20℃ ????30℃ ????40℃ ????50℃
????1 ????0.017 ????0.012 ????0.046 ????0.069
????2 ????0.020 ????0.036 ????0.096 ????0.107
????3 ????0.092 ????0.020 ????0.043 ?????nd ?????nd
The nd-undetermined
Table 3: lubricant is to the effect of compression moulding ability
Lubricant Coat weight (g/m 2) Square plate degree of depth mm Dome height mm
????2 ????3.0 ????59.1 ????51.5
????1 ????3.0 ????74.3 ????52.0
Embodiment 3 prepares 1 as follows, 2-third-glycol SUNSOFT Q-182S (PG12DS): raw material: bp188.2 ℃ of dimethylbenzene bp137-140 ℃ equipment of stearic acid MW284.47 mp69-70 ℃ of 1,2 third-glycol MW76.09: 5 liters of reaction vessels that are equipped with the heating of thermometer, Dean and Stark and reflux exchanger.
Method:
With stearic acid (1500g) and 1,2-third-glycol (200g) is put into reaction vessel.
Add about 1.5L dimethylbenzene, stir the mixture.
Heating container continues about 10 hours of back flow reaction (about 135 ℃ of bp) to boiling.
Often remove the azeotropic liquid of in Dean and Stark, collecting, collect about 100ml altogether.Add 10ml 1 in reaction process again twice, 2-third-glycol is to compensate the glycol that loses in azeotrope.
In case the boiling point of mixture rises to 137 ℃, remove removal xylene by distillation, when boiling point reaches 142 ℃, stop distillation.
The cooling reaction product is placed in the opening tray, places 2 hours solvents (normally a kind of preferable methods of rotary evaporation) to remove any remnants at 75 ℃ in explosion-proof wind baking oven.
The mixture for preparing the technical pure EGML (referring to embodiment 1) of this product and different ratios.Be determined at the hardness of various lubricant formulations under the differing temps.
Ester ?????A ????B ????C ????D ????E
11 ℃ 20 ℃ 35 ℃ of PG12D S EGML hardness N/mm ????100 ????0 ????3.8 ????2.5 ????0.51 ????90 ????10 ????1.5 ????1.8 ????0.75 ????70 ????30 ????1.5 ????1.4 ????0.47 ????40 ????60 ????1.1 ????0.85 ????0.33 20 80 0.95 0.55 liquid
Lubricant A, B, C and D are of the present invention, and E then is not of the present invention.

Claims (13)

1. Run Hua metal, wherein this metallic surface has the skim lubricant, described lubricant
A) mainly by at least a two or polyol and C 8To C 18The full ester of saturated carboxylic acid form, and at random with a spot of at least a long-chain carboxylic acid and/or a spot of at least a two or polyol and C 8-C 18The partial ester of saturated carboxylic acid mixes,
B) under all temperature of 15-35 ℃, has the hardness of 0.1-10N/mm.
2. according to the lubricated metal of claim 1, wherein full ester is ethylene glycol dilaurate and/or propylene glycol SUNSOFT Q-182S.
3. according to the lubricated metal of claim 1 or claim 2, wherein partial ester is an ethylene glycol monolaurate.
4. according to the lubricated metal of arbitrary claim among the claim 1-3, wherein the lubricant thin layer has the hardness of 0.1-5N/mm under all temperature of specialized range Inner.
5. according to the lubricated metal of arbitrary claim among the claim 1-4, wherein the lubricant thin layer has the hardness of specialized range Inner under all temperature of 15-40 ℃.
6. according to the lubricated metal of arbitrary claim among the claim 1-5, wherein lubricant is mainly formed (by weight) by following component:
Ethylene glycol dilaurate 50-85%
Ethylene glycol monolaurate 10-30%
Stearic acid is to as many as 20%
Other glycol, ester and carboxylic acid material are to as many as 20%
7. according to the lubricated metal of claim 6, wherein stearic acid content is 5-20% by weight.
8. according to the lubricated metal of arbitrary claim among the claim 1-7, wherein metal is a thin plate.
9. according to the lubricated metal of arbitrary claim among the claim 1-8, wherein metal is an aluminium.
10. according to the lubricated metal of claim 9, wherein aluminium strip has strong adherent artificial inorganic upper layer, has the film of lubricant in the above.
11. make the method for the structure of shaping aluminium part by the lubricated aluminum metal thin plate of arbitrary claim among the claim 8-10, it comprises the steps:
-section of thin plate is shaped to parts,
-parts are assembled into the structure of desired shape,
-and by machinery and/or adherent mode fixing part.
12. according to the method for claim 11, it comprises the steps:
-section of thin plate is shaped to parts,
-tackiness agent is coated on the parts,
-with parts be assembled into desired shape structure and
-cure adhesive.
13. according to the method for claim 11 or claim 12, it also comprises the step of using alkalis aqueous solution Processing Structure and being coated with brush configuration subsequently.
CN95193350A 1994-04-12 1995-04-12 Lubricated metal workpiece and method Expired - Fee Related CN1044003C (en)

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EP0755427A1 (en) 1997-01-29
DE69503773T2 (en) 1999-02-04
CA2186848A1 (en) 1995-10-19
MX9604675A (en) 1997-12-31
AU682599B2 (en) 1997-10-09
ATE169055T1 (en) 1998-08-15
CN1044003C (en) 1999-07-07
WO1995027767A1 (en) 1995-10-19
DE69503773D1 (en) 1998-09-03
KR100388008B1 (en) 2003-10-22
AU2218595A (en) 1995-10-30
JPH09511542A (en) 1997-11-18
BR9507319A (en) 1997-09-30
KR970702352A (en) 1997-05-13
ES2120742T3 (en) 1998-11-01
EP0755427B1 (en) 1998-07-29

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