EP0747494A1 - Matériau composite à base d'aluminium, ayant une propriété de résistance à l'adhésion, et procédé pour sa production - Google Patents

Matériau composite à base d'aluminium, ayant une propriété de résistance à l'adhésion, et procédé pour sa production Download PDF

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EP0747494A1
EP0747494A1 EP96108948A EP96108948A EP0747494A1 EP 0747494 A1 EP0747494 A1 EP 0747494A1 EP 96108948 A EP96108948 A EP 96108948A EP 96108948 A EP96108948 A EP 96108948A EP 0747494 A1 EP0747494 A1 EP 0747494A1
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particles
composite material
based composite
resistance property
powder
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EP0747494B2 (fr
EP0747494B1 (fr
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Tetsuya c/o Toyota Jidosha K.K. Nukami
Tetsuya C/O Toyota Jidosha K.K. Suganuma
Yukio c/o Toyota Jidosha K.K. Okochi
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Toyota Motor Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F3/26—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent

Definitions

  • the present invention relates to an Al (aluminum)-based composite material having adhesion resistance property and a process for producing the same.
  • the present invention can be applied to an Al-based member which includes a reinforced portion formed by the Al-based composite material at a part thereof at least.
  • the present invention can be applied to, for example, a sliding material, at the concrete, a ring-shaped portion having wear resistance property and being provided with a piston ring groove whose sliding conditions are severe among pistons used in an engine.
  • a publication "Iron and Steel” (Association of Iron and Steel, the September number 1989, page 376) discloses a technique in which an Al-based composite material produces a ring-shaped portion having wear resistance property which forms a ring groove which maintains a piston ring in a piston.
  • reinforced materials such as titanate whiskers; carbon fibers; alumina fibers; alumina-silica fibers; NiAl 3 particles are used, and Al alloy (JIS AC8A) is impregnated in this reinforced material by high pressure casting so that the ring-shaped portion having wear resistance property is formed.
  • the ring-shaped portion having wear resistance property and which is formed by the above-mentioned Al-based composite material it is possible to reduced its weight and to improve adhesion resistance property compared with the ring-shaped portion having wear resistance property and being made of niresist cast iron.
  • the performance of engines has been advanced in recent years, it has been expected to improve adhesion resistance property more.
  • the present invention has been developed in view of the above-mentioned problems. It is a primary object of the present invention to provide an Al-based composite material in which parting property of Al matrix is improved, and also in which adhesion resistance property is improved more so that the Al-based composite material can be suitable to be used as a sliding member whose adhesion resistance property is improved and whose sliding conditions are severe. It is also an object of the present invention to provide a process for producing the above-mentioned Al-based composite material.
  • the present inventors earnestly carried out development about Al-based composite materials.
  • the present inventors found that if continuity of Al matrix is parted finely by Si particles, continuity of Al matrix is suppressed and transferring of Al components to the mating side is effectively suppressed so that adhesion resistance property in the Al-based composite materials is improved.
  • the present inventors completed the present invention.
  • an Al-based composite material having adhesion resistance property comprises:
  • the hardness of Fe alloy fine pieces is not less than Hv 250.
  • the mean particle diameter of the primary crystal Si particles falls in the range of from 3 to 10 ⁇ m (microns).
  • a process for producing an Al-based composite material having adhesion resistance property employs a powder compact which is made of the aggregate of Al powder particles and which has pores, according to a seventh aspect of the present invention comprises the steps of:
  • the mean particle diameter of the primary Si particles included in the Al matrix is not more than 20 ⁇ m (microns) and the primary Si particles are very minute; and also these Si particles are included in a large amount ranging from 20 to 36% by volume; so that the parting property of parting the continuity of Al matrix by using these Si particles is improved. Accordingly, even if the sliding condition are severe, transferring of Al components of the Al matrix to a mating side is effectively suppressed so that the adhesion resistance property thereof is improved.
  • Si particles take pavement effect on Al matrix so that the wear resistance property thereof is also secured.
  • the Si particles generally are primary crystal Si particles and eutectic Si particles which were crystallized at the time when Al-Si molten metal is solidified.
  • the first, second and third Si particles are included in the Al-based composite material so that the parting of Al matrix by using Si particles is improved more. Accordingly, transferring of Al components of the Al matrix to a mating member is effectively suppressed and adhesion resistance property thereof is improved.
  • the first Si particles whose particle diameter is minute and the second Si particles whose particle diameter is extremely minute can be supplied in crystallizing phenomenon during the atomizing of powder particles constituting the powder compact.
  • the third Si particles whose particle diameter is larger than that of the first Si particles can be supplied in crystallizing phenomenon of Al molten metal which is impregnated in the powder compact.
  • the ratio of Si particles can be changed in response to the kinds of Al-based composite materials.
  • the upper limit of the total amount of the first Si particles and the second Si particles can be set to be 35% or 30% by volume; and the lower limit of the total amount the first Si particles and the second Si particles can be set to be 23% or 27% by volume.
  • the upper limit of the third Si particles can be set to be 18% or 15% by volume and the lower limit of the third Si particles can be set to be 7% or 10% by volume.
  • Si particles but also Fe alloy micro pieces are added. Therefore, the parting of Al matrix is secured more and the adhesion resistance property is improved.
  • Si particles but also Fe alloy micro pieces can be expected to take pavement effect and to improve the wear resistance property thereof.
  • Fe alloy micro pieces they may be selected from shapes such as particles and fibers. When the Fe alloy micro pieces are in the shape of particles, the mean particle diameter may fall in the range of from 10 to 80 ⁇ m (microns).
  • Fe-Cr alloy, Fe-Mo alloy or stainless steel (SUS) may be adopted.
  • carbon as a carbide producing element may be included.
  • the fourth aspect of the present invention not only Si particles but also Fe alloy micro pieces and ceramic particles are added. Therefore, the parting of Al matrix is secured more and the adhesion resistance property is improved.
  • the hardness of Fe alloy micro pieces and ceramic particles are higher compared with that of Al matrix, so that Fe alloy micro pieces and ceramic particles can be expected to obtain pavement effect and wear resistance property thereof can be secured.
  • ceramic particles oxide, nitride or carbide may be employed.
  • the mean particle diameter of ceramic particles may fall in the range of from 1 to 80 ⁇ m (microns), especially from 3 to 50 ⁇ m (microns).
  • Fe alloy micro pieces of more than Hv250 are used so that wear resistance property thereof is advantageously secured.
  • Fe alloy micro pieces it may be selected from the group consisting of Fe alloy micro pieces whose hardness is more than Hv300, Hv 400, Hv500 Hv600 and Hv700.
  • the minute primary crystal Si particles whose mean particle diameter is in an amount of 3 to 10 ⁇ m (microns), so that the parting of Al matrix by Si particles is easily secured and adhesion resistance property thereof is improved.
  • oxide films is easy to be existed.
  • the oxide films existed on the surface of Al powder particles produce harmful effects.
  • matrix structure having no boundary or less boundary can be obtained.
  • the pressure at the time of the high pressure casting may be set from about 500 atmosphere to 1500 atmosphere. According to the process of the seventh aspect of the present invention, the Al-based composite materials in the first to sixth aspects of the present invention can be produced.
  • a large amount of minute Si particles are included so that the parting property in which Si particles part the continuity of the Al matrix is improved. Accordingly, the transferring of the Al matrix to a mating member is effectively suppressed and adhesion resistance property is improved.
  • the second aspect of the present invention a large amount of the first Si particles, second Si particles and third Si particles, all of which are minute and have different particles diameters, are included. Accordingly, the parting of Al matrix by using Si particles is improved more and therefore, adhesion resistance property thereof is improved.
  • the parting of Al matrix is secured more and the adhesion resistance property is improved.
  • the hardness of Fe alloy micro pieces are higher compared with that of the Al matrix, the wear resistance property is also secured.
  • the fourth aspect of the present invention not only Si particles but also Fe alloy micro pieces and ceramic particles are added. Therefore, the parting of Al matrix is secured more and the adhesion resistance property is improved.
  • the hardness of Fe alloy micro pieces and ceramic particles are higher compared with that of Al matrix, Fe alloy micro pieces and ceramic particles can be expected to secure wear resistance property.
  • Fe alloy micro pieces of more than Hv250 so that the above-mentioned effect is obtained and furthermore, wear resistance property thereof is advantageously secured.
  • the minute primary crystal Si particles whose mean particle diameter is in an amount of 3 to 10 ⁇ m (microns), so that the parting of Al matrix by primary crystal Si particles is easily secured and adhesion resistance property thereof is improved.
  • the oxide films are easy to be destroyed.
  • the existence of oxide films, which exist at the boundary of between the solidified portion of Al molten metal impregnated by the high pressure casting and the Al powder particles constituting the powder compact is suppressed or avoided. Therefore, Al matrix structure having no boundary or less boundaries is obtained so that not only adhesion resistance property of the Al-based composite material but also the strength thereof are improved.
  • the present invention is advantageously applied to the sliding member whose sliding conditions are severe, for example, a region for forming a piston ring (top ring) groove of a diesel engine or a gasoline engine.
  • Al-Si powder atomized powder, made by Toyo Aluminium Kabushiki Kaisha, mean particle diameter 50 ⁇ m (microns)) comprising the composition of Al-38wt%Si; and Fe-Cr powder (crushed powder, made by Fukuda Metal Corporation, mean particle diameter 60 ⁇ m (microns), including 7.4wt%C) comprising the composition of Fe-63wt%Cr are used.
  • primary crystal Si particles mean particle diameter 10 ⁇ m (microns)
  • eutectic Si particles of less than sub-micron that is, less than 1 ⁇ m (micron)
  • the mixed power in which both of powder are mixed was inserted in a cavity of a metallic die for a forming green compact.
  • the mixed powder was pressed by metallic die compressing method so that a green compact having a predetermined porosity, that is a powder compact (size: diameter 100mm, length 10mm) was produced.
  • the powder compact was pinched by a ceramic-fiber compact (made by isolite Industry Co., Ltd., Vf7%, size: 100mm x 100mm x 5mm) equipped with a weight for preventing float, and furthermore, by preheating the powder compact at 350°C for 30 minutes and it was arranged in a part of a cavity (diameter 110mm, length 200mm) of a metallic mold-die for high pressure casting.
  • a ceramic-fiber compact made by isolite Industry Co., Ltd., Vf7%, size: 100mm x 100mm x 5mm
  • Al molten metal JIS-AC8A
  • a temperature of 750°C was poured into the cavity of the metallic mold-die for high pressure casting method; the Al molten metal was impregnated in the pores at the inside of the powder compact by pressing by a plunger; that is, Al alloy was compounded by the high pressure casting so that a casting was molded.
  • the pressing pressure in the high pressure casting method falls in the range of from about 1200 to 1300 atmosphere
  • the target composition of AC8A in JIS standard is as follows: Si falls in the range of from 11 to 13wt%; Cu falls in the range of from 0.8 to 1.3wt%; and Mg falls in the range of from 0.7 to 1.3wt%.
  • Si amount of Al molten metal which was actually impregnated is 12wt%.
  • Vf(Al-Si) means % by volume in which the powder compact formed by Al-Si powder particles occupies.
  • Vf(Fe-Cr) means % by volume in which Fe-Cr particles occupy.
  • Vf(Si) means % by volume in which primary crystal Si particles and eutectic Si particles in the powder compact occupy.
  • Vf (Total) means the sum of Vf(Fe-Cr) and Vf(Si).
  • Vf (Total) means % by volume in which the sum of primary crystal Si particles and Fe-Cr particles in the powder compact occupy. Accordingly, in specimens (NO. 2, NO. 4 and the like) including no Fe-Cr particles, Vf (Total) means % by volume of Si particles when the Al-based composite material is set to be 100%.
  • Vf(MMC) means % by volume in which the sum of Si particles and Fe-Cr particles in the powder compact and Si in the AC8A alloy impregnated and solidified occupy.
  • Vf(Al-Si) meaning the ratio of the powder compact is 50% by volume
  • Vf(Si) meaning the ratio of primary crystal and eutectic Si particles is 21% by volume
  • Vf(MMC) including Si of Al molten metal impregnated is 28% by volume.
  • the platform 12 was removed in the arrow Y1 direction in the reciprocating movement; the specimen W was beaten by the nitride ring 13 at 280°C, at a bearing pressure of 0.1MPa and for ten minutes; and after beating, the adhesion area at the specimen W was measured so that the adhesion resistance property was evaluated.
  • Specimen NO. 2 (Vf(Si) : 21% by volume), specimen NO. 4 (Vf(Si) : 25% by volume) and specimen NO. 9 (Vf(Si) : 35% by volume) include no Fe-Cr particles, however, include a large amount of Si particles.
  • Si particles as mentioned above, are supplied from the atomized powder and Si particles comprises: the primary crystal Si particles whose mean particles diameter is 10 um; and the eutectic Si particles of less than submicron diameter.
  • the adhesion was "NO" for they include both of minute Si particles and Fe-Cr particles.
  • specimens NO. 3 and NO. 2 are 21% by volume in both cases.
  • specimen NO. 3 including both of Si particles and Fe-Cr particles has more improved adhesion resistance property compared with that of specimen NO. 2 including Si particles but including no Fe-Cr particles.
  • specimens NO. 4 and NO. 5 are 25% by volume in both cases.
  • specimen NO. 5 including both of Si particles and Fe-Cr particles has more improved adhesion resistance property compared with that of specimen NO. 4 including Si particles but including no Fe-Cr particles.
  • Figure 2 shows a metallographic structure.
  • AC8A molten metal was impregnated in the powder compact comprising: Al-Si powder whose composition is Al-38wt%Si; and Fe-Cr powder whose composition is Fe-63wt%Cr and they were solidified so as to get the specimen.
  • Figure 2 is the photograph in which the metallographic structure (no etch) of thus obtained specimen was observed by the electron microscope photograph (SEM) after the specimen was conducted T7 treatment. Concretely, Figure 2 shows the metallographic structure of specimen NO. 14. At the right bottom of the photograph, the reference length (10 ⁇ m (microns)) is shown.
  • the mean particle diameter of the primary crystal Si particles is not more than 10 ⁇ m (microns).
  • the hardness of Al matrix falls in the range of from about Hv110 to 150 at Al portions; and the hardness of Al matrix is about Hv200 if the Si particles are included.
  • the hardness of the primary crystal Si particles falls in the range of from Hv800 to 1000.
  • the hardness of Fe-Cr powder, in the state of the powder, is about Hv1600.
  • the mean particle diameter of the primary crystal Si particles grows so as to exceed to be 50 ⁇ m (microns) generally.
  • the solidifying speed is relatively low compared with that of the atomizing method so that, the mean particle diameter of the primary crystal Si particles at least falls in the range of from 40 to 50 ⁇ m (microns) at the minimum, and therefore, it is impossible to obtain the primary crystal Si particles whose mean particle diameter is not more than 20 ⁇ m (microns).
  • the mean particle diameter of Si particles is large so that the distance between neighboring Si particles is departed. Namely, the parting property of Al matrix by the Si particles is not sufficient so that Al components are easy to be transferred to a mating member side, and therefore, satisfactory adhesion property is not obtained.
  • the definition of the parting property will be conducted as follows. Picking up a point in Al matrix, and a plurality of Si particles which exist around that point are linked by straight lines so as to form a figure; and the longest distance in that figure is understood to be the parting property. For example, as shown in Figure 3, an attention was given to an arbitrary point M in Al matrix; six Si particles around the point M, for example, were connected by straight lines so as to be supposed to draw a figure of a polygonal shape; and then the average value of the longest distance L1 in the inside of that figure can be defined as a parting coefficient.
  • this parting coefficient can be set to be 10 ⁇ m (microns) and less.
  • the parting coefficient is generally about 30 ⁇ m (microns) at the minimum so that in this case satisfactory parting property cannot be expected.
  • the oxide films are easy to be destroyed by the pressure at the time of the high pressure casting.
  • a Second Preferred Embodiment of the present invention as in the same way as that of the First Preferred Embodiment, powder whose composition is Al-38wt%Si (made by Toyo Aluminium Kabushiki Kaisha, atomized powder, mean particle diameter is 50 ⁇ m (microns) and mean particle diameter of the primary crystal Si particles is 10 ⁇ m (microns)) was used. Then the powder compact (size: diameter 100 mm, length 10 mm) was produced by a metallic die compressing method.
  • the powder compact was pinched by a ceramic (kaowool) compact equipped with a weight for preventing float; and by preheating the powder compact at 350°C for 30 minutes, it was arranged in a cavity of a metallic mold-die.
  • a ceramic (kaowool) compact equipped with a weight for preventing float
  • Al molten metal of AC8A used in the First Preferred Embodiment, Al molten metal including more Si compared with those of AC8A, that is Al molten metal whose composition is Al-25wt%Si was used.
  • This Al molten metal (850°C) was poured into the cavity of the metallic mold-die; then this Al molten metal was impregnated and solidified in the pores of the powder compact by the high pressure casting; so that Al alloy was compounded and a casting was molded by this.
  • the pressure at the time of the high pressure casting falls in the range of from 1200 to 1300 atmosphere.
  • the Al-based composite material when the Al-based composite material was set to be 100 %, the sum volume of the first Si particles whose mean particle diameters are 10 ⁇ m (microns) and the second Si particles which are not more than submicron diameters amounted to be about 25% by volume; and the third Si particles whose mean particle diameters are 20 to 60 ⁇ m (microns) was 2 to 3% by volume.
  • a large number of pores are included in the inside of the powder compact and this specimen has the structure of three-dimensional grating. If the Al molten metal is forced to be impregnated to the above-mentioned powder compact, Al molten metal is forced to be contact with a grating surface of the three-dimensional grating structure of the powder compact. Furthermore, Al molten metal gets in contact with in the inside of the powder compact three-dimensionally so that between the powder compact and the Al molten metal, area of heat-transfer surface is increased. Accordingly, the solidifying speed of Al molten metal is increased and when the primary crystal Si particles are crystallized from the Al molten metal, it is advantageous to prevent the primary crystal Si particles from growing.
  • the mean particle diameter of the third Si particles, which are crystallized form the Al molten metal impregnated in the powder compact to be 20 to 60 ⁇ m (microns) so as to be small. Also in this sense, the parting of Al matrix by Si particles can be secured.
  • Fe-Cr powder having the composition of Fe-63wt%Cr used in the First preferred Embodiment Fe-63wt%Mo powder (made by Fukuda Metals. Ltd., crushed powder, mean particle diameter 60 ⁇ m (microns)) was used. In this case the same tendency was obtained with regard to the adhesion resistance property.
  • the hardness of Fe-Mo particles is about Hv1000, however, after high pressure casting and T7 treatment were conducted, it was found that the hardness of the Fe-Mo particles is decreased to be Hv600 to 750.
  • SKD61 powder made by Mitsubishi Steel Mfg. Co., Ltd., mean particle diameter 60 ⁇ m (microns), Hv500 to 600
  • the same type of test as that of the above-mentioned was conducted to the specimen concerning this Comparative Example. After the high pressure casting and T7 treatment were conducted to this Comparative Example, the hardness of SKD61 powder particles in the specimen was measured.
  • the hardness of Fe powder particles dispersed in the Al-based composite material in the state after treatments of high pressure casting and T7 treatment preferably amounts to HV250 and more .
  • Al-Si powder having the composition of Al-38wt%Si was used in 80% by volume ratio. Furthermore, the same type of test as that of the First Preferred Embodiment was conducted so as to evaluate adhesion resistance property, except that the Al 2 O 3 particles (made by Showa Denko K.K., mean particle diameter 10 ⁇ m (microns)) as ceramic particles were used only in 5% by volume as the substitute for Fe-Cr powder used in the First Preferred Embodiment. Also in this case, it was found that no adhesion was generated.
  • the rate of the above-mentioned ceramics particles are not limited to the above-mentioned ratios, however, depending on the kinds of the Al-based composite material, the above-mentioned ceramics particles can be properly adjusted in the range of 2 to 10% by volume.
  • the sum of Si particles, ceramics particles Fe alloy micro pieces can be adjusted in the range of from 25 to 73% by volume so as to secure adhesion resistance property.
  • the hardness of each of particles are mentioned as follows: the hardness of Al 2 O 3 particles amount to about Hv1800; the hardness of mullite particles amount to about Hv1000; the hardness of SiC particles amount to about Hv2900; the hardness of Si 3 N 4 particles amount to about Hv2300; and the hardness of TiC particles amount to about Hv1800.
  • Al-Si powder having the composition of Al-38wt%Si in which mean particle diameter varies in 3 ⁇ m, 10 ⁇ m and 15 ⁇ m. Except that Si is included only in 30% by volume, the specimen was produced under the same conditions as those of the specimen of NO. 4 in the First Preferred Embodiment; and the test was conducted so as to evaluate adhesion resistance property of that specimen. The test results are shown in Figure 4.
  • the mean particle diameter of the primary crystal Si particles When the mean particle diameter of the primary crystal Si particles is relatively large to be 25 ⁇ m (microns), the adhesion area thereof generally exceeds 25 mm 2 . Accordingly, the mean particle diameter of the primary crystal Si particles is set to be not more than 20 ⁇ m (microns), the adhesion resistance property of the Al-based composite material is improved. Based on the characteristic line X of Figure 4, when the mean particle diameter of the primary crystal Si particles is not more than 10 ⁇ m (microns), it is clear that it is preferable to improve the adhesion resistance property.
  • FIG. 5 shows an application example.
  • the present invention is applied to a piston used for a diesel engine.
  • This piston 5 comprises: a piston body 50 having a piston head 50a and a cavity 50b; a reinforced portion 51b which is connected to the piston head 50a side in the piston 50 and which is in ring shaped.
  • This reinforced portion 51 is composed of the above-mentioned Al-based composite material.
  • the Al-based composite material constituting the reinforced portion 51 is selected from the group consisting of the Al-based composite material concerning Claims 1 through 7.
  • the Al-based composite material constituting the reinforced portion 51 comprises Al matrix including the primary crystal Si particles and the eutectic Si particles whose mean particle diameter is not more than 20 ⁇ m (microns); and when the Al-based composite material constituting the reinforced portion 51 is set to be 100%, Si particles amount to 20 to 36% by volume.
  • a top ring groove 52 was formed by a cutting work method by the use of a cutting tool.
  • a top ring is provided and when a diesel engine is driven, that is, in the state of high temperature, a groove forming surface of the top ring groove 52 and the top ring slide each other.
  • adhesion resistance property at the reinforced portion 51 made of the Al-based composite material was found to be satisfactory.
  • An Al alloy piston comprises a piston body and a reinforced portion forming a piston groove.
  • the reinforced portion is composed of Al-based composite material. Namely, Al molten metal (AC8A) forming the piston body was impregnated to the powder compact which is non-sintered compact so as to be solidified so that the reinforced portion was formed.
  • the powder compact is made by compressing atomized powder having the primary crystal Si particles whose mean particle diameter is 10 ⁇ m (microns). To the powder compact Fe-Cr powder particles may be added. Accordingly, the present invention provide Al-based composite material whose adhesion resistance property is improved and the process for producing the same.

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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EP19960108948 1995-06-06 1996-06-04 Matériau composite à base d'aluminium, ayant une propriété de résistance à l'adhésion, et procédé pour sa production Expired - Lifetime EP0747494B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP13974095 1995-06-06
JP13974095A JPH08333645A (ja) 1995-06-06 1995-06-06 耐凝着性に優れたＡｌ基複合材料及びその製造方法
JP139740/95 1995-06-06

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EP0747494A1 true EP0747494A1 (fr) 1996-12-11
EP0747494B1 EP0747494B1 (fr) 2002-03-13
EP0747494B2 EP0747494B2 (fr) 2005-08-24

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WO1992007676A1 (fr) * 1990-10-31 1992-05-14 Sumitomo Electric Industries, Ltd. Poudre a base d'un alliage aluminium/silicium hypereutectique et production de cette poudre
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EP0747494B2 (fr) 2005-08-24
EP0747494B1 (fr) 2002-03-13
JPH08333645A (ja) 1996-12-17
DE69619731T3 (de) 2006-03-16
DE69619731T2 (de) 2002-08-08
DE69619731D1 (de) 2002-04-18

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