WO2017171056A1 - チタン複合材およびその製造方法、ならびに、梱包体 - Google Patents

チタン複合材およびその製造方法、ならびに、梱包体 Download PDF

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WO2017171056A1
WO2017171056A1 PCT/JP2017/013754 JP2017013754W WO2017171056A1 WO 2017171056 A1 WO2017171056 A1 WO 2017171056A1 JP 2017013754 W JP2017013754 W JP 2017013754W WO 2017171056 A1 WO2017171056 A1 WO 2017171056A1
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titanium
less
inner layer
composite material
layer portion
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PCT/JP2017/013754
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English (en)
French (fr)
Japanese (ja)
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善久 白井
知之 北浦
知徳 國枝
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新日鐵住金株式会社
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Priority to JP2018509689A priority Critical patent/JP6756363B2/ja
Publication of WO2017171056A1 publication Critical patent/WO2017171056A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium

Definitions

  • the present invention relates to a titanium composite material, a manufacturing method thereof, and a package.
  • Titanium is a metal material with excellent corrosion resistance, and is used in heat exchangers using seawater, various chemical plants, and the like. Moreover, since the density is smaller than that of carbon steel and excellent in specific strength (strength per unit weight), it is often used in aircraft bodies. In addition, by using titanium material for land transportation equipment such as automobiles, the land transportation equipment itself is light and expected to improve fuel efficiency.
  • titanium materials are more complicated than steel materials and are manufactured through many processes.
  • a typical manufacturing process is illustrated below.
  • Smelting process Titanium oxide as a raw material is chlorinated to titanium tetrachloride, and then reduced with magnesium or sodium to form sponge-like (lumped) metal titanium (hereinafter referred to as “sponge titanium”).
  • Manufacturing process (2) Melting process: Titanium sponge is press-molded to form an electrode and melted in a vacuum arc melting furnace to produce an ingot.
  • Hot working process A slab or billet is heated and rolled or extruded hot to produce a plate or a round shape (hot rolled material) or billet (material such as hot extrusion or hot rolling) Steps for manufacturing bars, etc.
  • Cold working step Steps for producing thin plates, round bars, wires, etc. by further cold rolling and extruding plates and round bars.
  • Titanium material is very expensive because it is manufactured in many processes. For this reason, titanium materials are hardly applied to land transportation equipment such as automobiles. For this reason, in order to promote utilization of the titanium material, it is necessary to increase the productivity of the manufacturing process. In order to cope with this problem, efforts have been made to simplify the manufacturing process of the titanium material.
  • Patent Document 1 discloses a method for producing a titanium thin plate by forming a composition containing titanium powder, a binder, a plasticizer, and a solvent into a thin plate shape, drying, sintering, compacting, and re-sintering. . According to this method, the melting step, the forging step, the hot rolling step, and the cold rolling step can be omitted.
  • Patent Document 2 discloses a method of manufacturing a titanium alloy round bar by adding copper powder, chromium powder or iron powder to titanium alloy powder, enclosing it in a carbon steel capsule, heating and extruding it hot. It is disclosed. According to this method, since the melting step and the forging step can be omitted, the manufacturing cost can be reduced.
  • Patent Document 3 discloses a method of manufacturing a round bar by filling sponge titanium powder in a copper capsule, heating to 700 ° C. or lower, and performing a warm extrusion process. In this method, since the melting step and the forging step can be omitted, the manufacturing cost can be reduced.
  • conventionally known pack rolling is a method in which a core material such as a titanium alloy having poor workability is covered with a cover material such as inexpensive carbon steel having good workability and hot rolling is performed.
  • a core material such as a titanium alloy having poor workability
  • a cover material such as inexpensive carbon steel having good workability and hot rolling is performed.
  • the release agent is applied to the surface of the core material, at least two upper and lower surfaces thereof are covered with a cover material, or in addition to the upper and lower surfaces, four peripheral surfaces are also covered with a cover material, and a seam is welded and hermetically covered A box is manufactured, the inside of which is evacuated and sealed, and then hot rolled.
  • Patent Document 4 discloses a method for assembling a hermetically sealed box
  • Patent Document 5 discloses that a cover material is sealed (packed) at a vacuum degree of 10 ⁇ 3 torr (about 0.133 Pa) or more. Further, a method for producing a hermetically sealed box is disclosed. Further, Patent Document 6 covers carbon steel (cover material) and performs high energy density welding under a vacuum of 10 ⁇ 2 torr (about 1.33 Pa) or less. A method for producing a hermetically sealed box by sealing (packing) is disclosed.
  • the core material which is the material to be rolled
  • the core material is covered with a cover material and hot-rolled, so the surface of the core material does not come into direct contact with the cold medium (air or roll), and the temperature of the core material decreases. Therefore, even a core material with poor workability can be manufactured.
  • cover material carbon steel, etc., which is different from the core material, has good workability and is inexpensive. Since the cover material becomes unnecessary after hot rolling, a release agent is applied to the surface of the core material in order to facilitate separation from the core material.
  • Patent Document 1 an expensive titanium powder (average particle size of 4 to 200 ⁇ m) is used as a raw material, and many processes such as sintering and compaction are required. Is very expensive and has not yet promoted the use of titanium.
  • Patent Documents 4 to 6 are stripped and discarded after rolling as in pack rolling, the manufacturing cost is higher than that in a normal process, and the obtained titanium material has a high The cost remains the same.
  • an object of the present invention is to provide a titanium material such as a titanium plate or a titanium round bar at a low cost.
  • amorphous and sponge-like (lumped) sponge titanium is used as a raw material. Since sponge-like sponge titanium has been conventionally produced, it can be obtained at a relatively low cost. In addition, since titanium sponge has main impurities such as iron and chlorine removed in the smelting process, there is no problem in chemical composition even if a titanium material is directly produced from sponge titanium. Moreover, titanium materials (hereinafter referred to as “titanium scrap”) such as mill ends that cannot be manufactured can be obtained at a relatively low cost. However, since titanium scrap is indefinite, it cannot be directly processed to produce a titanium material.
  • (B) If it is a titanium package that contains a filler such as sponge titanium in a container (hereinafter referred to as “packaging material”) manufactured using a pure industrial titanium material or a titanium alloy material, Generation of surface defects such as surface cracks and shavings can be suppressed during the hot working.
  • packing material a filler such as sponge titanium in a container
  • the chemical composition of the filler the same type as that of pure titanium material, it is not necessary to peel off and discard the cover material after rolling as in conventional pack rolling. Can also be used effectively as part of a titanium composite (product).
  • (E) That is, selected from carbon, carbide, nitride, and oxide that can increase the tensile strength of titanium sponge and titanium composite material in the titanium packing material that is an expanded material of industrial pure titanium Fill and enclose one or more powders, depressurize the inside to form a titanium package, perform hot working on this titanium package, and further cold work as necessary to obtain a titanium composite.
  • the titanium package which is a collection of titanium ingots before hot working, becomes a titanium composite material (three-layer clad material) that is compressed and integrated as a whole after hot working.
  • the titanium composite is a compression-molded body of titanium containing only one or more titanium compounds selected from carbides, nitrides and oxides whose only inner layer portion can increase the tensile strength of the titanium composite.
  • the surface layer is a wrought material of industrial pure titanium or titanium alloy material, it has excellent workability and high tensile strength, and can be manufactured without the conventional melting process and forging process. Can be greatly reduced.
  • the present invention is as listed below.
  • a titanium composite material having an inner layer portion and a surface layer portion covering the inner layer portion is made of an industrial pure titanium material or a titanium alloy material having a chemical composition belonging to any one of JIS types 1 to 4,
  • one or more kinds of titanium compounds selected from carbide, nitride and oxide are dispersed in titanium, carbon around the carbide, nitrogen around the nitride, and the oxidation Oxygen around each object has a portion where each diffuses, and the area ratio has voids of more than 0% and not more than 30%. Titanium composite.
  • the inner layer portion has a total content of carbon, nitrogen and oxygen of 0.05 to 2.0% by mass, and the titanium compound is formed into a titanium material as a streak compound aggregate in which the titanium compounds are arranged in the rolling direction.
  • the chemical composition of the industrial pure titanium material is mass%, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, Balance: Ti and impurities,
  • Titanium packing material made of industrial pure titanium material or titanium alloy material belonging to any one of JIS 1-4, one or more selected from sponge titanium, titanium briquette and titanium scrap, and carbon, carbide, nitriding Filled with one or more powders selected from products and oxides, sealed, and reduced in pressure to 10 Pa or less inside to form a titanium package, and hot processing the titanium package, A method for producing a titanium composite material.
  • a packing body comprising a titanium packing material made of an industrial pure titanium material or a titanium alloy material belonging to any one of JIS 1-4, and a filler filled in the titanium packing material,
  • the filler has at least one selected from sponge titanium, titanium briquette and titanium scrap, and at least one powder selected from carbon, carbide, nitride and oxide, and the internal pressure is 10 Pa or less, Package for hot working.
  • the titanium composite material according to the present invention is excellent in mechanical properties such as tensile strength and Young's modulus, and can be manufactured without undergoing a melting step, a forging step, and the like, so that the manufacturing cost can be greatly reduced.
  • the titanium composite material according to the present invention includes a large amount of titanium material such as cutting and removal of many defective portions on the surface layer and bottom surface of the ingot, and removal of surface cracks and badly shaped front and rear ends (crop) after forging. Since it can manufacture without performing cutting removal and cutting removal, a manufacturing yield improves significantly and the manufacturing cost is also reduced significantly also from this point.
  • FIG. 1 is an explanatory view showing an example of the configuration of a titanium composite material according to the present invention.
  • FIG. 2 is a diagram schematically showing the streak-like compound aggregate 42a.
  • FIG. 4 is an explanatory view showing an example of a configuration of a titanium package that is a material for hot working of a titanium composite material according to the present invention.
  • FIG. 5 is an explanatory view showing an example of the structure of the titanium briquette.
  • FIG. 6 is an explanatory view showing an example of another configuration of the titanium package according to the present invention.
  • FIG. 7 is a cross-sectional microstructure photograph of a Ti-0.1% N plate.
  • FIG. 1 is an explanatory diagram showing an example of the configuration of the titanium composite 1 according to the present invention.
  • the titanium composite material 1 includes surface layer portions 2 and 3 and an inner layer portion 4.
  • each layer will be described.
  • an industrial pure titanium material having a chemical composition belonging to any of JIS 1-4 can be used.
  • the surface layer portions 2 and 3 are: C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, the balance It has a chemical composition of Ti and impurities.
  • JIS types 1 to 4 are defined in JIS 4600: 2012.
  • JIS class 1 is C: 0.08% or less, H: 0.013% or less, O: 0.15% or less, N: 0.03% or less, Fe: 0.20% or less, the balance of Ti and impurities
  • JIS type 2 is C: 0.08% or less, H: 0.013% or less, O: 0.20% or less, N: 0.03% or less, Fe: 0.25% or less, the balance of Ti and impurities Having a composition.
  • JIS class 3 means C: 0.08% or less, H: 0.014% or less, O: 0.30% or less, N: 0.05% or less, Fe: 0.30% or less, the balance of Ti and impurities Having a composition.
  • JIS class 4 means C: 0.08% or less, H: 0.013% or less, O: 0.40% or less, N: 0.05% or less, Fe: 0.50% or less, the balance of Ti and impurities Having a composition.
  • an ⁇ -type titanium alloy, an ⁇ + ⁇ -type titanium alloy, or a ⁇ -type titanium alloy can be used as the titanium alloy material forming the surface layer portions 2 and 3.
  • Examples of the ⁇ -type titanium alloy include Ti-0.06% Pd, Ti-0.2Pd, Ti-0.02Pd-0.05Mm (where Mm represents Misch metal), Ti-0.5Ni. -0.05Ru, Ti-0.5Cu, Ti-1.0Cu, Ti-1.0Cu-0.5Nb, Ti-1.0Cu-1.0Sn-0.3Si-0.25Nb, Ti-0.5Al -0.45Si, Ti-0.9Al-0.35Si, Ti-3Al-2.5V, Ti-5Al-2.5Sn, Ti-6Al-2Sn-4Zr-2Mo, Ti-6Al-2.75Sn-4Zr -0.4Mo-0.45Si.
  • Examples of ⁇ + ⁇ type titanium alloys include Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-7V, Ti-3Al-5V, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-6Al. -2Sn-4Zr-6Mo, Ti-1Fe-0.35O, Ti-1.5Fe-0.5O, Ti-5Al-1Fe, Ti-5Al-1Fe-0.3Si, Ti-5Al-2Fe, Ti-5Al -2Fe-0.3Si, Ti-5Al-2Fe-3Mo, Ti-4.5Al-2Fe-2V-3Mo, and the like.
  • ⁇ -type titanium alloy for example, Ti-11.5Mo-6Zr-4.5Sn, Ti-8V-3Al-6Cr-4Mo-4Zr, Ti-10V-2Fe-3Mo, Ti-13V-11Cr-3Al Ti-15V-3Al-3Cr-3Sn, Ti-6.8Mo-4.5Fe-1.5Al, Ti-20V-4Al-1Sn, Ti-22V-4Al, and the like.
  • the thickness of the surface layer portions 2 and 3 is preferably 40% or less per side with respect to the total thickness of the titanium composite 1, and more preferably 25% or less per side.
  • the thickness of the inner layer portion 4 is increased, so that the mechanical property improving effect is improved.
  • the surface layer portions 2 and 3 are too thin, when the titanium composite material 1 is processed, the surface layer portions 2 and 3 are cracked and the inner layer portion 4 appears on the surface, and the titanium compound in the inner layer portion 4 falls off, Surface cracks and edge cracks occur with the titanium compound appearing in Further, when a liquid such as water comes into contact with the liquid, the problem that the liquid enters the inner layer portion 4 occurs. For this reason, it is preferable that the thickness of the surface layer portions 2 and 3 is 0.1 mm or more.
  • a titanium compound 42 is dispersed in titanium 41, and each constituent element (that is, carbon around a carbide, nitrogen around a nitride, or oxygen around an oxide) around the titanium compound. ) Are diffused (not shown), and have a void 43 that is greater than 0% and not more than 30% in terms of area ratio.
  • (B-1) Chemical composition of the inner layer part 4
  • JIS class 1 to JIS class 4 industrial pure titanium can be used. That is, as general impurities, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, and the balance It is an industrial pure titanium which is Ti.
  • JIS 1 to 3 types of industrial pure titanium has sufficient workability, does not generate cracks, etc., and industrial pure titanium that forms the above-mentioned surface portions 2 and 3 after hot working. And the titanium composite material 1 integrated.
  • impurities As an impurity, it can contain in the range which does not reduce processability and a mechanical characteristic improvement effect. Impurities other than the above include Al, V, Cr, Nb, Si, Sn, Mo, Cu, and the like as impurity elements mainly mixed from scrap, and general impurity elements (C, N, Fe, O, H, etc.) In addition, a total amount of 5% or less is allowed.
  • the inner layer portion 4 is made of a material in which one or more titanium compounds selected from carbides, nitrides and oxides are dispersed in titanium in order to make the titanium composite 1 have good mechanical properties.
  • the total of the average contents of carbon, nitrogen and oxygen is preferably 0.05 to 2.0% by mass. The preferable range of the average content of each element and the reason for limitation will be described.
  • the average concentration of C in the inner layer portion 4 is preferably 0.001 to 0.1%.
  • the average concentration of N in the inner layer portion 4 is preferably 0.001 to 0.5%.
  • the average concentration of O in the inner layer portion 4 is preferably 0.01 to 1.0%.
  • Component analysis of the surface layer portion and the inner layer portion is performed by a known method (for example, JIS H 1612 (1993), JIS H 1614 (1995), JIS H 1615 (1997), JIS H 1617 (1995), JIS H 1619 (2012). , JIS H 1620 (1995)).
  • measurement is performed after cutting out the surface layer portion and the inner layer portion from the titanium composite material. It is efficient to collect and analyze an analysis sample from a chip obtained by machining the surface layer portion and the inner layer portion from the remaining material after the surface layer is deleted.
  • As an analysis sample 0.5 g or more is collected from the center portion in the thickness direction of the surface layer portion and the inner layer portion.
  • the surface layer or inner layer is thin and a sufficient amount of chips cannot be obtained, analyze the entire composition of the titanium composite and its analysis value and either the surface layer or inner layer analysis value And the component of the surface layer or the inner layer part may be calculated (reverse calculation) from each plate thickness.
  • the voids 43 are contained to such an extent that the mechanical properties (strength, ductility, etc.) sufficient to maintain the structure as the titanium composite material 1 are contained, the density of the inner layer portion 4 becomes low, and the titanium composite The weight of the material 1 can be reduced.
  • the porosity can be selected according to the application.
  • the range of the porosity is preferably more than 0% and 30% or less, more preferably more than 0% and 10% or less.
  • the porosity it is possible to have mechanical characteristics comparable to general industrial pure titanium.
  • the ratio (void ratio) of the voids 43 remaining in the inner layer portion 4 of the titanium composite material 1 is calculated as follows. After embedding in the resin so that a cross section with a thickness parallel to the length direction (rolling direction) of the titanium composite material 1 can be observed, the observation surface is polished with a diamond or alumina suspension (mirror finish) and observed. Finish the sample.
  • the observation sample that has been subjected to the mirror finish is photographed at 20 thickness centers at different positions with an optical microscope.
  • the center portion is the thickness center when the titanium composite material 1 is a plate, and the center of the circular cross section when the titanium composite material 1 is a round bar.
  • the area ratio of the voids 43 observed in the optical micrograph is measured, and the result of averaging the porosity values of the 20 photographs is calculated as the void ratio.
  • a suitable magnification is selected according to the magnitude
  • the porosity is 1% or less, since the void is small, it is preferable to take a picture while observing at a high magnification of about 500 times.
  • the porosity is 10% or more, there are many large voids, so it is preferable to perform photography at a low magnification of about 20 times.
  • the void ratio is 1% or less so that the voids become small, it is possible to observe more clearly than a normal optical microscope by using a differential interference microscope capable of observing polarized light.
  • the inner layer part 4 in the titanium composite 1 contains a large amount of the titanium compound 42.
  • the titanium compound 42 is made of each constituent element (that is, carbon around the carbide, nitrogen around the nitride, nitrogen, or oxide) around the titanium compound 42 by hot working or the like in the manufacturing process of the titanium composite 1.
  • Each constituent element that cannot be dissolved in the titanium 41 remains as a titanium compound 42 in a dispersed state in the titanium material 41.
  • the titanium compound 42 is aligned in the processing (rolling) direction and constitutes a streak-like compound aggregate 42a.
  • the titanium compound 42 includes a compound in which carbon is present in addition to a compound that completely forms a compound. For example, when carbon is used as a material for a titanium compound, carbon reacts with titanium in a manufacturing process such as hot rolling to form a titanium compound, but the carbon that has not reacted with titanium inside the titanium compound. May remain.
  • FIG. 2 is a diagram schematically showing the streak compound aggregate 42a.
  • the streak-like compound aggregate 42a has a plurality of distances D (hereinafter referred to as “inter-particle distances”) obtained by projecting the distance between the centers of the grains of the titanium compound 42 in the rolling direction to 20 ⁇ m or less.
  • An aggregate of titanium compounds 42 is meant. In the present specification, when the interparticle distance exceeds 20 ⁇ m, it is treated as another streak compound aggregate.
  • the thickness t (that is, the size in the compression processing direction) of the streak compound aggregate 42a is 100 ⁇ m or less. This is because when the thickness exceeds 100 ⁇ m, the possibility of cracking starting from the titanium compound 42 increases when the titanium composite material is processed.
  • the length L (that is, the size in the processing direction) of the streak compound aggregate 42a is 2.0 times or more the thickness (the thickness) t in the thickness direction (that is, L / t ⁇ 2). 0.0), more preferably 3.0 times or more (that is, L / t ⁇ 3.0). This is because when the length L is small, the inner layer portion is likely to be broken starting from this titanium compound when subjected to tensile stress. Note that L / t ⁇ 100 is preferable, and L / t ⁇ 40 is more preferable.
  • the size (length L and thickness t) of the streak-like compound aggregate 42a is calculated as follows. After embedding in the resin so that the cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite 1 is the observation surface, the observation surface is formed using diamond or alumina suspension. Polish to finish the sample for observation.
  • the thickness center portion is the plate thickness center portion when the titanium composite material 1 is a plate, and is the center of the circular cross section when the titanium composite material 1 is a round bar.
  • the length L and the thickness t of the streak-like compound aggregate 42a are measured, and the average value of each value is taken as the length L and the thickness t, and L / t is calculated.
  • each constituent element that is, carbon for carbide, nitrogen for nitride, oxygen for oxide
  • the diffusion layer is a titanium compound 42 dispersed in titanium 41 in the inner layer portion 4, and its constituent elements (carbon, nitrogen or oxygen) diffuse into the surrounding titanium 41 with the titanium compound 42 as the center, and a concentration gradient is formed. Refers to the layer.
  • FIG. 3 shows a concept of the distance in the thickness direction of one grain and the concentration distribution of constituent elements around it in a cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite material 1.
  • FIG. 3 When the diffusion layer is heated and held in the process of manufacturing the titanium composite material 1 (heating before hot rolling, during hot rolling, heat treatment after hot rolling, etc.), This is a layer formed by diffusing each constituent element in titanium 41. As shown in FIG. 3, the diffusion layer is contained in a larger amount than the value of each constituent element contained in the titanium 41 of the inner layer part 4. Due to the presence of this diffusion layer, the grains of the titanium compound 42 in the inner layer portion 4 and the titanium 41 are firmly bonded. For this reason, when the titanium composite material 1 is processed, the titanium compound 42 does not break from the starting point.
  • This diffusion layer can be grasped as follows. After embedding in the resin so that the cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite 1 is the observation surface, the observation surface is formed using diamond or alumina suspension. Polish to finish the sample for observation. Using EPMA, line analysis is performed in the thickness direction so that the grain of the titanium compound 42 observed in the observation sample is centered.
  • the object of analysis is each constituent element (that is, carbon in the case of carbide, nitrogen in the case of nitride, oxygen in the case of oxide).
  • a region having a higher concentration than the value of titanium 41 in the inner layer portion 4 and excluding particles is a diffusion layer.
  • the thickness of the diffusion layer varies depending on various factors. For example, when a titanium compound is added, since it is formed by (1) decomposition of the titanium compound and (2) diffusion of each constituent element to the periphery, the decomposition rate of the titanium compound and the titanium material of each constituent element Varies depending on the diffusion rate. It also varies depending on the thermal history during manufacture. Furthermore, it changes also with the contact degree of sponge titanium etc. and a titanium compound at the time of the heating of the package as a hot rolling raw material. Therefore, the thickness of the diffusion layer has various diffusion layer thicknesses within the same material, and it is difficult to uniquely determine, but the titanium compound and each constituent element exist or exist. It is formed not a little around the part.
  • (B-4) Thickness of the inner layer portion 4 As the thickness of the inner layer portion 4 with respect to the total thickness of the titanium composite material 1 increases, the mechanical characteristics improve. % Is preferable, and more preferably 50%. On the other hand, if the thickness is too large, the workability deteriorates. Therefore, the thickness of the inner layer portion 4 is preferably 95% or less with respect to the total thickness of the titanium composite material 1.
  • Titanium packing body 5 includes a titanium packing material 6 and fillers 7 and 8.
  • the shape of the titanium package 5 is not limited to a specific shape, but is determined by the shape of the titanium composite material 1 to be manufactured.
  • a rectangular parallelepiped titanium package 5 is used.
  • a cylindrical packing or a polygonal column shape titanium packing 5 such as an octagonal column is used.
  • the size of the titanium package 5 is determined by the product size (thickness, width and length) and the production amount (mass).
  • Titanium packing material 6 (A) Titanium packing material 6 (A-1) Titanium Packing Material 6 Chemical Composition
  • the titanium packing material 6 is made of industrial pure titanium or titanium alloy material belonging to JIS class 1 to JIS class 4, similar to the surface layers 2 and 3 of the titanium composite material 1.
  • Titanium packing material 6 shape Since the shape of the titanium packing material 6 depends on the shape of the titanium packing body 5 used as a material for hot working, there is no particular shape, and a plate material, a pipe material, or the like can be used. it can.
  • the thickness of the titanium packing material 6 Is important.
  • the thickness of the titanium packing material 6 is as thin as less than 1 mm, the titanium packing material 6 is broken in the course of hot working along with plastic deformation, and a part of the titanium packing body 5 falls off. In this case, the vacuum is broken at the same time, and the titanium material 7 filled in the titanium package 5 is oxidized. Further, the undulations of the titanium material 7 filled in the titanium package 5 are transferred to the surface of the titanium package 5, and there is a possibility that a large surface undulation may occur during hot working.
  • the manufactured titanium composite material 1 deteriorates mechanical properties such as surface properties or ductility. Furthermore, when the titanium packing material 6 becomes too thin, there is a possibility that the weight of the titanium material 7 filled therein cannot be supported. For this reason, there exists a possibility that the rigidity of the titanium package 5 may be insufficient and deform during room temperature, hot holding or processing.
  • the thickness of the titanium packing material 6 is , Preferably it is 1 mm or more, More preferably, it is 2 mm or more.
  • the thickness of the titanium packing material 6 is preferably 25% or less of the total thickness of the titanium packing body 5. If the thickness of the titanium packing material 6 is greater than 25% of the total thickness of the titanium packing body 5, there is no particular problem in manufacturing, but the ratio of the titanium packing material 6 to the total thickness of the titanium packing body 5 is It becomes large and the thickness of the inside or the inner layer part 4 becomes thin. For this reason, the amount of the titanium compound in the titanium package 5 is reduced, and the effect of improving the mechanical properties is lowered, which is not preferable.
  • Titanium material 7 The titanium material 7 as the filler is at least one selected from sponge titanium, titanium briquette and titanium scrap.
  • (B-1-1) Chemical Composition of Titanium Material 7
  • industrially pure titanium corresponding to JIS class 1 to JIS class 4 can be used. That is, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, the balance Ti and the chemical composition of impurities Have.
  • (B-1-2) Shape of Titanium Material 7 As the titanium material 7, normal sponge titanium produced by a refining process such as a conventional crawl method can be used.
  • the size is preferably 20 mm or less in terms of average particle size.
  • the average particle size is larger than 20 mm, it is difficult to uniformly mix with the powder 8 such as a titanium compound, and there is a possibility that unevenness of the titanium compound occurs in the inner layer portion 4 of the titanium composite 1 manufactured by hot working.
  • the average particle size is small, there is no problem in terms of characteristics, but if the average particle size of the titanium material 7 is less than 0.5 mm, it takes time to crush and a lot of fine dust is scattered. Therefore, the production efficiency is deteriorated. For this reason, it is preferable that the average particle diameter of a titanium material is 0.5 mm or more.
  • titanium scrap can be used as the titanium material 7.
  • titanium scrap is used as a scrap that does not become a product generated in the manufacturing process of industrial pure titanium material, titanium chips generated when cutting and grinding to make industrial pure titanium material into a product shape, product It is a pure titanium material for industrial use that has become unnecessary after the processing. If the titanium scrap is too large, there is a problem that it is difficult to convey and difficult to put in the titanium package 5.
  • sponge titanium or titanium scrap is in a lump shape, there is a gap (gap) 9 between the materials.
  • powder 8 such as sponge titanium and titanium compound is mixed in advance and then compression molded to form briquette 10 as shown in FIG. You may put in.
  • Powder of titanium compound or the like 8 (B-2-1) Chemical composition of powder 8 such as titanium compound
  • the powder 8 such as titanium compound include carbon powder and TiC powder in the case of carbide, and TiN powder in the case of nitride. Fe 3 N powder, Fe 4 N powder, etc. (however, the Fe concentration of titanium in the inner layer portion 4 should not exceed the JIS standard) are exemplified. In the case of an oxide, TiO powder, TiO 2 powder, Ti 2 O In addition to the three powders, FeO powder, Fe 2 O 3 powder, Fe 3 O 4 powder, etc. (however, the Fe concentration of titanium in the inner layer portion 4 must not exceed the JIS standard) are exemplified. What is necessary is just to use what is marketed for these powders 8.
  • the average particle diameter of the powder 8 such as a titanium compound exceeds 50 ⁇ m, it is difficult to uniformly mix with the titanium material 7. Therefore, the titanium compound cannot be uniformly dispersed in the inner layer portion 4 of the titanium composite material 1. For this reason, the average particle diameter of the powder 8 such as a titanium compound is preferably 50 ⁇ m or less.
  • the average particle size of the powder 8 such as a titanium compound is smaller, there is no problem in terms of characteristics, but if it is too small, when mixing with the titanium material 7 or filling in the titanium package 5, There is a risk that the scattering of dust may cause problems. For this reason, it is preferable that the average particle diameter of the powder 8 such as a titanium compound is 0.1 ⁇ m or more.
  • the internal pressure (absolute pressure) of the titanium package 5 should be 10 Pa or less, preferably 1 Pa or less.
  • the internal pressure of the titanium package 5 is greater than 10 Pa, the titanium material 7 is oxidized or nitrided by the remaining air.
  • Making the internal pressure extremely small requires improvement of the airtightness of the device and enhancement of the vacuum exhaust device, etc., leading to an increase in manufacturing cost. Therefore, the lower limit of the internal pressure is set to 1 ⁇ 10 ⁇ 3 Pa. Is good.
  • the titanium composite material 1 is produced by subjecting the titanium package 5 to hot working or further cold working.
  • the hot working method can be selected according to the shape of the product.
  • the rectangular parallelepiped (slab) titanium package 5 is heated and hot-rolled to obtain a titanium plate. If necessary, after the hot rolling, the surface oxide layer may be removed by pickling or the like after hot rolling, and then cold rolling may be performed to further reduce the thickness.
  • the cylindrical packing or polygonal (billet) titanium packing body 5 is heated and hot rolled or hot extruded to obtain a titanium round bar or wire.
  • the oxide layer may be removed by pickling or the like, and then cold-rolled and further thinned as in the conventional process.
  • (A-1) Heating temperature for hot working Further, when manufacturing the extruded titanium composite material 1, the cylindrical packing or polygonal (billet) titanium package 5 is heated to perform hot extrusion. Titanium profiles with various cross-sectional shapes are used. The heating temperature before hot working may be the same as that used when hot working a normal titanium slab or billet. The heating temperature varies depending on the size of the titanium package 5 and the degree of hot working (working rate), but it is preferable to heat to 600 ° C. or more and 1200 ° C. or less.
  • the heating temperature is too low, the high temperature strength of the titanium package 5 is high and the deformability is low, so that cracking is likely to occur during hot working.
  • the welded portion of the titanium package 5 is cracked and the inside is exposed and partly falls off or the inside is oxidized, the characteristics necessary for the titanium composite 1 cannot be obtained.
  • the diffusion layer of the constituent elements around the titanium compound grains is not formed, and the titanium compound grains and titanium in the inner layer portion cannot be sufficiently bonded. For this reason, when processing a titanium composite material, a crack may generate
  • the heating temperature is too high, the structure of the obtained titanium composite 1 becomes rough, and sufficient material properties cannot be obtained. Further, the packing material 6 on the surface is thinned by oxidation. Therefore, it is recommended that the heating temperature be 600 ° C. to 1200 ° C.
  • the degree of hot working ie, the working rate, can be selected to control the porosity of the inner layer portion 4 of the titanium composite 1.
  • the processing rate here is a ratio (percentage) obtained by dividing the difference between the cross-sectional area of the titanium package 5 and the cross-sectional area of the titanium composite 1 after hot working by the cross-sectional area of the titanium package 5.
  • the gap 43 inside the titanium package 5 is not sufficiently crimped, so that the gap 43 remains even after hot working.
  • the titanium composite material 1 containing a large amount of voids is lighter by the amount of voids contained, and there is no problem in the effect of improving mechanical properties.
  • the processing rate is increased, the porosity is decreased and the mechanical properties are improved. For this reason, when the mechanical characteristics of the titanium composite material 1 to be manufactured are regarded as important, it is preferable that the processing rate is high.
  • the titanium composite material 1 has no significant difference in the effect of improving the mechanical properties, whether it is a hot-worked material (for example, hot-rolled plate) or a cold-worked material (for example, cold-rolled plate). Further, the surface state may be any state of rolling, pickling finish and annealing finish, and the effect of improving mechanical properties is not changed.
  • Manufacturing method of titanium package 5 (a) Mixing of fillers 7 and 8
  • the titanium material 7 needs to be uniformly and densely filled with powder 8 such as a titanium compound.
  • powder 8 such as a titanium compound.
  • these titanium material 7 and titanium compound powder 8 are filled in a container and rotated or vibrated, and mixed so that the internal titanium material 7 and titanium compound powder 8 are uniformly dispersed. do it.
  • Stirring can be done by rotating the container up and down, tilting it 20 to 70 ° from the horizontal and rotating it in an oblique direction, vibrating the container in the vertical and horizontal directions, or inserting a stirring bar into the container and stirring. Examples include a method of rotating the child.
  • the stirring time varies depending on the size of the container and the amount of the titanium material 7 to be mixed and the powder 8 of the titanium compound or the like, but is preferably 1 to 30 minutes. In consideration of productivity, it is preferable to determine the size of the container and the processing amount so that the mixture can be uniformly mixed within a few minutes.
  • the mixed titanium material 7 and powder 8 such as titanium compound are filled in the titanium package 5 as they are.
  • the titanium briquette 10 as shown in FIG.
  • the method of welding the titanium packing material 6 with the welded portion 11 includes arc welding such as TIG welding or MIG welding, electron beam welding, laser welding, and the like, and is not particularly limited. However, it is preferable that welding is performed in a vacuum atmosphere or an inert gas atmosphere so that the surfaces of the titanium material 7 and the titanium packing material 6 are not oxidized or nitrided.
  • the titanium packing body 5 is put in a vacuum atmosphere container (chamber) and welded to keep the inside of the titanium packing body 5 in a vacuum. Is preferred.
  • a titanium briquette 10 mixed with a powder 8 such as a titanium compound and compression-molded is covered with a titanium expanded material as a packing material, and the entire circumference of the titanium expanded material is seam welded (using a rotating electrode).
  • the titanium package 12 may be manufactured by sealing with resistance welding.
  • the inside of the titanium wrought material is depressurized to a predetermined pressure through a copper pipe in which a hole is drilled at the end in advance and the copper pipe is solder-welded. The pressure inside the material may be maintained.
  • titanium composite 1 Since it has high tensile strength and good workability and can be manufactured at low cost, it can be used as a structural member for land transportation equipment such as automobiles.
  • a titanium package shown in Table 1 was produced, and a titanium composite 1 (plate material) was produced in the production process shown in Table 1 on the titanium package.
  • the particle size produced by the crawl method is 2.5 mm or more and 6 mm or less, and the chemical composition is equivalent to JIS class 1 (C: 0.002%, H: 0.001%, O: 0.03%, N: 0.001%, Fe: 0.03%, balance Ti and impurities) were used.
  • the filler commercially available TiO 2 powder (average particle size 2 ⁇ m), TiC powder (average particle size 3 ⁇ m) or TiN powder (average particle size 5 ⁇ m) was used.
  • the above-mentioned sponge titanium and powders of titanium compound and the like were mixed by feeding a predetermined amount into a V-type mixer.
  • the mixed material was put into a mold and compression molded to form a titanium briquette shown in FIG. 5 having a thickness of 15 mm, a width of 50 mm, and a length of 60 mm.
  • Sample No. In No. 11 only titanium titanium particles 7 were added, and titanium briquette was prepared without adding the powder raw material 8.
  • JIS type 1 As a titanium packing material, JIS type 1 (TP270C; C: 0.001%, H: 0.005%, O: 0.04%, N: 0.001%, Fe: 0.03%, balance Ti and impurities) Or JIS type 2 (TP340C; C: 0.002%, H: 0.004%, O: 0.09%, N: 0.001%, Fe: 0.05%, balance Ti and impurities) industrial pure titanium A thin plate made of a material and having a thickness of 1.0 mm was used.
  • the titanium briquette was covered with an industrial pure titanium material as a packing material, and the entire circumference of the industrial pure titanium material was sealed by seam welding (resistance welding using a rotating electrode).
  • This pure titanium material for industrial use was previously welded to a copper tube by making a hole in the end.
  • the pressure inside the industrial pure titanium material is reduced to a predetermined pressure (0.06 to 1.2 Pa) through the copper tube. The pressure was maintained.
  • Sample No. 12 when the pressure was reduced to 38 Pa, a copper tube was pressure-bonded to form a package.
  • the produced titanium package was heated at 850 ° C. for 4 hours in an air atmosphere and then hot-rolled to produce a 2.0 mm-thick titanium composite.
  • the titanium composite was annealed at 725 ° C. for 15 minutes, then pickled to remove the scale of the surface layer, and subjected to a structure observation and a tensile test.
  • the observation surface is polished with diamond or alumina suspension ( Mirror finish) and finished the sample for observation.
  • the porosity was obtained by taking 20 photographs of the central portion of the thickness of the observation sample with an optical microscope, measuring the area ratio of the void for each individual photograph, and obtaining the average value thereof.
  • the shape of the streak-like compound aggregate was determined by observing the central portion of the thickness of the observation sample with an optical microscope. Moreover, about 20 observed streak compound aggregates, thickness t and length L were measured, L / t was calculated, and those average values were calculated
  • the thickness of the diffusion layer is No. 1 to which TiO 2 powder, TiC powder and TiN powder were added. 2, No. 4, no. As for No. 6, the five titanium compound grains observed in the central portion of the thickness of the observation sample were measured with EPMA for the three titanium compound grains observed therein. Perform line analysis in the thickness direction so that the grains of the titanium compound are in the center, and based on the value of titanium in the inner layer, the concentration of the constituent elements (carbon, nitrogen or oxygen) of the titanium compound is higher than that, The distance of the area
  • the tensile test was evaluated in the rolling direction of the titanium composite material.
  • the tensile rate was 0.4% / min until exceeding the yield point, and 30% / min after exceeding the yield point, and the strength was measured.
  • the Young's modulus was obtained from the slope of the stress-strain curve until yielding.
  • FIG. 7 is an example of a photograph of a cross-sectional microstructure of a Ti-0.1% N plate.
  • Sample No. of the present invention example in which one or more titanium compounds selected from carbides, nitrides and oxides are dispersed in titanium. Samples Nos. 1 to 8 have no titanium compound. Compared to 10, the strength and Young's modulus of the titanium composite were improved. Note that when the titanium package 5 was manufactured, the sample No. 1 with the degree of vacuum inside the titanium package greater than 10 Pa was used. In No. 9, the inside of the titanium composite was partially oxidized and the strength decreased, but the Young's modulus was maintained at a certain value or more. No. with TiO 2 powder added. In No. 2, the thickness of the oxygen diffusion layer was 4 to 6 ⁇ m. No. to which TiC powder was added. In No. 4, the thickness of the carbon diffusion layer was 25 to 32 ⁇ m. No. with TiN powder added. In No. 6, the thickness of the nitrogen diffusion layer was 1-2 ⁇ m.
  • Sample No. with a large amount of oxide powder added In No. 11, an internal crack occurred during hot rolling, and a healthy titanium composite material could not be obtained.
  • the oxide was interspersed with the voids without directionality, and cracked when the tensile test piece was manufactured.
  • a titanium composite material was manufactured from a titanium package.
  • Sponge titanium used as a filler has a chemical composition produced by the crawl method equivalent to JIS class 1 (C: 0.001%, H: 0.001%, O: 0.04%, N: 0.001%, Fe : 0.03%, balance Ti and impurities), sponge titanium B has a particle size of 6 mm to 13 mm, sponge titanium C has a particle size of 2.5 mm to 6 mm, and sponge titanium D has a particle size of Each having a thickness of 0.8 mm to 2.5 mm.
  • TiO 2 powder average particle size 2 ⁇ m
  • TiC powder average particle size 3 ⁇ m
  • TiN powder average particle size 5 ⁇ m
  • industrial pure titanium material is JIS type 1 (TP270HC: 0.002%, H: 0.006%, O: 0.04%, N: 0.002%, Fe: 0.03%) , Balance Ti and impurities), JIS type 2 (TP340H; C: 0.001%, H: 0.002%, O: 0.10%, N: 0.002%, Fe: 0.06%, balance Ti and Impurities), and a 10 mm thick plate washed with Ti-0.06% Pd.
  • a titanium packing body was prepared in which the inside was filled with a mixture of titanium sponge, titanium scrap, and a powder of a titanium compound, and the atmosphere was vacuum.
  • the size of the titanium package was 80 x thickness 100 x length 120 mm.
  • the produced titanium package was heated at 850 ° C. for 6 hours in an air atmosphere, and then hot-rolled to produce a titanium composite plate having a thickness of 5 mm. Thereafter, the titanium composite was annealed at 725 ° C. for 15 minutes, and then pickled to remove the scale of the surface layer and subjected to a tensile test.
  • the structure observation and the tensile test were performed in the same manner as in Example 1, and the porosity of the titanium composite material, the form and size L / t of the titanium compound, the thickness, strength, and Young's modulus of the diffusion layer were determined.
  • sample No. which is an example of the present invention to which titanium compound powder is added.
  • Samples Nos. 13 to 19 are sample Nos. To which no titanium compound was added. Compared to 20, the strength and Young's modulus of the titanium composite were improved.
  • the titanium composite material 1 with good workability is obtained as compared with the packaging material using JIS type 2.
  • Sample No. 6 using Ti-0.06% Pd as the packing material 6 was used.
  • No. 23 is a titanium composite material with better corrosion resistance than the packaging material 6 using JIS type 2.
  • the thickness of the oxygen diffusion layer was 2 to 6 ⁇ m.
  • the thickness of the carbon diffusion layer was 12 to 18 ⁇ m.
  • the thickness of the nitrogen diffusion layer was 1-2 ⁇ m.
  • Sample No. 5 which is a titanium composite material having a thickness of 5 mm shown in Table 2 obtained by hot rolling. 13, 14, 16, and 20 were annealed at 725 ° C. for 15 minutes, and then pickled to remove scale on the surface layer.
  • the titanium composite from which the scale was removed (hot-rolled material) was cold-rolled to a thickness of 1.0 mm, and then annealed at 700 ° C. for 15 minutes using a vacuum heating furnace and subjected to a tensile test. Microstructure observation and a tensile test were performed in the same manner as in Example 1 to determine the porosity of the titanium composite, the form and size L / t of the titanium compound, the thickness, strength, and Young's modulus of the diffusion layer.
  • Sample No. which is an example of the present invention Samples Nos. 28 to 30 were prepared by adding the titanium compound powder, so that no sample no. Compared to 31, the strength and Young's modulus of the titanium composite were improved. In addition, No. to which TiO 2 powder was added. In No. 29, the thickness of the oxygen diffusion layer was 1 to 4 ⁇ m. No. to which TiC powder was added. In No. 30, the thickness of the carbon diffusion layer was 2 to 6 ⁇ m.

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PCT/JP2017/013754 2016-04-01 2017-03-31 チタン複合材およびその製造方法、ならびに、梱包体 WO2017171056A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH042742A (ja) * 1990-04-19 1992-01-07 Fuso Off Service:Kk 複合チタン合金、複層チタン材、チタン刃物とそれらの製造方法
JPH0570805A (ja) * 1991-09-11 1993-03-23 Osaka Titanium Co Ltd 高融点活性金属及びその合金の切削屑の成型法
JP2000178671A (ja) * 1998-12-11 2000-06-27 Sumitomo Sitix Amagasaki:Kk 熱間加工性に優れた粒子分散型チタン基複合材、並びにその製造方法及び熱間加工方法
JP2012041583A (ja) * 2010-08-17 2012-03-01 Sanyo Special Steel Co Ltd チタン製品またはチタン合金製品の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH042742A (ja) * 1990-04-19 1992-01-07 Fuso Off Service:Kk 複合チタン合金、複層チタン材、チタン刃物とそれらの製造方法
JPH0570805A (ja) * 1991-09-11 1993-03-23 Osaka Titanium Co Ltd 高融点活性金属及びその合金の切削屑の成型法
JP2000178671A (ja) * 1998-12-11 2000-06-27 Sumitomo Sitix Amagasaki:Kk 熱間加工性に優れた粒子分散型チタン基複合材、並びにその製造方法及び熱間加工方法
JP2012041583A (ja) * 2010-08-17 2012-03-01 Sanyo Special Steel Co Ltd チタン製品またはチタン合金製品の製造方法

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