WO2016038974A1 - 白金族金属又は白金族基合金の製造方法 - Google Patents
白金族金属又は白金族基合金の製造方法 Download PDFInfo
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- WO2016038974A1 WO2016038974A1 PCT/JP2015/068098 JP2015068098W WO2016038974A1 WO 2016038974 A1 WO2016038974 A1 WO 2016038974A1 JP 2015068098 W JP2015068098 W JP 2015068098W WO 2016038974 A1 WO2016038974 A1 WO 2016038974A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/041—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for vertical casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/022—Casting heavy metals, with exceedingly high melting points, i.e. more than 1600 degrees C, e.g. W 3380 degrees C, Ta 3000 degrees C, Mo 2620 degrees C, Zr 1860 degrees C, Cr 1765 degrees C, V 1715 degrees C
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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
- B22F3/16—Both compacting and sintering in successive or repeated steps
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
Definitions
- the present invention relates to a method for producing a platinum group metal or a platinum group base alloy, and more particularly to manufacturing a molten ingot in a method for producing a platinum group metal or a platinum group base alloy.
- Platinum group metals or platinum group base alloys are designed using the heat resistance, oxidation resistance, and chemical resistance of platinum group metals, and are widely used as high-temperature components and corrosion-resistant products.
- the platinum group metal is a general term for Pt, Pd, Rh, Ir, Ru, and Os.
- the manufacturing process of platinum group metals or platinum group based alloys generally consists of a blending process of alloy raw materials, a melting process, a plastic working process, etc.
- the melting method for manufacturing a molten ingot in the melting process is divided into several types. It is done. Since the main component platinum group metal has a very high melting point (1500 ° C. or higher), an induction heating melting furnace or energy beam melting furnace having a melting ability of 2000 ° C. or higher is used.
- Energy beam melting includes non-consumable arc melting, vacuum plasma melting, atmospheric pressure plasma arc melting, electron beam melting, etc., which are common in that the material in the water-cooled copper crucible is irradiated with the energy beam for melting.
- the melting raw material is in the form of an ingot, a plate / wire containing scrap, powder, or the like, and is used by appropriately blending a predetermined amount.
- a boat-shaped water-cooled copper crucible is a water-cooled copper crucible having a cavity (recess) having a circular shape or a square shape, and a molten ingot is obtained by melting the entire amount of raw material placed in the cavity (Patent Document 1).
- the other is a method using a water-cooled copper crucible with a cavity penetrating the lower surface.
- a raw material rod as a raw material horizontally
- one end of the raw material rod is inserted and melted into an energy beam, and molten metal is continuously dropped, and a molten pool is formed in a cavity for receiving the molten metal.
- the bottom of the molten pool is continuously pulled down to obtain a rod-shaped melted ingot (Patent Document 2).
- the raw material rod is manufactured by dissolving the raw material in advance.
- the melting raw material is powder
- the powder when it is melted in a powder state, it is swollen or scattered by the flow of energy beam.
- the powder may be compression-molded in advance by a molding method such as press molding or CIP molding (Patent Document 3).
- the compression-molded powder comes in contact with each other and is intertwined and apparently integrated, so that it is suppressed that the powder is blown away and rises even when irradiated with an energy beam.
- a normal molded body has a relative density of about 30% to 60% and includes a considerable amount of voids, and atmosphere gas or residual gas exists in the voids.
- the material yield mentioned here refers to the ratio of the mass of the molten ingot to the mass of the molten raw material.
- the raw material is a mixed powder
- the composition may be changed. If the molded body breaks and the fragments fall, the powder on the surface of the molded body peels off, or the molten metal scatters during melting, the components contained in that part are not included in the molten ingot. It is not possible to obtain a stable alloy composition.
- energy beam melting using a boat-shaped water-cooled copper crucible is melted by irradiating the energy beam from the top surface. Usually, the raw material is turned upside down and melted from the opposite surface, and this is repeated to dissolve the uniform composition. Ingot. At this time, the fallen fragments and the peeled off powder may remain undissolved in the corners of the boat-shaped cavity of the water-cooled copper hearth. Such a case also hinders an accurate alloy composition.
- JP 2002-105631 A JP2009-93681A JP-A-2004-137580
- the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a method for producing a platinum group metal or a platinum group base alloy having a high material yield.
- the present invention relates to a method for producing a platinum group metal or platinum group alloy, wherein a part or all of the raw material is a powder, the raw material is weighed, and the measured raw material is used for alloy production.
- Mixing step for obtaining mixed powder by mixing molding step for solidifying the weighed raw materials to obtain a molded body, sintering step for sintering the molded body to obtain a sintered body, and firing
- a melting step for producing a melted ingot by melting the ligature and a plastic working step for processing the melted ingot, wherein a plurality of the molded bodies are fired while being stacked in the sintering step. It is a manufacturing method of the platinum group metal or platinum group base alloy characterized by making it a sintered compact.
- the blending step is a step of weighing raw materials in accordance with a desired amount of melted ingot.
- each raw material is weighed so as to have a predetermined alloy composition.
- the raw material may have any shape, but at least a part or all of the raw material is powder.
- the molding process is a process in which a part or all of the powder raw material is molded and solidified to obtain a molded body.
- dry molding such as uniaxial pressure molding, tablet molding, CIP (cold isostatic pressing), rubber press, etc.
- the law is suitable.
- the shape can be arbitrarily selected, and can be selected from a circular plate / cylindrical shape, a square plate / polygonal shape including a polygon, an irregular briquette, and the like.
- the number of formed bodies can be determined according to the shape and dimensions of the water-cooled copper crucible and is one or more.
- the sintering step is a step of sintering the formed body so as to be substantially integrated.
- a known firing furnace such as a gas furnace or an electric furnace can be used, and both a batch type and a continuous type are suitable.
- the firing temperature can be appropriately selected depending on the type of raw material, but a range of 1000 ° C. or higher and not exceeding the melting point of the raw material is more suitable for a platinum group metal or platinum group alloy whose melting point exceeds 1500 ° C.
- the firing atmosphere can be air, inert gas, or vacuum, and is appropriately selected depending on the type of raw material.
- the sintered body has high strength because the individual particles are integrated, and has a high density due to sintering shrinkage.
- the relative density is not particularly limited, but is preferably 60% or more, more preferably 70% or more.
- the particles are integrated to increase the strength, so that no debris can be dropped and powder can be peeled off. Furthermore, since scattering during melting in the melting step can be suppressed, fluctuations in the alloy composition can also be suppressed.
- the molded body lacks strength, so when used as a raw material rod in the lowering-type melting process, there is a risk of breakage during melting, and it collapses with a slight force, so the raw material rod feed mechanism. It is also difficult to grip and difficult to use as it is.
- the particles are integrated by sintering to obtain high strength, so that they can be used as a raw material rod without fear of breakage or collapse.
- a plurality of the molded bodies are fired while being stacked and fired to obtain a sintered body that is a joined body.
- the shape of the molded body can be arbitrarily selected, and can be selected from a disc / column, a square plate / polygon including a polygon, and the like. That is, in the sintering process, when the compacts are stacked and fired, not only the particles are sintered inside the individual compacts, but also the particles that are in contact with each other at the interface between the stacked compacts are sintered and integrated. Turn into. In this way, a rod-like sintered body (joined body) is obtained.
- a conventional raw material rod was manufactured in advance with a boat-shaped water-cooled copper crucible in an energy beam melting furnace, and the melting ingot was used as a long raw material rod.
- the shape of the molten ingot produced in this way is not constant.
- the shape of the boat-shaped water-cooled copper crucible is transferred to the bottom of the molten ingot to have a fixed shape, but the side surface and the upper surface of the molten ingot are in a shape as the molten metal is solidified.
- the constant volume latent heat of melting is high, such as platinum group metals and platinum group alloys, the molten metal tends to solidify immediately when it leaves the energy beam (heating source).
- the constant volume latent heat (kJ / cm 3 ) is a latent heat necessary for melting a unit volume of a substance, and the heat of fusion (kJ / mol), molar mass (g / mol), and density (g / cm 3). ).
- the heat of fusion (kJ / mol), molar mass (g / mol), and density (g / cm 3).
- the molten metal to be dropped is insufficient, and the molten ingot tends to have defects such as vacancies.
- the amount of molten metal dripping is excessive, and the trouble of overflowing and solidifying from the cavity of the water-cooled copper crucible tends to occur.
- a molded body having a certain size can be sintered in the sintering process, and the molded body can be used as a raw material rod having a certain size, so that such a problem does not occur.
- a special melting equipment melting furnace, crucible, etc.
- such equipment is not required at all, and the raw material can be very easily used using a general electric furnace or the like.
- a rod (sintered body) can be manufactured.
- the molded body used for this raw material rod can take any shape, but if it is a substantially rectangular parallelepiped by uniaxial pressure molding, it is particularly easy to mold and very convenient for stacking during sintering (Claim 2).
- the furnace pressure of energy beam melting differs depending on the melting method and melting raw material (high vacuum to atmospheric pressure).
- an electron beam melting furnace requires a high vacuum region of 0.1 Pa or less.
- the degree of vacuum is high as described above, the pressure difference from the gas component remaining in the voids of the sintered body is large, so that it may be slightly scattered. Therefore, the furnace pressure during melting is more preferably 1 Pa or more.
- the melting step is a step of manufacturing a melting ingot using a sintered body as a raw material.
- a conventional melting furnace or melting method widely used for the production of platinum group noble metals and platinum group base alloys can be applied.
- induction heating and melting of the powder raw material is inappropriate because a sufficient induction current cannot be obtained because the contact area between the particles is small, but according to the present invention, the particles are substantially integrated by sintering.
- a sufficient induced current can be obtained, it can be applied to induction heating dissolution.
- the melting process uses an energy beam melting furnace equipped with a water-cooled copper crucible with a cavity penetrating the lower surface.
- a rod-shaped sintered body (joined body) is used as a raw material rod and one end thereof is inserted into the energy beam. It melt
- the present invention provides a method for producing a platinum group metal or a platinum group alloy, wherein a part or all of the raw material is powder, and the raw material is weighed when the raw material is weighed and the alloy is produced.
- Mixing step to obtain mixed powder molding step to solidify the blended raw material to obtain a molded body, sintering step to sinter the molded body to obtain a sintered body, and cavity
- the shape and size of the sintered body are matched to the cavity, and in the melting step, the sintered body matched to the cavity is closely arranged in the cavity of the boat-shaped water-cooled copper crucible.
- a method for producing a platinum group metal or a platinum group alloy characterized in that to produce the dissolution ingot.
- An energy beam melting boat-shaped water-cooled copper crucible usually has a circular or square cavity (recess) formed on the upper surface of copper embedded in a water-cooling circuit.
- a melting raw material is placed in a cavity, and an energy beam is irradiated from the upper surface to melt by heating.
- the shape and dimensions of the sintered body are designed according to the cavity, a larger number of melting ingots can be obtained.
- a cylindrical, disk-shaped or hexagonal prism shaped body is sintered and arranged in a circular cavity, it can be arranged closely in a plane and can be easily stacked. .
- the plastic working step is a step of processing the molten ingot into a desired shape such as a plate or wire, and a known method can be applied.
- the melted ingot produced by the present invention can be plastically processed in the same manner as the melted ingot obtained by a process that does not go through a conventional sintering process.
- processing into a plate when processing into a plate, it undergoes forging and rolling.
- processing into a wire it undergoes forging, groove rolling, and wire drawing.
- heat treatment is appropriately performed in the middle of processing to soften it.
- processing such as cutting, bending, and welding can be performed depending on the purpose of use.
- Each process can be either a cold process or a hot process in which a material is heated and processed.
- the manufacturing method of the present invention it is possible to effectively suppress the scattering of raw materials during melting compared to the conventional manufacturing method, and to improve the material yield of expensive platinum group metals or platinum group base alloys. be able to.
- the sintered body has higher strength than the molded body and is not easily broken, and the powder can be prevented from peeling off during conveyance. This has an advantage that a part of the raw material falls or peels off and does not cause a composition fluctuation, and further, when used as a raw material rod, there is an advantage that it can be supported and gripped without difficulty in the apparatus. Further, since the density is higher than that of the molded body, that is, the volume per the same mass can be reduced, more raw materials can be placed in the water-cooled copper crucible, and there is an advantage that contributes to the improvement of productivity.
- a method for manufacturing an electrode tip for a spark plug for an internal combustion engine will be described as an example to explain in more detail.
- an iridium-based alloy or a platinum-based alloy is preferably used as the electrode tip of the spark plug.
- the raw materials are all powder, and Ir powder and Pt powder are used.
- the mixed powder is filled in the hopper of an automatic press molding machine (uniaxial pressure molding).
- the molding die is provided with a rectangular cavity having a short side of 20 mm and a long side of 50 mm, and the four corners are R2 mm.
- the size of the compact is 20 ⁇ 20 ⁇ 50 mm and a substantially rectangular parallelepiped with a corner of R2 mm (FIG. 1).
- the molding pressure is 200 MPa. Although this can be arbitrarily set, it is preferable to set it to 120 MPa or more, and if it is set to 200 MPa or more, a higher density molded body having a relative density of about 50% or more can be obtained.
- a mixed powder is filled in a rubber hose and sealed and CIP-molded, a round bar-shaped molded body can be obtained.
- the molding pressure may be 120 MPa or more, and about 300 MPa is preferable.
- This raw material rod is horizontally held by the raw material bar feed mechanism of an atmospheric pressure plasma arc melting furnace (down type), and continuously melted and dropped in an argon atmosphere of 0.9 to 1.2 atm (atmospheric pressure) to produce water-cooled copper
- an atmospheric pressure plasma arc melting furnace down type
- argon atmosphere 0.9 to 1.2 atm (atmospheric pressure)
- the molten ingot is formed into a square bar by hot forging, and then is formed into a line having a substantially rectangular cross section by hot grooving. Further, a round wire having a predetermined outer diameter is formed by hot drawing with a die.
- the round wire is cut to a length suitable for a wire saw.
- a plurality of lines are arranged in parallel, fixed with resin, and cut with a wire saw to obtain a spark plug electrode chip having a predetermined length.
- Table 1 shows the results, which were evaluated according to the following criteria.
- the mass reduction represents the mass reduction between the raw material powder and the dissolved ingot at the time of blending, expressed as a percentage, and over 3% ⁇ 3% or less.
- powder peeling when the sintered body or molded body before melting was lifted with fingers, the case where powder adhered to the fingers was indicated as x, and the case where there was no adhesion at all was indicated as ⁇ .
- the dissolution state was visually observed during the dissolution, and X in which a spark-like scattering phenomenon was continuously observed was indicated as ⁇ , in rare cases, ⁇ , and in the case of almost being observed, ⁇ . Comprehensive judgment was based on these results.
- the case where the effect of the present invention was not effective was evaluated as “x”, the case where the effect was effective as “good”, and the case where the effect was higher as “good”.
- Example 1 is an example of the above description (best mode for carrying out the invention).
- the density of the compact calculated from the dimensions and mass was 52% as a relative density, and the density of the sintered body was 74%.
- a molten ingot of about ⁇ 35 ⁇ L150 mm was produced.
- the raw material rod was not broken or peeled off after the sintering until the dissolution was completed. In the furnace after melting, almost no material was scattered and no adhesion to the water-cooled copper crucible was observed.
- Example 2 a molded body was produced in the same manner as in Example 1.
- the compact has a dimension of 20 ⁇ 20 ⁇ 50 mm and a substantially rectangular parallelepiped with a corner portion of R2 mm.
- the molded bodies were individually fired without being stacked to produce a sintered body of about 16 ⁇ 16 ⁇ 44 mm.
- This sintered body was placed on a boat-shaped water-cooled copper crucible and melted by a vacuum plasma melting method to prepare a melting ingot of about 15 ⁇ 30 ⁇ 100 mm.
- the pressure during dissolution was adjusted to 5 ⁇ 10 ⁇ 1 Pa (Ar).
- Comparative Example 1 In Comparative Example 1, a raw material powder was mixed with a V-type mixer, and then a cylindrical molded body with a diameter of 30 mm was produced by the CIP method. The molding pressure was 300 MPa, and the compact density calculated from the dimensions and mass was 48% in terms of relative density. This molded body was divided into lengths of about 30 mm, placed on a boat-shaped water-cooled copper crucible, and melted by an arc melting method to prepare a melting ingot of about t15 ⁇ w30 ⁇ L100 mm. The pressure during dissolution was adjusted to 8 ⁇ 10 4 Pa (Ar).
- the molded body was not low enough to be broken by touching with a hand, but when it was taken out from the CIP mold, powder adhered to the fingers and the powder adhered to the inner wall of the CIP mold could be confirmed.
- By visual observation during melting it was confirmed that scattering from the melting portion continued intermittently until the entire molded body melted down.
- scattered material and powder peeled off from the molded body remained in the bottom corner of the boat-shaped water-cooled copper crucible.
- a part of the blended raw material powder remained undissolved, and the mass loss from the blending process of the dissolved ingot was 3.2%.
- the shape of the melted ingot was burr-like protrusions and waves.
- Comparative Example 2 In Comparative Example 2, a molded body prepared in the same manner as in Comparative Example 1 was placed on a boat-shaped water-cooled copper crucible, and a melting ingot of about t15 ⁇ w30 ⁇ L100 mm was manufactured by a vacuum plasma melting method. The pressure during dissolution was adjusted to 5 ⁇ 10 ⁇ 1 Pa (Ar). By visual observation during melting, it was confirmed that scattering from the melting portion continued intermittently until the entire molded body melted down. More material was scattered in the furnace after melting, and adhesion to the water-cooled copper crucible was more remarkable. Further, scattered material and powder peeled off from the molded body remained in the bottom corner of the boat-shaped water-cooled copper crucible. Thus, a part of the blended raw material powder remained undissolved, and the mass reduction from the blending step of the dissolved ingot was 4.5%.
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Abstract
Description
圧縮成形された粉末は、粒子同士が接触し、絡み合って見かけ上一体化しており、エネルギビームが照射されても吹き飛ばされて舞い上がるということは抑制される。通常の成形体は相対密度が30%ないし60%程度であって、相当程度の空隙を含んでおり、空隙には雰囲気ガス又は残留ガスが存在する。
また、成形体は見かけ上一体化しているだけなので、落下等の衝撃によって容易に破壊するばかりか、搬送中にも表面の粉末が剥落し、材料歩留を低下させる。ここで言う材料歩留りとは、溶解原料の質量に対する溶解インゴットの質量の割合を指す。
このような焼結体とすると、粒子同士が一体化して強度が高くなり、成形体の破片の落下及び粉末の剥落が生じ得ない。さらには溶解工程における溶解時の飛散を抑制することができるので、合金組成の変動も抑制することができる。
前記の通り、成形体は強度が不足することにより、引下げ方式の溶解工程で原料棒として用いる場合には、溶解中に折損する危険性があり、わずかな力で崩壊するので原料棒送り機構に把持することも難しく、そのまま使用することは困難である。本発明によれば、焼結により粒子同士が一体化して高い強度が得られるので、折損・崩壊の恐れもなく原料棒として用いることができる。
このような原料棒を用いて引下げ溶解すると溶湯を一定速度で滴下することが困難で、小断面積の部分では滴下する溶湯が不足し溶解インゴットに空孔などの欠陥を生じやすく、大断面積の部分では滴下する溶湯が過多となり水冷銅るつぼのキャビティから溢れ出て凝固するトラブルが発生しやすい。
また、成形体に比較して焼結体は強度が高く容易に破壊することはなく、搬送中に粉末が剥落することも抑制できる。このことは、原料の一部が落下又は剥落して、組成変動が生じない利点、さらには原料棒として用いた場合に、装置内で無理なく支持、把持できる利点がある。
さらに成形体に比べ密度が高く、すなわち同一質量当たりの体積が小さくできるため、水冷銅るつぼにより多くの原料を載せることができ生産性向上に寄与する利点もある。
スパークプラグの電極チップは、イリジウム基合金又は白金基合金が好んで用いられている。この例では、原料は全量が粉末で、Ir粉末とPt粉末を用いる。
所定の組成となるように各々の粉末を所定量秤量し、V型混合機を用いて混合し、均一な混合粉末とする。
自動プレス成形機(一軸加圧成形)のホッパに混合粉末を充填する。成形金型には、短辺20mm、長辺50mmの長方形のキャビティが設けてあり四隅はR2mmとなっている。成形体寸法は20×20×50mmで隅角部がR2mmの略直方体となる(図1)。成形圧力は200MPaとする。これは任意に設定可能だが、おおむね120MPa以上とするとよく、200MPa以上とすれば相対密度が約50%以上のより高密度な成形体が得られる。成形体密度は高いほど焼結に必要な熱エネルギを低減でき有利であるが、過剰であれば成形体が割れる原因となる。このほか、混合粉末をゴムホースに充填、密封しCIP成形すると、丸棒状の成形体を得ることもできる。この場合にも、成形圧力を120MPa以上とするとよく、300MPa程度が好適である。
この2例の成形体を従来のようにそのまま溶解すると、溶解炉内に加熱された粉末及び溶融金属の一部が飛散し、火花を散らす様子が視認できる。また、手で触れると手指に粉末が付着し、5cmほどの高さから落下させると隅角部が割れる程度の強度である。
成形体の20×20mm面を上下面として縦に5個積み重ね、これを1本と数える(図2)。4本分をカーボン製セッタ内に配置し、セッタごとカーボンヒータを備えた雰囲気炉内に挿入し、1500℃で3時間、アルゴン気流下にて焼成する。焼結体は焼結収縮し、相対密度70%以上、約16×16×220mmの原料棒が得られる(図2)。
この原料棒を大気圧プラズマアーク溶解炉(引下げ方式)の原料棒送り機構に水平に把持し、0.9~1.2atm(大気圧)のアルゴン雰囲気で連続的に溶解・滴下させ、水冷銅るつぼ底部を引下げると、φ35mmの円柱状インゴットが得られる。溶解中に飛散する様子は見られず、焼結工程の効果が確認できる。また、このとき原料棒は片持ち梁の状態だが、工程中折れることもなく、粉末が剥落することもない。
溶解インゴットは、熱間鍛造によって角棒に形成し、次いで熱間溝圧延加工によって略四角形断面の線とする。さらに、ダイスによる熱間引抜き加工によって所定外径の丸線とする。
丸線は、ワイヤソーに適した長さに切断する。複数の線を各々平行に並べ、樹脂固定し、ワイヤソーによって切断して、所定長さのスパークプラグ用電極チップとする。
表1は結果であり、つぎの基準で評価した。
粉末剥落について、溶解前の焼結体又は成形体を手指で持ち上げたとき、手指に粉末の付着が見られたものを×、まったく付着がないものを○とした。
溶解状態は、溶解中に目視観察し、火花様の飛散現象が継続的に観察されたものを×、まれに観察されたものを△、ほとんど観察されたかったものを○とした。
総合判定はこれらの結果を斟酌し、本発明の効果のないものは×、効果があるものは○、より効果が高いものは◎とした。
実施例1は、前記説明(発明を実施するための最良の形態)の例である。
寸法と質量から計算した成形体密度は相対密度で52%、焼結体密度は74%であった。この焼結体を原料棒として、約φ35×L150mmの溶解インゴットを作製した。
溶解中(圧力1.1×105Pa)に目視観察したところ飛散する現象はまったく見られず、溶解インゴットの配合工程からの質量減少は0.6%以下であった。また、焼結後、溶解が完了するまでの間、原料棒が折れたり、剥落したりすることもなかった。
溶解後の炉内には、飛散した材料はほとんどなく、水冷銅るつぼへの付着も認められなかった。
実施例2では、成形体を実施例1と同様に作製した。成形体寸法は20×20×50mmで隅角部がR2mmの略直方体である。この成形体を積み重ねることなく個別に焼成し、約16×16×44mmの焼結体を作製した。この焼結体を舟形水冷銅るつぼに載せて、真空プラズマ溶解法で溶解し、約15×30×100mmの溶解インゴットを作製した。溶解時の圧力は5×10-1Pa(Ar)に調整した。
溶解中の目視観察では、ときおり飛散する様子が観察され、溶解後の炉内には、飛散した材料がわずかにあり、その一部が水冷銅るつぼに付着していた。
溶解インゴットの質量減少は2.5%であった。また、溶解インゴットの形状は、底部が舟形水冷銅るつぼの形状に沿っておよそ平滑であったが、側面にはバリ状の突起があり、上面は凝固したまま波打っていた。
比較例1では、原料粉末をV型混合機にて混合後、CIP法にてφ30mmの円柱状成形体を作製した。成形圧力は300MPaで、寸法と質量から計算した成形体密度は相対密度で48%であった。この成形体を長さ約30mmに割り、舟形水冷銅るつぼに載せて、アーク溶解法で溶解し、約t15×w30×L100mmの溶解インゴットを作製した。溶解時の圧力は8×104Pa(Ar)に調整した。
成形体は、手で触れて壊れるほどの低強度ではなかったが、CIP型から取りだすとき、手指に粉末が付着し、また、CIP型内壁に付着した粉末が確認できた。
溶解中の目視観察では、成形体の全体が溶け落ちるまでの間、溶解部からの飛散が断続的に続くことが確認された。溶解後の炉内には、飛散した材料があり、水冷銅るつぼへの付着も顕著であった。また、舟形水冷銅るつぼの底部隅角部には、飛散した材料及び成形体から剥落した粉末が残留していた。このように、配合した原料粉末の一部は溶解されずに残り、溶解インゴットの配合工程からの質量減少は3.2%であった。
溶解インゴットの形状は、実施例2と同様にバリ状の突起や波うちがあった。
比較例2では、比較例1と同様に作製した成形体を舟形水冷銅るつぼに載せて、真空プラズマ溶解法で約t15×w30×L100mmの溶解インゴットを作製した。溶解時の圧力は5×10-1Pa(Ar)に調整した。
溶解中の目視観察では、成形体の全体が溶け落ちるまでの間、溶解部からの飛散が断続的に続くことが確認された。溶解後の炉内には、飛散した材料がより多くあり、水冷銅るつぼへの付着もより顕著であった。また、舟形水冷銅るつぼの底部隅角部には、飛散した材料及び成形体から剥落した粉末が残留していた。このように、配合した原料粉末の一部は溶解されずに残り、溶解インゴットの配合工程からの質量減少は4.5%であった。
Claims (5)
- 白金族金属又は白金族基合金の製造方法において、
原料の一部又は全部が粉末であって、前記原料を秤量し、合金製造を目的とする場合には前記秤量された原料を混合して混合粉を得る、配合工程と、
前記秤量された原料を成形固化して成形体を得る成形工程と、
前記成形体を焼結して焼結体を得る焼結工程と、
前記焼結体を溶解して溶解インゴットを製造する溶解工程と、
前記溶解インゴットを加工する塑性加工工程と、
を含み、
前記焼結工程において複数の該成形体同士を積み重ねつつ焼成して接合体である焼結体とすることを特徴とする白金族金属又は白金族基合金の製造方法。 - 前記成形工程において成形体の形状を略直方体となすことを特徴とする請求項1に記載の白金族金属又は白金族基合金の製造方法。
- 前記溶解工程において、溶解時の圧力が1Pa以上であることを特徴とする請求項1または2に記載の白金族金属又は白金族基合金の製造方法。
- 前記溶解工程は、下面に貫通するキャビティを備えた水冷銅るつぼを備えたプラズマアーク溶解炉を用い、前記キャビティに形成された前記焼結体の溶湯による溶融池の底部を引下げて、溶解インゴットを得ることを特徴とする請求項3に記載の白金族金属又は白金族基合金の製造方法。
- 白金族金属又は白金族基合金の製造方法において、
原料の一部又は全部が粉末であって、前記原料を秤量し、合金製造を目的する場合には前記秤量された原料を混合して混合粉を得る、配合工程と、
前記配合された原料を成形固化して成形体を得る成形工程と、
前記成形体を焼結して焼結体を得る焼結工程と、
キャビティが形成されている舟形水冷銅るつぼを用いたエネルギビーム溶解法を用いて前記焼結体を溶解して溶解インゴットを製造する溶解工程と、
前記溶解インゴットを加工する塑性加工工程と、
を含み、
前記焼結工程において、前記焼結体の形状・寸法を前記キャビティに合わせ、
前記溶解工程において、前記キャビティに合わせた前記焼結体を前記舟形水冷銅るつぼの前記キャビティ内に密に並べて配置して、前記溶解インゴットを製造することを特徴とする白金族金属又は白金族基合金の製造方法。
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| CN201580010698.8A CN106102958B (zh) | 2014-09-08 | 2015-06-23 | 铂族金属或铂族基合金的制造方法 |
| US15/307,149 US20170043392A1 (en) | 2014-09-08 | 2015-06-23 | Method for producing platinum group metal or platinum group-based alloy |
| US16/281,847 US20190184453A1 (en) | 2014-09-08 | 2019-02-21 | Method for producing platinum group metal or platinum group-based alloy |
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| CN107971707B (zh) * | 2017-12-01 | 2019-07-16 | 贵研资源(易门)有限公司 | 高纯标准钯锭的制备方法 |
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| JP2002332528A (ja) * | 2001-05-09 | 2002-11-22 | Nikko Materials Co Ltd | 高純度ルテニウムのリサイクル方法及びリサイクルされた高純度ルテニウムからのターゲットの製造方法 |
| JP2004137580A (ja) * | 2002-10-21 | 2004-05-13 | Sumitomo Metal Mining Co Ltd | イリジウムスパッタリングターゲットの製造方法及びその方法で得られたターゲット |
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| US3416919A (en) | 1967-09-18 | 1968-12-17 | Titanium Metals Corp | Method for forming electrodes |
| US3758662A (en) * | 1971-04-30 | 1973-09-11 | Westinghouse Electric Corp | In carbonaceous mold forming dense carbide articles from molten refractory metal contained |
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| JP2016065264A (ja) | 2016-04-28 |
| JP5769854B1 (ja) | 2015-08-26 |
| CN106102958A (zh) | 2016-11-09 |
| US20170043392A1 (en) | 2017-02-16 |
| CN106102958B (zh) | 2018-10-12 |
| DE112015004106B4 (de) | 2025-10-09 |
| DE112015004106T5 (de) | 2017-05-24 |
| US20190184453A1 (en) | 2019-06-20 |
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