WO2013179773A1 - Alliage de molybdène résistant à la chaleur, outil de soudage par friction/malaxage et leur procédé de fabrication - Google Patents

Alliage de molybdène résistant à la chaleur, outil de soudage par friction/malaxage et leur procédé de fabrication Download PDF

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WO2013179773A1
WO2013179773A1 PCT/JP2013/060593 JP2013060593W WO2013179773A1 WO 2013179773 A1 WO2013179773 A1 WO 2013179773A1 JP 2013060593 W JP2013060593 W JP 2013060593W WO 2013179773 A1 WO2013179773 A1 WO 2013179773A1
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Prior art keywords
resistant alloy
phase
carbonitride
molybdenum heat
friction stir
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PCT/JP2013/060593
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English (en)
Japanese (ja)
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繁一 山▲崎▼
あゆ里 辻
重彦 高岡
角倉　孝典
成恒 西野
明彦 池ヶ谷
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株式会社アライドマテリアル
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/12—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding
    • B23K20/122—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding using a non-consumable tool, e.g. friction stir welding
    • B23K20/1245—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating the heat being generated by friction; Friction welding using a non-consumable tool, e.g. friction stir welding characterised by the apparatus
    • B23K20/1255—Tools therefor, e.g. characterised by the shape of the probe
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass

Definitions

  • the present invention relates to a molybdenum heat-resistant alloy suitable for a plastic working tool used in a high-temperature environment, particularly a friction stir welding tool, a friction stir welding tool using the same, and a method for producing a molybdenum heat-resistant alloy.
  • FSW friction stir welding
  • Friction stir welding is a method in which a rotating tool is pressed against a joining portion of a metal member, and a material to be joined that has been softened by the frictional heat is plastically flowed and joined. Friction stir welding has already been put into practical use in joining low melting point, soft materials such as aluminum and magnesium, and its application range is expanding. However, at present, there is a demand for the development of a tool having a practical life with improved high-temperature strength and wear resistance in order to be applied to a material to be bonded having a higher melting point and harder.
  • the temperature of the tool when the material to be joined is softened by frictional heat, the temperature of the tool generally rises to around 70% of the melting point of the material to be joined, although there are differences depending on the joining conditions and the material to be joined. Because there are things. In other words, this temperature is about 400 ° C. for low melting point aluminum, whereas it reaches 1000 to 1200 ° C. for steel materials. Therefore, the tool material is a high temperature that can cause the material to be joined to plastically flow even in this temperature range. Strength, toughness and wear resistance are required. This is a problem common to tools used in FSW, FSJ (Friction Spot Joining) and friction stir application technology.
  • Mo alloy that has relatively high availability of Mo as a main component, and carbides of Ti, Zr, and Hf, which are hard materials, are added to increase the high temperature strength.
  • carbides of Ti, Zr, and Hf which are hard materials
  • Mo alloy a molybdenum alloy in which 0.03 to 9.5 mass% of Ti, Zr, and Hf carbides are added and a structure having a fine structure is obtained by mechanical alloying (Patent Document 1).
  • Patent Document 1 This molybdenum alloy was developed with a focus on recrystallization temperature and brittle-ductile transition temperature, and a microstructure by mechanical alloying is essential.
  • molybdenum becomes very oxidizable by making it finer, it is very difficult to sufficiently remove oxygen from the mechanical alloying vessel on an industrial level.
  • Patent Document 2 there is a molybdenum two-phase alloy having a eutectic structure, and a good structure is obtained by utilizing the mutual diffusion reaction and eutectic reaction between Mo and added carbide.
  • Such a giant columnar crystal causes a significant decrease in strength, and its presence and size are difficult to control, leading to variations in strength of the entire material. Therefore, preventing the formation of giant columnar crystals is an effective means for ensuring the strength of the tool and for preventing variation.
  • the carbides of Zr and Hf which are elements similar to Ti, have a crystal structure and non-stoichiometric composition similar to those of TiC, and form giant columnar crystals similar to TiC.
  • TiCN-based hard material cermet
  • Mo is added to TiCN.
  • these hard materials are ceramic-based, and low toughness is a problem, and other metals and carbides such as Ni, Co, and Mo are added as binders and sintering aids. Mainly tools.
  • the object to be joined is gradually increased in melting point from Al, which has been widely used in the past, to Fe-based, FeCr-based (stainless steel), Ti-based alloy, Ni-based alloy in recent years. Higher metals have come to be used, and tools for friction stir welding are required to have plastic deformation resistance, toughness and wear resistance corresponding to higher melting points, that is, higher proof stress and hardness. .
  • the alloys described in the above documents are difficult to control the alloy structure in order to stabilize the strength, or are expensive materials that require a special manufacturing method or a rare material, and are a tool material for plastic working. There was a problem that practicality was not satisfied.
  • the present invention has been made in view of the above-mentioned problems, and its purpose is for a tool for plastic working that satisfies both physical properties and practicality such as proof stress and hardness corresponding to higher melting point of an object to be processed than before. It is to provide a heat-resistant alloy.
  • the present inventor focuses on a Mo-carbide two-phase alloy, particularly its solid solution phase, and improves the yield strength and hardness of the alloy by suppressing grain growth due to contact between the solid solution phases. We sought to determine whether this is possible.
  • the first aspect of the present invention includes a first phase mainly composed of Mo, a second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf, and the second phase. And a third phase having a solid solution of Mo and at least one carbonitride of Ti, Zr, and Hf provided around the phase, and the remainder being an inevitable impurity. is there.
  • the surface of the friction stir welding tool described in the first aspect is selected from the group consisting of periodic table IVa, Va, VIa, IIIb group elements and IVb group elements other than C.
  • a friction stir welding tool comprising a coating layer containing carbide, nitride, or carbonitride of at least one element selected from the group consisting of at least one element or at least one element selected from these element groups.
  • a third aspect of the present invention is a friction stirrer characterized by having the friction stir welding tool according to the second aspect.
  • Mo powder and carbonitride powder are mixed (a), and the mixed powder obtained by (a) is compression-molded at room temperature (b), and (b (C) is sintered by heating at 1600 ° C. or more and 2000 ° C. or less in an atmosphere containing at least hydrogen and nitrogen, and the sintered body obtained by (c) is inert.
  • a method for producing the molybdenum heat-resistant alloy according to the first aspect comprising: (d) hot isostatic pressing in an atmosphere.
  • the molybdenum heat-resistant alloy used in the friction stir welding tool of the present invention includes a first phase mainly composed of Mo and a second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf. And a third phase having a solid solution containing Mo and at least one carbonitride of Ti, Zr, and Hf provided around the second phase, the balance being inevitable impurities Molybdenum heat-resistant alloy.
  • the first phase is a phase mainly composed of Mo.
  • the main component here means a component having the highest content (the same applies hereinafter).
  • the first phase is composed of, for example, Mo and inevitable impurities, but depending on the content of carbonitride described later, the elements constituting the carbonitride are in solid solution in the first phase. In some cases.
  • Mo in the first phase has a high melting point, high hardness and excellent strength at high temperatures, and is essential for imparting physical properties as a metal to the heat-resistant alloy.
  • the content of Mo in the alloy is determined by the relationship with the content of carbonitride described later, but it is preferably 50% by mass or more in order to give the heat resistant alloy physical properties.
  • the second phase is a phase mainly composed of at least one of Ti, Zr, and Hf carbonitride, and specifically includes, for example, the above-described carbonitride and inevitable impurities.
  • TiC 0.5 N 0.5 is known as a typical one, but titanium carbonitride, zirconium carbonitride, and hafnium carbonitride having other compositions are also TiC 0.5 N 0.5.
  • the effect of crystal grain refinement can be obtained in the same manner as above.
  • the content of TiCN in the alloy is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and further preferably 30% by mass or more and 40% by mass or less. Is good.
  • the third phase is a layer formed around the second phase, and is mainly composed of a solid solution of Mo of the first phase and carbonitride of the second phase, and is composed of this and inevitable impurities. .
  • the added Ti carbide forms a solid solution of Mo as shown in FIG. 2 by the interdiffusion reaction and eutectic reaction of the added carbide (see FIG. 1). It has Ti carbide particles and produces a (Mo, Ti) C solid solution around the particles.
  • Ti carbonitride when Ti carbonitride is added to Mo, Ti carbonitride (TiCN) produces a solid solution (third phase) with Mo, and Ti carbonitride ( A (Mo, Ti) C solid solution is formed around the particles.
  • the molybdenum heat-resistant alloy forming the FSW tool according to the present invention may contain inevitable impurities in addition to the above-described essential components.
  • Inevitable impurities include metal components such as Fe, Ni, and Cr, and C, N, and O.
  • TiCN is described as an example of carbonitride, but the same applies to zirconium carbonitride, hafnium carbonitride, and the like.
  • the average particle diameter of TiCN in the sintered molybdenum heat-resistant alloy forming the friction stir welding tool of the present invention is preferably 0.3 ⁇ m or more and 10 ⁇ m or less. This is due to the following reason.
  • the average particle size of the TiCN powder to be blended needs to be smaller than 0.3 ⁇ m.
  • the average particle size of the TiCN powder to be blended needs to be smaller than 0.3 ⁇ m.
  • such fine particles generally tend to be easily aggregated, and the aggregated secondary particles are liable to form remarkable coarse particles by sintering and also facilitate the generation of pores.
  • the lowering of the sintering temperature causes a decrease in the density of the sintered body. Therefore, the average particle size of TiCN is preferably 0.3 ⁇ m or more.
  • the average particle size of TiCN in the molybdenum heat-resistant alloy is made larger than 10 ⁇ m, coarse TiCN inhibits the sintering, resulting in extremely poor sintering yield and may not be industrial. Further, even if sintering is possible, coarse TiCN particles may be the starting point of fracture, which may reduce the mechanical strength. Therefore, the average particle size of TiCN is preferably 10 ⁇ m or less.
  • the average particle size of TiCN is more preferably 0.3 ⁇ m to 6 ⁇ m.
  • the average particle diameter here is the value calculated
  • the TiCN grains in the alloy preferably have a number ratio of 3.0 to 5.0 ⁇ m of 40-60% of the entire TiCN grains in the alloy.
  • the average particle size of the TiCN particles is 0.3 to 6 ⁇ m.
  • the particle size distribution is too broad when the particle size distribution is too broad, This is because there is a possibility that it may lead to non-uniformity of the properties of the sintered body, that is, it is difficult to obtain a powder with a very uniform particle size, and there is a disadvantage in terms of manufacturing cost. is there.
  • the effect of the addition of TiCN grains can be further enhanced by interweaving fine grains and coarse grains.
  • the number ratio of particles having a particle size of 1.5 to 3.5 ⁇ m is 20 to 40% of the whole TiCN grains in the alloy, and is 5.0 to 7.0 ⁇ m. More preferably, the number ratio of the particles is 10-30% of the total TiCN grains in the alloy.
  • TiCN grains with a grain size of 1.5 ⁇ m to 3.5 ⁇ m on the fine grain side mainly contribute to the effect of increasing the grain boundary strength of Mo by intervening at the grain boundary of Mo (effect A).
  • TiCN grains having a grain size of 5.0 to 7.0 ⁇ m on the coarse grain side contribute to the effect of increasing the hardness of the entire molybdenum heat-resistant alloy (effect B).
  • the ratio of the number of particles having a particle size of 1.5 to 3.5 ⁇ m is lower than 20%, the ratio of coarse particles becomes high, so that the effect A is difficult to be obtained. Since it is too high and it is difficult to obtain the effect B, it is not preferable.
  • the ratio of coarse particles becomes low, so that the effect B is difficult to be obtained, and if it is higher than 30%, the ratio of coarse particles Increases, and it is difficult to obtain the effect A, which is not preferable.
  • the 0.2% proof stress at 1200 ° C. is 400 MPa or more, preferably 600 MPa or more, and the Vickers hardness (room temperature hardness) at 20 ° C. is 400 Hv or more, preferably 600 Hv or more.
  • molybdenum heat-resistant alloys such physical properties
  • molybdenum heat-resistant alloys are applied to heat-resistant members that require high melting points and high strength, such as friction stir welding members for Fe-based, FeCr-based, Ti-based, etc. can do.
  • the present invention is a molybdenum “heat-resistant” alloy
  • the room temperature hardness is a condition for the following reason.
  • the wear amount of the tool is closely related to the hardness of the tool material, and the higher the hardness is, the more effective the tool wear amount can be reduced.
  • friction stir welding since a high load is applied to the tool when the tool is inserted, wear during insertion appears significantly. At the time of insertion, both the tool and the work still generate little heat, and the temperature of both is not high. Therefore, the wear amount of the tool depends on the hardness at room temperature.
  • the molybdenum heat-resistant alloy of the present invention may be used as a friction stir welding tool itself, but in many cases it is used as a friction stir welding tool base material, and the periodic table IVa, Va, VIa, IIIb A coating containing at least one element selected from the group consisting of Group IV elements and Group IVb elements other than C, or a carbide, nitride or carbonitride of at least one element selected from these element groups
  • the surface is coated and used as a tool.
  • the tool is rotated while being strongly pushed into the material to be joined at room temperature, and the temperature of the object to be joined is increased by frictional heat.
  • the base material has a high room temperature hardness so that the base material is not deformed or broken at the initial stage of rotation or the base material and the coating film are not peeled off.
  • the above is the condition of the molybdenum heat-resistant alloy.
  • the method for manufacturing the molybdenum heat-resistant alloy of the present invention and the friction stir welding tool using the same is not particularly limited as long as the friction stir welding tool that satisfies the above conditions can be manufactured. Examples of such a method can be given.
  • the raw material powder is mixed at a predetermined ratio to generate a mixed powder (S1 in FIG. 6).
  • Examples of the raw material include Mo powder and TiCN powder (or carbonitride powders such as titanium carbonitride, zirconium carbonitride, hafnium carbonitride, etc.). The conditions of each powder will be briefly described below.
  • Mo powder having a purity of 99.99% by mass or more and an Fsss (Fisher Sub-Sieve Sizer) average particle size of 3.5 to 5.0 ⁇ m.
  • Mo powder purity here is obtained by the analysis method of the molybdenum material described in JIS H 1404, and includes Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Si, and Sn. It means the pure metal part excluding the value.
  • TiCN powder having a purity of 99.9% or more and an Fsss average particle size of 0.1 to 10.0 ⁇ m.
  • the purity of the TiCN powder here means a pure component excluding Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Si, and Sn.
  • the apparatus and method used for mixing the powder are not particularly limited, and for example, a known mixer such as a mortar, a V-type mixer, or a ball mill can be used.
  • the obtained mixed powder is compression molded to form a molded body (S2 in FIG. 6).
  • the apparatus used for compression molding is not particularly limited, and a known molding machine such as a uniaxial pressing machine or CIP (Cold Isostatic Pressing) may be used.
  • a condition at the time of compression the temperature at the time of compression may be room temperature (20 ° C.).
  • the molding pressure is preferably 1 to 3 ton / cm 2 . If this is the molding pressure is less than 1 ton / cm 2 not obtained molded body a sufficient density, also exceeds 3 ton / cm 2, compression system and the mold is large, which is disadvantageous in cost Because.
  • heating is performed at 1600 ° C. or more and 2000 ° C. or less in an atmosphere containing at least hydrogen or nitrogen (for example, H 2 , H 2 —Ar, H 2 —N 2 mixed atmosphere, reduced pressure N 2 atmosphere, etc.). preferable.
  • atmosphere containing at least hydrogen or nitrogen for example, H 2 , H 2 —Ar, H 2 —N 2 mixed atmosphere, reduced pressure N 2 atmosphere, etc.
  • the heating temperature is less than 1600 ° C.
  • the sintering is insufficient and the density of the sintered body becomes low, and when the heating temperature is higher than 2000 ° C., the decomposition of TiCN proceeds to cause a huge columnar shape. This is because crystal grains are grown, and as a result, the strength of the molybdenum heat-resistant alloy is lowered. Therefore, when sintering, it is preferable to sinter at 1600 degreeC or more and 2000 degrees C or less.
  • the reason for the atmosphere containing at least hydrogen or nitrogen is that hydrogen has an action of reducing oxygen contained in the raw material powder, and nitrogen has an effect of preventing denitrification during sintering.
  • the pressure at the time of sintering can be atmospheric pressure, but is not limited to this, and sintering can be performed by either pressurization or reduced pressure.
  • HIP hot isostatic pressing
  • the material of the FSW tool thus obtained is subjected to processes such as cutting, grinding and polishing, and a friction stir welding tool is produced.
  • the molybdenum heat-resistant alloy forming the FSW of the present invention has the above-described configuration.
  • the configuration of the friction stir welding tool using the molybdenum heat-resistant alloy of the present invention is simply described with reference to FIG. Explained.
  • the friction stir welding tool 101 includes a shank 102 connected to a main shaft (not shown) of the joining device, a shoulder portion 103 that comes into contact with the surface of the joining object at the time of joining, and a joining object at the time of joining. It has the pin part 104 inserted.
  • At least the base material of the shoulder 103 and the pin portion 104 is formed of the molybdenum heat-resistant alloy according to the present invention.
  • the surface is coated with at least one element selected from the group consisting of group IVb elements or a carbide, nitride or carbonitride of at least one element selected from these elements. Is preferred.
  • the thickness of the coating layer is preferably 1 to 20 ⁇ m. When the thickness of the coating layer is less than 1 ⁇ m, the effect of providing the coating layer cannot be expected. On the other hand, when the thickness of the coating layer is 20 ⁇ m or more, an excessive stress may be generated and the film may be peeled off, so that the yield may be extremely deteriorated.
  • TiC TiC
  • TiN TiCN
  • ZrC ZrN
  • ZrCN VC
  • VN VCN
  • CrC CrN
  • CrCN TiAlN
  • TiSiN TiCrN
  • TiCrN TiCrN
  • TiAlN TiSiN
  • TiCrN TiCrN
  • the method for forming the coating layer is not particularly limited, and a film can be formed by a known method.
  • Typical methods include PVD (Physical Vapor Deposition) such as arc ion plating and sputtering, CVD (Chemical Vapor Deposition) that coats by chemical reaction, and plasma CVD that decomposes and ionizes gaseous elements by plasma.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • plasma CVD that decomposes and ionizes gaseous elements by plasma.
  • any method can process from a single layer film to a multilayer film, and when the molybdenum heat-resistant alloy of the present invention is used as a base material, excellent adhesion can be exhibited.
  • the molybdenum heat-resistant alloy of the present invention includes a first phase mainly composed of Mo, a second phase mainly composed of at least one carbonitride of Ti, Zr, and Hf, and a second phase. And a third phase having Mo and a solid solution containing at least one carbonitride of Ti, Zr, and Hf, the balance being inevitable impurities.
  • the friction stir welding tool using the molybdenum heat-resistant alloy of the present invention satisfies both physical properties such as proof stress and hardness corresponding to the high melting point of the object to be joined (working object) and practicality.
  • Friction stir welding tools were prepared using molybdenum heat-resistant alloys having different TiCN contents, the characteristics of the obtained molybdenum heat-resistant alloys were evaluated, and the performance of the friction stir welding tools was further evaluated.
  • the specific procedure is as follows.
  • Mo powder and TiCN powder were prepared as raw materials. Specifically, Mo powder having a purity of 99.99% by mass or more and an average particle diameter by the Fsss method of 4.3 ⁇ m was used.
  • TiCN powder manufactured by Allied Material Co., Ltd. having a product name of 5OR08 and having an average particle diameter of 0.8 ⁇ m by the Fsss method was used as the TiCN powder.
  • paraffin as a binder for promoting moldability, 2% by mass was added to the total weight of the powder.
  • these powders are mixed in a mortar at the blending ratio shown in Table 1 to be described later to produce a mixed powder, and using a single screw press machine, at a temperature of 20 ° C. and a molding pressure of 3 ton / cm 3 .
  • the molded product was obtained by compression molding.
  • the obtained compact was heated at a temperature of 1900 ° C. in a hydrogen atmosphere (atmospheric pressure) to attempt sintering.
  • the sintered body was subjected to HIP treatment at a temperature of 1600 ° C. under an Ar atmosphere at a pressure of 202.7 MPa to prepare a heat-resistant molybdenum alloy, and a FSW tool was manufactured through cutting and grinding.
  • the relative density is a value expressed by% by dividing the density measured for the prepared sample (bulk) by the theoretical density.
  • the mass ratio of Ti in the bulk material (0 to 1) is determined by ICP-AES, the mass ratio of C and N is also determined by chemical analysis, the mass ratio of TiCN (Zc) is calculated, and the mass ratio of Mo (Zm) was calculated as 1-Zc.
  • an enlarged photograph at a magnification of 1000 times is taken with respect to the cross section to be measured, and on this photograph, as shown in FIG. 8, a straight line is arbitrarily drawn, and the crystal grains to be crossed by the straight line are drawn. For the particles, the particle size of each crystal grain crossing this straight line was measured, and the total sum was calculated. Next, an average crystal grain size was obtained from the total diameter of the measured particles and the number of measured particles.
  • the field of measurement was 120 ⁇ m ⁇ 90 ⁇ m, and 50 or more particles were measured.
  • the hardness of the molybdenum heat-resistant alloy was measured by using a micro Vickers hardness meter (model number: AVK) manufactured by Akashi Co., Ltd. and applying a measurement load of 20 kg at 20 ° C. in the atmosphere. The number of measurement points was 5 and the average value was calculated.
  • AVK micro Vickers hardness meter
  • the 0.2% proof stress was measured by the following procedure. First, a molybdenum heat-resistant alloy was processed to have a length: about 25 mm, a width: 2.5 mm, and a thickness: 1.0 mm, and the surface was polished using # 600 SiC polishing paper.
  • the sample is set in an Instron high-temperature universal testing machine (model number: 5867 type) so that the pin interval is 16 mm, and the head is sampled at 1200 ° C. and a crosshead speed of 1 mm / min in an Ar atmosphere.
  • a three-point bending test was performed by pressing to a 0.2% proof stress.
  • the 0.2% proof stress was obtained by calculating the bending stress and strain in the three-point bending test using the following formula, drawing a stress-strain diagram, and analyzing the stress that causes 0.2% permanent strain. .
  • F test load (N)
  • L distance between support points (mm)
  • b width of test piece (mm)
  • h thickness of test piece (mm)
  • s deflection amount
  • Mo powder is 70% by mass
  • TiCN powder is 30% by mass
  • Mo powder is 60% by mass
  • TiCN powder is 40% by mass
  • Mo powder is 50% by mass. %
  • an alloy produced with 50% by mass of TiCN powder was subjected to X-ray diffraction under the following conditions. Specific conditions are as follows.
  • Apparatus X-ray diffractometer manufactured by Rigaku Corporation (model number: RAD-IIB) Tube: Cu (K ⁇ X-ray diffraction) Divergence slit and scattering slit opening angle: 1 ° Opening width of light receiving slit: 0.3 mm Opening width of monochromator light receiving slit: 0.6mm Tube current: 30 mA Tube voltage: 40 kV Scan speed: 1.0 ° / min The results are shown in FIG.
  • the peak obtained by X-ray diffraction is only observed due to Mo and TiCN, and TiCN is decomposed when the mass ratio of TiCN is 30%, 40%, or 50%. As a result, no peak due to the inevitable compound produced was found, so that it was found that TiCN was not decomposed.
  • Example 2 a friction stir welding tool in which the mixing ratio of the TiCN powder was 30% by mass, the TiCN particle size and the maximum particle size in the second phase, and the average particle size of Mo were changed was manufactured. .2% proof stress was evaluated and a friction stir welding test was conducted. The test conditions and test results are shown in Table 2.
  • the TiCN phase shown in the present invention has an average particle size of 0.3 to 10 ⁇ m and a maximum particle size of 1.4 to 30 ⁇ m, which is outside the range (Comparative Examples 5 to 8). ), The room temperature hardness and the 0.2% proof stress were superior. In Comparative Examples 5 and 6, variations occurred in the density range of 75 to 93% or less, and therefore many test specimens that could not be evaluated were recognized, resulting in poor reliability.
  • Example 3 an alloy was manufactured in the same manner as in Example 1 except that the Mo powder was 70% by mass and the TiCN powder was 30% by mass. Among the TiCN particles in the alloy, the particle size was 3.0 to 5.0 ⁇ m. Evaluation was made on the relationship between the number ratio of the alloy and the characteristics of the alloy. Test conditions and test results are shown in Table 3. The number ratio of 3.0 to 5.0 ⁇ m was controlled by using titanium carbonitride powder (variety names 5MP15, 5MP30) manufactured by Allied Material Co., Ltd.
  • the number ratio of particles having a particle size of 3.0 to 5.0 ⁇ m is 40% and 60%, and the room temperature hardness and 0% compared to 30%. .2% yield strength was excellent.
  • Example 4 an alloy was manufactured in the same manner as in Example 1 except that the Mo powder was 70% by mass and the TiCN powder was 30% by mass. Among the TiCN particles in the alloy, the particle size was 1.5 to 3.5 ⁇ m. Evaluation was made on the ratio of the number of materials and the relationship between the number of materials of 5.0 to 7.0 ⁇ m and the characteristics of the alloy. Test conditions and test results are shown in Table 4. The number ratio of 1.5 to 3.5 ⁇ m and the ratio of 5.0 to 7.0 ⁇ m are obtained by mixing TiCN powder having an average particle diameter of 2.0 ⁇ m and TiCN powder having 5.5 ⁇ m. It was controlled by changing the mixing ratio of the raw material powder.
  • the number ratio of particles with a particle size of 1.5 to 3.5 ⁇ m is 20% and 40% at room temperature compared to those with 15% and 45%. Hardness, 0.2% proof stress, and relative density were excellent.
  • the number ratio of particles having a particle size of 5.0 to 7.0 ⁇ m is 10% and 30%, and the hardness at room temperature is less than that of 5% and 35%. 2% yield strength and relative density were excellent.
  • the number ratio of particles having a particle size of 1.5 to 3.5 ⁇ m is 20% to 40%, and the number ratio of particles having a particle size of 5.0 to 7.0 ⁇ m is 10% to 30% were found to have excellent room temperature hardness, 0.2% proof stress, and relative density.
  • the number ratio of TiCN grains having a particle size of 1.5 to 3.5 ⁇ m is 15% and the number ratio of 5.0 to 7.0 ⁇ m is 35%.
  • Example 5 The samples of Examples and Comparative Examples were photographed with an electron microscope, and the tissues were quantitatively analyzed. The specific procedure is as follows.
  • the surface was polished with # 180 SiC paper, and further, rough polishing was performed with a diamond slurry having a particle diameter of 9 ⁇ m using a known polishing machine.
  • intermediate finishing polishing was performed with a diamond slurry having a particle diameter of 3 ⁇ m using a known polishing machine, and then final polishing was performed with a nonwoven fabric sprayed with a diamond slurry having a particle diameter of 3 ⁇ m.
  • Au was vapor-deposited on the surface of the sample using an ion coater (model name: ION COATER, IC50) manufactured by Shimadzu Corporation under the conditions of an ion current of 3.5 mA and a vapor deposition time of 3 min.
  • an ion coater model name: ION COATER, IC50
  • the acceleration voltage was 15 kV
  • the emission current was 10 ⁇ A
  • the imaging magnification was 8000 times for “Invention 3” and 5000 times for “Comparative Example 4”.
  • the analysis was carried out by measuring the mass% of Ti and Mo by selecting three locations, the dark color portion, the light color portion, and the intermediate portion of the intermediate color between the dark color portion and the light color portion, from the density of the photographed image.
  • FIGS. 10 and 11 are diagrams simulating the photographed electron micrographs, and Table 5 shows the analysis results.
  • the circled numbers in Table 1 indicate the locations analyzed in FIGS. 10 and 11, and are represented by square areas surrounded by white lines in FIGS. 10 and 11.
  • the light color portion is mainly composed of Mo
  • the dark color portion is mainly composed of Ti
  • the intermediate color portion is intermediate between the dark color portion and the light color portion. It was a composition. Further, the area of the intermediate color portion was larger than the area of the dark color portion.
  • the light color part is mainly composed of Mo
  • the dark color part is mainly composed of Ti
  • the intermediate color part is composed of the dark color part and the light color part.
  • a molybdenum heat-resistant alloy is applied to a friction stir welding tool.
  • the present invention is not limited to this, and a glass melting jig, a high-temperature industrial furnace member , Hot extrusion dies, seamless pipe piercer plugs, injection molding hot runner nozzles, casting insert molds, resistance heating vapor deposition containers, aircraft jet engines and rocket engines, etc. It can be applied to sex members.

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Abstract

Un objectif de la présente invention est de fournir un alliage résistant à la chaleur pour un outil de travail en plastique, qui présente des propriétés telles que la force d'appui et la dureté, correspondant à un objet à traiter qui a un point de fusion supérieur à celui observé dans le passé. L'alliage de molybdène résistant à la chaleur de la présente invention comprend une première phase comprenant principalement Mo, une deuxième phase comprenant principalement au moins un carbonitrure de Ti, Zr et Hf, une troisième phase qui est agencée entre la première phase et la deuxième phase et comporte une solution solide de Mo et au moins un carbonitrure de Ti, Zr et Hf, et le reste comprenant des impuretés inévitables.
PCT/JP2013/060593 2012-05-31 2013-04-08 Alliage de molybdène résistant à la chaleur, outil de soudage par friction/malaxage et leur procédé de fabrication WO2013179773A1 (fr)

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US9970082B2 (en) 2011-12-16 2018-05-15 A.L.M.T.Corp. Heat-resistant alloy and method of manufacturing the same
WO2015182497A1 (fr) 2014-05-30 2015-12-03 株式会社アライドマテリアル Alliage de tungstène résistant à la chaleur, outil de soudage par friction-malaxage et procédé de fabrication de ces derniers
JP7429432B2 (ja) 2019-03-29 2024-02-08 国立研究開発法人産業技術総合研究所 加圧焼結体及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5747845A (en) * 1980-09-05 1982-03-18 Toshiba Tungaloy Co Ltd Hard sintered alloy
JPS599140A (ja) * 1982-07-09 1984-01-18 Mitsubishi Metal Corp 高温特性のすぐれた切削工具用焼結材料の製造法
JPH08170141A (ja) * 1994-10-20 1996-07-02 Mitsubishi Materials Corp 耐摩耗性および靭性のすぐれた耐食性サーメット材
JP2007517978A (ja) * 2003-05-20 2007-07-05 エクソンモービル　リサーチ　アンド　エンジニアリング　カンパニー 高温浸食−腐食サービスのためのマルチスケールサーメット
JP2008246553A (ja) * 2007-03-30 2008-10-16 Tohoku Univ 摩擦攪拌接合用撹拌工具

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5747845A (en) * 1980-09-05 1982-03-18 Toshiba Tungaloy Co Ltd Hard sintered alloy
JPS599140A (ja) * 1982-07-09 1984-01-18 Mitsubishi Metal Corp 高温特性のすぐれた切削工具用焼結材料の製造法
JPH08170141A (ja) * 1994-10-20 1996-07-02 Mitsubishi Materials Corp 耐摩耗性および靭性のすぐれた耐食性サーメット材
JP2007517978A (ja) * 2003-05-20 2007-07-05 エクソンモービル　リサーチ　アンド　エンジニアリング　カンパニー 高温浸食−腐食サービスのためのマルチスケールサーメット
JP2008246553A (ja) * 2007-03-30 2008-10-16 Tohoku Univ 摩擦攪拌接合用撹拌工具

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