CN100485232C - Sliding member and production process thereof - Google Patents
Sliding member and production process thereof Download PDFInfo
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- CN100485232C CN100485232C CNB2006101453396A CN200610145339A CN100485232C CN 100485232 C CN100485232 C CN 100485232C CN B2006101453396 A CNB2006101453396 A CN B2006101453396A CN 200610145339 A CN200610145339 A CN 200610145339A CN 100485232 C CN100485232 C CN 100485232C
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Abstract
There is provided a sliding member including a base body and a hard carbon coating formed on the base body to define a sliding surface for sliding contact with an opposing member under lubrication according to one embodiment of the present invention. The hard carbon coating has an outermost surface portion lower in hydrogen content than a remaining portion thereof, or an outermost coating layer lower in hydrogen content than at least one other coating layer.
Description
The application be that August 6, application number in 2004 are 200410056325.8 the applying date, denomination of invention divides an application for the application of " slider and production method thereof ".
Technical field
The present invention relates to a kind of slider, particularly have the slider of the shallow layer of hard carbon such as diamond-like-carbon, it shows good low frictional behavior and durability in the presence of particular lubricants.The invention still further relates to the method for producing described slider.
Background technique
Grobal environment problem for example global warming and depletion of the ozone layer is close at hand.Global warming mainly is subjected to CO
2CO is set in the discharging influence
2Emission standard is to reduce CO
2Discharging has become each country major issue deeply concerned.In order to reduce CO
2Discharging, the fuel efficiency of improving vehicle is very important.Therefore, wish to reduce the friction in the vehicle motor, to obtain the direct improvement of fuel efficiency aspect.
Have multiple possible method and reduce the friction of motor.A kind of method that reduces engine friction provides to be had under extreme friction/abrasive conditions than low coefficient of friction with than the motor slider of high wear resistance.For example imagine hard carbon coating coated materials (as valve lifter and valve lifter pad) and use a kind of so-called roller rocking arm of wearing the roller needle bearing to the cam follower of motor slider.The expection of described DLC coating confirmed that diamond-like-carbon (DLC) coating has lower friction factor than titanium nitride (TiN) film and chromium nitride (CrN) film in air, so can be used for the motor slider.Another method that reduces engine friction is to improve the lubricated oil properties that is used for slider.Imagination reduces oil body, so that be reduced in viscous resistance in the lubricated district of waterpower and the stirring resistance in mechanical sliding parts.Also imagination provides and is mixed with the suitable friction improver and the lubricant oil of other additive in addition, so that be reduced in the frictional loss of motor under Mixed lubrication condition and the condition of boundary lubrication.For various differentiated friction improving agents, carried out many research, these improving agents comprise organic molybdenum, for example molybdenum dithiocarbamate (MoDTC) and molybdenum dithiophosphate (MoDTP), and the verified lubricant oil that contains this class organic-molybdenum friction improver is effective at the early stage that uses for the friction that reduces between the steel slider.
The low frictional behavior of described DLC coating and the friction adjusting function of described organic molybdenum, be reported in people's such as KANO Japan Tribology Congress 1999.5, Tokyo, people's such as Proceeding Page 11-12 and KANO World Tribology Congress2001.9, Vienna is among the Proceeding Page 342.
Summary of the invention
But this DLC coating can not always show low coefficient of friction in the presence of lubricant oil.Even in the presence of the lubricant oil that contains the organic-molybdenum friction improver, described DLC coating can not suitably show its low coefficient of friction.
And when described DLC coating had low hydrogen content, described DLC coating was easy to improve to the stickability of substrate material.When described DLC coating is not hydrogeneous, then be difficult to improve coating thickness.Like this, the durability of described DLC coating just is easy to improve.
Therefore, an object of the present invention is to provide a kind of slider with hard carbon shallow layer, it shows good low frictional behavior and durability in the presence of oiling agent, thereby can obtain the further improvement of fuel efficiency when being used for vehicle motor.Another object of the present invention provides a kind of method of producing described slider.
As the result of broad research, the applicant can show good low frictional behavior and durability when having been found that hard carbon shallow layer with a fixed structure and particular lubricants combination.The present invention just is based on that above-mentioned discovery finishes.
According to a first aspect of the invention, provide a kind of slider, it comprises: matrix; Be formed at described matrix on be used for being limited to the hard carbon coating that carries out the slidingsurface of sliding contact under the lubrication with relative member, described hard carbon coating has the outermost surface part that hydrogen content is lower than its remainder.
According to a second aspect of the invention, provide a kind of slider, it comprises: matrix; Be formed at described matrix on be used for being limited to the hard carbon coating that carries out the slidingsurface of sliding contact under the lubrication with relative member, described hard carbon coating has along its thickness direction two-layer or laminated coating laminated together, and described lamination coating comprises that hydrogen content is lower than the outermost surface coating of at least one other coating.
According to a third aspect of the invention we, provide a kind of method of producing slider, it comprises: the matrix that described slider is provided; With on described matrix, form hard carbon coating, its generation type should make hard carbon coating have the outermost surface part that hydrogen content is lower than its remainder.
According to a forth aspect of the invention, provide a kind of method of producing slider, it comprises: the matrix that described slider is provided; With on described matrix, form hard carbon coating, its generation type should make hard carbon coating have the outermost surface coating that hydrogen content is lower than at least one other coating.
Can further understand other purpose of the present invention and feature by following content.
Description of drawings
Figure 1A is depicted as the planimetric map of the piston ring of a kind of illustrative embodiments of the present invention.
Figure 1B is the partial section of piston ring shown in Figure 1A.
Fig. 1 C is a zoomed-in view of drawing the circle part shown in Figure 1B.
Fig. 2 is reciprocating type friction/wear testing schematic representation of apparatus.
Embodiment
To elaborate to the present invention below.In following explanation, unless otherwise prescribed, all percentages (%) are all with quality representation.
The slider of a kind of illustrative embodiments of the present invention (being called " slider " hereinafter), comprise matrix, be formed at be used on the described matrix limiting with relative member carry out sliding contact slidingsurface hard carbon coating and be administered to lubricant film on the described slidingsurface, thereby described slider is sliding by the lubricant film that is arranged between described slider and the described relative member on the described relative member.
Though described slider has many purposes, be under extreme friction/abrasive conditions, to use described slider ideally, to make full use of the good low frictional behavior and the durability of described slider.For example described slider may be molded to piston ring such as apical ring and the disc that is used for motor car engine, shown in Figure 1A, 1B and 1C.Described hard carbon coating is preferably formed on the relative anchor ring 1 of described piston ring matrix, the piston ring groove of this face and piston is (as relative member, do not draw among the figure) contact, so not only can effectively reduce the friction between described piston and described piston ring, but also can improve the anti-stuck property of described piston.And described hard carbon coating is preferably formed on the peripheral surface 2 of described piston ring body portion, the cylinder bore of this face and engine body is (as relative member, do not draw among the figure) carry out sliding contact, so that effectively reduce the friction between described piston and described cylinder wall.Replacedly, also can adopt described hard carbon coating to apply whole piston ring, also can on described cylinder wall, form one deck hard carbon coating.
Slider
Described matrix is formed by any known substrate material, as iron-based (steel) material or aluminium base (aluminum alloy) material, before applying with described hard carbon coating, can carry out surface treatment to it.
Usually, described hard carbon coating is made by amorphous carbon, and carbon wherein is present in two kinds of sp
2And sp
3In the hydridization to form graphite and adamantine composite structure.The instantiation of described amorphous carbon comprises: not hydrogeneous amorphous carbon (a-C), hydrogeneous amorphous carbon (a-C:H) and/or contain metallic element titanium (Ti) or molybdenum (Mo) as the metal carbide or the metal carbon (MeC) of a part.The amorphous carbon that not hydrogeneous amorphous carbon and hydrogen content are low is also referred to as " diamond-like-carbon (DLC) ".
According to first kind of mode of execution of the present invention, the hydrogen content of the outermost surface of described hard carbon coating part is lower than its remainder.Utilize such hydrogen content to be distributed with and to improve the stickability of described hard carbon coating, and the thickness that might improve described hard carbon coating is to enough degree, thereby guarantee or improve low frictional behavior, wear resistance and the durability of described slider described matrix.Herein, " the outermost surface part " of described hard carbon coating is defined as the part below described slidingsurface, for example the part of extending in coating thickness 5% scope or the part of extending in thickness is 1.0 mu m ranges.
In order to obtain bigger reduction friction effect, wish to make the hydrogen content minimum in the outermost surface part of hard carbon coating described in first mode of execution.The average hydrogen content of the outermost surface part of described hard carbon coating preferably is controlled to be 20 atom % or lower, 10 atom % or lower more preferably, further be preferably 5 atom % or lower, and then 0.5 atom % or lower more preferably, most preferably be zero substantially.
In the first embodiment, the hydrogen content of described hard carbon coating distributes and is not particularly limited, as long as the hydrogen content of the outermost surface of described hard carbon coating part is lower than remainder.Consider step and the condition and the preparation cost of painting method, the hydrogen content of described hard carbon coating distributes and can be suitably changes according to low frictional behavior, wear resistance and the durability of described hard carbon coating needs.Even so, the hydrogen content of still wishing described hard carbon coating reduces to slidingsurface side (being outermost surface coating surface side) gradually along the coating thickness direction from the matrix side.When described hard carbon coating is when being made by the functionalization functionally gradient material (FGM) that this class has a continuous hydrogen content gradient, the internal stress of described hard carbon coating obtains discharging.This just may prevent to break in the described hard carbon coating, thereby further improves the durability of described hard carbon coating.A kind of replacement scheme is that the hydrogen content of described hard carbon coating can reduce by step-wise manner.
According to second mode of execution of the present invention, described hard carbon coating has along coating thickness direction two-layer or multilayer laminated together, and comprises that hydrogen content is lower than the outermost surface of at least one other layer.Preferably, the outermost hydrogen content of described hard carbon coating is lower than all other layers.By such layer structure, can improve the stickability of described hard carbon coating, and the thickness that may improve described hard carbon coating is to enough degree, thereby guarantees or improve low frictional behavior, wear resistance and the durability of described slider described matrix.Herein, " layer " of described hard carbon coating is defined as and has the basic part of hydrogen content uniformly in its whole thickness.
In second mode of execution, the layer structure of described hard carbon coating is not particularly limited, as long as the hydrogen content of described outermost surface coating is lower than any other coating.Consider step and the condition and the preparation cost of painting method, the layer structure of described hard carbon coating can suitably be determined according to low frictional behavior, wear resistance and the durability of described hard carbon coating needs.Even so, the hydrogen content of still wishing described hard carbon coating successively reduces to the slidingsurface side gradually from the matrix side.A kind of replacement scheme is that the hydrogen content of described hard carbon coating can reduce by step-wise manner.
In order to obtain bigger reduction friction effect, also wish to make the outermost hydrogen content minimum of hard carbon coating described in second mode of execution.The outermost hydrogen content of described hard carbon coating preferably is controlled to be 20 atom % or lower, and more preferably 10 atom % or lower further are preferably 5 atom % or lower, and then 0.5 atom % or lower more preferably, most preferably is zero substantially.
In each of first mode of execution and second mode of execution, described hard carbon coating all can be combined to form by physical vapor deposition (PVD) method, chemical vapor deposition (CVD) method or its.In order to reduce the hydrogen content in described hard carbon coating outermost surface part or the outermost surface, when employing for example formed described hard carbon coating by PVD arc ions galvanoplastic, it was effective reducing the content that applies hydrogen in the atmosphere.
And before applying with described hard carbon coating, described matrix preferably can be endowed undercoat by chromium plating, chromium nitride method, nitriding process or its combination, so that improve the stickability of described hard carbon coating to described matrix, improves its durability.
Oiling agent
In following lubricant oil and the oiling agent each all can be used as oiling agent.
Described lubricant oil mainly is made up of base oil, preferably contains the derivative of ashless fatty acid ester friction improver, ashless aliphatic amine friction improver, polybutylene-based succinimide, polybutylene-based succinimide and at least a material in the zinc dithiophosphate.Particularly, the described lubricant oil that contains in ashless fatty acid ester friction improver and the ashless aliphatic amine friction improver one or both can be for producing bigger friction with sliding friction between the relative member of being made by iron-based or alumina-base material and reduce effect at the slider of hard carbon thin film that is coated with of the present invention.
Described base oil is not done special restriction, and it can be selected from base oil compound commonly used arbitrarily, as mineral oil, synthetic oil ﹠ fat.
The instantiation of described mineral oil comprises normal paraffin hydrocarbon ils and paraffinic base oil or cycloalkane base oil, and they extract lubricating oil distillate, adopt following arbitrarily processing method that resulting lubricating oil distillate is carried out purifying then to make by air-distillation or decompression distillation from oil: solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrofinishing, wax isomerization, sulfuric acid treatment and clay-filtered.Though described lubricating oil distillate generally carries out purifying by hydrofinishing or solvent refining, the preferred use reduced the mineral oil that arene content comes the described lubricating oil distillate of purifying to make in the described oil by overhydrocracking or GTL (gas is to liquid) wax isomerization method.
The instantiation of described artificial oil comprises; Poly alpha olefin (PAO) is as 1-octene oligomer, 1-decylene oligomer and ethylene-propylene oligomer and hydrogenation products thereof; Isobutylene oligomer and hydrogenation products thereof; Isoparaffin; Alkylbenzene; Fluhyzon; Diester is as glutaric acid two (tridecyl) ester, adipic acid dioctyl ester, adipic acid diiso decyl ester, adipic acid two (tridecyl) ester and decanedioic acid dioctyl ester; Polyol ester is as trihydroxymethylpropanyl ester (for example trimethylolpropane caprylate, trimethylolpropane pelargonate and trimethylolpropane isostearate) and pentaerythritol ester (for example caproic acid pentaerythritol-2-ethyl ester and n-nonanoic acid pentaerythritol ester); Polyoxyalkylene glycols; Dialkyl diphenyl ether; With polyphenylene ether.In these artificial oil compounds, poly alpha olefin preferably is as 1-octene oligomer and 1-decylene oligomer and hydrogenation products thereof.
Above-mentioned base oil compound can use separately, use also capable of being combined.When using mixture by two or more base oil compounds, be not particularly limited for the proportions of ingredients of base oil compound as base oil.
The Sulpher content of described base oil is not particularly limited, and based on the gross mass of described base oil, is preferably 0.2% or lower, and more preferably 0.1% or lower, further be preferably 0.05% or lower.Wish to use hydrorefined mineral oils or artificial oil, this is because hydrorefined mineral oils and artificial oil all have no more than 0.005% Sulpher content for every kind, or sulfur-bearing (no more than 5ppm) not substantially.
The arene content of described base oil is not particularly limited.Herein, described arene content is defined as the content of the aromatic fraction that records according to ASTM D2549.In order in the time bar that prolongs, to make described lubricant oil keep being suitable for the low frictional behavior of internal-combustion engine, the arene content of base oil is preferably 15% or lower based on the gross mass of base oil, more preferably 10% or lower, further be preferably 5% or lower.When the arene content of base oil surpasses 15%, deterioration will take place in oil ageing stability unfriendly.
The kinematical viscosity of described base oil is not particularly limited.In order to use described lubricant oil in internal-combustion engine, the kinematical viscosity of described base oil is preferably 2mm
2/ s or higher, more preferably 3mm
2/ s or higher, and be preferably 20mm simultaneously
2/ s or lower, more preferably 10mm
2/ s or lower further is preferably 8mm
2/ s or lower, they all record in the time of 100 ℃.When the kinematical viscosity of described base oil is lower than 2mm at 100 ℃
2During/s, described lubricant oil just might be able to not provide sufficient wear resistance, and causes sizable evaporation loss.When the kinematical viscosity of described base oil surpasses 20mm at 100 ℃
2During/s, described lubricant oil just might can not provide low frictional behavior, and makes cryogenic property generation deterioration.When being used in combination two or more base oil compounds, do not need to limit the kinematical viscosity of every kind of base oil compound all in this particular range, as long as the kinematical viscosity of mixture in the time of 100 ℃ of described base oil compound is in the afore mentioned rules scope.
The viscosity index of described base oil is not particularly limited, and in order to use described lubricant oil in internal-combustion engine, described viscosity index is preferably 80 or higher, and more preferably 100 or higher, most preferably be 120 or higher.When described base oil had the viscosity higher index, described lubricant oil can improve oil consumption performance and low temperature viscosity performance.
As for fatty acid ester friction improver and aliphatic amine friction improver, can use each all to have C
6-C
30The fatty acid ester of straight or branched hydrocarbon chain and aliphatic amine preferably have C
8-C
24The straight or branched hydrocarbon chain more preferably has C
10-C
20The straight or branched hydrocarbon chain.When the carbon number of described friction improver hydrocarbon chain is not in the 6-30 scope, may not produces the friction of wanting and reduce effect.The C of described fatty acid ester and aliphatic amine friction improver
6-C
30The instantiation of straight or branched hydrocarbon chain comprises: alkyl such as hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerul, heptacosane base, octacosyl, nonacosyl and melissyl; Alkenyl such as hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the hexadecene base, the heptadecene base, the vaccenic acid base, 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, the cerotene base, the cerotene base, two vaccenic acid bases, 29 carbene bases and melene base.Abovementioned alkyl and alkenyl include all possible isomer.
The preferred example of described fatty acid ester has and has above-mentioned C
6-C
30The ester of the fatty acid of alkyl and monohydroxy or aliphatic polyhydroxy alcohol.The instantiation of this class fatty acid ester comprises glycerin mono-fatty acid ester, diolein, sorbitan monoleate and sorbitan dioleate.
The preferred example of described aliphatic amine has each all to have above-mentioned C
6-C
30The aliphatic monoamine of alkyl and alkylene oxide adduct, aliphatic polyamines, imidazoline and derivative thereof.The instantiation of this class aliphatic amine comprises: aliphatic amine compound such as lauryl amine, lauryl diethylamine, lauryl diethanol amine, dodecyl dipropanolamine, palmitamide, stearylamine, stearyl tetren, oil base amine, oil base trimethylene diamine, oil base diethanol amine and N-ethoxy oil-based imidazoline (N-hydroxyethyloleylimidazolyne); The alkylene oxide adduct of above-mentioned aliphatic amine compound, as N, N-two polyoxyalkylenes-N-alkyl or alkenyl (C
6-C
28) compound of amine and sour modification is (by making above-mentioned aliphatic amine compound and C
2-C
30Monocarboxylic acid such as fatty acid or C
2-C
30Polybasic carboxylic acid (as oxalic acid, phthalic acid, trimellitic acid and 1,2,4,5-benzenetetracarboxylic acid) reaction makes with all or part of residue amino of neutralization or amidatioon and/or imino group).N wherein, N-two polyoxies ethylidene-N-oil base amine are preferred the uses.
Described fatty acid ester friction improver and/or the content of aliphatic amine friction improver in lubricant oil are not particularly limited, and based on described lubricant oil gross mass, are preferably 0.05-3.0%, and more preferably 0.1-2.0% most preferably is 0.5-1.4%.When the content of fatty acid ester friction improver in the lubricant oil and/or aliphatic amine friction improver is lower than 0.05%, just might be able to not obtains enough frictions and reduce effect.When the content of fatty acid ester friction improver in the lubricant oil and/or aliphatic amine friction improver surpassed 3.0%, the solubility of friction improver just might become very low in the described base oil, to cause described lubricated bin stability deterioration, causes precipitation.
As for polybutylene-based succinimide, can use compound by following general formula (1) and (2) expression:
In general formula (1) and (2), PIB represents derived from number-average molecular weight to be the polybutylene group of 900-3500 polybutylene, preferred molecular weight is 1000-2000, and it can make by the mixture of the high-purity isobutylene of polymerization or 1-butylene and isobutylene in the presence of boron fluoride catalyst or aluminum chloride catalyst.When the number-average molecular weight of described polybutylene is lower than 900, just sufficient cleaning action might can not be provided.When the number-average molecular weight of described polybutylene surpassed 3500, the low temperature flow of described polybutylene-based succinimide tended to deterioration.Before being used to prepare polybutylene-based succinimide, polybutylene can be removed by the processing method (as adsorption method or washing methods) that adopts any appropriate and be derived from polybutylene and prepare the trace fluorine of catalyzer and cl residue and it is carried out purifying, control thus that the content of fluorine and cl residue is 50ppm or lower in the polybutylene, wish to be 10ppm or lower, more wish to be 1ppm or lower.
And consider cleaning effect, in general formula (1) and (2), n represents the integer of 1-5, is preferably the integer of 2-4.
The preparation method of described polybutylene-based succinimide is not particularly limited.For example described polybutylene-based succinimide can make by following method: make the chloride of polybutylene or polybutylene (fluorine and cl residue are therefrom fully removed) form polybutylene-based succinate with maleic anhydride 100-200 ℃ of reaction, described polybutylene-based succinate and polyamines (as diethylenetriamines, trien, tetren or penten) are reacted.
As for polybutylene-based succinimide derivatives, they can use the compound of boron or sour modification, can make by described polybutylene-based succinimide in general formula (1) or (2) and boron compound or oxygen-containing organic compound are reacted with neutralization or all or part of residue amino and/or the acid imide of amidatioon.Wherein the polybutylene-based succinimide of boracic, especially boracic two (polybutylene-based) succinimide are preferred the uses.Nitrogen is generally 0.1-3 in mass with the ratio (B/N) of the content of boron in the polybutylene-based succinimide compound of boracic, is preferably 0.2-1.
The boron compound that is used to prepare polybutylene-based succinimide derivatives can be boric acid, borate or borate ester.The instantiation of described boric acid comprises ortho-boric acid, metaboric acid and tetraboric acid.Described boratory instantiation comprises: ammonium salt such as ammonium borate, for example ammonium metaborate, tetraboric acid ammonium, ammonium pentaborate and eight ammonium borates.The instantiation of described borate ester comprises: boric acid and alkylol (are preferably C
1-C
6Alkylol) ester is as boric acid monomethyl ester, boric acid dimethyl esters, boric acid trimethyl ester, boric acid list ethyl ester, boric acid diethyl ester, boric acid triethyl group ester, boric acid list propyl diester, boric acid dipropyl, boric acid tripropyl ester, boric acid monobutyl ester, boric acid dibutyl ester and boric acid tributyl ester.
The oxygen-containing organic compound that is used to prepare polybutylene-based succinimide derivatives can be any C
1-C
30Monocarboxylic acid is as formic acid, acetate, glycol acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, hendecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palustric acid, margaric acid, stearic acid, oleic acid, nonadecylic acid, arachic acid; C
2-C
30Polybasic carboxylic acid is as oxalic acid, phthalic acid, trimellitic acid and 1,2,4,5-benzenetetracarboxylic acid, its acid anhydrides and ester; C
2-C
6Alkylene oxide; And hydroxyl (many) oxyalkylene carbonic ester.
The content that described polybutylene-based succinimide and/or polybutylene-based succinimide derivatives are present in the described lubricant oil is not particularly limited, and based on described lubricant oil gross mass, is preferably 0.1-15%, more preferably 1.0-12%.When the content of polybutylene-based succinimide and/or polybutylene-based succinimide derivatives in the described lubricant oil is lower than 0.1%, just sufficient cleaning effect might can not be obtained.When the content of polybutylene-based succinimide and/or polybutylene-based succinimide derivatives in the described lubricant oil surpassed 15%, the breaking ability of described lubricant oil may deterioration.In addition, adding so a large amount of described polybutylene-based succinimide and/or polybutylene-based succinimide derivatives in described lubricant oil, also is uneconomic.
For described zinc dithiophosphate, it can adopt the compound by following general formula (3) expression:
In general formula (3), R
4, R
5, R
6And R
7In each all represents C
1-C
24Alkyl.Described C
1-C
24Alkyl is preferably C
1-C
24Straight or branched alkyl, C
3-C
24Straight or branched alkenyl, C
5-C
13Cycloalkyl or straight or branched alkyl-cycloalkyl, C
6-C
18Aryl or straight or branched alkylaryl or C
7-C
19Aryl alkyl.Abovementioned alkyl or alkenyl can be primary, the second month in a season or uncle's base.R
4, R
5, R
6And R
7Instantiation comprise: alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl and tetracosyl; Alkenyl such as allyl, isopropenyl, cyclobutenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, hexadecene base, heptadecene base, vaccenic acid base (oil base), 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinic, tricosene base and tetracosa carbon thiazolinyl; Cycloalkyl such as cyclopenta, cyclohexyl and suberyl; Alkyl-cycloalkyl such as methylcyclopentyl, dimethylcyclopentyl, the ethyl cyclopenta, the propyl group cyclopenta, the ethyl-methyl cyclopenta, the trimethyl cyclopenta, the diethyl cyclopenta, the ethyl dimethylcyclopentyl, the propyl group methylcyclopentyl, propyl group ethyl cyclopenta, the dipropyl cyclopenta, propyl group ethyl-methyl cyclopenta, methylcyclohexyl, Dimethylcyclohexyl, the ethyl cyclohexyl, the propyl group cyclohexyl, the ethyl-methyl cyclohexyl, trimethylcyclohexyl, the diethyl cyclohexyl, the ethyl Dimethylcyclohexyl, the propyl group methylcyclohexyl, propyl group ethyl cyclohexyl, the dipropyl cyclohexyl, propyl group ethyl-methyl cyclohexyl, the methyl suberyl, the dimethyl suberyl, the ethyl suberyl, the propyl group suberyl, the ethyl-methyl suberyl, the trimethyl suberyl, the diethyl suberyl, ethyl dimethyl suberyl, propyl group methyl suberyl, propyl group ethyl suberyl, dipropyl suberyl and propyl group ethyl-methyl suberyl; Aryl such as phenyl and naphthyl; Alkylaryl such as tolyl, xylyl, ethylphenyl, propyl group phenyl, ethyl methyl phenyl, trimethylphenyl, butyl phenyl, propyl group aminomethyl phenyl, diethyl phenyl, ethyl 3,5-dimethylphenyl, tetramethylphenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl and dodecylphenyl; And aryl alkyl, as benzyl, methyl-benzyl, dimethyl benzyl, phenethyl, methylbenzene ethyl and dimethyl benzene ethyl.Above-mentioned alkyl comprises all possible isomer.Especially preferred is C
1-C
18Straight or branched alkyl and C
6-C
18Aryl or straight or branched alkylaryl.
The preferred example of described phosphordithiic acid zinc compound has: zinc diisopropyl dithio-phosphate, diisobutyl zinc dithiophosphate, two sec-butyl zinc dithiophosphates, di-sec-amyl zinc dithiophosphate, di-n-hexyl zinc dithiophosphate, two Sec-Hexyl zinc dithiophosphates, dioctyl zinc dithiophosphate, two-2-ethylhexyl zinc dithiophosphate, two positive decyl zinc dithiophosphates, two dodecyl zinc dithiophosphates and two isotridecyl zinc dithiophosphates.
The content of zinc dithiophosphate is not particularly limited described in the described lubricant oil.Reduce effect in order to obtain bigger friction, the content of described zinc dithiophosphate is preferably 0.1% or lower based on described lubricant oil gross mass in described P elements, and more preferably 0.06% or lower, most preferably be least effective dose (LED).When zinc dithiophosphate content in the described lubricant oil surpasses 0.1%, the friction that just might suppress ashless fatty acid ester friction improver and/or ashless aliphatic amine friction improver reduces effect, particularly for the sliding friction between the relative member with described iron-based of slider of described DLC coating.
The preparation method of described zinc dithiophosphate is not particularly limited, and described zinc dithiophosphate can make by any known process.For example described zinc dithiophosphate can have above-mentioned R by making
4, R
5, R
6And R
7The alcohol of alkyl or phenol and phosphoric sulfide (P
2O
5) reaction formation phosphordithiic acid, then with making with phosphordithiic acid in the zine oxide.It is to be noted that the structure of molecule of zinc dithiophosphate can be along with as the alcohol of raw material of the described zinc dithiophosphate of preparation or phenol and difference.
Above-mentioned phosphordithiic acid zinc compound can use separately, also can use the mixture of two or more compounds.When being used in combination two or more phosphordithiic acid zinc compounds, be not particularly limited for the proportions of ingredients of described phosphordithiic acid zinc compound.
In order to improve the performance of the lubricant oil that is used for internal-combustion engine, described lubricant oil also can contain other additive, as metal detergent, antioxidant, viscosity index improver, be different from above-mentioned fatty acid ester friction improver of mentioning and aliphatic amine friction improver friction improver, be different from ashless dispersant, anti-wear agent or extreme pressure agent, rust preventing agent, nonionic surface active agent, demulsifier, matal deactivator and/or the defoamer of above-mentioned polybutylene-based succinimide of mentioning and polybutylene-based succinimide derivatives.
Described metal detergent can be selected from the metal cleaning immunomodulator compounds that is usually used in engine lubricant arbitrarily.The instantiation of described metal detergent comprises such as sodium (Na) and potassium (K) alkali metal or sulfonate, phenates and the salicylate of alkaline-earth metal such as calcium (Ca) and magnesium (Mg); And two or more mixture.Wherein the salicylate of the phenates of the sulfonate of sodium and calcium, sodium and calcium and sodium and calcium is to be fit to use.The total base number of described metal detergent and content can be selected according to the needed performance of lubricant oil.The total base number of described metal detergent is generally 0-500mgKOH/g, is preferably 150-400mgKOH/g, and it utilizes perchloric acid to record according to ISO 3771.The content of described metal detergent is generally the 0.1-10% of described lubricant oil gross mass.
Described antioxidant can be selected from the anti-oxidant compounds that is usually used in engine lubricating oil arbitrarily.The instantiation of described antioxidant comprises: phenol antioxidant, and as 4,4 '-methylene two (2,6-two-tert-butyl phenol) and octadecyl-3-(3,5-two-tert-butyl-hydroxy phenyl) propionate; Amino antioxidant is as phenyl-a-naphthylamine, alkyl phenyl-alpha-naphthylamine and alkyl diphenyl base amine; And two or more mixture.The content of described antioxidant is generally the 0.01-5% of described lubricant oil gross mass.
For described viscosity index improver, operable have: non-dispersive type polymethacrylate viscosity index improver, as the copolymer and the hydrogenation products thereof of one or more methacrylic acids; Decentralized polymethacrylate viscosity index improver is as the copolymer of the methacrylate that also contains nitrogen compound; And other viscosity index agent, as copolymer and hydrogenation products, polyisobutylene and hydrogenation products thereof, vinyl benzene-diolefin hydrogenation copolymer, styrene-maleic anhydride copolymer and the polyoxyethylene alkylphenyl ethene of ethene and α-alkene (for example propylene, 1-butylene and 1-amylene).Consider shear stability, need select the molecular weight of described viscosity index improver.For example the number-average molecular weight of described viscosity index improver for described decentralized or non-dispersive type polymethacrylate, is wished in the 5000-1000000 scope, more wishes to be 100000-800000; For described polyisobutylene or its hydrogenation products, this molecular weight is in the 800-5000 scope; For described ethylene/alpha-olefin copolymer or its hydrogenation products, this molecular weight in the 800-300000 scope, 10000-200000 more preferably.Above-mentioned viscosity index is improved compound and can be used separately, also can use with its two or more form of mixtures.The content of described viscosity index improver is preferably the 0.1-40.0% of described lubricant oil gross mass.
The described friction improver that is different from above-mentioned fatty acid ester friction improver of mentioning and aliphatic amine friction improver, that can enumerate has: ashless friction improver, as borate ester, more senior pure and mild aliphatic ether, with the metal friction improving agent, as molybdenum dithiophosphate, molybdenum dithiocarbamate and molybdenum disulfide.
Describedly be different from the above-mentioned ashless dispersant of mentioning polybutylene-based succinimide and polybutylene-based succinimide derivatives, can be any one and have polybutylene-based polybutylene-based benzylamine and polybutylene-based amine that number-average molecular weight is 900-3500, have number-average molecular weight and be lower than 900 polybutylene-based polybutylene-based succinimide and derivative thereof.
For described anti-wear agent or extreme pressure agent, can use: disulfide, sulfurized fatty, alkene sulphide, have 1-3 C
2-C
20The amine salt of the phosphate ester of alkyl, thiophosphate, phosphite, thiophosphite and these esters.
For described rust preventing agent, can use: the ester of benzene sulfonamide acid esters, dinonylnaphthalene sulfonic acid ester, alkenyl succinic acid and the ester of polyatomic alcohol polybasic alcohol.
For described nonionic surface active agent and demulsifier, can use: nonionic PAG surface active agent, as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl naphthyl ether.
What described matal deactivator can be enumerated has: imidazoline, pyrimidine derivatives, thiazole and benzotriazole.
What described defoamer can be enumerated has: silicone, fluorosilicones and fluoroalkanes base ether.
Describedly be different from the friction improver of fatty acid ester and aliphatic amine friction improver, described being different from the ashless dispersant of polybutylene-based succinimide and polybutylene-based succinimide derivatives, described anti-wear agent or extreme pressure agent, described rust preventing agent and the described demulsifier, the content of every kind of material is the 0.01-5% of described lubricant oil gross mass usually, the content of described matal deactivator is generally the 0.005-1% of described lubricant oil gross mass, and the content of described defoamer is generally the 0.0005-1% of described lubricant oil gross mass.
Described oiling agent mainly is made up of the compound with hydroxyl, and it can produce bigger friction to described slider that is coated with hard carbon coating of present embodiment and sliding friction between the relative member of being made by iron-based or alumina-base material and reduce effect.The instantiation of described hydroxy-containing compounds comprises alcohol.In various alcohol, glycerine or ethylene glycol are preferably used as described oiling agent.
With reference to following embodiment, the present invention will be described in more detail.But it is pointed out that following embodiment only is illustrative, rather than limitation of the present invention.
[setup test sample]
Be half-terete steel part (as matrix) substantially down from S45C steel (according to JIS G4051) cutting at first, it is of a size of 8 * 12 * 40mm.Adopt the CVD method, forming one deck hydrogen content on the semi-cylindrical face of described cutting member is that 20 atom % and thickness are the DLC coating (as undercoating) of 10 μ m.Adopt PVD arc ions galvanoplastic then, forming another layer hydrogen content is that 5 atom % and thickness are the DLC coating (as external coating) of 0.5 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that does not contain additive, described specimen is carried out following friction/wear testing as lubricant oil.
Be half-terete steel part (as matrix) substantially down from S45C steel (according to JIS G4051) cutting at first, it is of a size of 8 * 12 * 40mm.Adopt the CVD method, forming one deck hydrogen content on the semi-cylindrical face of described cutting member is that 20 atom % and thickness are the DLC coating (as undercoating) of 10 μ m.Adopt PVD arc ions galvanoplastic then, forming another layer hydrogen content is that 0.5 atom % and thickness are the DLC coating (as external coating) of 0.5 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that does not contain additive, described specimen is rubbed/wear testing as lubricant oil.
Embodiment 3
Be half-terete steel part (as matrix) substantially down from S45C steel (according to JIS G4051) cutting at first, it is of a size of 8 * 12 * 40mm.Adopt the CVD method, forming one deck hydrogen content on the semi-cylindrical face of described cutting member is that 20 atom % and thickness are the DLC coating (as undercoating) of 10 μ m.Adopt PVD arc ions galvanoplastic then, forming another layer hydrogen content is that 0.5 atom % and thickness are the DLC coating (as external coating) of 0.5 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that is mixed with 1 quality % glycerin mono-fatty acid ester (as ashless fatty acid ester friction improver), described specimen is rubbed/wear testing as lubricant oil.
Embodiment 4
Be half-terete steel part (as matrix) substantially down from S45C steel (according to JIS G4051) cutting at first, it is of a size of 8 * 12 * 40mm.Adopt the CVD method, forming one deck hydrogen content on the semi-cylindrical face of described cutting member is that 20 atom % and thickness are the DLC coating (as undercoating) of 10 μ m.Adopt PVD arc ions galvanoplastic then, forming another layer hydrogen content is that 0.5 atom % and thickness are the DLC coating (as external coating) of 0.5 μ m, thereby obtains specimen.Then, adopt glycerine, described specimen is rubbed/wear testing as oiling agent.
Comparative Examples 1
From S45C steel (according to JIS G4051) cutting is half-terete steel part (as matrix) down substantially, and it is of a size of 8 * 12 * 40mm.Forming a layer thickness on the semi-cylindrical face of described cutting member is the chrome plating coating of 50 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that does not contain additive, described specimen is rubbed/wear testing as lubricant oil.
Comparative Examples 2
From S45C steel (according to JIS G4051) cutting is half-terete steel part (as matrix) down substantially, and it is of a size of 8 * 12 * 40mm.Forming a layer thickness on the semi-cylindrical face of described cutting member is titanium nitride (TiN) coating of 20 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that does not contain additive, described specimen is rubbed/wear testing as lubricant oil.
Comparative Examples 3
From S45C steel (according to JIS G4051) cutting is half-terete steel part (as matrix) down substantially, and it is of a size of 8 * 12 * 40mm.Forming a layer thickness on the semi-cylindrical face of described cutting member is chromium nitride (CrN) coating of 20 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that does not contain additive, described specimen is rubbed/wear testing as lubricant oil.
Comparative Examples 4
From S45C steel (according to JIS G4051) cutting is half-terete steel part (as matrix) down substantially, and it is of a size of 8 * 12 * 40mm.Adopt the CVD method, forming one deck hydrogen content on the semi-cylindrical face of described cutting member is that 20 atom % and thickness are the DLC coating of 10 μ m, thereby obtains specimen.Then, adopt the poly ﹠ Alpha ,-olefin oil that is mixed with 1 quality % glycerin mono-fatty acid ester (as ashless fatty acid ester friction improver), described specimen is rubbed/wear testing as lubricant oil.
[carrying out performance evaluation] according to friction/wear testing
Friction/wear testing uses a kind of reciprocating type friction/wear testing device to carry out under the following conditions.In described friction/wear testing device, specimen (10) among each embodiment 1-4 and the Comparative Examples 1-4 is placed by shown in Figure 2, thereby when the semi-cylindrical of described specimen (10) part (10a) in going up when sliding at the regional A of tabular relative sample (11) under the load L, it can move back and forth along direction S and T.Herein, described relative sample is made by FC250 cast iron (according to JIS G5501).In test, be that the end that turns at described regional A records at described specimen (10) and friction factor between the described relative sample (11).And the wear extent of described specimen (10) records after test.Measurement result as shown in Table.In this table, embodiment 1,2 and 4 and the wear extent of the specimen of Comparative Examples 1-4 be to represent with reference to the wear extent (1.0) of embodiment 3 specimen.
(test condition)
Specimen (10): by S45C steel matrix and on coating form and have 8 * 12 * 40
The semi-cylindrical spare of mm size
Relative sample (11): the plate-like piece of making and having 40 * 60 * 7mm size by FC250 cast iron
Testing apparatus: reciprocating friction/wear testing device
To-and-fro motion: 600 cycles per minute
Probe temperature: 25 ℃
Apply load (P): 98N
Test time: 60min
The slider of embodiment 1-4 has lower friction factor and littler wear extent than the slider of Comparative Examples 1-4, and unexpected result of the present invention clearly illustrates in this table.The slider of wherein considering embodiment 4 thinks that than the more fact of low coefficient of friction and littler wear extent that has of embodiment 1-3 embodiment 4 provides best result.
As mentioned above, by the hard carbon coating of definite structure of the present invention and the combination of particular lubricants, described slider shows good low frictional behavior and durability.Therefore, by in internal-combustion engine, using slider of the present invention, might be than using the bigger improvement that contains the oil lubrication steel slider acquisition fuel efficiency of organic molybdenum compound than the usefulness of Zao technology.
The full content of Japanese patent application No.2003-206809 (application on August 8th, 2003) and application No.2004-225411 (application on August 2nd, 2004) is introduced herein as a reference.
Though describe the present invention with reference to specific implementations of the present invention, the present invention is not limited to above-mentioned mode of execution.According to above-mentioned instruction, those skilled in the art will carry out various improvement and change to above-mentioned mode of execution.Scope of the present invention is limited by claims.
Table
| Friction factor | | |
| Embodiment | ||
| 1 | 0.07 | 1.5 |
| |
0.06 | 1.2 |
| Embodiment 3 | 0.04 | (1.0 reference) |
| Embodiment 4 | 0.02 | 1.0 |
| Comparative Examples 1 | 0.18 | 5.4 |
| Comparative Examples 2 | 0.17 | 3.5 |
| Comparative Examples 3 | 0.15 | 2.0 |
| Comparative Examples 4 | 0.13 | 1.8 |
Claims (19)
1. slider comprises:
Matrix;
Hard carbon coating, it is formed on the described matrix to be limited under the lubrication slidingsurface with relative member sliding contact, and the hydrogen content of the outermost surface part of described hard carbon coating is lower than its remainder; With
Be administered to the oiling agent on the described slidingsurface, described oiling agent mainly is made up of glycerine or ethylene glycol.
2. the described slider of claim 1, the hydrogen content of the outermost surface part of wherein said hard carbon coating is 20 atom % or lower.
3. the described slider of claim 2, the hydrogen content of the outermost surface part of wherein said hard carbon coating is 10 atom % or lower.
4. the described slider of claim 3, the hydrogen content of the outermost surface part of wherein said hard carbon coating is 5 atom % or lower.
5. the described slider of claim 4, the hydrogen content of the outermost surface part of wherein said hard carbon coating is 0.5 atom % or lower.
6. the described slider of claim 1, the hydrogen content of wherein said hard carbon coating reduces to the slidingsurface side from the matrix side gradually along its thickness direction.
7. slider comprises:
Matrix;
Hard carbon coating, it is formed on the described matrix to be limited under the lubrication slidingsurface with relative member sliding contact, described hard carbon coating has along its thickness direction two-layer or laminated coating laminated together, and described two-layer or laminated coating comprises that hydrogen content is lower than the outermost surface coating of at least one other coating; With
Be administered to the oiling agent on the described slidingsurface, described oiling agent mainly is made up of glycerine or ethylene glycol.
8. the described slip moving part of claim 7, the hydrogen content of wherein said outermost surface coating is lower than all other coatings.
9. the described slider of claim 7, the hydrogen content of wherein said outermost surface coating is 20 atom % or lower.
10. the described slider of claim 9, the hydrogen content of wherein said outermost surface coating is 10 atom % or lower.
11. the described slider of claim 10, the hydrogen content of wherein said outermost surface coating are 5 atom % or lower.
12. the described slider of claim 11, the hydrogen content of wherein said outermost surface coating are 0.5 atom % or lower.
13. claim 1 or 7 described sliders, wherein before forming described hard carbon coating, described matrix is endowed undercoat by at least a method that is selected from chromium plating, chromium nitride method and nitriding process.
14. claim 1 or 7 described sliders, wherein said slider is an engine piston ring.
15. the described slider of claim 14, wherein said piston ring are at least a in apical ring and the disc.
16. a method of producing slider comprises:
The matrix of described slider is provided;
Form hard carbon coating on described matrix, its generation type should make the hydrogen content of the outermost surface part of described hard carbon coating be lower than its remainder; With
Use oiling agent on described hard carbon coating, wherein said oiling agent mainly is made up of glycerine or ethylene glycol.
17. the described method of claim 16, wherein said formation step comprise that the hydrogen content of control outermost surface part is 20 atom % or lower.
18. a method of producing slider comprises:
The matrix of described slider is provided;
Form hard carbon coating on described matrix, its generation type should make the hydrogen content of the outermost surface coating of described hard carbon coating be lower than at least one other coating; With
Use oiling agent on described hard carbon coating, wherein said oiling agent mainly is made up of glycerine or ethylene glycol.
19. the described method of claim 18, wherein said formation step comprise that the hydrogen content of control outermost surface coating is 20 atom % or lower.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003206809 | 2003-08-08 | ||
| JP2003206809 | 2003-08-08 | ||
| JP2004225411 | 2004-08-02 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100563258A Division CN100344890C (en) | 2003-08-08 | 2004-08-06 | Sliding member and production process thereof |
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| Publication Number | Publication Date |
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| CN1975214A CN1975214A (en) | 2007-06-06 |
| CN100485232C true CN100485232C (en) | 2009-05-06 |
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| CNB2006101453396A Active CN100485232C (en) | 2003-08-08 | 2004-08-06 | Sliding member and production process thereof |
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| JP5080505B2 (en) * | 2009-01-13 | 2012-11-21 | 大同メタル工業株式会社 | Sliding member |
| CN102002684B (en) * | 2009-08-31 | 2014-07-30 | 日立金属株式会社 | Slide part |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB768226A (en) * | 1952-02-19 | 1957-02-13 | Hoechst Ag | Improvements in hydraulic fluids |
| CN1033834A (en) * | 1988-10-11 | 1989-07-12 | 淄博塑料助剂厂 | The preparation method of polyhydric alcohol fatty acid ester |
| EP0553100B1 (en) * | 1990-07-31 | 1996-01-24 | Exxon Chemical Patents Inc. | Synergystic blend of amine/amide and ester/alcohol friction modifying agents for improved fuel economy of an internal combustion engine |
| EP1067211A1 (en) * | 1999-07-08 | 2001-01-10 | Sumitomo Electric Industries, Ltd. | Hard coating and coated member |
-
2004
- 2004-08-06 CN CNB2006101453396A patent/CN100485232C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB768226A (en) * | 1952-02-19 | 1957-02-13 | Hoechst Ag | Improvements in hydraulic fluids |
| CN1033834A (en) * | 1988-10-11 | 1989-07-12 | 淄博塑料助剂厂 | The preparation method of polyhydric alcohol fatty acid ester |
| EP0553100B1 (en) * | 1990-07-31 | 1996-01-24 | Exxon Chemical Patents Inc. | Synergystic blend of amine/amide and ester/alcohol friction modifying agents for improved fuel economy of an internal combustion engine |
| EP1067211A1 (en) * | 1999-07-08 | 2001-01-10 | Sumitomo Electric Industries, Ltd. | Hard coating and coated member |
Non-Patent Citations (4)
| Title |
|---|
| Si3N4-高速钢摩擦副在不同润滑剂润滑下的摩擦磨损性能研究. 曲建俊，齐毓霖.摩擦学学报，第14卷第3期. 1994 |
| Si3N4-高速钢摩擦副在不同润滑剂润滑下的摩擦磨损性能研究. 曲建俊，齐毓霖.摩擦学学报，第14卷第3期. 1994 * |
| 金属塑料复合材料在甘油或三乙醇胺润滑下的摩擦磨损性能研究. 张招柱，沈维长，赵家政.摩擦学学报，第15卷第3期. 1995 |
| 金属塑料复合材料在甘油或三乙醇胺润滑下的摩擦磨损性能研究. 张招柱，沈维长，赵家政.摩擦学学报，第15卷第3期. 1995 * |
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