CN101576118B - Unleaded Cu-based sliding bearing material and preparation method thereof - Google Patents

Unleaded Cu-based sliding bearing material and preparation method thereof Download PDF

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Publication number
CN101576118B
CN101576118B CN2009101169764A CN200910116976A CN101576118B CN 101576118 B CN101576118 B CN 101576118B CN 2009101169764 A CN2009101169764 A CN 2009101169764A CN 200910116976 A CN200910116976 A CN 200910116976A CN 101576118 B CN101576118 B CN 101576118B
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bearing material
graphite
copper
unleaded
friction
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CN101576118A (en
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尹延国
焦明华
俞建卫
解挺
田明
马少波
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention relates to an unleaded Cu-based sliding bearing material and a preparation method thereof and the invention has the characteristics that: the material is composed of nickel, tin, zinc, iron, graphite, bismuth, copper and assistants, the substrate of the material is unleaded copper alloy, and the antifriction and antisticking constituent element is bismuth and graphite. The Cu-based bearing material features high intensity, and good antifriction and antisticking, thus realizing an unleaded Cu-based bearing material. The lead is cancelled in an original bearing material with lead and copper, and a synergistic effect of bismuth and graphite can replace the use of lead, thus completely overcoming the defect of lead pollution; moreover, the service performance of the bearing remains nearly the same, therefore the unleaded Cu-based sliding bearing material can completely replace the bearing material with lead and copper. The material of the invention can be applied in food machinery, drugs machinery, construction machinery, automobile and other products, and has advantages of good antifriction and antisticking, good heat dissipation effect, oxidation resistance and corrosive resistance.

Description

Unleaded Cu-based sliding bearing material and preparation method thereof
Technical field
The present invention relates to material for sliding bearing, a kind of unleaded Cu-based sliding bearing material and preparation method thereof of more specifically saying so.
Background technique
Lead has soft yielding, the characteristic such as fusing point is low, the boundary lubrication characteristic is good of matter, as the important constituent element of Cu-based sliding bearing material and generally used, as Cu-10Sn-10Pb, Cu-3Sn-24Pb is the most common motor car engine material for sliding bearing, and leaded Cu-based sliding bearing material has characteristic such as antifriction, antisticking preferably.Yet lead and compound thereof belong to extremely toxic substance, use products containing lead to bring very important harm to human environment.For Cu-based sliding bearing material, how under unleaded condition, still to keep characteristics such as good antifriction, antisticking, seem particularly important.
The application of the soft preferably phase graphite of antifriction characteristic in Cu-base composites is comparatively general, the copper-base graphite composite material can be used as unleaded Cu-based sliding bearing material and uses, it is poor that but copper combines with graphite interface, graphite isolates effect to copper alloy matrix, the performance of copper-base graphite material for sliding bearing is subjected to the restriction of content of graphite, when content of graphite hangs down, antifriction, antisticking performance deficiency, when content of graphite is high, intensity, hardness descend, and the antisticking characteristic of simple graphite is also not as low melting metal lead.
Nontoxic low melting metal element bismuth is to plumbous similar, insoluble with copper, aluminium, be present in copper, the aluminum alloy with the free state form, intensity effect to alloy substrate is less, because of causing the bismuth fusing, frictional heat has film anti-stick, antifriction function in the friction process in friction surface formation, thereby improve the friction and wear characteristic of composite material, taken the lead in aluminum matrix composite, being applied.
The metallic element bismuth is incorporated into also can plays antifriction, antisticking effect in the copper base bearing material, yet the hardness ratio of bismuth is plumbous slightly high, ductility is also poor slightly than lead, thereby a little less than making its antifriction, antisticking performance than lead, so the tribological property of copper bismuth bearing material is not as the copper-lead bearing material.
Summary of the invention
The present invention be directed to above-mentioned existing in prior technology deficiency, a kind of unleaded Cu-based sliding bearing material and preparation method thereof is provided, replace in the copper base bearing material plumbously in the hope of the synergy of the antisticking characteristic of the antifriction characteristic of utilizing graphite and bismuth, realize the unleaded of copper base bearing material.
Technical solution problem of the present invention adopts following technological scheme:
The characteristics of unleaded Cu-based sliding bearing material of the present invention are described material constituting by weight percentage:
Nickel 5-15%, tin 3-10%, zinc 0-5%, iron 0-5%, graphite 1-5%,
Bismuth 2-15%, copper 60-80%, auxiliary agent 0.1-1%.
The characteristics of unleaded Cu-based sliding bearing material of the present invention also are:
Described graphite surface has the copper nickel composite deposite, described copper and mickel comprises the copper and mickel in the copper nickel composite deposite that graphite surface forms, and the content of the copper and mickel in the described copper nickel composite deposite is 30% of graphite total amount with copper nickel composite deposite by weight percentage.
Described auxiliary agent be polyvinyl alcohol, polyethyleneglycol, stearic acid, zine stearate, silane coupler, silicate, phosphate, boratory any, or its composite.
The preparation method's of unleaded Cu-based sliding bearing material of the present invention characteristics are to operate as follows:
A, the weight percent concentration of auxiliary agent by 2-25% is dissolved in water or the solvent, mixes with graphite again and stir, the mixture of auxiliary agent and graphite;
B, step a gained auxiliary agent mixed with other constituent elements with the graphite mixture and stir, mixed material;
C, the described mixed material of step b is made unleaded Cu-based sliding bearing material through repressing and re-sintering.
The preparation method's of unleaded Cu-based sliding bearing material of the present invention characteristics also are to operate as follows:
A, employing chemical plating method form the copper and mickel composite deposite at graphite surface;
B, the weight percent concentration of auxiliary agent by 2-25% is dissolved in water or the solvent, mixes with the graphite that contains composite deposite again and stir, the mixture of auxiliary agent and graphite;
C, step b gained auxiliary agent mixed with other constituent elements with the graphite mixture and stir, mixed material;
D, the described mixed material of step c is made unleaded Cu-based sliding bearing material through repressing and re-sintering.
The preparation method's of unleaded Cu-based sliding bearing material of the present invention characteristics are that also the process of described repressing and re-sintering is: finish the mixed material that is mixed and pack in the steel die, it at specific mo(u)lding pressure the pressed compact that is pressed into required form on the hydraulic press of 600Mpa, described pressed compact is put into ammonia decomposing protection atmosphere carry out sintering, sintering temperature is 880 ℃, and holding time is 60 minutes; The blank that sinters is repressing and re-sintering again, and multiple pressure pressure is 500MPa, and the resintering temperature is 700 ℃, is incubated 30 minutes, makes unleaded Cu-based sliding bearing material.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention as composite lubricated constituent element, utilizes the synergy of the antisticking characteristic of the antifriction characteristic of graphite and bismuth to replace plumbous effect in the copper base bearing material with graphite and bismuth, has realized that copper base bearing material is unleaded.
2, the application of the preferably soft phase graphite of antifriction characteristic in Cu-base composites is comparatively general, but because copper and graphite exist the interface to combine poor, graphite to the copper alloy matrix effect of isolating, the unequal problem of batch mixing, and the antisticking characteristic of simple graphite is also not as low melting metal lead, and the performance of copper-base graphite material for sliding bearing is restricted by content of graphite, when content of graphite hangs down, antifriction, antisticking performance deficiency, when content of graphite was high, intensity, hardness descended.Therefore, the present invention uses electrochemical method at graphite granule surface deposition multicomponent composite deposite, realizes the metallization of nonmetallic surface, has effectively improved the wettability between graphite and the copper alloy matrix, improve interface bond strength, thereby improve the mechanics and the tribological property of copper base bearing material.
3, the present invention adds corresponding additive when material preparation, has effectively improved the attaching property between the various powders, makes composite material not stratified, not segregation, the uniformity of realization microstructure of composite structure and performance.
4, the present invention utilizes the compound interpolation of the nontoxic preferably low melting metal element of antisticking performance bismuth, has improved the deficiency of simple graphite antisticking characteristic, reduces the consumption of graphite as far as possible, has solved the intensity and the toughness problem of copper-base graphite material for sliding bearing.
5, no matter bearing material of the present invention is antifriction, antisticking characteristic, or intensity, toughness have have all met or exceeded and existingly contains lead bronze base bearing material C u-10Sn-10Pb, have realized that copper base bearing material is unleaded, meet the development trend of green, environmental protection.
Below the invention will be further described by embodiment.
Embodiment
In concrete the enforcement, unleaded Cu-based sliding bearing material constituting by weight percentage:
Nickel 5-15%, tin 3-10%, zinc 0-5%, iron 0-5%, graphite 1-5%,
Bismuth 2-15%, copper 60-80%, auxiliary agent 0.1-1%.
Copper and mickel in the above-mentioned composition comprises the copper and mickel in the copper nickel composite deposite that graphite surface forms, and the content of the copper and mickel in the copper nickel composite deposite is 30% of graphite total amount with copper nickel composite deposite by weight percentage.
Auxiliary agent be polyvinyl alcohol, polyethyleneglycol, stearic acid, zine stearate, silane coupler, silicate, phosphate, boratory any, or its composite;
In concrete the enforcement, unleaded Cu-based sliding bearing material can be made according to the following procedure:
Step 1, the weight percent concentration of auxiliary agent by 2-25% is dissolved in water or the solvent, mixes with graphite again and stir, the mixture of auxiliary agent and graphite;
Step 2, step 1 gained auxiliary agent mixed with other constituent elements with the graphite mixture and stir, mixed material;
Step 3, the described mixed material of step 2 is made unleaded Cu-based sliding bearing material through repressing and re-sintering.
In concrete the enforcement, unleaded Cu-based sliding bearing material also can be operated according to the following procedure:
Step 1, employing chemical plating method form the copper and mickel composite deposite at graphite surface;
Step 2, the weight percent concentration of auxiliary agent by 2-25% is dissolved in water or the solvent, mixes with the graphite that contains composite deposite again and stir, the mixture of auxiliary agent and graphite;
Step 3, step 2 gained auxiliary agent mixed with other constituent elements with the graphite mixture and stir, mixed material;
Step 4, step 3 gained mixed material is made unleaded Cu-based sliding bearing material through repressing and re-sintering.
The process of repressing and re-sintering is: finish the mixed material that is mixed and pack in the steel die, it at specific mo(u)lding pressure the pressed compact that is pressed into required form on the hydraulic press of 600Mpa, pressed compact is put into ammonia decomposing protection atmosphere carry out sintering, sintering temperature is 880 ℃, and holding time is 60 minutes; The blank that sinters is repressing and re-sintering again, and multiple pressure pressure is 500MPa, and the resintering temperature is 700 ℃, is incubated 30 minutes, makes unleaded Cu-based sliding bearing material.
Embodiment 1, and present embodiment carries out the preparation of material as follows:
1, with 200 order tin bronze pre-alloyed powder, adds 200 purpose nickel powders, zinc powder, iron powder and the abundant mixing of bismuth meal;
2, the weight percent concentration of auxiliary agent by 2-25% fully is dissolved in water or the alcohol solvent, and 300 purpose plumbago mixings of composite deposite arranged with the surface;
3,, make unleaded Cu-based sliding bearing material through repressing and re-sintering two kinds of abundant mixings of powder of step 1 and 2 and dry.
Concrete Chemical composition sees Table 1, the mechanical property of prepared leadless copper base bearing material sees Table 2, friction and wear behavior sees Table 3, wear test is carried out on end face frictional wear tester, to the mill material is the Cr12 steel, pressure 5Mpa, and linear velocity is 0.4m/s, soak machinery oil No. 32, test period 3 hours.
Table 1 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 5 8 3 3 5 1.5 0.5 Surplus
Table 2 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.82 69 7.18 354
The friction and wear behavior of table 3 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.038 1.45 75
Dry friction 0.26 36.83 160
In the friction-wear test process, antifriction, the pick resistance of the little expression copper of friction factor and friction Temperature Rise base bearing material are good, and the wear-resisting property of the low expression of wear extent copper base bearing material is good.Through 3 hours friction-wear test, find out that by table 3 the friction pair average friction coefficient is 0.26 under the DRY SLIDING, friction Temperature Rise is 160 ℃, wear extent 36.83 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.
Embodiment 2:
Material preparation method, method for testing performance and condition are identical with embodiment 1, adjust the Chemical composition of leadless copper base bearing material, and concrete Chemical composition sees Table 4, and the mechanical property of leadless copper base bearing material sees Table 5, and leadless copper base pivot friction polishing machine sees Table 6.
Table 4 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 8 8 0 2 8 1 0.8 Surplus
Table 5 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.86 71 7.23 367
The friction and wear behavior of table 6 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.032 1.26 72
Dry friction 0.23 31.67 152
Through 3 hours friction-wear test, find out that by table 6 the friction pair average friction coefficient is 0.23 under the DRY SLIDING, friction Temperature Rise is 152 ℃, wear extent 31.67 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.
Embodiment 3:
Material preparation method, method for testing performance and condition are identical with embodiment 1,2, different is the composition of adjusting the leadless copper base bearing material, concrete Chemical composition sees Table 7, and the mechanical property of leadless copper base bearing material sees Table 8, and leadless copper base pivot friction polishing machine sees Table 9.
Table 7 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 6 10 3 0 6 3 0.5 Surplus
Table 8 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.39 62 5.78 323
The friction and wear behavior of table 9 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.027 1.15 68
Dry friction 0.21 26.13 147
Through 3 hours friction-wear test, find out that by table 9 the friction pair average friction coefficient is 0.21 under the DRY SLIDING, friction Temperature Rise is 147 ℃, wear extent 26.13 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.
Embodiment 4:
Material preparation method, method for testing performance and condition are identical with embodiment 1,2,3, adjust the Chemical composition of leadless copper base bearing material, concrete Chemical composition sees Table 10, and the mechanical property of leadless copper base bearing material sees Table 11, and leadless copper base pivot friction polishing machine sees Table 12.
Table 10 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 15 6 6 2 10 1 1 Surplus
Table 11 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.89 73 7.31 362
The friction and wear behavior of table 12 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.031 1.23 72
Dry friction 0.22 30.59 150
Through 3 hours friction-wear test, find out that by table 12 the friction pair average friction coefficient is 0.22 under the DRY SLIDING, friction Temperature Rise is 150 ℃, wear extent 30.59 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.
Embodiment 5:
Material preparation method, method for testing performance and condition are identical with embodiment 1,2,3,4, adjust the Chemical composition of leadless copper base bearing material, concrete Chemical composition sees Table 13, and the mechanical property of leadless copper base bearing material sees Table 14, and leadless copper base pivot friction polishing machine sees Table 15.
Table 13 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 10 6 2 1 2 5 0.6 Surplus
Table 14 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.02 52 4.59 289
The friction and wear behavior of table 15 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.022 1.31 65
Dry friction 0.21 34.35 140
Through 3 hours friction-wear test, find out that by table 15 the friction pair average friction coefficient is 0.21 under the DRY SLIDING, friction Temperature Rise is 140 ℃, wear extent 34.35 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.
Embodiment 6: present embodiment carries out the preparation of material as follows:
1, with 200 order tin bronze pre-alloyed powder, adds 200 purpose nickel powders, zinc powder, iron powder and the abundant mixing of bismuth meal;
2, the weight percent concentration of auxiliary agent by 2-25% fully is dissolved in water or the alcohol solvent, and with 300 purpose plumbago mixings;
3,, make unleaded Cu-based sliding bearing material through repressing and re-sintering two kinds of abundant mixings of powder of step 1 and 2 and dry.
Method for testing performance is identical with embodiment 1,2,3,4,5 with condition, adjusts the Chemical composition of leadless copper base bearing material, and concrete Chemical composition sees Table 16, and the mechanical property of leadless copper base bearing material sees Table 17, and leadless copper base pivot friction polishing machine sees Table 18.
Table 16 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 5 8 3 3 5 1.5 0.5 Surplus
Table 17 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.80 68 5.83 271
The friction and wear behavior of table 18 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.045 2.31 81
Dry friction 0.28 57.35 187
Through 3 hours friction-wear test, find out that by table 18 the friction pair average friction coefficient is 0.28 under the DRY SLIDING, friction Temperature Rise is 187 ℃, wear extent 57.35 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.Identical recipe ingredient is the common graphite that does not have overlay coating owing to what select for use, so table 18 is compared with table 3, the properties of antifriction and wear resistance of corresponding leadless copper base bearing material is poor slightly.
Embodiment 7:
Material preparation method is identical with embodiment 6, method for testing performance is identical with embodiment 1,2,3,4,5,6 with condition, adjust the Chemical composition of leadless copper base bearing material, concrete Chemical composition sees Table 19, the mechanical property of leadless copper base bearing material sees Table 20, and leadless copper base pivot friction polishing machine sees Table 21.
Table 19 leadless copper base bearing material Chemical composition
Element Ni Sn Zn Fe Bi Gr Auxiliary agent Cu
W(%) 10 6 2 1 2 5 0.6 Surplus
Table 20 leadless copper base bearing material mechanical property
Density g/cm 3 Hardness HB Impact toughness J/cm 2 Crushing strength MPa
7.00 51 3.43 220
The friction and wear behavior of table 21 leadless copper base bearing material
Coefficientoffriction Wear extent 10 -9m 3 Friction Temperature Rise ℃
Flooding system lubrication 0.025 1.67 71
Dry friction 0.23 61.35 165
Through 3 hours friction-wear test, find out that by table 21 the friction pair average friction coefficient is 0.23 under the DRY SLIDING, friction Temperature Rise is 165 ℃, wear extent 61.35 * 10 -9m 3, show that the properties of antifriction and wear resistance of leadless copper base bearing material is better; Under the flooding system lubrication condition, because the synergy of liquid-solid lubrication antifriction, the friction pair average friction coefficient is littler, and friction Temperature Rise is very low, and wear extent is also very little, shows that the leadless copper base bearing material has embodied better properties of antifriction and wear resistance under the flooding system lubrication condition.Identical recipe ingredient is the common graphite that does not have overlay coating owing to what select for use, so table 21 is compared with table 15, the properties of antifriction and wear resistance of corresponding leadless copper base bearing material is poor slightly.

Claims (2)

1. unleaded Cu-based sliding bearing material is characterized in that described material constituting by weight percentage: nickel 5%, tin 8%, zinc 3%, iron 3%, graphite 1.5%, bismuth 5%, auxiliary agent 0.5%, copper surplus;
Wherein, described graphite surface has the copper nickel composite deposite, described copper and mickel comprises the copper and mickel in the copper nickel composite deposite that graphite surface forms, and the content of the copper and mickel in the described copper nickel composite deposite is 30% of graphite total amount with copper nickel composite deposite by weight percentage.
2. the preparation method of the described unleaded Cu-based sliding bearing material of claim 1 is characterized in that operating as follows:
A, employing chemical plating method form the copper and mickel composite deposite at graphite surface;
B, the weight percent concentration of auxiliary agent by 2-25% is dissolved in the solvent, mixes with the graphite that contains composite deposite again and stir, the mixture of auxiliary agent and graphite;
C, step b gained auxiliary agent mixed with other constituent elements with the graphite mixture and stir, mixed material;
D, the described mixed material of step c is made unleaded Cu-based sliding bearing material through repressing and re-sintering;
The process of described repressing and re-sintering is: finish the mixed material that is mixed and pack in the steel die, it at specific mo(u)lding pressure the pressed compact that is pressed into required form on the hydraulic press of 600MPa, described pressed compact is put into ammonia decomposing protection atmosphere carry out sintering, sintering temperature is 880 ℃, and holding time is 60 minutes; The blank that sinters is repressing and re-sintering again, and multiple pressure pressure is 500MPa, and the resintering temperature is 700 ℃, is incubated 30 minutes, makes unleaded Cu-based sliding bearing material.
CN2009101169764A 2009-06-15 2009-06-15 Unleaded Cu-based sliding bearing material and preparation method thereof Expired - Fee Related CN101576118B (en)

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