WO2010026794A1 - Materiau composite a base de magnesium dans lequel sont dispersees des particules de ti et procede de production associe - Google Patents

Materiau composite a base de magnesium dans lequel sont dispersees des particules de ti et procede de production associe Download PDF

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Publication number
WO2010026794A1
WO2010026794A1 PCT/JP2009/055027 JP2009055027W WO2010026794A1 WO 2010026794 A1 WO2010026794 A1 WO 2010026794A1 JP 2009055027 W JP2009055027 W JP 2009055027W WO 2010026794 A1 WO2010026794 A1 WO 2010026794A1
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magnesium
composite material
dispersed
titanium
particle
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PCT/JP2009/055027
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English (en)
Japanese (ja)
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勝義 近藤
金子 貫太郎
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株式会社栗本鐵工所
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Priority to EP09811323A priority Critical patent/EP2327809A1/fr
Priority to CN2009801141589A priority patent/CN102016093A/zh
Priority to US13/060,084 priority patent/US20110142710A1/en
Publication of WO2010026794A1 publication Critical patent/WO2010026794A1/fr

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/02Alloys based on magnesium with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0408Light metal alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/51Plural diverse manufacturing apparatus including means for metal shaping or assembling
    • Y10T29/5184Casting and working

Definitions

  • the present invention relates to magnesium alloys, and in particular, titanium (Ti) particle-dispersed magnesium-based composites that can be used in a wide range of fields such as home appliances, automobile parts, and aircraft parts by improving both strength and ductility. It relates to a material and a method of manufacturing the same.
  • magnesium (Mg) has the smallest specific gravity among industrial metal materials, it is expected to be used for parts and members such as motorcycles, automobiles and aircrafts, for which there is a strong need for weight reduction. However, since the strength is not sufficient as compared with conventional industrial materials such as steel materials and aluminum alloys, the use of magnesium alloys is currently limited.
  • Titanium (Ti) is considered as an effective second phase to be dispersed.
  • stiffness Mg: 45 GPa
  • Ti 105 GPa
  • hardness Mg: 35-45 Hv (Vickers hardness)
  • Ti 110-120 Hv
  • titanium particles as a dispersion reinforcing material in a magnesium base.
  • Non-Patent Document 1 As a technology relating to Ti particle-dispersed magnesium composite material that has been reported so far, for example, as Non-Patent Document 1, the Japan Institute of Metals Research Abstract (Mar. 26, 2008) p. 355, no. 464 (Kataoka, Hokusu: Influence of microstructure on mechanical properties of Ti particle-dispersed Mg-based composite material), as Non-Patent Document 2, Proceedings of the Light Metals Society of Japan (May 11, 2008) p. 13, No. 7 (Hokkaido, Kataoka, Komazu: Influence of addition of titanium particles on mechanical properties of magnesium), Non-Patent Document 3 as a summary of powder powder metallurgy lectures (June 6, 2007) p. 148, no. No.
  • Non-Patent Document 4 as powder and powder metallurgy, Vol. 55, No. 4 (2008), p. 244 (Hananami, Fujita, Motoe, Ohara, Igarashi, Kondo: Development of magnesium composite material by bulk mechanical alloying method), Non-Patent Document 5 as light metal, volume 54, 11 (2004), p. 522-526 (Sato, Watanabe, Miura, Miura: development of titanium particle-dispersed magnesium based functionally graded material by centrifugal solid phase method).
  • Non-Patent Document 1 and Non-Patent Document 2 pure titanium particles are dispersed on the surface of a pure magnesium plate and heated and pressed in a state where the pure magnesium plate is placed thereon, the titanium particles are made pure magnesium plate. It is disclosed that a Ti particle dispersed magnesium base composite material in which titanium particles are arranged in a plane direction of a plate is prepared by preparing a composite material in a sandwiched state, and further heating and pressing this composite material in layers. There is.
  • Non-Patent Document 3 and Non-Patent Document 4 after hot-extrusion processing is carried out after continuously applying strong plastic processing while mixing magnesium alloy powder and pure titanium powder and filling in a mold. It is disclosed to produce a Ti particle-dispersed magnesium based composite material.
  • the heating temperature is set to a temperature sufficiently lower than the melting point of magnesium, and the composite material is manufactured in a complete solid phase temperature range without melting.
  • the ductility break elongation
  • Non-Patent Document 5 centrifugal force is applied to a molten metal of magnesium or magnesium alloy (AZ91D) containing titanium particles present as a solid phase, and the difference is caused by the difference in centrifugal force due to the density difference between dispersed particles and molten metal.
  • a manufacturing method is described that uses compositional movement control to control compositional grading. Since the specific gravity of titanium is at least twice the specific gravity of magnesium, it is difficult to uniformly disperse titanium particles in a molten magnesium or magnesium alloy by the centrifugal solid phase method disclosed in Non-Patent Document 5 .
  • this document states that "It is difficult to disperse titanium particles by this method.” Furthermore, in this document, when the titanium particles are introduced into the melt of a magnesium alloy (AZ91D) containing aluminum and the centrifugal solid phase method is applied, the aluminum concentration is extremely high in the titanium particle aggregation portion. And, it is described that a region in which aluminum is solid-solved also exists in the outer peripheral portion of the titanium particles. The reason for this is that, in this document, "the initial melt with high aluminum concentration may have penetrated between the titanium particles by capillary action, and may have been involved in its aggregation and sintering. Thus, the AZ91D alloy containing aluminum The use of the centrifugal solid phase method was found to be problematic in view of the melt composition.
  • AZ91D magnesium alloy
  • the present invention has been made to solve the above-mentioned problems, and the object of the present invention is to achieve excellent properties by uniformly dispersing titanium particles in a magnesium base and improving the interfacial adhesion between titanium and magnesium. It is an object of the present invention to provide a Ti particle-dispersed magnesium-based composite material having a high strength.
  • the Ti particle-dispersed magnesium matrix composite material according to the present invention is obtained by uniformly dispersing titanium particles in a magnesium matrix, and titanium-aluminum is formed at the interface between titanium particles dispersed in a magnesium alloy matrix and the matrix. It is characterized by having a compound layer.
  • the Ti particle-dispersed magnesium-based composite material is obtained by subjecting a cast material obtained by solidifying a molten metal containing magnesium, aluminum and titanium particles to hot plastic working.
  • the Ti particle-dispersed magnesium-based composite material is obtained by machining a cast material obtained by solidifying a molten metal containing magnesium, aluminum and titanium particles into a powder.
  • the Ti particle-dispersed magnesium-based composite material is a powder obtained by solidifying a molten metal containing magnesium, aluminum and titanium particles into a powder by an atomizing method.
  • the Ti particle-dispersed magnesium-based composite material is a sintered and solidified body of a mixed powder of a magnesium alloy powder containing aluminum and titanium particles.
  • the Ti-particle-dispersed magnesium-based composite material may be obtained by subjecting the sintered and solidified body to hot plastic working.
  • the method for producing a Ti particle-dispersed magnesium-based composite material comprises the steps of: injecting titanium particles into a melt containing magnesium and aluminum; and uniformly dispersing titanium particles in the melt Stirring the molten metal, and solidifying the molten metal to obtain a composite material having a titanium-aluminum compound layer at an interface between a magnesium base and titanium particles dispersed in the base.
  • the step of obtaining the composite material includes solidifying the molten metal to obtain a cast material having a titanium-aluminum compound layer at an interface between a magnesium base and titanium particles dispersed in the base. Applying hot plastic working to the cast material.
  • the step of obtaining the composite material comprises solidifying the molten metal to obtain a cast material having a titanium-aluminum compound layer at an interface between a magnesium base and titanium particles dispersed in the base. And machining the cast material into a powder form.
  • the step of obtaining the composite material includes solidifying the molten metal into a powder by atomization.
  • the method for producing a Ti particle-dispersed magnesium-based composite material comprises the steps of mixing a magnesium alloy powder containing aluminum and titanium particles, and using the mixed powder as the liquid phase generation temperature of the magnesium alloy powder. And holding at a high temperature to sinter and solidify, forming a titanium-aluminum compound layer at the interface between the titanium particles and the base of magnesium.
  • the manufacturing method according to one embodiment further includes the step of subjecting the sintered body to hot plastic working.
  • the inventors of the present application have made use of the diffusion phenomenon of aluminum (Al) contained in a Mg alloy in order to develop a titanium particle-dispersed magnesium-based composite material capable of improving the interfacial bonding strength between titanium and magnesium.
  • Al aluminum
  • FIG. 1 A film having a thickness of about 2 ⁇ m is formed on the Ti plate side from the bonding interface, and the film has no voids in either of the AZ80 magnesium alloy and the pure Ti plate and has good adhesion.
  • FIG. 1 A film having a thickness of about 2 ⁇ m is formed on the Ti plate side from the bonding interface, and the film has no voids in either of the AZ80 magnesium alloy and the pure Ti plate and has good adhesion.
  • the above-mentioned film having a thickness of about 2 ⁇ m is a layer which is made of a Ti—Al component and which is formed by the reaction of an Al component contained in AZ80 with a Ti plate. By forming such a reaction layer, it is possible to obtain a good adhesion interface having a strong bonding force with both the magnesium alloy side and the Ti particle side.
  • the adhesion between Mg and Ti is not sufficient because heating and sintering are performed at a solid phase temperature below the melting point of Mg, and as a result, the strength and ductility in the composite material It is thought that no improvement was obtained.
  • a composite material in which titanium particles are uniformly dispersed in a magnesium base can be manufactured by a conventional casting method, die casting method or the like.
  • the cast materials can be machined such as cutting and crushing to form powders.
  • titanium particles are uniformly dispersed in the matrix of magnesium.
  • a magnesium-based composite powder in which titanium particles are uniformly dispersed in a magnesium base can also be obtained by solidifying a melt of a Mg—Al alloy in which titanium particles are uniformly dispersed by an atomizing method.
  • the atomizing method is a method of producing powder by injecting high pressure water or high pressure gas to a molten metal flow (spraying method). Also in this case, titanium particles are uniformly dispersed inside the obtained powder, and a Ti—Al based compound layer is formed at the interface between the Ti particles and the magnesium alloy base, and has good interfacial bonding strength. .
  • a magnesium base composite material is obtained by casting method or die casting method, or titanium particles are made uniform.
  • the titanium particles and the magnesium in the base have a void due to the excellent wettability and the high reactivity between Al and Ti. Not bond well with good bonding interface.
  • a Ti particle-dispersed magnesium-based composite material produced by casting or die casting After heating a Ti particle-dispersed magnesium-based composite material produced by casting or die casting to a predetermined temperature, the material is subjected to hot plastic working such as hot extrusion, hot rolling, forging, etc. Thus, the grains of the base are refined and the strength of the composite material is further improved.
  • Ti particle dispersed magnesium base composite powder manufactured by machining process such as cutting from cast material, or Ti particle dispersed magnesium base composite powder obtained by injecting high pressure water or high pressure gas to molten metal flow is compacted and solidified. Powdered compacts and sintered / solidified bodies are prepared, and if necessary, the composite powders are joined together metallurgically by subjecting them to hot plastic working such as hot extrusion, hot rolling, forging etc. Alternatively, it is possible to create a sintered Ti particle-dispersed magnesium-based composite material.
  • titanium particles of an appropriate amount were charged into the molten Mg-Al alloy, but as another embodiment, it is also possible to obtain a Ti particle-dispersed magnesium based composite material by the following method is there.
  • a magnesium alloy powder containing aluminum and titanium particles are mixed, and the mixed powder is held at a predetermined temperature to sinter and solidify.
  • the important thing here is to keep the mixed powder at a temperature higher than the liquid phase generation temperature of the magnesium alloy powder.
  • the magnesium and titanium particles constituting the base intervene the titanium-aluminum compound layer at the interface, and good wettability and It is strongly bonded with excellent interfacial bonding strength.
  • the strength of the composite material is further improved by subjecting the sintered and solidified body to hot plastic working.
  • the titanium-aluminum compound layer formed at the interface between magnesium and titanium particles constituting the base body may completely surround the titanium particles, or the surface of the titanium particles It may be partially covered.
  • AZ61 (Mg-5.9% Al-1.1% Zn) magnesium alloy block and titanium powder with an average particle size of 29.8 ⁇ m as starting materials, and heat the magnesium alloy block to 700 ° C in a carbon crucible
  • 5 mass% of the above-mentioned titanium particles were added in the total weight ratio. Thereafter, in order to prevent segregation of titanium particles and settling to the bottom, the molten metal was sufficiently uniformly stirred for 30 minutes, and then the molten material was cast into a water-cooled mold to produce a cast material.
  • the uniform stirring treatment is performed for 30 minutes, the diffraction peak of the Al 3 Ti intermetallic compound is detected, but the peak of the above compound is not detected in the stirring treatment material for 10 minutes. That is, when the stirring time is not sufficient, the diffusion reaction between the Al component in the magnesium alloy and the titanium particles does not proceed, as a result, it becomes difficult to form the Ti—Al compound layer which is the feature of the present invention. Therefore, it is desirable that the uniform stirring process be performed for 30 minutes or more after the titanium particles are charged into the molten magnesium alloy.
  • Pure magnesium powder and Al-Mn alloy powder were prepared, and the two powders were blended so as to have an AZ61 alloy composition (Mg-6% Al-1% Zn) as a whole.
  • the mixed powder was compacted and solidified by a hydraulic press, and the molded and solidified body was charged into a carbon crucible and heated and held at 700 ° C. to produce a molten AZ61 magnesium alloy.
  • the titanium particles described above were added to the molten metal so that the total weight ratio was 10 mass%. Thereafter, in order to prevent segregation of titanium particles and settling to the bottom, the molten metal was uniformly stirred for 30 minutes, and then the molten material was cast into a water-cooled mold to produce a cast material.
  • a bulk sample of AZ91D magnesium alloy (Mg-9.1% Al-1.1% Zn-0.2% Mn) and titanium powder with an average particle diameter of 29.8 ⁇ m are prepared as starting materials, and AZ91D magnesium alloy ingot is prepared.
  • a billet for extrusion with a diameter of 45 mm is produced by machining from the above-described Ti particle-dispersed AZ91D cast billet, and the billet is heated and held at 350 ° C. for 5 minutes in an argon gas atmosphere, and hot extrusion processing immediately (extrusion ratio: 37) ) To produce a round bar extruded material with a diameter of 7 mm.
  • the tensile test piece was extract
  • the tensile strength and yield strength of the AZ91D cast billet extruded material to which 3 mass% of titanium particles are added are significantly increased as compared with the material obtained by extruding the AZ91D cast billet containing no titanium particles, and on the other hand, the elongation at break There is no major decline. Further, in the Ti particle-dispersed AZ91D composite material according to the present invention, the formation of TiAl 3 intermetallic compound is confirmed from the result of X-ray diffraction, and there is no void at the titanium particle / AZ91D base interface, and a good bonding interface is formed.
  • a Ti-Al based compound is formed on the surface of the titanium particles without aggregation / segregation of the titanium particles, The bonding strength between the titanium particles and the base is improved, and as a result, the strength of the magnesium-based composite material can be improved.
  • Ti-6Al-4V alloy powder average particle diameter: 22.8 ⁇ m
  • titanium alloy particles are aggregated and It is uniformly dispersed in the base without segregation, and the formation of a TiAl 3 intermetallic compound is confirmed at the interface between the titanium alloy powder and the AZ91D base, and there is no void at the interface, and a good bonding state Was found to have
  • the tensile strength in the case of adding 3 mass% of Ti-6Al-4V alloy powder is 414 MPa, and it is possible to confirm the increase in strength more than the composite material in which 3 mass% of pure titanium particles are added.
  • the hardness and strength of the titanium particles dispersed in the magnesium alloy base are further increased, so that the strength of the magnesium composite is further improved.
  • a bulk sample of AZ91D magnesium alloy (Mg-9.1% Al-1.1% Zn-0.2% Mn) and titanium powder with an average particle diameter of 29.8 ⁇ m are prepared as starting materials, and AZ91D magnesium alloy ingot is prepared.
  • a chip with a total length of about 1 to 4 mm is produced from this Ti particle-dispersed AZ91D cast billet by cutting, this chip is filled in a SKD11 die, and a pressing force of 600 MPa is applied by a hydraulic press to make a 45 mm diameter powder.
  • a molded billet was produced.
  • the green compact billet was heated and held at 350 ° C. for 5 minutes in an argon gas atmosphere, and immediately subjected to hot extrusion (extrusion ratio: 37) to produce a round bar extruded material with a diameter of 7 mm.
  • the tensile test piece was extract
  • an AZ91D magnesium cast billet to which titanium particles were not added was produced under the same conditions as above, and similarly, chips having a total length of about 1 to 4 mm were produced by cutting.
  • the mixed powder is compacted with a hydraulic press in the same manner as above, and passed through a 350 ° C. heating process It was extruded.
  • the tensile test was similarly performed on the obtained extruded material at normal temperature. The tensile test results are shown in Table 2.
  • the heating temperature was as low as 350 ° C.
  • the Al component contained in AZ91D did not react with the titanium particles, and as a result, no Ti—Al based compound was formed on the surface of the titanium particles.
  • a sufficiently high bonding strength can not be obtained at the interface between the titanium particles and the base material, and as a result, both the tensile strength and the yield strength decrease compared to the strength characteristics of the extruded material of only AZ91D shown in Example 3. And the elongation at break also decreased.
  • a Ti—Al based compound is formed on the surface of the titanium particles without aggregation / segregation of the titanium particles, and titanium
  • the bonding strength between the particles and the base is improved, and as a result, the strength of the magnesium-based composite material can be improved.
  • the present invention can be advantageously used as a Ti particle-dispersed magnesium-based composite material having excellent strength and a method for producing the same.

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  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Physics & Mathematics (AREA)
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Abstract

L'invention concerne un matériau composite à base de magnésium dans lequel sont dispersées des particules de Ti, comprenant une matrice de magnésium et des particules de titane dispersées de façon homogène dans cette matrice. Une couche de composé titane-aluminium est formée au niveau des interfaces entre les particules de titane dispersées dans la matrice d'alliage de magnésium et la matrice.
PCT/JP2009/055027 2008-09-03 2009-03-16 Materiau composite a base de magnesium dans lequel sont dispersees des particules de ti et procede de production associe WO2010026794A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP09811323A EP2327809A1 (fr) 2008-09-03 2009-03-16 Materiau composite a base de magnesium dans lequel sont dispersees des particules de ti et procede de production associe
CN2009801141589A CN102016093A (zh) 2008-09-03 2009-03-16 Ti粒子分散镁基复合材料及其制造方法
US13/060,084 US20110142710A1 (en) 2008-09-03 2009-03-16 Ti PARTICLE-DISPERSED MAGNESIUM-BASED COMPOSITE MATERIAL, AND MANUFACTURING METHOD THEREOF

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Application Number Priority Date Filing Date Title
JP2008226261A JP4451913B2 (ja) 2008-09-03 2008-09-03 Ti粒子分散マグネシウム基複合材料の製造方法
JP2008-226261 2008-09-03

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WO2010026794A1 true WO2010026794A1 (fr) 2010-03-11

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US (1) US20110142710A1 (fr)
EP (1) EP2327809A1 (fr)
JP (1) JP4451913B2 (fr)
KR (1) KR20100092969A (fr)
CN (1) CN102016093A (fr)
WO (1) WO2010026794A1 (fr)

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CN112775436A (zh) * 2020-12-22 2021-05-11 西安交通大学 一种促进钛合金增材制造过程生成等轴晶的制造方法

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JPH02129329A (ja) * 1988-11-08 1990-05-17 Katsuhiro Nishiyama マグネシウム―チタン系焼結合金およびその製造方法
JPH05214477A (ja) * 1992-01-31 1993-08-24 Suzuki Motor Corp 複合材料とその製造方法
JPH10102163A (ja) * 1996-09-24 1998-04-21 Hiroshima Pref Gov 金属間化合物強化マグネシウム基複合材料及びその製造方法
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