WO2007105738A1 - Matériau composite métallique amorphe, procédé de production afférent et article obtenu a partir dudit procédé - Google Patents

Matériau composite métallique amorphe, procédé de production afférent et article obtenu a partir dudit procédé Download PDF

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Publication number
WO2007105738A1
WO2007105738A1 PCT/JP2007/055003 JP2007055003W WO2007105738A1 WO 2007105738 A1 WO2007105738 A1 WO 2007105738A1 JP 2007055003 W JP2007055003 W JP 2007055003W WO 2007105738 A1 WO2007105738 A1 WO 2007105738A1
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WO
WIPO (PCT)
Prior art keywords
amorphous metal
metal composite
amorphous
base material
composite material
Prior art date
Application number
PCT/JP2007/055003
Other languages
English (en)
Japanese (ja)
Inventor
Norio Maruyama
Jin Kawakita
Sachiko Hiromoto
Akiko Yamamoto
Seiji Kuroda
Original Assignee
National Institute For Materials Science
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute For Materials Science filed Critical National Institute For Materials Science
Priority to JP2008505171A priority Critical patent/JP4900617B2/ja
Publication of WO2007105738A1 publication Critical patent/WO2007105738A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • 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
    • B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • Amorphous metal composite method for producing the same, and article thereby
  • the present invention relates to an amorphous metal composite material, a method for producing the same, and an article thereby. More specifically, a new amorphous metal useful as a material for medical articles such as bone plates for implants, sports equipment such as Gonoref club heads, and various industrial articles such as aircraft materials, automobiles, and construction.
  • the present invention relates to a composite material, a method for producing the same, and an article made thereby.
  • amorphous metals having various chemical compositions are known. These amorphous metals are known to have excellent properties such as high mechanical strength, low Young's modulus (suppleness), high corrosion resistance, high wear resistance, and high magnetic permeability. Studies on these applications are underway.
  • the conventional dispersion-type composite material has a drawback that it is very difficult to control the production method relating to the formation of the amorphous metal and the production of the composite material. There is a problem that it is difficult to manufacture a shaped article.
  • Patent Document 1 JP-A-5-70880
  • Patent Document 2 JP-A-5-70877
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-221657
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-775
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2005-126795
  • the present invention solves the conventional problems, and as a composite material integrated with a base material, material design, manufacturing method, and formation of an article having a complicated shape are easy.
  • the objective is to provide an amorphous metal composite that can control even mechanical properties such as mechanical strength and Young's modulus, a method for producing the same, and an article made thereby.
  • the present invention is characterized by the following in order to solve the above problems.
  • An amorphous metal composite characterized in that a layer of an amorphous metal is provided on the surface of a base material that has been previously adjusted to an elastic range similar to that of an amorphous metal.
  • Amorphous metal characterized in that the volume ratio of the amorphous metal laminated and integrated is 10% or more with respect to the volume of the portion covered with the amorphous metal of the base material Composite material.
  • a method for producing an amorphous metal composite characterized in that the type of amorphous metal used and the layer thickness thereof are adjusted in accordance with desired mechanical properties.
  • the amorphous metal composite of the present invention as described above, even if the base material and the amorphous metal are subjected to stress such as tension and compression, the same distortion is generated and peeling is suppressed. Therefore, the mechanical strength of the amorphous metal can be weighted to the original mechanical strength of the base material. Furthermore, by adjusting the thickness of the amorphous metal, it is possible to control mechanical properties such as mechanical strength and yang ratio of the amorphous metal composite material.
  • FIG. 1 is a schematic diagram of the HVOF thermal spraying method.
  • Fig. 2 is a schematic diagram of the improved HVOF thermal spraying method.
  • Fig. 3 is a cross-sectional photograph of a composite material laminated and integrated by the improved HVOF thermal spraying method.
  • FIG. 4 is an XRD pattern diagram in the case of an amorphous metal as a laminated material and its powder raw material.
  • FIG. 5 is a process diagram (a) to (c) before the tensile test in Example 1 and Example 2 and a schematic diagram (d) of the tensile test.
  • FIG. 6 is a graph showing the relationship between the volume ratio and the Yang ratio in the tensile test of the amorphous metal composite material in Example 1.
  • FIG. 7 shows the tensile test results of the base material itself after preliminary processing and the composite material of amorphous metal composite material (volume ratio (base material / composite material) of 0.765 in Example 2).
  • A is the load-displacement curve of the base material itself after the pre-processing
  • (b) is the load cell and strain gauge of the base material after the pre-processing.
  • C is a load-displacement curve by the load cell of the amorphous metal composite material of Example 2
  • (d) is a load cell of the amorphous metal composite material of Example 2
  • Strain-stress curve by strain gauge is the base material that is not pre-processed (stainless steel 316U has been confirmed to be the following materials.
  • FIG. 8 is a graph showing the relationship between the volume ratio and the Yang ratio in the tensile test of the amorphous metal composite material in Example 2.
  • the coating-type amorphous metal composite material of Patent Document 5 and the like is a common technical knowledge that the amorphous metal is peeled off from the base material.
  • Fig. 5 only about 50 ⁇ , more than 100 / im, is considered as the formed film, and only this level has been tried. For this reason, those skilled in the art could not expect that the laminated amorphous metal will affect the mechanical properties of the amorphous metal composite such as the mechanical strength and Young's modulus.
  • the base material of the amorphous metal composite material of the present invention for example, various metals such as stainless steel, titanium, or titanium alloys may be used. These metals may be crystalline or amorphous. Or a metal such as microcrystalline precipitation. Or oxide or non-oxide ceramics, or even plastics. Of course, FRP and FRM These composites may be used. Depending on these base materials, the composite characteristics of the laminated amorphous metal are realized as shown in Table 1 below.
  • the amorphous metal as the laminate of the present invention may have various chemical compositions known so far, such as Fe_Cr_Mo, Zr_Cu_Ni, Zr_Ni_A1, etc. Is selected in consideration of the application of the composite material of the present invention, required mechanical properties, and surface modification properties such as corrosion resistance and wear resistance. Further, these may be selected in consideration of the use of powder, plate, block, or melt as the method for stacking integration.
  • the amorphous metal that is laminated and integrated with the base material is unavoidable in the process of lamination and integration, that is, at the time of manufacture.
  • the crystal phase that precipitates is included.
  • Amorphous metal that is laminated and integrated according to the present invention is defined as including the inevitable crystal phase.
  • the feature of the laminated integration of the present invention is essentially localized alteration such as amorphization of the surface layer accompanying fabrication as in the conventional composite method, or uniform dispersion compression molding of mixed powder. Is different.
  • the laminated integration of the present invention is essentially different from conventional means for forming a sprayed coating of amorphous metal.
  • the technical idea is different from conventional film formation.
  • the means for stacking and integration may be any of various means such as thermal spraying, bonding, powder sintering, and forging on the substrate.
  • thermal spraying bonding
  • powder sintering powder sintering
  • forging on the substrate.
  • HV OF spraying improved HVOF spraying
  • atmosphere control plasma spraying atmosphere control plasma spraying
  • the thermal spraying method having such features and advantages will be further described.
  • the high-speed flame spraying (HVOF) method see, for example, Journal of Thermal Spray Technology, Vol. 8 (3), Sep. 19 99, 351-356).
  • the target powder particles are applied to the combustion jet generated by the combustion of a large amount of 'high-pressure auxiliary gas (oxygen gas) and combustible gas' liquid (hydrogen, propane, kerosene, etc.).
  • This is a process in which it is charged and heated to about 3000 ° C to about 800m / s, accelerated, and then continuously collided with the base material, mainly using plastic deformation of particles.
  • This process provides the effect of peening at low temperatures, so it has a high quality that suppresses thermal degradation such as chemical composition and phase transition, and has a high density and high adhesion. it can.
  • an improved HVOF spraying method eg, Proceedings of International Thermal Spray Conference 2005, CD-ROM, in Basel, Switzerland, May 2005. “Dense Titanium Coatings by Modified HVOF Spraying J, J. Kawakita et al.
  • the amorphous metal has a particle diameter of 25 to 63 xm.
  • the conditions shown in Table 3 below can be applied to base materials such as stainless steel 316L, carbon steel SS400, nickel-base alloy Hastelloy C296, pure titanium, and refractory ceramics.
  • FIG. 3 shows a case where an amorphous metal having a composition of Zr-12.3Cu-7.6Ni-3.5A1 is laminated and integrated on the surface of carbon steel in the present invention by an improved HVOF spraying method.
  • a cross-sectional photograph is shown. It is clear that amorphous metal is laminated on the carbon steel surface (base material). It is clearly understood.
  • the raw material powder Zr-12.3Cu-7.6Ni-3.5A1 has an amorphous metal particle size in the range of 25 to 53 / im. It is possible to apply the conditions shown in Table 4 below to metal substrates such as carbon steel S S400, stainless steel 316L, and pure titanium.
  • the control of the mechanical characteristics by the lamination integration in the present invention is made possible, for example, by adjusting the volume ratio of the amorphous metal in the entire laminated amorphous metal composite.
  • this volume ratio the force that can be achieved from the level of several percent as the control of the mechanical property is a remarkable range of 5% or more, further 10% or more, 95% or less, and further 90% or less. Is a practical guideline.
  • the control of the mechanical characteristics by the volume ratio also takes into account the corrosion resistance, wear resistance, specific gravity, etc. associated with the type and composition of the amorphous metal.
  • the composite material of the present invention taking advantage of the composite characteristics of the base material and the amorphous metal, for example, medical articles such as bone plates for implants, sports equipment such as golf club heads, Or various industrial articles, such as an aircraft material, a motor vehicle, construction, are comprised.
  • an amorphous metal composite article in which at least one of the strength and Young's modulus of the composite material is optimized is realized.
  • FIG. 4 is an XRD pattern showing that the coated amorphous metal in Example 1 is the same amorphous as the raw material powder.
  • Example 1 The relationship between the Young's modulus and the volume ratio when using an amorphous metal different from that in Example 1 was examined.
  • Example 1 using stainless steel 316L as a base material, processing was performed so that the elastic base material and amorphous metal had the same elastic range, and then by HVOF thermal spraying method, Amorphous metal with a composition of Zr_ 12.3Cu-7.6 6-3.5A1 was sprayed on the surface so as to obtain various volume fractions, laminated and integrated, and a tensile test was conducted. The relationship between rates was examined. It was confirmed by XRD that the amorphous metal coated in Example 2 was the same amorphous as the raw material powder.
  • Example 1 and Example 2 will be described in detail.
  • FIG. 5 is a process diagram (a) to (c) before the tensile test in Example 1 and Example 2 and a schematic diagram (d) of the tensile test.
  • a tensile test base material (matri X) having a shape as shown in FIG. 5 (a) was produced.
  • UTS Usertimate Tensile Strength, Ultimate Tensile Strength
  • the amorphous metal was sprayed by HVOF spraying as shown in (c), and further polished in the axial direction with emery polishing paper # 600.
  • FIG. 6 is a graph showing the relationship between the volume ratio and the Young's modulus of the amorphous metal composite material in Example 1 as determined by a tensile test.
  • the volume ratio when the volume ratio is 1, the Young's modulus of the stainless steel 316L as a base material is shown, and when the volume ratio is 0, the Young's modulus of the amorphous metal itself is shown.
  • the volume ratio was calculated by measuring the area of the vertical cross section of the amorphous metal composite with respect to the axial direction of the tensile test because the film thickness was uniformly formed by polishing. is there.
  • the Young's modulus can be controlled by the volume ratio. Furthermore, it can be seen that the relationship between volume fraction and Young's modulus is linear, and the mechanical properties can be accurately controlled.
  • Fig. 7 shows the tensile test results of the base material itself after the preliminary processing and the composite material of amorphous metal composite material (volume ratio (base material / composite material) of 0.765 in Example 2).
  • A is the load-displacement curve by the load cell of the base material itself after preliminary processing
  • B is the strain stress by the strain gauge of the base material itself after preliminary processing.
  • C is the load-displacement curve by the load cell of the amorphous metal composite material of Example 2
  • (d) is the strain-stress curve by the strain gauge of the amorphous metal composite material of Example 2. Is a line. It is confirmed that the base material (stainless steel 316L) that is not pre-processed is made of the following materials. Material: 0.2% PS (Proof Stress), 293MPa, UTS 586MPa, uniform elongation 58%, total elongation 85%, aperture 77%.
  • FIG. 8 is a graph showing the relationship between the volume ratio and the hang ratio in the tensile test of the amorphous metal composite material in Example 2.
  • the volume ratio when the volume ratio is 1, the Young's modulus of the stainless steel 316L as a base material is shown, and when the volume ratio is 0, the Young's modulus of the amorphous metal itself is shown.
  • Table 6 also summarizes the relationship between volume fraction and Young's modulus. The volume ratio was calculated by measuring the area of the vertical cross section of the amorphous metal composite as in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

L'invention concerne un matériau métallique amorphe comprenant une base et un métal amorphe superposé sur et associé à une surface de la base. Le matériau composite est obtenue par association d'une couche d'un métal amorphe à une surface d'une base qui a été traitée auparavant de manière à présenter une élasticité dans la même région que celle du métal amorphe. Le délaminage du métal amorphe peut ainsi être évité. Ainsi, la résistance mécanique due au métal amorphe peut être ajoutée à la résistance mécanique de la base. Le fait de régler l'épaisseur du métal amorphe permet de contrôler les propriétés mécaniques du matériau composite de métal amorphe, telles que la résistance et le module de Young. Le matériau composite métallique amorphe peut ensuite être obtenu par superposition de couches par pulvérisation thermique; ceci permet de réaliser facilement un article de forme complexe.
PCT/JP2007/055003 2006-03-13 2007-03-13 Matériau composite métallique amorphe, procédé de production afférent et article obtenu a partir dudit procédé WO2007105738A1 (fr)

Priority Applications (1)

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JP2008505171A JP4900617B2 (ja) 2006-03-13 2007-03-13 非晶質金属複合材とその製造方法およびそれによる物品

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JP2006-068070 2006-03-13
JP2006068070 2006-03-13

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WO2007105738A1 true WO2007105738A1 (fr) 2007-09-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180029241A1 (en) * 2016-07-29 2018-02-01 Liquidmetal Coatings, Llc Method of forming cutting tools with amorphous alloys on an edge thereof
US10144992B2 (en) 2012-12-31 2018-12-04 Byd Company Limited Amorphous alloy and method for preparing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160092357A (ko) 2015-01-27 2016-08-04 삼성전자주식회사 비정질 및 나노질화물 복합박막, 그 형성방법 및 그 복합박막이 형성된 전자기기

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2004090391A (ja) * 2002-08-30 2004-03-25 Mitsui Chemicals Inc 樹脂層が形成された非晶質合金薄帯およびその製造方法
JP2005126795A (ja) * 2003-10-27 2005-05-19 Takao Kurahashi アモルファス皮膜の形成方法
JP2006159108A (ja) * 2004-12-08 2006-06-22 Topy Ind Ltd 複合積層体、これを用いたガス分離膜ならびにその製造方法

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Publication number Priority date Publication date Assignee Title
JP4025046B2 (ja) * 1997-04-16 2007-12-19 Ｓｒｉスポーツ株式会社 ゴルフクラブヘッド
JP2001269427A (ja) * 2000-03-24 2001-10-02 Sumitomo Rubber Ind Ltd 金属バット

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004090391A (ja) * 2002-08-30 2004-03-25 Mitsui Chemicals Inc 樹脂層が形成された非晶質合金薄帯およびその製造方法
JP2005126795A (ja) * 2003-10-27 2005-05-19 Takao Kurahashi アモルファス皮膜の形成方法
JP2006159108A (ja) * 2004-12-08 2006-06-22 Topy Ind Ltd 複合積層体、これを用いたガス分離膜ならびにその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10144992B2 (en) 2012-12-31 2018-12-04 Byd Company Limited Amorphous alloy and method for preparing the same
US20180029241A1 (en) * 2016-07-29 2018-02-01 Liquidmetal Coatings, Llc Method of forming cutting tools with amorphous alloys on an edge thereof

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JPWO2007105738A1 (ja) 2009-07-30

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