JP2002371301A - Tungsten sintered compact and manufacturing method therefor - Google Patents
Tungsten sintered compact and manufacturing method thereforInfo
- Publication number
- JP2002371301A JP2002371301A JP2001183666A JP2001183666A JP2002371301A JP 2002371301 A JP2002371301 A JP 2002371301A JP 2001183666 A JP2001183666 A JP 2001183666A JP 2001183666 A JP2001183666 A JP 2001183666A JP 2002371301 A JP2002371301 A JP 2002371301A
- Authority
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- Japan
- Prior art keywords
- tungsten
- sintered body
- tensile strength
- mass
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｗ材料およびその
製造方法に関し、詳しくは高温炉用反射板および炉用構
造部材および高輝度電極素材等に用いられるＷ材料およ
びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a W material and a method for producing the same, and more particularly, to a W material used for a reflector for a high-temperature furnace, a structural member for a furnace, a high-luminance electrode material, and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】高融点金属材料の特長は優れた耐熱性で
ある。高融点金属材料中でもＷは、最高融点３３８０℃
を有する金属であり、高温における多用が期待されるも
のである。しかしながら、現行市販されているＷ板材お
よび線棒材は純Ｗであり、次の理由から使用の制限を受
けている。その理由は、例えばＷ板材を１１００℃以上
の高温下で使用すると再結晶粒成長を起こし、圧延加工
により形成された伸長した積層の繊維組織が等軸状の球
状組織に変貌し高温強度が低下してしまうことである。
また、この組織の変貌は、元々延性に乏しい性質を更に
脆弱な材料へ変質させてしまい実用性に欠く原因となっ
ている。2. Description of the Related Art A refractory metal material is characterized by excellent heat resistance. Among the high melting point metal materials, W has a maximum melting point of 3380 ° C.
And is expected to be used frequently at high temperatures. However, currently commercially available W plate materials and wire rods are pure W, and their use is restricted for the following reasons. The reason is that, for example, when a W plate material is used at a high temperature of 1100 ° C. or more, recrystallized grain growth occurs, and the fiber structure of the stretched laminate formed by rolling is transformed into an equiaxed spherical structure, and the high-temperature strength is reduced. It is to do.
In addition, this transformation of the structure causes the originally poor ductility to be transformed into a more brittle material, which is a cause of lack of practicality.
【０００３】そのような再結晶粒成長は、Ｗの本質的性
質であり、これを防止することは不可能であるが、粒成
長を抑制することによって、Ｗ本来の特質が活かされた
用途の展望が開かれると考える。[0003] Such recrystallized grain growth is an essential property of W, and it is impossible to prevent such growth. However, by suppressing the grain growth, it is possible to use the inherent properties of W in applications. I think the prospects are open.
【０００４】次に、純Ｗ板および線棒材の欠点について
述べる。これらの材料は、再結晶開始温度が１１００℃
である。保持時間との関連もあるが、１１００℃から再
結晶粒成長が始まる。Next, defects of the pure W plate and the wire rod will be described. These materials have a recrystallization initiation temperature of 1100 ° C.
It is. Although related to the holding time, recrystallized grain growth starts at 1100 ° C.
【０００５】また、Ｗに期待される実用温度は１７００
℃以上である。Ｗに代用できる材料としては、モリブデ
ン（Ｍｏ）があるが、Ｍｏの融点は、２６３０℃とＷに
比べて低いため、強度の低下が大きい。また１７００℃
における蒸気圧は、Ｗ（１０ −１１ｔｏｒｒ）がＭｏ
（１０−７ｔｏｒｒ）に比べ４桁以上小さく、消耗が少
ないため長寿命である。[0005] The expected practical temperature of W is 1700.
° C or higher. Materials that can be substituted for W include molybdenum
(Mo), but the melting point of Mo is 2630 ° C and W
Because of the lower strength, the strength is greatly reduced. 1700 ° C
Is W (10 -11torr) is Mo
(10-7torr), which is at least 4 orders of magnitude smaller and less wear
No long life.
【０００６】さらに、再結晶開始と同時に組織が変化す
る。高温強度が維持されている組織であれば問題無い
が、組織変化により高温強度が低下し、且つ脆性材料へ
と変質する。Further, the structure changes simultaneously with the start of recrystallization. Although there is no problem as long as the structure maintains the high-temperature strength, the high-temperature strength is reduced due to the structure change, and the structure is changed to a brittle material.
【０００７】[0007]
【発明が解決しようとする課題】そこで、Ｗ材料の高温
特性の改善を進める方法が種々提案されている。それら
の改善方法は、次のように大別される。Therefore, various methods for improving the high-temperature characteristics of W materials have been proposed. These improvement methods are roughly classified as follows.
【０００８】（１）ＴｈＯ２などの酸化物分散効果によ
る改善、（２）ＨｆＣなどの炭化物析出効果による改
善、（３）Ｎｂなどの異種金属の合金固溶効果による改
善等。(1) Improvement by the effect of dispersing oxides such as ThO 2 , (2) Improvement by the effect of precipitation of carbides such as HfC, and (3) Improvement by the effect of dissolving alloys of dissimilar metals such as Nb.
【０００９】上記（２）の改善方法は、大きさがｎｍオ
ーダーの微細な炭化物を析出間距離を小さくし、析出物
とＷマトリックスの転位との相互作用によるものであ
る。炭化物を微細にドープ，析出させる方法としてメカ
ニカルアロイング（ＭＡ）法がある。The improvement method (2) is based on the interaction between the precipitates and the dislocations of the W matrix by reducing the inter-precipitation distance of fine carbides having a size on the order of nm. As a method of finely doping and depositing carbide, there is a mechanical alloying (MA) method.
【００１０】しかしながら、この（２）の方法では、Ｗ
粒子も非常に微細になることにより活性となり空気との
反応により着火，爆発の恐れのため取扱が困難であり、
Ｗの工業的生産手法としては難がある。However, according to the method (2), W
Particles become very fine and become active due to reaction with air, which makes them difficult to handle due to the risk of ignition and explosion.
There is difficulty as an industrial production method for W.
【００１１】一方、上記（３）の改善方法は、高融点金
属同士の固溶による強化を狙うものではあるが、Ｎｂは
非常に高価な金属であるため数％の添加を考えても、コ
ストが高く商用規模の材料提供には非現実的であり、特
殊部材向けなどの限定的用途となる。On the other hand, the above-mentioned improvement method (3) aims at strengthening by solid solution of high melting point metals. However, since Nb is a very expensive metal, even if addition of several% is considered, cost is low. Therefore, it is impractical to provide materials on a commercial scale, and is limited to applications for special components.
【００１２】そこで、上記（１）の酸化物分散効果は、
Ｗの組織を高温化においても安定せしめ、再結晶温度を
上昇させる働きがあるためと考えられる。Therefore, the oxide dispersion effect of the above (1) is as follows.
It is considered that the structure of W stabilizes even at a high temperature and has a function of increasing the recrystallization temperature.
【００１３】しかしながら、上記（１）の改善方法にお
いてＴｈＯ２は、放射性物質であるため、取扱の法規制
や使用時の環境への飛散による汚染などの観点から使用
困難な物質である。However, in the above-mentioned improvement method (1), since ThO 2 is a radioactive substance, it is a substance that is difficult to use from the viewpoint of legal restrictions on handling and pollution due to scattering into the environment during use.
【００１４】先行技術として、ＴｈＯ２の代わる代替材
として、希土類元素のうちランタン酸化物（Ｌａ
２Ｏ３，融点２３００℃）を選定し、ＷにＬａ２Ｏ３を
０．４〜１．２質量％分散させ、再結晶後に加工方向に
伸長した長大結晶粒の積層組織を形成させることによっ
て、高温域においても高い引張強度を有した板材が提案
されている（特開平１１−１５２５３４号公報、参
照）。As a prior art, lanthanum oxide (La) among rare earth elements has been used as an alternative to ThO 2.
2 O 3 , melting point 2300 ° C.), disperse 0.4 to 1.2 mass% of La 2 O 3 in W, and form a lamination structure of long crystal grains elongated in the processing direction after recrystallization. In addition, a plate material having high tensile strength even in a high temperature range has been proposed (see JP-A-11-152534).
【００１５】このように従来技術において、再結晶後に
高温特性に優れた長大結晶粒の積層組織を有する板材を
得るためには高加工率の塑性加工が不可欠となり、バル
ク，厚板への適用には限界がある。As described above, in the prior art, in order to obtain a sheet having a laminated structure of long crystal grains having excellent high-temperature characteristics after recrystallization, plastic working at a high working rate is indispensable, and application to bulk and thick plates is required. Has limitations.
【００１６】そこで、本発明の一技術的課題は、高温下
においても結晶粒が殆ど粗大化しない優れた組織安定性
を有する焼結体とその製造方法とを提供することにあ
る。It is an object of the present invention to provide a sintered body having excellent structural stability in which crystal grains hardly become coarse even at a high temperature, and a method for producing the same.
【００１７】また、本発明のもう一つの技術的課題は、
前記焼結体を素材として塑性加工を施した板材および線
棒材において、先行技術品より高い高温強度を有するモ
リブデン板材及び線棒材を提供することにある。Another technical problem of the present invention is that
It is an object of the present invention to provide a molybdenum plate and a wire rod having higher high-temperature strength than a prior art product in a plate and a wire rod which have been subjected to plastic working using the sintered body as a raw material.
【００１８】[0018]
【課題を解決するための手段】本発明によれば、タング
ステン焼結体において、前記焼結体はランタン酸化物お
よびレニウムを含有し、高温加熱を施しても結晶粒が粗
大化しない組織安定性を有することを特徴とするタング
ステン焼結体が得られる。According to the present invention, in a tungsten sintered body, the sintered body contains lanthanum oxide and rhenium, and the crystal grains do not become coarse even when heated at a high temperature. Is obtained.
【００１９】また、本発明によれば、前記タングステン
焼結体において、タングステン中に含まれるランタン酸
化物は５〜１０質量％，レニウムが３〜２０質量％，残
部がタングステンおよび不可避不純物分からなることを
特徴とするタングステン焼結体が得られる。According to the present invention, in the tungsten sintered body, the lanthanum oxide contained in tungsten is 5 to 10% by mass, rhenium is 3 to 20% by mass, and the balance is tungsten and unavoidable impurities. Is obtained.
【００２０】また、本発明によれば，前記いずれかのタ
ングステン焼結体を素材として加工した板材であって、
１０００℃以上の加熱時において、４５０ＭＰａを超え
る引張強度を有し、１５００℃〜１７００℃の温度範囲
において、２３０ＭＰａを超える引張強度を有するタン
グステン板材が得られる。According to the present invention, there is provided a plate processed by using any one of the above-mentioned tungsten sintered bodies as a raw material,
At the time of heating at 1000 ° C. or more, a tungsten plate material having a tensile strength exceeding 450 MPa and having a tensile strength exceeding 230 MPa in a temperature range of 1500 ° C. to 1700 ° C. is obtained.
【００２１】また、本発明によれば、前記いずれかのタ
ングステン焼結体を素材として加工した線棒材であっ
て、１０００℃以上の加熱時において、４５０ＭＰａを
超える引張強度を有し、１５００℃〜１７００℃の温度
範囲において、２３０ＭＰａを超える引張強度を有する
タングステン線棒材が得られる。Further, according to the present invention, there is provided a wire rod formed by using any of the above-mentioned tungsten sintered bodies as a raw material, having a tensile strength exceeding 450 MPa when heated at 1000 ° C. or more, and having a tensile strength of 1500 ° C. In a temperature range of １1700 ° C., a tungsten wire rod having a tensile strength exceeding 230 MPa can be obtained.
【００２２】また、本発明によれば、前記タングステン
焼結体を製造する方法であって、等方加圧焼結（ＨＩ
Ｐ）を用いることによって高緻密且つ１０μｍ以下の微
細結晶粒からなるタングステン焼結体の製造方法が得ら
れる。Further, according to the present invention, there is provided a method for producing the above-mentioned tungsten sintered body, comprising the steps of isostatic pressing (HI)
By using P), it is possible to obtain a method for producing a tungsten sintered body having high density and fine crystal grains of 10 μm or less.
【００２３】また、本発明によれば、前記タングステン
板材を製造する方法であって、タングステンの青色酸化
物にランタン酸化物を５〜１０質量％添加した後、還元
し、その粉末にレニウムを添加・混合した後、等方加圧
焼結（ＨＩＰ）を用いて焼結し、総板厚減少率９３％以
上で鍛造あるいは圧延することを特徴とするタングステ
ン板材の製造方法が得られる。Further, according to the present invention, there is provided a method for producing the above-mentioned tungsten plate material, comprising adding 5 to 10% by mass of lanthanum oxide to a blue oxide of tungsten, reducing the same, and then adding rhenium to the powder. After the mixing, a method for producing a tungsten sheet material characterized by sintering using isotropic pressure sintering (HIP) and forging or rolling at a total sheet thickness reduction rate of 93% or more is obtained.
【００２４】さらに、本発明によれば、前記タングステ
ン線棒材を製造する方法であって、タングステンの青色
酸化物にランタン酸化物を５〜１０質量％添加した後、
還元し、その粉末にレニウムを添加・混合した後、等方
加圧焼結（ＨＩＰ）を用いて焼結し、総断面減少率８３
％以上で孔型圧延加工，転打加工，線引き加工の内すく
なくとも一種の一方向加工することを特徴とするタング
ステン線棒材の製造方法が得られる。Further, according to the present invention, there is provided the method for producing the tungsten wire rod, wherein 5 to 10% by mass of lanthanum oxide is added to blue tungsten oxide.
After reducing, adding and mixing rhenium to the powder, sintering it using isotropic pressure sintering (HIP) to reduce the total area reduction rate to 83%.
% Or more, a method of manufacturing a tungsten wire rod characterized by at least one type of unidirectional working out of grooved rolling, rolling and drawing.
【００２５】[0025]
【発明の実施の形態】まず、本発明について更に詳細に
説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the present invention will be described in more detail.
【００２６】本発明では、Ｗ材料の高温強度を図るた
め、ランタン酸化物分散効果に加え、Ｒｅの固溶強化に
よる改善を狙った。In the present invention, in order to increase the high-temperature strength of the W material, in addition to the effect of dispersing the lanthanum oxide, the improvement by solid solution strengthening of Re is aimed.
【００２７】Ｗ材料中にドープ酸化物を均一微細分散さ
せるには、Ｗ材料製造工程の上流、すなわち原料に近い
ほうが良い。安定な酸化物として、三酸化タングステン
（ＷＯ３），青色酸化物（Ｗ４Ｏ１１）がある。In order to uniformly and finely disperse the doped oxide in the W material, it is better upstream of the W material manufacturing process, that is, closer to the raw material. Stable oxides include tungsten trioxide (WO 3 ) and blue oxide (W 4 O 11 ).
【００２８】本発明では、酸化物粒子表面に微細なクラ
ックが存在する青色酸化物がドープ元素量のコントロー
ルの点で優位であると考え、これを使用することにし
た。In the present invention, the blue oxide having fine cracks on the surface of the oxide particles is considered to be superior in controlling the amount of the doping element, and is used.
【００２９】ドープ元素は高温強度向上に不可欠である
が、少なくてもその効果は発揮できず、多すぎると圧粉
体の焼結密度が不足し、後工程の熱間加工が不可能とな
る欠点がある。The doping element is indispensable for improving the high-temperature strength, but the effect cannot be exerted even if the amount is small. If the amount is too large, the sintered density of the green compact becomes insufficient, so that hot working in a later step becomes impossible. There are drawbacks.
【００３０】そこで、本発明ではＬａ２Ｏ３添加量を５
〜１０％にし、且つ固溶強化元素であるＲｅを３〜２０
％添加したＷ圧粉体を作製し、焼結体の焼結密度を上げ
るため、真空焼結の後、等方加圧焼結（ＨＩＰ）を用い
て高緻密化させた焼結体を作製した。Therefore, in the present invention, the amount of La 2 O 3 added is 5
And the solid solution strengthening element Re is 3 to 20%.
% Of W powder compact, and to increase the sintering density of the sintered compact, after vacuum sintering, produce a highly densified sintered compact using isotropic pressure sintering (HIP) did.
【００３１】ここで、本発明において、最大Ｌａ２Ｏ３
添加量を１０％にしたのは、これ以上添加量を増やすと
ＨＩＰを用いても焼結密度が上がらないためである。Here, in the present invention, the maximum La 2 O 3
The addition amount is set to 10% because if the addition amount is further increased, the sintering density does not increase even when HIP is used.
【００３２】また、本発明において、Ｒｅ量を３〜２０
％にしたのは、３％以下だと固溶強化としての効果を示
さないためであり、２０％以上になると、コストが高く
商用規模の材料提供には非現実的になるためである。In the present invention, the amount of Re is 3 to 20.
The reason is that if it is 3% or less, the effect of solid solution strengthening is not exhibited, and if it is 20% or more, the cost becomes high and it becomes impractical to provide a commercial-scale material.
【００３３】次に、本発明の実施の形態によるＷ材料の
作製方法と、材料評価方法の具体例を純Ｗ材料と比較し
て述べる。Next, a method of manufacturing a W material according to the embodiment of the present invention and a specific example of a material evaluation method will be described in comparison with a pure W material.
【００３４】（材料作製方法）本発明の実施の形態によ
るＷ材料は、粉末冶金法に拠り作製される。平均粒径１
５μｍ，高純度の青色Ｗ酸化物粉（通称，代表的組成式
Ｗ４Ｏ１１，Ｗ純度９９．９８％）を原料とし、これに
所定量のＬａ２Ｏ３を分散含有させた。酸化物を数十質
量ｐｐｍから数質量％の範囲で微細均一分散させるため
に湿式法を用いた。まずＬａ２Ｏ３を試薬特級の硝酸に
て溶解後、エチルアルコールにて希釈し、Ｌａ２Ｏ３濃
度１０ｇ／ｌのドープ用原液を作製する。磁器製蒸発皿
に、１ｌのエチルアルコールを計量注入し、さらに目的
ドープ量に見合うドープ原液をメスビュレットにて計量
注入した蒸発皿の中に、予め秤量した青色酸化物（酸素
量１９．４％）５，０００ｇを投入し、スラリー状にな
るまで十分攪拌する。この蒸発皿を乾燥機の上に乗せ、
約１００℃に加熱しながら攪拌を続け、アルコール臭が
無くなるまで乾燥した後冷却する。元の状態に戻った青
色酸化物は、Ｌａ２Ｏ３を分散させたＷ酸化物となる。(Material Manufacturing Method) The W material according to the embodiment of the present invention is manufactured by powder metallurgy. Average particle size 1
A 5 μm, high-purity blue W oxide powder (commonly referred to as a typical composition formula W 4 O 11 , W purity 99.98%) was used as a raw material, and a predetermined amount of La 2 O 3 was dispersed and contained therein. A wet method was used to finely and uniformly disperse the oxide in the range of tens of ppm by mass to several percent by mass. First, La 2 O 3 is dissolved in nitric acid of a reagent grade, and then diluted with ethyl alcohol to prepare a stock solution for doping having a La 2 O 3 concentration of 10 g / l. 1 l of ethyl alcohol was metered into a porcelain evaporating dish, and a dope stock solution corresponding to the target dope amount was metered into the evaporating dish with a mess burette. ) Charge 5,000 g and stir well until a slurry is formed. Place this evaporating dish on the dryer,
Stirring is continued while heating to about 100 ° C., followed by drying until there is no alcohol odor and then cooling. The blue oxide that has returned to the original state becomes a W oxide in which La 2 O 3 is dispersed.
【００３５】ドープＷ酸化物を８５０℃の水素還元炉中
のて還元し、ドープＷ粉を得る。このドープＷ粉の平均
粒径は２．５０μｍ，Ｗ純度９９．９５％であり、Ｌａ
２Ｏ ３濃度はドープＷ酸化物状態と同一濃度である。The doped W oxide is placed in a hydrogen reduction furnace at 850 ° C.
And reduced to obtain a dope W powder. Average of this dope W powder
The particle size is 2.50 μm, the W purity is 99.95%, and La
2O 3The concentration is the same as that of the doped W oxide state.
【００３６】それぞれ所定量のＬａ２Ｏ３を添加したド
ープＷ粉に所定量の金属Ｒｅ粉を添加し、混合した。A predetermined amount of metal Re powder was added to a dope W powder to which a predetermined amount of La 2 O 3 was added, respectively, and mixed.
【００３７】このようにして得られたＷ−Ｌａ２Ｏ３−
Ｒｅ粉をラバーバックに充填、密閉後、真空引きし、静
水圧プレス機により成型した。成型圧力は２２３ＭＰａ
とした。この成型体を２０００℃の真空焼結炉で１０時
間焼結した後、２０００℃−１９６ＭＰａ−３時間の条
件でＨＩＰを行い、高緻密化させたＷ合金を得た。本発
明にて作製したＷ焼結体の密度を表１に示す。上記手法
にて得られたこれらの焼結体の組織を確認したところ、
純Ｗと比較して非常に微細な結晶粒を有するものであっ
た。測定した結晶粒径の値も併せて下記表１に示す。The thus obtained W-La 2 O 3 −
The rubber powder was filled in a rubber bag, sealed, and then evacuated and molded by a hydrostatic press. Molding pressure is 223MPa
And After sintering this molded body in a vacuum sintering furnace at 2000 ° C. for 10 hours, HIP was performed under the conditions of 2000 ° C. and 196 MPa for 3 hours to obtain a highly densified W alloy. Table 1 shows the density of the W sintered body produced according to the present invention. When the structure of these sintered bodies obtained by the above method was confirmed,
It had very fine crystal grains as compared with pure W. The measured crystal grain size values are also shown in Table 1 below.
【００３８】[0038]
【表１】 [Table 1]
【００３９】焼結体の寸法は厚さ１５ｍｍ，幅６０ｍ
ｍ，長さ１００ｍｍである。焼結体中のランタン酸化物
は、Ｗ焼結粒の粒界および粒内に平均粒径サブミクロン
ないし１μｍの粒状に分布・存在していた。またＲｅ
は、ＥＰＭＡにて固溶状態を調べたところ、Ｗマトリッ
クス中に均一に固溶していた。The dimensions of the sintered body are 15 mm in thickness and 60 m in width.
m, length 100 mm. The lanthanum oxide in the sintered body was distributed and existed in the form of particles having an average particle diameter of submicron to 1 μm in the grain boundaries and in the grains of the W sintered grains. Also Re
When the solid solution state was examined by EPMA, it was found to be uniformly dissolved in the W matrix.
【００４０】これらの焼結体を小さく切り出し、真空中
２２００℃にて１時間から最長１００時間まで加熱処理
を行い、それらの結晶粒径を測定することによって、高
温加熱による組織安定性を調べた。加熱時間と結晶粒径
の関係を図１に示す。図１に示すように、焼結温度より
２００℃高い温度にて１００時間加熱を施しても、その
結晶粒は殆ど粗大化はせず、１０μｍ以下の微細結晶粒
を保持していた。These sintered bodies were cut into small pieces, heat-treated in vacuum at 2200 ° C. for 1 hour to a maximum of 100 hours, and their crystal grain size was measured to examine the structural stability due to high-temperature heating. . FIG. 1 shows the relationship between the heating time and the crystal grain size. As shown in FIG. 1, even when heating was performed at a temperature 200 ° C. higher than the sintering temperature for 100 hours, the crystal grains hardly became coarse and fine crystal grains of 10 μm or less were retained.
【００４１】これらの焼結体を次の手順で熱間圧延し、
最終板厚１ｍｍ（総板厚減少率９３％）に仕上げた。熱
間圧延の初期段階では加熱温度１３００℃〜１５００
℃，圧延パス当りの圧延率を１５〜３０％とした。圧延
終期では加熱温度８００℃〜１０００℃，圧延率を１０
〜２５％とし、板厚１ｍｍ×幅７０ｍｍ×長さ６００ｍ
ｍ（圧延作業に支障のため中間で長手方向半分に切断）
の表面が酸化物で覆われた圧延板を得た。この圧延板を
水素中，１２００℃，３０分の歪取焼鈍処理の後、酸洗
化学処理により洗浄し金属光沢面の板となし、引張試験
用素材に使用した。These sintered bodies were hot-rolled in the following procedure,
Finished to a final thickness of 1 mm (total thickness reduction rate 93%). In the initial stage of hot rolling, the heating temperature is 1300 ° C. to 1500
° C, and the rolling reduction per rolling pass was 15 to 30%. At the end of rolling, the heating temperature is 800-1000 ° C and the rolling rate is 10
２５25%, board thickness 1mm × width 70mm × length 600m
m (cut in half in the longitudinal direction at the middle for trouble in rolling work)
A rolled plate having the surface covered with oxide was obtained. The rolled sheet was subjected to a strain relief annealing treatment in hydrogen at 1200 ° C. for 30 minutes, and then washed by a pickling chemical treatment to form a plate having a metallic glossy surface, and used as a material for a tensile test.
【００４２】引張試験片の作製には、放電ワイヤ加工機
を用いた。その試験片は全長６０ｍｍ，平行部長さ３０
ｍｍ，幅４ｍｍとし、平行部は１５００番のエメリー紙
で最終研磨し、切断時の変形層を除去した。For the production of the tensile test pieces, an electric discharge wire machine was used. The test piece has a total length of 60 mm and a parallel part length of 30
mm and a width of 4 mm, and the parallel portion was finally polished with a 1500 emery paper to remove a deformed layer at the time of cutting.
【００４３】一方、比較材の純Ｗ材料の作製はドープ工
程を除き同じプロセスを踏襲して実施した。On the other hand, a pure W material as a comparative material was manufactured by following the same process except for the doping step.
【００４４】本発明と比較材との両試験片に、真空中１
５００℃，１時間の焼鈍処理を行った後、引張試験に供
した。高温引張試験は、窒素雰囲気中，歪速度５×１０
−４Ｓ−１で行った。Each of the test pieces of the present invention and the comparative material was subjected to
After an annealing treatment at 500 ° C. for 1 hour, it was subjected to a tensile test. The high-temperature tensile test was performed in a nitrogen atmosphere at a strain rate of 5 × 10
-4 S- 1 .
【００４５】図２は１７００℃における本発明材（Ｗ−
１０％Ｌａ２Ｏ３−３〜２０％Ｒｅ）のＲｅ量と引張強
度の関係を示す図である。図２に示すように、Ｌａ２Ｏ
３およびＲｅを添加した本発明材の引張強度が比較材よ
り高い値を示した。更にＲｅ添加量を増やすほど、引張
強度は高い値を示した。FIG. 2 shows the material of the present invention (W-
Is a diagram showing a relationship of Re amount and tensile strength of 10% La 2 O 3 -3~20% Re). As shown in FIG. 2, La 2 O
The tensile strength of the material of the present invention to which 3 and Re were added showed a higher value than the comparative material. As the amount of Re added was further increased, the tensile strength showed a higher value.
【００４６】図３は１０００℃〜１７００℃の高温域に
おける本発明材（Ｗ−１０％Ｌａ２Ｏ３−２０％Ｒｅ）
と比較材の引張強度と温度の関係を示す図である。図３
に示すように、試験を行った全ての温度域において、本
発明材の引張強度が比較材の約２．５倍の引張強度を示
した。更に先行技術により提案されたＷ−１％Ｌａ２Ｏ
３板（圧延等の条件は同じ）と比較しても高い引張強度
を示した。尚、他の組成のＷ板材の強度の例を下記表２
に示す。FIG. 3 shows the material of the present invention (W-10% La 2 O 3 -20% Re) in a high temperature range of 1000 ° C. to 1700 ° C.
FIG. 6 is a diagram showing a relationship between tensile strength and temperature of a comparative material. FIG.
As shown in Table 2, the tensile strength of the material of the present invention was about 2.5 times that of the comparative material in all the temperature ranges where the test was performed. Further, W-1% La 2 O proposed by the prior art
Even when compared with three sheets (the conditions of rolling and the like are the same), high tensile strength was shown. Table 2 below shows examples of the strength of W plate materials having other compositions.
Shown in
【００４７】[0047]
【表２】 [Table 2]
【００４８】[0048]
【発明の効果】以上、説明したように、本発明によれ
ば、ランタン酸化物およびレニウムを均一に分散・固溶
させることによって、純Ｗに比べ、非常に微細な結晶粒
を有し、これらの焼結体は高温加熱においても結晶粒粗
大化は起こらない非常に安定した焼結体およびその製造
方法を提供することができる。As described above, according to the present invention, lanthanum oxide and rhenium are uniformly dispersed and dissolved to have very fine crystal grains as compared with pure W. Can provide a very stable sintered body which does not cause crystal grain coarsening even when heated at a high temperature, and a method for producing the same.
【００４９】さらに、本発明によれば、前述の焼結体を
素材として、例えば２．５倍程度の高温強度を有する新
規なタングステン板および線棒材およびその製造方法を
提供することができる。Further, according to the present invention, it is possible to provide a novel tungsten plate and wire rod having a high temperature strength of, for example, about 2.5 times, using the above-mentioned sintered body as a raw material, and a method for producing the same.
【００５０】また、本発明に用いたランタン酸化物は、
ＴｈＯ２に比べ取り扱いが容易で放射能汚染も全く無
く、無公害の材料である。したがって本発明によれば、
Ｌａ２Ｏ３のドープ技術，当該ドープ焼結体の圧延技術
は量産志向の高いものであり、工業化も容易であるタン
グステン焼結体ならびにそれらを素材として塑性加工を
施した板材および線棒材の製造方法を提供することがで
きる。The lanthanum oxide used in the present invention is:
Compared to ThO 2, it is easier to handle, has no radioactive contamination, and is a pollution-free material. Therefore, according to the present invention,
The La 2 O 3 doping technology and the rolling technology of the dope sintered body are high in mass production and are easy to industrialize. Tungsten sintered bodies and sheet and wire rods subjected to plastic working using them are used as raw materials. A manufacturing method can be provided.
【００５１】また、本発明によるタングステン焼結体な
らびにそれらを素材として塑性加工を施した板材および
線棒材は、優れた組織安定性や高温強度を生かし、高温
炉用反射板および炉用構造部材等の耐高温脆性，耐高温
変形性が要求される用途に最適である。Further, the tungsten sintered body according to the present invention, and the plate material and the wire rod obtained by subjecting them to plastic working by using them as a raw material, make use of excellent structural stability and high-temperature strength, and provide a reflector for a high-temperature furnace and a structural member for a furnace. Ideal for applications requiring high temperature brittleness resistance and high temperature deformation resistance.
【００５２】さらに、本発明によるタングステン焼結体
ならびにそれらを素材として塑性加工を施した板材およ
び線棒材は、優れた高温強度を有するので、高温負荷
や、高エネルギーが入力される高輝度電極の耐垂下性，
耐消耗性および耐熱変形も改善することができる。Further, the tungsten sintered body according to the present invention and the plate and wire rod obtained by subjecting them to plastic working have excellent high-temperature strength, so that a high-temperature load or a high-luminance electrode to which high energy is input can be obtained. Droop resistance,
Wear resistance and heat deformation can also be improved.
【図１】本発明の実施の形態による焼結体を真空中２２
００℃にて１時間〜１００時間まで加熱処理したもの
の、加熱時間と結晶粒径との関係を示す図である。FIG. 1 shows a sintered compact according to an embodiment of the present invention in a vacuum.
It is a figure which shows the relationship between a heating time and a crystal grain size after performing heat processing for 1 hour-100 hours at 00 degreeC.
【図２】本発明の実施の形態による焼鈍材（Ｗ−１０％
Ｌａ２Ｏ３−３〜２０％Ｒｅ）における、Ｒｅ量と引張
強度との関係を示す図であり、併せて比較材として純Ｗ
の焼鈍材も示している。FIG. 2 shows an annealed material (W-10%) according to an embodiment of the present invention.
In La 2 O 3 -3~20% Re) , a diagram showing the relationship between Re quantity and tensile strength, together with pure W as a comparative material
The annealed material is also shown.
【図３】本発明の実施の形態による焼鈍材（Ｗ−１０％
Ｌａ２Ｏ３−２０％Ｒｅ）における、試験温度と引張強
度との関係を示す図であり、併せて比較材として純Ｗの
焼鈍材も示している。FIG. 3 shows an annealed material (W-10%) according to an embodiment of the present invention.
In La 2 O 3 -20% Re) , a diagram showing the relationship between the tensile strength and the test temperature are also shown annealed material of pure W as comparative material together.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡本 謙一 富山県富山市岩瀬古志町２番地 株式会社 アライドマテリアル富山製作所内 Ｆターム(参考） 4K018 AA20 BC09 BC11 BC17 EA13 FA02 KA07 KA37 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kenichi Okamoto 2nd Iwase Koshimachi, Toyama City, Toyama Prefecture Allied Materials Toyama Works F-term (reference) 4K018 AA20 BC09 BC11 BC17 EA13 FA02 KA07 KA37 KA37
Claims (7)
体はランタン酸化物およびレニウムを含有し、高温加熱
を施しても結晶粒が粗大化しない組織安定性を有するこ
とを特徴とするタングステン焼結体。1. A tungsten sintered body, characterized in that said sintered body contains lanthanum oxide and rhenium, and has a structural stability such that crystal grains are not coarsened even when subjected to high-temperature heating. body.
体において、タングステン中に含まれるランタン酸化物
は５〜１０質量％，レニウムが３〜２０質量％，残部が
タングステンおよび不可避不純物分からなることを特徴
とするタングステン焼結体。2. The tungsten sintered body according to claim 1, wherein the lanthanum oxide contained in the tungsten is 5 to 10% by mass, rhenium is 3 to 20% by mass, and the balance is tungsten and unavoidable impurities. A tungsten sintered body characterized by the following.
ン焼結体を素材として加工した板材であって、１０００
℃以上の加熱時において、４５０ＭＰａを超える引張強
度を有し、１５００℃〜１７００℃の温度範囲におい
て、２３０ＭＰａを超える引張強度を有するタングステ
ン板材。3. A plate processed using the tungsten sintered body according to claim 1 as a raw material,
A tungsten sheet material having a tensile strength of more than 450 MPa at the time of heating at not less than ℃ and having a tensile strength of more than 230 MPa in a temperature range of 1500 to 1700 ℃.
ン焼結体を素材として加工した線棒材であって、１００
０℃以上の加熱時において、４５０ＭＰａを超える引張
強度を有し、１５００℃〜１７００℃の温度範囲におい
て、２３０ＭＰａを超える引張強度を有するタングステ
ン線棒材。4. A wire rod processed by using the tungsten sintered body according to claim 1 as a raw material,
A tungsten wire rod having a tensile strength exceeding 450 MPa when heated at 0 ° C. or higher and having a tensile strength exceeding 230 MPa in a temperature range of 1500 ° C. to 1700 ° C.
体を製造する方法であって、等方加圧焼結（ＨＩＰ）を
用いることによって高緻密且つ１０μｍ以下の微細結晶
粒からなるタングステン焼結体の製造方法。5. A method for producing a tungsten sintered body according to claim 1, wherein the tungsten sintered body is made of high-density and fine crystal grains of 10 μm or less by using isotropic pressure sintering (HIP). The method of manufacturing the aggregate.
を製造する方法であって、タングステンの青色酸化物に
ランタン酸化物を５〜１０質量％添加した後、還元し、
その粉末にレニウムを添加・混合した後、等方加圧焼結
（ＨＩＰ）を用いて焼結し、総板厚減少率９３％以上で
鍛造あるいは圧延することを特徴とするタングステン板
材の製造方法。6. The method for producing a tungsten plate material according to claim 3, wherein 5 to 10% by mass of lanthanum oxide is added to a blue oxide of tungsten, and then reduced.
A method of manufacturing a tungsten sheet material, comprising adding and mixing rhenium to the powder, sintering using isotropic pressure sintering (HIP), and forging or rolling at a total sheet thickness reduction rate of 93% or more. .
材を製造する方法であって、タングステンの青色酸化物
にランタン酸化物を５〜１０質量％添加した後、還元
し、その粉末にレニウムを添加・混合した後、等方加圧
焼結（ＨＩＰ）を用いて焼結し、総断面減少率８３％以
上で孔型圧延加工，転打加工，線引き加工の内すくなく
とも一種の一方向加工することを特徴とするタングステ
ン線棒材の製造方法。7. The method for producing a tungsten wire rod according to claim 4, wherein after adding 5 to 10% by mass of lanthanum oxide to tungsten blue oxide, reduction is performed, and the powder is rhenium. After adding and mixing, sintering is performed using isotropic pressure sintering (HIP), and at least 83% or more of the total cross-sectional reduction rate is at least one type of one-way processing among the die rolling, rolling, and drawing. A method for producing a tungsten wire rod.
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| JPH11152534A (en) * | 1997-11-17 | 1999-06-08 | Tokyo Tungsten Co Ltd | Tungsten sheet and its production |
-
2001
- 2001-06-18 JP JP2001183666A patent/JP4659278B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02137694A (en) * | 1988-10-17 | 1990-05-25 | Wolfram Ind Mbh:G | Manufacture of tungsten alloy rod |
| JPH11152534A (en) * | 1997-11-17 | 1999-06-08 | Tokyo Tungsten Co Ltd | Tungsten sheet and its production |
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| WO2005073418A1 (en) * | 2004-01-30 | 2005-08-11 | Nippon Tungsten Co., Ltd. | Tungsten based sintered compact and method for production thereof |
| CN100340365C (en) * | 2004-09-30 | 2007-10-03 | 北京科技大学 | Preparation of low-temperature primary sintering high-density superfine crystal particle pure tungsten material |
| JP2007169789A (en) * | 2005-12-23 | 2007-07-05 | Plansee Metall Gmbh | Method for producing semi-manufactured product or component having high density |
| CN100439522C (en) * | 2006-12-15 | 2008-12-03 | 西部金属材料股份有限公司 | Process for preparing molybdenum-lanthanum alloy |
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| DE102012217188A1 (en) * | 2012-09-24 | 2014-03-27 | Siemens Aktiengesellschaft | Producing a refractory metal component |
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