GB2489601A - Sliding bearing with a layer of a copper-bismuth-tin-phosphorous alloy - Google Patents
Sliding bearing with a layer of a copper-bismuth-tin-phosphorous alloy Download PDFInfo
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- GB2489601A GB2489601A GB1205639.6A GB201205639A GB2489601A GB 2489601 A GB2489601 A GB 2489601A GB 201205639 A GB201205639 A GB 201205639A GB 2489601 A GB2489601 A GB 2489601A
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- 229910045601 alloy Inorganic materials 0.000 title claims description 144
- 239000000956 alloy Substances 0.000 title claims description 144
- 239000010949 copper Substances 0.000 claims abstract description 169
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 241000357293 Leptobrama muelleri Species 0.000 claims abstract description 13
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims abstract 16
- 239000012791 sliding layer Substances 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims description 45
- 229910009038 Sn—P Inorganic materials 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 abstract description 12
- 229910052797 bismuth Inorganic materials 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 35
- 239000007791 liquid phase Substances 0.000 description 32
- 239000000843 powder Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 28
- 230000007423 decrease Effects 0.000 description 24
- 238000001816 cooling Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 229910017755 Cu-Sn Inorganic materials 0.000 description 10
- 229910017927 Cu—Sn Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- -1 Cu-Sn compound Chemical class 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009661 fatigue test Methods 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 206010010144 Completed suicide Diseases 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910020830 Sn-Bi Inorganic materials 0.000 description 1
- 229910018728 Sn—Bi Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 102220259718 rs34120878 Human genes 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/06—Sliding surface mainly made of metal
- F16C33/12—Structural composition; Use of special materials or surface treatments, e.g. for rust-proofing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/06—Sliding surface mainly made of metal
- F16C33/12—Structural composition; Use of special materials or surface treatments, e.g. for rust-proofing
- F16C33/121—Use of special materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C2204/00—Metallic materials; Alloys
- F16C2204/10—Alloys based on copper
- F16C2204/18—Alloys based on copper with bismuth as the next major constituent
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Sliding-Contact Bearings (AREA)
Abstract
A sliding bearing comprises steel back layer 1 and a copper-based sliding layer 2. The copper-based sliding layer 2 comprises (by weight): 6-12 % tin, 11-30 % bismuth, 0.01-0.05 % phosphorous, optionally 0.1-10 % in total of nickel, iron and/or silver, optionally 0.1-10 % in total of inorganic compounds, with the balance being Cu and impurities. The mass ratio of Bi to Sn is 1.7-3.4 and the mass ratio of Bi to P is 500-2100. The copper based sliding layer 2 comprises a copper-tin-phosphorous compound and bismuth grains 3 with an average area of 60-350 um2 when observed in a cross section parallel to a thickness direction of the layer.
Description
COPPER-BASED SLIDING MATERIAL
Technical Field
The invention relates to a copper-based sliding material having improved fatigue resistance and seizure resistance. Particularly, the material is suitable for half bearings, bushings, thrust washers or the like in automobiles, industrial machinery or the like.
S Background of the invention
In general, a copper-based sliding material for sliding bearings for internal combustion engines has been conventionally produced by a continuous sintering process. In the sintering process, a Cu-based alloy powder is spread continuously on a steel strip and then continuously sintered and rolled. The copper-based sliding material has been required to be free of Pb in order to meet recent environmental restrictions. Thus, it has been proposed that the sintered Cu-based alloy contains Bi instead of Pb (see JP Patent No. 3421724, US200310068 I 06A 1, .JP-A-20 10-535287, JP-A-04-28836, and JP-A-05-263 166 for example,).
Brief summary of the invention
A crank shaft for an internal combustion engine has tendency to increase its rotation speed in recent years and thus a sliding bearing is required to have a higher seizure resistance. The sintered Cu-based alloy containing Bi is used as the copper-based sliding material and preferably contains not less than 10 mass% of Si in order to improve the seizure resistance.
JP Patent No. 3421724, US2003/0068106A1, and JP-A-20l0-535287 disclose that a Cu-based alloy containing Si is sintered by the continuous sintcring process. It depends largely on an amount of Si whether the sintered Cu-based alloy has a high strength. As shown in Fig. 4A, a large number of spaces are present in a copper alloy layer when a Cu-based alloy powder 4 is spread onto a steel strip or a back steel 1. As shown in Fig. 45, Si 6 in the Cu-based alloy powder 4 melts at around 271CC and form a liquid phase when a temperature is elevated in a first sintering step. When the temperature reaches a sintering temperature and then cooling begins, Bi melt 6 is pushed out from the Cu-based alloy powder 4 and flows into the spaces between the Cu-based alloy powder 4 particles because a Cu-based alloy 5 has a faster shrinkage rate than Si 6, as shown in Fig. 4C. The Bi melt 6 having flowed into the spaces spreads along a surface of the Cu-based alloy powder 4, which results in coarsening of Si grains 3 in a Cu-based alloy layer 2, as shown in Figs. 3 and 4D. It is noted that Fig. 3 illustrates a structure of a Cu-based alloy after a rolling step and a second sintering step on a sintered Cu-based alloy which has been subjected to the first sintering step shown in Fig. 4D. The coarsening of the Di grains 3 occurs especially when the Cu-based alloy layer contains not less than 10% by mass of Di. Ri is present solely in the Cu-based alloy layer 2 because Bi is hardly solid-solutes in the Cu-based alloy. In addition, Bi has a remarkably lower strength than the Cu-based alloy. When a bearing is subjected to a dynamic load, cracks likely generates from the coarsened Di grain or a grain boundary between the Di grain and the Cu-based alloy, which leads to a fatigue destruction in the Cu-based alloy layer, as described on paragraph [0030] in JO US2003100681 06A1.
In addition, US2003/0068106A1 and JP-A-2010-535287 propose a bearing including a Cu-based alloy layer having a composition of Cu-Sn-P-Ri. A matrix thereof is composed of a solid solution of Cu, Sn and P. It is described that when a sliding load is applied to the bearing during operation, Sn in the matrix migrates on a sliding surface of the bearing and forms a Sn-rich layer there, whereby a seizure resistance of the bearing is improved. When Sn is concentrated on the surface of the Cu-based alloy which is the sliding surface of the bearing, however, the seizure resistance decreases because the Cu-based alloy around the sliding surface becomes hardened.
On the other hand, JP-A-04-28836 and JP-A-05-263 166 disclose that a Cu-based alloy powder containing Di is produced by a mechanical alloying method and the Cu-based alloy powder is sintered at a relatively lower temperature (400 to 800°C, preferably 400 to 700°C) to obtain a copper-based sliding material including fine Di grains. However, when the sintering is carried out at a temperature of not higher than 8 00°C in the continuous sintering process, bonding strength between a steel back layer and a Cu-based alloy layer is insufficient, which leads to a decrease in a fatigue resistance. On the contrary, when the sintering is carried out at a temperature above 800°C, a high bonding strength to the steel back layer can be achieved.
However, since the sintering of the Cu-based alloy powder proceeds excessively, the Di grains are coarsened in the Cu-based alloy layer, as described in JP-A-04-28836.
The invention is made in view of the above, and an object of the invention is to provide a copper-based sliding material having improved fatigue resistance and seizure resistance by suppressing coarsening of Bi grains in a Cu-based alloy layer produced by a continuous sintering process.
To achieve the above object, the invention provides a copper-based sliding material including a steel back layer and a Cu-based alloy layer. The Cu-based alloy layer has a composition of, by mass percent, 6 to 12% of Sn, 11 to 30% of Di, 0.01 to 0.05% P, and the balance being Cu and inevitable impurities. A mass ratio of Bi to Sn (BiISn) is 1.7 to 3.4, and a mass ratio of Bi to P (Bi/P) is 500 to 2100. A Cu-Sn-P based compound is dispersed in the Cu-based alloy layer and thus Di grains are dispersed in the Cu-based alloy layer so that an average grain area of the Di grains is 60 to 350 sm2 in a cross section in a direction parallel to a thickness direction of the Cu-based alloy layer.
In the invention, high sliding properties can be obtained by containing II to 30% by mass of Di, although it is known that a copper-based sliding material can exhibit sliding properties when Di is added. When the content of Di is less than 11% by mass, sufficient sliding properties can not be obtained and a seizure resistance decreases. On the other hand, when the content of Di exceeds 30% by mass, a fatigue resistance decreases.
In the invention, the average grain area of the Di grains can be finely controlled at to 350 gm2 by dispersing a Cu-Sn-P based compound in the Cu-based alloy layer. This is assumed to be based on the following mechanism. The copper-based sliding material of the invention is produced by spreading a copper alloy powder onto a steel strip continuously, and carrying out sintering and rolling repeatedly. As shown in Fig. 2A, a Cu-based alloy layer has a porous structure after a Cu-based alloy powder 4 is spread onto a steel strip or a steel back layer I in the spraying step. As shown in Fig. 28, Di 6 is present in the Cu-based alloy powder 4, and Bi 6 melts at around 271°C to form a liquid phase when temperature is elevated in the subsequent sintering step. When sintering is carried out at a temperature of 800 to 900°C and cooling is started in the subsequent cooling step, a Di melt 6 is pushed out from the Cu-based alloy powder 4to flow in spaces between the Cu-based alloy powder 4 particles because a Cu-based alloy 5 shrinks more rapidly due to its larger thermal shrinkage rate than Di 6. At this time, the shrinkage of the Cu-based alloy 5 is suppressed by precipitated Cu-Sn-P based compound 7 in the Cu-based alloy 5. In this way, a difference in the thermal shrinkage rate between the Cu-based alloy 5 and Di 6 is reduced, whereby the liquid phase of Di 6 is prevented from being pushed out from the Cu-based alloy powder 4 as shown in Fig. 2C, which provides a structure shown in Fig. 2D. After that, the Di grains 3 can be finely dispersed in the Cu-based alloy layer 2 by rolling and sintering for densifleation, as shown in Fig. 1.
The Cu-Sn-P based compound is precipitated in the Cu-based alloy by following mechanism, At the sintering temperature (800 to 900°C), larger amounts of Sn and P can be dissolves in the Di liquid phase than at ambient temperature (20°C), and therefore, Sn and P diffuse from the Cu-based alloy into the Bi liquid phase. After that, when the temperature is decreased in the cooling step, the Di liquid phase becomes super-saturated with Sn and P, and Sn and P diffuse from the Si liquid phase into the Cu-based alloy. This makes Sn and P to be concentrated around the boundary between the Di liquid phase and the Cu-based alloy. At this time, when a cooling rate from 800°C to 450°C in the cooling step is fast, Sn and P solid-solute in the Cu-based alloy in a super-saturation state. However, when the cooling is carried out from 800°C to 450°C in 4 to 10 minutes, the Cu-Sn-P based compound can be precipitated in the Cu-based alloy. As a result, the difference in the thermal shrinkage rate between the Cu-based alloy and the Si liquid phase is reduced, and the Si liquid phase remains in the Cu-based alloy powder, whereby the coarsening of the Di grains can be suppressed.
While the coarsening of the Si grains can be suppressed by precipitating of the Cu-Sn-P based compound in the Cu-based alloy as described above, a Cu-Sn compound or a Sn-P compound may be precipitated. However, it is proved to be ineffective to use a Cu-Sn-Bi alloy and to precipitate only a Cu-Sn compound by the same process for suppressing the coarsening of the Si grains.
In addition, concentration of Sn on a bearing surface during sliding operation can be prevented and decrease in seizure resistance can be suppressed by precipitating of the Cu-Sn-P based compound in the Cu-based alloy and preventing the Cu-based alloy from solid-soluting of Sn in a super-saturation state. If the Cu-based alloy is super-saturated with Sn, Sn is unstable and easy to migrate. Th,erefore, a Sn concentrated layer is formed on the bearing surface during sliding operation. On the contrary, when the Cu-Sn-P based compound is precipitated in the Cu-based alloy, a smaller amount of Sn is present in the Cu-based alloy in a super-saturation state. As a result, the Sn concentrated layer is not formed on the bearing surface during sliding operation, whereby a high seizure resistance can be achieved.
In the invention, a high fatigue resistance can be achieved by making a mass ratio of Di to Sn (Bi/Sn) at 1.7 to 3.4 and a mass ratio of Bi toP (Bi/P) at 500 to 2100. By controlling the mass ratio of Si to Sn and Bi to P as described above, the Cu-Sn-P based compound can be precipitated in the Cu-based alloy, and then an average grain area of the Si grains can be controlled at 60 to 350.un2. When the mass ratio of Di to Sn (Bi/Sn) is less than 1.7, an amount of Sn dissolved in the Si liquid phase is larger relative to the Si liquid phase.
Sn diffuses into Si more easily than P, and in the sintering step, Sn dissolves in the Si liquid phase in a saturated state, which makes it difficult that P diffuses in the Bi liquid phase. As a result, the Cu-Sn-P based compound is not precipitated in the Cu-based alloy, and the effect of suppressing the coarsening of the Si grains can not be obtained. On the other hand, when the mass ratio of Si to Sn (BiJSn) exceeds 3,4, an amount of Sn dissolved in the Si liquid phase is too small relative to the Di liquid phase. As a result, the Cu-Sn-P based compound is not precipitated sufficiently, and the effect of suppressing the coarsening of the Di grains can not be obtained.
When the mass ratio of Si to P (SuP) is less than 500, the P content is larger relative to Di. The Di liquid phase solutes a large amount of P in the sintering step, and in the S subsequent cooling step, a part of excessive P in the Di liquid phase reacts with the steel back layer to form a brittle Fe-P compound around the surface where the Cu-based alloy bonds to the steel back layer, which results in a decrease in a fatigue resistance. On the other hand, when the mass ratio of Bi to P(Bi/P) exceeds 2100, the content of P is too small relative to Di. As a result, the Cu-Sn-P based compound is not precipitated sufficiently, and the effect of suppressing the coarsening of the Si grains can not be obtained.
In the invention, the Cu-based alloy contains 6 to 12% by mass of Sn. When the content of Sn is less than 6% by mass, Sn solid-so lutes in the Cu-based alloy and no excessive Sn remain. As a result, the Cu-Sn-P based compound is not precipitated in the Cu-based alloy, and the effect of suppressing the coarsening of the Di grains can not be obtained. On the other hand, when the content of Sn exceeds 12% by mass, a large amount of liquid phase of Cu-Sn is generated in the sintering step, and the Cu-based alloy powder partly flows. As a result, the Bi liquid phase can not be suppressed from flowing out of' the Cu-based alloy powder, and the effect of suppressing the coarsening of the Di grains can not be obtained.
In the invention, the Cu-based alloy contains 0.01 to 0.05% by mass of R When the P content is less than 0.01% by mass, P solid-solutes in the Cu-based alloy and no excessive P is present. As a result, the Cu-Sn-P based compound is not precipitated sufficiently, and the effect of suppressing the coarsening of the Di grains can not be obtained. On the other hand, when the content of P exceeds 0.05% by mass, a large amount of P dissolves in the Si liquid phase in the sintering step, and in the subsequent cooling step, a part of excessive P in the Di liquid phase reacts with the steel back layer to form a brittle Fe-P compound around the surface where the Cu-based alloy bonds to the steel back layer, which results in a decrease in a fatigue resistance.
In the invention, a high fatigue. resistance can be obtained by controlling the average area of the Di grains dispersed in the Cu-based alloy layer to be 60 to 350.Lm2. It is noted that the average grain area of Di is an average value of areas of the Bi grains in a cross section in a direction parallel to the thickness direction of the Cu-based alloy layer. Di has a remarkably lower strength in comparison with the Cu-based alloy, and therefore, fatigue cracking is likely to occur from the Si grains. When the average area of the Bi grains is greater than 350 m2, cracks generate in the coarsened Di grains, which leads to a significant decrease in the fatigue resistance.
In an embodiment, a higher seizure resistance can be obtained by making the mass ratio of Bi to Sn (Bi/Sn) to be 2.1 to 3.1 and the Sn content to be 6.8 to 9% by mass. This is assumed to be based on the following mechanism. A Cu-Sn compound and a Sn-P compound are precipitated in addition to the Cu-Sn-P based compound in the Cu-based alloy.
Since the compounds are harder in comparison with the Cu-based alloy, the Cu-based alloy becomes too hard when the compounds are precipitated in large amounts. On the other hand, when these compounds are precipitated in small amounts, Sn solid-sotutes in the Cu-based alloy in a super-saturation state. As a result, a Sn concentrated layer is formed on the bearing surface during sliding operation, and the concentrated portion becomes hardened. Therefore, conformability of the bearing surface during sliding operation is impaired, and a seizure resistance decreases.
As described above, when the mass ratio of Bi to Sn (Bi/Sn) becomes larger, the amount of the precipitated Cu-Sn-P based compound becomes smaller. This facilitates formation of the Sn concentrated layer on the bearing surface during sliding operation and the concentrated portion is liable to be hardened. On the other hand, when the mass ratio of Bi to Sn (Bi/Sn) becomes smaller, an amount of the precipitated Cu-Sn-P based compound becomes larger. However, at the same time, amounts of the precipitated Cu-Sn compound and Sn-P compound become larger, and thus the Cu-based alloy is liable to be hardened. Under such circumstances, by setting the mass ratio of Bi to Sn (Bi/Sn) to be 2.1 to 3.1, Sn does not solid-solute in the Cu-based alloy in a super-saturation state, which makes it difficult to form the Sn concentrated layer on the bearing surface during sliding operation. In addition, since the amounts of the precipitated Cu-Sn compound and Sn-P compound in the Cu-based alloy are small, the Cu-based alloy is hard to be hardened anid a higher seizure resistance can be achieved.
When the mass ratio of Bi to Sn(Bi/Sn) is 2.1 to 3.1, not only the amount of the precipitated Cu-Sn-P based compound but also the amount of the precipitated Cu-Sn compound increase as the Sn content increases. Highest seizure resistance can be achieved by making the Sn content of to be not more than 9°/o by mass. On the other hand, while the Sn content is preferred to be smaller, when the Sn content is less than 6.8% by mass, the amount of the precipitated Cu-Sn-P based compound is too small, which leads to a decrease in the seizure resistance.
In a further embodiment, the Cu-based alloy layer may further contain a total amount of 0.1 to 10% by mass of at least one or more selected from Ni, Fe, and Ag in order to strengthen the Cu-based alloy layer. When the total amount is less than 0.1 % by mass, the Cu-based alloy layer is not strengthened sufficiently. On the other hand, when the total amount of these exceeds 10% by mass) the Cu-based alloy layer becomes fragile and a fatigue resistance decreases.
In other embodiment, the Cu-based alloy layer may further contain 0.1 to 10% by mass of an inorganic compound in order to strengthen the Cu-based alloy layer. The inorganic compound may include a carbide, a nitride, a suicide, an oxide, and the like. Preferably, an inorganic compound may have an average grain size of I to 10 kim. When the content of the inorganic compound is less than 0.1% by mass, the Cu-based alloy layer is not strengthened sufficiently. On thc other hand, when the content of the inorganic compound exceeds 10% by mass) the inorganic compound grains aggregate in the Cu-based alloy layer, which leads to a decrease in a strength.
Brief description of the drawings
Fig. I is a schematic cross sectional view illustrating a structure of a copper based sliding material including a Cu-Sn-P-li based layer; Figs. 2A to 2D are diagrams for explaining behavior of Bi in a process of producing the Cu-Sn-P-Bi based alloy layer, respectively in a spreading step (Fig. 2A), in a sintering step (Fig. 2B), in a cooling step (Fig. 2C), and in a state after sintering (Fig. 2D); Fig. 3 is a schematic cross sectional view illustrating a structure of a copper based sliding material including a conventional Cu-Bi based Cu-based alloy layer; and Figs. 4A to 4D are diagrams for explaining behavior of Bi in a process of producing the conventional Cu-Bi based Cu-based alloy layer, respectively in a spreading step (Fig. 4A), in a sintering step (Fig. 48), in a cooling step (Fig. 4C), and in a state after sintering (Fig. 4D).
Detailed description of the invention
Measurement of the average area of Bi grains and a fatigue test of a bearing were conducted for Examples 1 to 17 using a Cu-based alloy containing Bi according to embodiments of the invention and Comparative Examples 21 to 33. ln addition, a seizure test of a bearing was conducted for Examples 1 to 17 and Comparative Example 21. Table I shows Compositions (% by mass), mass ratios of Ii to Sn (Bi/Sn), and mass ratios of Si to P (Bi/P) of Examples I to 17 and Comparative Examples 21 to 33. Examples 1 to 17 were produced as follows. A Cu-based alloy powder having the composition shown in Table 1 was produced by an atomizing process. The powder was spread on a steel strip, and sintered and rolled repeatedly to producing a sliding material. It is noted that the powder was sintered at 830°C, and then cooled from 83 0°C to 450°C in 7 minutes, so that a Cu-Sn-P compound was precipitated in the Cu-based alloy. The sliding material was then formed into a semi-cylindrical shape, thus producing a sliding bearing.
[Table 1]
Average Fatigue Seizure Si/Sn Si/P grain area of Composition (% by moss) . . . resistance resistance (mass ratio) (mass ratio) Si grains (MV) (MPa) ____________________________ __________ _________ (pin) ________ ________ Cu-7.8Sn-2OBi-0.O iSP 2.56 1300 1 18 70 75 2 Cu-6.2Sn-21B1-0.016P 3.39 1300 248 60 65 3 Cu-)1.SSn-205i-0OISP 1.74 1300 266 60 65 4 Cu-8Sn-218i-0.OIP 2.63 2100 301 55 75 Cu-7.8Sn-20131-0,04P 2.56 500 61 65 75 6 Cu-11.SSn-30B1-0.023P 2.61 1300 186 60 65 7 Cu6Sn-1113i-0,0tP 1.83 1100 164 65 60 8 Cu-128n-308i-0.023P 2.50 1300 159 65 65 0.
9 Cu-6Sn-1551-0,011P 250 1400 131 65 70 x Cu-) ).55n-30131-0,05P 2.61 600 98 63 60 11 Cu-6Sn-1381-0.OIP 2.17 1300 188 63 65 12 Cu-6.2Sn-21131-0.O1P 3.39 2100 346 55 60 13 Cu-6.SSn-2I131-0.016P 3.09 (300 201 60 75 14 Cu-9Sn-19B1-0.OISP 2.11 1300 194 60 75 Cu-9Sn-23B1-0.018P 2.56 (300 161 65 75 16 Cu.78Sn-2013i-0.OISP-7N1-0.SFe-2Ag 2.56 1300 138 75 75 17 Cu-7.SSn-205i-0,015P-2Mo2C 2.56 --1300 125 75 2) Cu-7,8Sn-20Si0.015P 2.56 1300 525 40 50 22 Cu-7.8Sn-205i 2.56 -539 40 23 Cu-7.SSn-2031 2.56 -141 45 24 -__Cu-7.85n-2OBi 2.56 492 45__-_______ !?L 1300 512 40- -Cu-lOSn-15131-0.012P --1.50 1300 453 45 27 --Cu-7.8Sn-2051-0.05P 2.36 400 _ -_________ 28 -Cu-8.SSn-2251-0.O1P 29__---. 2200 ----_______ L> 29 Cu-125n-3581-0.026P 2.92 1300 234 -45 Cu-l3Sn-2551-0,03P 1.92 800 477 45 31 -Cu-SSn-ISBi-0.03P 3.00 500 504 --40 -_______ 32 Cu-9Sn-2001-0.06P 222 300 56 40 -33 Cu-9Sn-20f3-0.005P --2.22 4000 -. 5(6 --40 A Cu-based alloy of Comparative Example 21 is that disclosed in US200310068106A1 and JP-A-2010-535287, and a sliding bearing having the composition shown in Table I was produced. The process differed from the process of Examples 1-17 in that the cooling step after sintering was carried out so that the temperature was decreased from 830°C to 450°C in 2 minutes, whereby Sn and P solid-solute in the Cu-based alloy in super-saturation states and the Cu-Sn-P based compound was not precipitated. A Cu-based alloy in Comparative Example 22 is that disclosed in JP Patent No. 3421724. A sliding bearing having the composition shown in Table I was produced by the same process as that of Examples 1-17.
Cu-based alloys in Comparative Examples 23 and 24 are those disclosed itt JP-A-04-28836 and JP-A-05-263 166. A Cu-based alloy powder having the composition shown in Table I was produced by a mechanical alloying method. The powder was spread on a steel strip, and sintering and rolling were carried out repeatedly, thus producing a sliding material. The sintering was carried out, respectively, at 700°C in Comparative Example 23, and at 830°C in Comparative Example 24. The sliding material was then formed into a semi-cylindrical shape, thus producing a sliding bearing. Sliding bearings of Comparative Examples 25 to 33 have the compositions shown in Table I and were produced by the same process as that of Examples 1-17.
For the produced sliding bearing, an image of about the middle of a Cu-based alloy layer in a cross section in a direction parallel to the thickness direction of the Cu-based alloy layer was taken at 200-fold magnification (observation view has a rectangular area defined by a length in the thickness direction of the Cu-based alloy layer of 200 pm and a length in a direction perpendicular to the thickness direction of the Cu-based alloy layer of 300 m) by an electronic microscope. The image was processed by a general image analysis technique (analysis soft: Image-Pro Plus (Version 4.5); manufactured by Planetron, Inc.), whereby areas of 131 grains were measured and an average value thereof was calculated. The obtained value is regarded as the average grain area of the Bi grains, and the measured results are shown in Table 1. in addition, a general TEM analysis confirmed that the Cu-Sn-P based compound was dispersed in the Cu-based alloy layer of Examples I to 17.
The test conditions in the fatigue test of the bearing are shown in Table 2. In Examples Ito 17 and Comparative Examples 21 to 33, the fatigue test was carried out under the test conditions shown in Table 2 using a bearing testing machine. In addition, for Examples 1 to 17 and Comparative Example 21, the seizure test of the bearing was carried out under the test conditions shown in Table 3 using a bearing testing machine. The test results are shown in Table 1. In Table 1, fatigue resistance means a critical stress, below which fatigue does not occur in a sample, and seizure resistance means a critical stress below which seizure does not occur in a sample.
[Table 2]
Item Condition Loading method Dynamic load Test time 30 hr Sliding velocity 20 rn/mm -Lubricating oil SAE#30 Lubricating temperature 130°C Material of shaft Hardened S55C Roughness of shaft Rz 1.0 jm or lower
[Table 3]
Item Condition Load Cumulative load 5 MPaIIO minutes Loading method Static load Sliding velocity 15 rn/mm Lubricating oil SAE#30 Lubricating temperature 130°C Material of shaft Hardened 555C Roughness of shaft Rz 1.0 çzm or lower Each Example I to 17 has higher fatigue resistance than those in Comparative Examples 2! to 33. ExampLes Ito 17 have a mass ratio of 131 to Sn (Bi(Sn) oft.? to 3.4 and a mass ratio of Bi to P (Bi/P) of 500 to 2100, whereby a Cu-Sn-P based compound can be precipitated in the Cu-based alloy in the cooling step after sintering as described above, As a result, a difference in a thermal shrinkage rate between the Cu-based alloy of the Cu-based alloy powder and a 131 liquid phase is reduced, and the Bi liquid phase remains in the Cu-based alloy powder, whereby coarsening of the Bi grains can be suppressed and a fatigue resistance of the Cu-based alloy layer can be improved. I2-
Each Example 1 to 17 has higher seizure resistance in comparison with Comparative Example 21. Examples 1, 4, 5, and 13 to 17 have especially higher seizure resistance. Examples 1, 4,5, and 13 to 17 have a mass ratio of Bi to Sn (l3iJSn) of 2.1 to 3.1 and a Sn content is 6.8 to 9% by mass, whereby Sn does not solid-solute in the Cu-based alloy in a super-saturation state, which makes it difficult to form a Sn concentrated layer on a bearing surface during sliding operation as described above. In addition, an amounts of a Cu-Sn compound and a precipitated Sn-P compound in the Cu-based alloy are small, and therefore, the Cu-based allay is hard to be hardened and the seizure resistance of the Cu-based alloy layer can be improved.
In Example 16, the Cu-based alloy contains Ni, Fe, and Ag. In Example 17, the Cu-based alloy contains an inorganic compound (Mo2C in this example). In these Examples, a coarsening of the Bi grains can be suppressed and a fatigue resistance of the Cu-based allay layer can be improved, as in Examples I to 15. In addition, the Cu-based alloy is hard to be hardened and a seizure resistance of the Cu-based alloy layer can be improved.
Comparative Example 21 has a larger average grain area of Bi grains and a fatigue resistance and a seizure resistance are inferior in comparison with Example I, Comparative Example 21 has a same composition of the Cu alloy as that in Example 1, However, a cooling rate in the cooling step is larger than that in Example 1. Sri and P solid-solute in the Cu-based alloy in super-saturation states, and therefore, a Cu-Sn-P based compound is not precipitated. As a result, difference in the thermal shrinkage rate between the Cu-based alloy and Di is not reduced, and a Di melt flows out into spaces between the Cu-based alloy powders, which leads to coarsening of the Di grains and further leads to a decrease in fatigue resistance. In addition, a Sn concentrated layer is formed on a bearing surface during sliding operation and concentrated portion is hardened, which leads to a decrease in the seizure resistance.
Comparative Example 22 has a larger average grain area of Di grains and a fatigue resistance is inferior in comparison with Example I, Comparative Example 22 does not contain P, and therefore, a Cu-Sn-P based compound is not precipitated but a Cu-Sn compound is precipitated. As a result, a difference in the thermal shrinkage rate between the Cu-based alloy and Di is not reduced, and a Di melt flows out into spaces between the Cu-based alloy powders, which leads to coarsening of Di grains and further leads to a decrease in a fatigue resistance.
Comparative Example 23 has an average grain area of Di grains as small as Example 1. However, a fatigue resistance is inferior in comparison with Example 1. This is because the sintering temperature was lower that is at 700°C, and a bonding strength of the Cu- -13-based alloy layer to a steel strip was not sufficient. Comparative Example 24 has a larger average grain area of Hi grains and a fatigue resistance is inferior in comparison with Example 1.
This is because the sintering temperature was as high as 830°C, which led to excessive sintering of the Cu-based alloy powders, and an effect of a mechanical alloying powder that fine Bi grains can be produced was impaired.
Comparative Example 25 has a larger mass ratio of Bi to Sn (B i/Sn) in comparison with Examples. That is, a Sn content is small relative to Bi, and a Cu-Sn-P based compound is not precipitated sufficiently, which results in a large average grain area of Hi grains and a fatigue resistance decreases. Comparative Example 26 has a smaller mass ratio of Bi to Sn (BiISn) in comparison with Examples. That is, a Sn content is large relative to a Bi content, and only Sn dissolves in a Bi liquid phase in a saturated state in the sintering step. This makes it difficult that P diffuses into the Hi liquid phase, and therefore, a Cu-Sn-P based compound is not precipitated. As a result, an average grain area of Di grains is large and a fatigue resistance decreases.
Comparative Example 27 has a smaller mass ratio of Hi to P (BiIP) in comparison with Examples. That is, a P content of is large relative to a Bi content, and a Hi liquid phase contains an excessive amount of P in the sintering step. Therefore, a part of excessive P in the Hi liquid phase reacts with a steel back layer to form a brittle Fe-P compound in the cooling step.
As a result, a fatigue resistance decreases, while an average grain area of Bi grains is small.
Comparative Example 28 has a larger mass ratio of Hi toP (Bi/P) in comparison with Examples.
That is, a P content is small relative to a Di content, which leads to an extremely small amount of Cu-Sn-P based compound to be precipitated. As a result, an average grain area of Hi grains is large and a fatigue resistance decreases.
Comparative Example 29 has a larger Hi content in comparison with Examples.
Since Di has a remarkably lower strength in comparison with the Cu-based alloy, a fatigue resistance decreases, while an average grain area of Hi grains is small.
Comparative Example 30 has a larger Sn content in comparison with Examples.
A large amount of Cu-Sn liquid phase is generated in the sintering step, and therefoTe, a surface of the Cu-based alloy powder partly flows and a Hi liquid phase flows out from the Cu-based alloy powder. As a result, an average grain area of Hi grains is large and a fatigue resistance decreases. Comparative Example 31 has a smaller Sn content in comparison with Examples.
All of Sn is dissolved in the Cu-based alloy, and therefore, a Cu-Sn-P based compound is not precipitated. As a result, an average grain area of Hi grains is large and a fatigue resistance decreases.
Comparative Example 32 has a larger P content in comparison with Examples.
A Bi liquid phase contains an excessive amount of P in the sintering step, and therefore, excessive P in the Bi liquid phase forms not only a Cu-Sn-P based compound but also a brittle Fe-P compound with a steel back layer in the cooling step, As a result, a fatigue resistance decreases, while an average grain area of Bi grains is small. Comparative Example 33 has a smaller P content in comparison with Examples. An amount of a precipitated Cu-Sn-P based compound is not sufficient, and therefore, an average grain area of Si grains is large and a fatigue resistance decreases.
The copper-based sliding material according to the invention can be utilized as a material for sliding bearings in internal combustion engines and sliding bearings in various types of industrial machinery. Also, the copper-based sliding material can be utilized as a multi layer bearing composed of a Cu-based alloy layer and an overlay layer formed thereon. -15-
Claims (3)
- C (aims 1. A copper-based sliding material comprising a steel back layer (1) and a Cu-based alloy layer (2), the Cu-based alloy layer (2) consisting of, by mass percent 6 to 12% of Sn, 11 to3O%ofBi, 0.0! to 0.05% of P, optionally a total amount of 0.1 to 10% of at least one selected from the group consisting of Ni, Fe and Ag, optionally a total amount of 0.1 to 10% of at least one inorganic compound, and the balance being Cu and inevitable impurities, wherein a mass ratio of 131 to Sn (131/Sn) is 1.7 to 3.4, and a mass ratio of 131 to P (13i/P) is 500 to 2100, and wherein a Cu-Sn-P based compound (7) is dispersed in the Cu-based alloy layer (2) and Bi grains are dispersed in the Cu-based alloy layer (2) so that an average grain area of the 131 grains is 60 to 350 j.tm2 when observed in a cross section parallel to a thickness direction of the Cu-based alloy layer (2).
- 2. The copper-based sliding material according to claim 1, wherein the mass ratio of Ri to Sn (Ri/Sn) is 21 to 3,1 and the Cu-based alloy layer (2) contains 6.8 to 9% of Sn by mass.
- 3. The copper-based sliding material as hereinbefore described with reference to any of Examples I to 17 of the specific embodiments.Amendment to the claims have been filed as foHows Claims 1, A sliding bearing comprising a steel back layer (1) and a Cu-based alloy layer (2), the Cu-based alloy layer (2) being a sliding layer and consisting of, by mass percent 6to 12% of Sn, 11 to 30% of Di, 0.01 to 0.05% of P optionally a total amount of 0.1. to 10% of at least one selected from the group consisting of Ni, Fe and Ag, optionally a total amount of 0.1 to 10% of at least one inorganic compound, and the balance being Cu and inevitable impurities, wherein a mass ratio of Di to Sn(BiISn) is 1.7 to 3.4, ánda mass ratio of Bi toP (Bi/P) is 500 to 2100, and wherein a Cu-Sn-P based compound (7) is dispersed in the Cu-based alloy layer (2) and Bi grains are dispersed in the Cu-based alloy layer (2) so that an average grain area of the Bi grains is 60 to 350 p.m2 when observed in a cross section parallel to a thickness direction of the Cu-based alloy layer (2).2. The copper-based sliding material according to claim 1, wherein the mass ratio of Bi to Sn (BitSn) is 2.1 to 3.1 and the Cu-based alloy layer (2) contains 6.8 to 9% of Sn by mass.3. The copper-based sliding material as hereinbefore described with reference to any of Examples 1 to 17 of the specific embodiments. Se a * CS * *SS*55*55 * S * S * SS*S 5*5 * * SS* *. S *5* S *5 S * S S * S.
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| JP2011074248A JP5377557B2 (en) | 2011-03-30 | 2011-03-30 | Copper-based sliding material |
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| GB2489601A true GB2489601A (en) | 2012-10-03 |
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| JP (1) | JP5377557B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3521464A4 (en) * | 2016-09-30 | 2020-05-13 | Daido Metal Company Ltd. | Slide material and method for manufacturing same, and slide member |
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| JP5403636B2 (en) * | 2011-08-22 | 2014-01-29 | 大同メタル工業株式会社 | Copper-based sliding material |
| DE102016208485A1 (en) * | 2016-05-18 | 2017-11-23 | Federal-Mogul Wiesbaden Gmbh | Process for the production of sliding bearing composite materials, sliding bearing composite material and sliding element made of such sliding bearing composite materials |
| JP6752672B2 (en) * | 2016-09-30 | 2020-09-09 | 大同メタル工業株式会社 | Sliding member and its manufacturing method |
| JP6503393B2 (en) * | 2017-03-08 | 2019-04-17 | 大同メタル工業株式会社 | Sliding material, method of manufacturing the same, sliding member and bearing device |
| JP7111484B2 (en) * | 2018-03-27 | 2022-08-02 | 大同メタル工業株式会社 | sliding member |
| JP6940801B1 (en) * | 2020-12-25 | 2021-09-29 | 千住金属工業株式会社 | Sliding member, bearing, manufacturing method of sliding member, manufacturing method of bearing |
| JP7503089B2 (en) | 2022-03-30 | 2024-06-19 | 大同メタル工業株式会社 | Slide member and method for manufacturing slide member |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030008169A1 (en) * | 2001-03-23 | 2003-01-09 | Kenji Sakai | Composite sliding material |
| US20030064239A1 (en) * | 2001-12-27 | 2003-04-03 | Daido Metal Company Ltd. | Copper-based, sintered sliding material and method of producing same |
| US20080166578A1 (en) * | 2007-01-05 | 2008-07-10 | Federal-Mogul World Wide, Inc. | Wear Resistant Lead Free Alloy Bushing and Method of Making |
| US20100266444A1 (en) * | 2006-08-05 | 2010-10-21 | Taiho Kogyo Co., Ltd. | Pb-FREE COPPER ALLOY SLIDING MATERIAL |
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| JP2918292B2 (en) * | 1990-05-25 | 1999-07-12 | 大豊工業株式会社 | Sliding material |
| JP3195042B2 (en) * | 1992-03-19 | 2001-08-06 | 大豊工業株式会社 | Manufacturing method of plain bearing alloy |
| JP3421724B2 (en) * | 1999-09-13 | 2003-06-30 | 大同メタル工業株式会社 | Copper-based sliding material |
| EP1434665B1 (en) * | 2001-10-08 | 2008-09-10 | Federal-Mogul Corporation | Lead-free bearing |
| CN102728839B (en) * | 2007-05-15 | 2014-09-17 | 大丰工业株式会社 | Method of manufacturing Pb-free copper-alloy sliding material |
| WO2010030031A1 (en) * | 2008-09-10 | 2010-03-18 | 大豊工業株式会社 | SLIDING COMPONENT CONSISTING OF Pb-FREE Cu-Bi TYPE SINTERED MATERIAL |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030008169A1 (en) * | 2001-03-23 | 2003-01-09 | Kenji Sakai | Composite sliding material |
| US20030064239A1 (en) * | 2001-12-27 | 2003-04-03 | Daido Metal Company Ltd. | Copper-based, sintered sliding material and method of producing same |
| US20100266444A1 (en) * | 2006-08-05 | 2010-10-21 | Taiho Kogyo Co., Ltd. | Pb-FREE COPPER ALLOY SLIDING MATERIAL |
| US20080166578A1 (en) * | 2007-01-05 | 2008-07-10 | Federal-Mogul World Wide, Inc. | Wear Resistant Lead Free Alloy Bushing and Method of Making |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3521464A4 (en) * | 2016-09-30 | 2020-05-13 | Daido Metal Company Ltd. | Slide material and method for manufacturing same, and slide member |
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| GB201205639D0 (en) | 2012-05-16 |
| DE102012204967A1 (en) | 2012-10-04 |
| GB2489601B (en) | 2013-03-13 |
| DE102012204967B4 (en) | 2017-08-24 |
| JP5377557B2 (en) | 2013-12-25 |
| JP2012207277A (en) | 2012-10-25 |
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