WO2023238699A1 - Tungsten alloy wire and metal products - Google Patents

Tungsten alloy wire and metal products Download PDF

Info

Publication number
WO2023238699A1
WO2023238699A1 PCT/JP2023/019619 JP2023019619W WO2023238699A1 WO 2023238699 A1 WO2023238699 A1 WO 2023238699A1 JP 2023019619 W JP2023019619 W JP 2023019619W WO 2023238699 A1 WO2023238699 A1 WO 2023238699A1
Authority
WO
WIPO (PCT)
Prior art keywords
tungsten alloy
alloy wire
tungsten
wire
rhenium
Prior art date
Application number
PCT/JP2023/019619
Other languages
French (fr)
Japanese (ja)
Inventor
建史郎 武田
雄広 前川
昌紀 笠原
達也 谷脇
Original Assignee
パナソニックＩｐマネジメント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Publication of WO2023238699A1 publication Critical patent/WO2023238699A1/en

Links

Images

Classifications

    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
    • 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon

Definitions

  • Patent Document 1 discloses a tungsten wire with a tensile strength of 3900 MPa or more.
  • An object of the present invention is to provide a tungsten alloy wire with excellent bending resistance and a metal product equipped with the tungsten alloy wire.
  • the tungsten alloy wire according to one aspect of the present invention is a tungsten alloy wire used in an environment where it is subjected to at least one thermal effect of 1100° C. or higher, and contains rhenium in a content of 5 wt% or more and 26 wt% or less.
  • a metal product according to one embodiment of the present invention includes the tungsten alloy wire according to the above one embodiment.
  • FIG. 1 is a schematic perspective view of a tungsten alloy wire according to an embodiment.
  • FIG. 2A is a schematic perspective view of a rod including a tungsten alloy wire according to an embodiment.
  • FIG. 2B is a schematic perspective view of an electrode including a tungsten alloy wire according to an embodiment.
  • FIG. 2C is a schematic perspective view of a stranded wire including a tungsten alloy wire according to an embodiment.
  • FIG. 3 is a diagram showing the bending resistance of the tungsten alloy wire according to the embodiment after being affected by heat.
  • FIG. 4 is a diagram showing an outline of a coiling test for a tungsten alloy wire according to an embodiment.
  • each figure is a schematic diagram and is not necessarily strictly illustrated. Therefore, for example, the scales and the like in each figure do not necessarily match. Further, in each figure, substantially the same configurations are denoted by the same reference numerals, and overlapping explanations will be omitted or simplified.
  • FIG. 1 is a schematic perspective view of a tungsten alloy wire 1 according to the present embodiment.
  • the tungsten alloy wire 1 is wound around a winding frame 2 and stored.
  • the winding frame 2 is sometimes referred to as a bobbin, reel, spool, or drum.
  • the tungsten alloy wire 1 has, for example, a total length on the order of meters (m) of about 100 m to a total length on the order of kilometers (km), but is not particularly limited.
  • the electrode 12 shown in FIG. 2B is an example of a metal product, and includes a tungsten alloy wire 1. Specifically, the electrode 12 is made by processing the tip of the tungsten alloy wire 1 of a predetermined length into a thinner one.
  • the tip shape of the electrode 12 is, for example, a conical shape, but is not limited to this.
  • the shape of the tip of the electrode 12 may be a rounded cone or truncated cone, or a pyramid or truncated pyramid.
  • the electrode 12 is used, for example, in electric discharge machining, but its use is not particularly limited.
  • examples of metal products using the tungsten alloy wire 1 are not limited to those shown in FIGS. 2A to 2C.
  • the metal product may be a saw wire, a mesh, a catheter, a textile product, etc.
  • the metal product may include the tungsten alloy wire 1 and a member formed using a material other than metal (for example, resin).
  • the tungsten alloy wire 1 is resistant to bending even if it is affected by heat of 1100° C. or higher. That is, the tungsten alloy wire 1 has excellent bending resistance. Even if the tungsten alloy wire 1 is bent at a predetermined curvature, no breakage or surface peeling occurs. Note that 1100° C. is an example of the temperature at which tungsten undergoes primary recrystallization.
  • tungsten has the property of being able to withstand high temperatures.
  • tungsten has a problem in that its grain boundaries are weak, that is, cracks tend to form starting from the grain boundaries.
  • the tungsten crystal grains are affected by heat to a degree that changes the size of the crystal grains (specifically, the temperature at which tungsten recrystallizes (1100°C) or higher)
  • the tungsten crystal grains become larger.
  • oxygen also enters the grain boundaries.
  • the number of grain boundaries decreases, the amount of oxygen that enters the grain boundaries also increases, which weakens the strength of tungsten.
  • stress such as bending or bending is applied to tungsten after being affected by heat, cracks tend to form starting from the grain boundaries, resulting in poor bending resistance.
  • the tungsten alloy wire 1 contains tungsten and rhenium (Re), and the tungsten and rhenium are alloyed to form a solid solution.
  • the content of rhenium in the tungsten alloy wire 1 is 5 wt% or more and 26 wt% or less.
  • the rhenium content in the tungsten alloy wire 1 may be 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more, or 10 wt% or more. % or more, 12 wt% or more, 15 wt% or more, or 20 wt% or more.
  • the content of rhenium in the tungsten alloy wire 1 may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 12 wt% or less, or 10 wt% or less. % or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, or 6 wt% or less.
  • the rhenium content is 5 wt% or more, the rhenium present in the crystal grains can take in oxygen that enters when it is affected by heat. This makes it possible to reduce the amount of oxygen present in the grain boundaries, making it difficult for cracks to form and suppressing deterioration in bending resistance.
  • the rhenium content is 26 wt% or less, a solid solution of rhenium and tungsten can be formed. If the rhenium content exceeds 26 wt%, a solid solution cannot be formed, and the strength of the tungsten alloy wire 1 may decrease and become brittle.
  • FIG. 3 also illustrates the bending resistance of the tungsten wires according to Comparative Examples 1 to 7.
  • Comparative Examples 1 to 3 are tungsten alloy wires containing rhenium. The content of rhenium in the tungsten alloy wires according to Comparative Examples 1 to 3 is 1 wt% or 3 wt% or less. The wire diameter of the tungsten alloy wires according to Comparative Examples 1 to 3 is 0.10 mm or 0.50 mm.
  • Comparative Examples 4 to 6 are tungsten wires containing potassium (potassium-doped tungsten wires). The potassium content in the potassium-doped tungsten wires according to Comparative Examples 4 to 6 is 0.007 wt%.
  • the inventors of the present application heat-treated the tungsten alloy wires according to Examples 1 to 8, and the tungsten alloy wires, potassium-doped tungsten wires, and pure tungsten wires according to Comparative Examples 1 to 7 at a predetermined temperature. .
  • Five samples were prepared for each example and each comparative example, and each sample was heat treated at different temperatures (1100°C, 1300°C, 1500°C, 1700°C, 2000°C).
  • the heat treatment time has no particular influence, but is, for example, about 1 minute.
  • FIG. 4 is a diagram showing an outline of a coiling test of the tungsten alloy wire 1 according to the present embodiment.
  • the tungsten alloy wire 1 was wound around a rod-shaped core material 20 with a circular cross-sectional shape and a uniform diameter, and it was confirmed whether the tungsten alloy wire 1 would break or the surface would peel off.
  • the diameter R of the cross section of the core material 20 used in the coiling test was made the same as the wire diameter ⁇ of the tungsten alloy wire 1 to be tested. That is, the smaller the wire diameter of the tungsten alloy wire 1 is, the smaller the radius of curvature (larger curvature) is bent (coiling).
  • a cylindrical core material 20 with a wire diameter of 1.00 mm was used.
  • Comparative Examples 1 to 3 when the rhenium content is 1wt% or 3wt%, all cases break except for the case where the rhenium content was affected by heat at 1100°C in Comparative Example 3. Or surface peeling occurred (represented by "NG" in the figure).
  • the wire diameter was 0.10 mm, which was small, so it is assumed that at a low temperature (1100° C.), less oxygen was taken into the grain boundaries and the wire did not break.
  • the metal product according to this embodiment includes a tungsten alloy wire 1.
  • the metal products are rods 11, electrodes 12 or strands 13.
  • the tungsten alloy wire 1 is resistant to bending even if it is affected by heat during manufacturing or use of the metal product. Therefore, deterioration in the quality of metal products can be suppressed.
  • the tungsten alloy wire 1 according to this embodiment can be manufactured, for example, by the following method.
  • tungsten powder and rhenium powder are mixed, press-molded, and sintered to form an ingot.
  • the content of rhenium can be adjusted to 5 wt% or more and 26 wt% or less.
  • tungsten alloy wire 1 having a diameter ranging from 0.02 mm to 1.00 mm as shown in FIG. Note that during wire drawing, heating may be performed at a predetermined temperature. Further, the tungsten alloy wire 1 after drawing may be subjected to surface treatment such as electrolytic polishing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metal Extraction Processes (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)

Abstract

The tungsten alloy wire (1) is used in an environment that receives at least one thermal impact of at least 1100°C. The tungsten alloy wire (1) contains rhenium at a content of 5-26 wt%.

Description

タングステン合金線及び金属製品Tungsten alloy wire and metal products
　本発明は、タングステン合金線及び金属製品に関する。 The present invention relates to tungsten alloy wires and metal products.
　特許文献１には、引張強度が３９００ＭＰａ以上のタングステン線が開示されている。 Patent Document 1 discloses a tungsten wire with a tensile strength of 3900 MPa or more.
特開２０２２－００１６６０号公報JP2022-001660A
　本発明は、耐屈曲性に優れたタングステン合金線及び当該タングステン合金線を備える金属製品を提供することを目的とする。 An object of the present invention is to provide a tungsten alloy wire with excellent bending resistance and a metal product equipped with the tungsten alloy wire.
　本発明の一態様に係るタングステン合金線は、１１００℃以上の熱影響を少なくとも１回受ける環境下で使用されるタングステン合金線であって、レニウムを５ｗｔ％以上２６ｗｔ％以下の含有量で含む。 The tungsten alloy wire according to one aspect of the present invention is a tungsten alloy wire used in an environment where it is subjected to at least one thermal effect of 1100° C. or higher, and contains rhenium in a content of 5 wt% or more and 26 wt% or less.
　本発明の一態様に係る金属製品は、上記一態様に係るタングステン合金線を備える。 A metal product according to one embodiment of the present invention includes the tungsten alloy wire according to the above one embodiment.
　本発明によれば、耐屈曲性に優れたタングステン合金線及び当該タングステン合金線を備える金属製品を提供することができる。 According to the present invention, it is possible to provide a tungsten alloy wire with excellent bending resistance and a metal product equipped with the tungsten alloy wire.
図１は、実施の形態に係るタングステン合金線の模式的な斜視図である。FIG. 1 is a schematic perspective view of a tungsten alloy wire according to an embodiment. 図２Ａは、実施の形態に係るタングステン合金線を備える棒の模式的な斜視図である。FIG. 2A is a schematic perspective view of a rod including a tungsten alloy wire according to an embodiment. 図２Ｂは、実施の形態に係るタングステン合金線を備える電極の模式的な斜視図である。FIG. 2B is a schematic perspective view of an electrode including a tungsten alloy wire according to an embodiment. 図２Ｃは、実施の形態に係るタングステン合金線を備える撚り線の模式的な斜視図である。FIG. 2C is a schematic perspective view of a stranded wire including a tungsten alloy wire according to an embodiment. 図３は、実施の形態に係るタングステン合金線の熱影響を受けた後の耐屈曲性を示す図である。FIG. 3 is a diagram showing the bending resistance of the tungsten alloy wire according to the embodiment after being affected by heat. 図４は、実施の形態に係るタングステン合金線のコイリング試験の概要を示す図である。FIG. 4 is a diagram showing an outline of a coiling test for a tungsten alloy wire according to an embodiment.
　以下では、本発明の実施の形態に係るタングステン合金線及び金属製品について、図面を用いて詳細に説明する。なお、以下に説明する実施の形態は、いずれも本発明の一具体例を示すものである。したがって、以下の実施の形態で示される数値、形状、材料、構成要素、構成要素の配置及び接続形態、ステップ、ステップの順序などは、一例であり、本発明を限定する趣旨ではない。よって、以下の実施の形態における構成要素のうち、独立請求項に記載されていない構成要素については、任意の構成要素として説明される。 Below, tungsten alloy wires and metal products according to embodiments of the present invention will be explained in detail using the drawings. Note that all of the embodiments described below are specific examples of the present invention. Therefore, the numerical values, shapes, materials, components, arrangement and connection forms of the components, steps, order of steps, etc. shown in the following embodiments are merely examples, and are not intended to limit the present invention. Therefore, among the constituent elements in the following embodiments, constituent elements that are not described in the independent claims will be described as arbitrary constituent elements.
　また、各図は、模式図であり、必ずしも厳密に図示されたものではない。したがって、例えば、各図において縮尺などは必ずしも一致しない。また、各図において、実質的に同一の構成については同一の符号を付しており、重複する説明は省略又は簡略化する。 Furthermore, each figure is a schematic diagram and is not necessarily strictly illustrated. Therefore, for example, the scales and the like in each figure do not necessarily match. Further, in each figure, substantially the same configurations are denoted by the same reference numerals, and overlapping explanations will be omitted or simplified.
　また、本明細書において、円柱又は円形などの要素の形状を示す用語、並びに、数値範囲は、厳格な意味のみを表す表現ではなく、実質的に同等な範囲、例えば数％程度の差異をも含むことを意味する表現である。 In addition, in this specification, terms indicating the shape of elements such as cylinder or circle, and numerical ranges are not expressions that express only strict meanings, but include substantially equivalent ranges, for example, differences of about a few percent. It is an expression that means to include.
　（実施の形態）
　［構成］
　まず、本実施の形態に係るタングステン合金線について、図１を用いて説明する。図１は、本実施の形態に係るタングステン合金線１の模式的な斜視図である。 (Embodiment)
[composition]
First, a tungsten alloy wire according to the present embodiment will be explained using FIG. 1. FIG. 1 is a schematic perspective view of a tungsten alloy wire 1 according to the present embodiment.
　図１に示されるように、タングステン合金線１は、巻枠２に巻回されて保管される。巻枠２は、ボビン、リール、スプール又はドラムなどと称される場合がある。タングステン合金線１は、例えば、１００ｍ程度のメートル（ｍ）オーダーの全長からキロメートル（ｋｍ）オーダーの全長を有するが、特に限定されない。 As shown in FIG. 1, the tungsten alloy wire 1 is wound around a winding frame 2 and stored. The winding frame 2 is sometimes referred to as a bobbin, reel, spool, or drum. The tungsten alloy wire 1 has, for example, a total length on the order of meters (m) of about 100 m to a total length on the order of kilometers (km), but is not particularly limited.
　図１に示されるタングステン合金線１は、金属製品の製造に利用される。図２Ａ～図２Ｃはそれぞれ、本実施の形態に係るタングステン合金線１を備える金属製品の一例を示す模式的な斜視図である。 The tungsten alloy wire 1 shown in FIG. 1 is used for manufacturing metal products. 2A to 2C are each a schematic perspective view showing an example of a metal product including the tungsten alloy wire 1 according to the present embodiment.
　図２Ａに示される棒１１は、金属製品の一例であり、タングステン合金線１を備える。具体的には、棒１１は、所定の長さのタングステン合金線１である。棒１１の長さは、特に限定されず、用途に応じて適切な長さとすることができる。棒１１は、タングステン合金線１を備える様々な金属製品の一部又は中間加工部材として利用されるが、用途は特に限定されない。なお、棒は、ピンと称される場合もある。 The rod 11 shown in FIG. 2A is an example of a metal product, and includes a tungsten alloy wire 1. Specifically, the rod 11 is a tungsten alloy wire 1 of a predetermined length. The length of the rod 11 is not particularly limited, and can be set to an appropriate length depending on the purpose. The rod 11 is used as a part of various metal products including the tungsten alloy wire 1 or as an intermediate processed member, but its use is not particularly limited. Note that the rod may also be referred to as a pin.
　図２Ｂに示される電極１２は、金属製品の一例であり、タングステン合金線１を備える。具体的には、電極１２は、所定の長さのタングステン合金線１の先端部分を細く加工したものである。電極１２の先端形状は、例えば円錐形状であるが、これに限定されない。電極１２の先端形状は、先端部が丸い円錐形状若しくは円錐台形状、又は、角錐若しくは角錐台形状などであってもよい。電極１２は、例えば放電加工に利用されるが、用途は特に限定されない。 The electrode 12 shown in FIG. 2B is an example of a metal product, and includes a tungsten alloy wire 1. Specifically, the electrode 12 is made by processing the tip of the tungsten alloy wire 1 of a predetermined length into a thinner one. The tip shape of the electrode 12 is, for example, a conical shape, but is not limited to this. The shape of the tip of the electrode 12 may be a rounded cone or truncated cone, or a pyramid or truncated pyramid. The electrode 12 is used, for example, in electric discharge machining, but its use is not particularly limited.
　図２Ｃに示される撚り線１３は、金属製品の一例であり、複数のタングステン合金線１を備える。具体的には、撚り線１３は、所定の長さの複数のタングステン合金線１に対して合撚加工を行うことで製造される合撚糸である。なお、撚り線１３は、タングステン合金線１を芯糸又は鞘糸として備えるカバーリング糸であってもよい。芯糸及び鞘糸の一方は、タングステン合金線１以外の金属線であってもよく、化学繊維、天然繊維、再生繊維などであってもよい。撚り線１３は、さらに束ねられてロープ又は紐などに利用されてもよく、用途は特に限定されない。 The stranded wire 13 shown in FIG. 2C is an example of a metal product, and includes a plurality of tungsten alloy wires 1. Specifically, the stranded wire 13 is a twisted yarn manufactured by performing a twisting process on a plurality of tungsten alloy wires 1 having a predetermined length. Note that the stranded wire 13 may be a covering thread that includes the tungsten alloy wire 1 as a core thread or a sheath thread. One of the core thread and the sheath thread may be a metal wire other than the tungsten alloy wire 1, or may be a chemical fiber, a natural fiber, a recycled fiber, or the like. The stranded wire 13 may be further bundled and used as a rope or string, and the use thereof is not particularly limited.
　なお、タングステン合金線１を利用した金属製品の例は、図２Ａ～図２Ｃに示されるものには限定されない。例えば、金属製品は、ソーワイヤ、メッシュ、カテーテル、繊維製品などであってもよい。金属製品は、タングステン合金線１と、金属以外の材料（例えば樹脂）を用いて形成された部材と、を備えてもよい。 Note that examples of metal products using the tungsten alloy wire 1 are not limited to those shown in FIGS. 2A to 2C. For example, the metal product may be a saw wire, a mesh, a catheter, a textile product, etc. The metal product may include the tungsten alloy wire 1 and a member formed using a material other than metal (for example, resin).
　本実施の形態に係るタングステン合金線１は、１１００℃以上の熱影響を少なくとも１回受ける環境下で使用される。具体的には、タングステン合金線１は、金属製品の製造のための加工時、又は、金属製品としての使用時に熱影響を少なくとも１回受ける。熱影響の具体例としては、例えば、タングステン合金線１を鉄などの他の金属部材に溶接する場合、又は、放電電極として使用された場合などであるが、特に限定されない。 The tungsten alloy wire 1 according to the present embodiment is used in an environment where it is subjected to heat effects of 1100° C. or more at least once. Specifically, the tungsten alloy wire 1 is affected by heat at least once during processing for manufacturing a metal product or when used as a metal product. Specific examples of thermal effects include, for example, when the tungsten alloy wire 1 is welded to another metal member such as iron, or when it is used as a discharge electrode, but is not particularly limited.
　タングステン合金線１は、１１００℃以上の熱影響を受けたとしても、折り曲げに強い。すなわち、タングステン合金線１は、耐屈曲性に優れている。タングステン合金線１を、所定の曲率で曲げたとしても破断又は表面剥離などが生じない。なお、１１００℃は、タングステンが一次再結晶する温度の一例である。 The tungsten alloy wire 1 is resistant to bending even if it is affected by heat of 1100° C. or higher. That is, the tungsten alloy wire 1 has excellent bending resistance. Even if the tungsten alloy wire 1 is bent at a predetermined curvature, no breakage or surface peeling occurs. Note that 1100° C. is an example of the temperature at which tungsten undergoes primary recrystallization.
　一般的に、タングステンは、高温に耐えられる特性を有する。しかしながら、タングステンは、結晶粒界が弱い、すなわち、結晶粒界を起点として亀裂が入りやすいという問題がある。具体的には、結晶粒のサイズが変化する程度（具体的には、タングステンが一次再結晶する温度（１１００℃）以上）の熱影響を受けた場合には、タングステンの結晶粒が大きくなって結晶粒界が少なくなるだけでなく、結晶粒界に酸素が入り込む。結晶粒界が少なくなることで、結晶粒界に入り込む酸素の量も相対的に多くなるので、タングステンの強度が弱くなる。この結果、熱影響後にタングステンに対する折り又は曲げなどの応力が加わった場合、結晶粒界を起点として亀裂が入りやすくなって耐屈曲性が悪化する。 Generally, tungsten has the property of being able to withstand high temperatures. However, tungsten has a problem in that its grain boundaries are weak, that is, cracks tend to form starting from the grain boundaries. Specifically, if the tungsten crystal grains are affected by heat to a degree that changes the size of the crystal grains (specifically, the temperature at which tungsten recrystallizes (1100°C) or higher), the tungsten crystal grains become larger. Not only are the number of grain boundaries reduced, but oxygen also enters the grain boundaries. As the number of grain boundaries decreases, the amount of oxygen that enters the grain boundaries also increases, which weakens the strength of tungsten. As a result, when stress such as bending or bending is applied to tungsten after being affected by heat, cracks tend to form starting from the grain boundaries, resulting in poor bending resistance.
　これに対して、本実施の形態に係るタングステン合金線１は、タングステンとレニウム（Ｒｅ）とを含み、タングステンとレニウムとが固溶体を形成して合金化されている。タングステン合金線１におけるレニウムの含有量は、５ｗｔ％以上２６ｗｔ％以下である。あるいは、タングステン合金線１におけるレニウムの含有量は、６ｗｔ％以上であってもよく、７ｗｔ％以上であってもよく、８ｗｔ％以上であってもよく、９ｗｔ％以上であってもよく、１０ｗｔ％以上であってもよく、１２ｗｔ％以上であってもよく、１５ｗｔ％以上であってもよく、２０ｗｔ％以上であってもよい。また、タングステン合金線１におけるレニウムの含有量は、２５ｗｔ％以下であってもよく、２０ｗｔ％以下であってもよく、１５ｗｔ％以下であってもよく、１２ｗｔ％以下であってもよく、１０ｗｔ％以下であってもよく、９ｗｔ％以下であってもよく、８ｗｔ％以下であってもよく、７ｗｔ％以下であってもよく、６ｗｔ％以下であってもよい。 On the other hand, the tungsten alloy wire 1 according to the present embodiment contains tungsten and rhenium (Re), and the tungsten and rhenium are alloyed to form a solid solution. The content of rhenium in the tungsten alloy wire 1 is 5 wt% or more and 26 wt% or less. Alternatively, the rhenium content in the tungsten alloy wire 1 may be 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more, or 10 wt% or more. % or more, 12 wt% or more, 15 wt% or more, or 20 wt% or more. Further, the content of rhenium in the tungsten alloy wire 1 may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 12 wt% or less, or 10 wt% or less. % or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, or 6 wt% or less.
　タングステン合金線１では、レニウムの含有量が５ｗｔ％以上であることによって、熱影響を受けた場合に入り込む酸素を、結晶粒内に存在するレニウムが取り込むことができる。これにより、結晶粒界に存在する酸素の量を少なくすることができるので、亀裂が入りにくくなって耐屈曲性の悪化を抑制することができる。 In the tungsten alloy wire 1, since the rhenium content is 5 wt% or more, the rhenium present in the crystal grains can take in oxygen that enters when it is affected by heat. This makes it possible to reduce the amount of oxygen present in the grain boundaries, making it difficult for cracks to form and suppressing deterioration in bending resistance.
　また、タングステン合金線１では、レニウムの含有量が２６ｗｔ％以下であることによって、レニウムとタングステンとの固溶体を形成することができる。レニウムの含有量が２６ｗｔ％を超えると固溶体が形成できなくなり、タングステン合金線１の強度が低下して脆くなるおそれがある。 Further, in the tungsten alloy wire 1, since the rhenium content is 26 wt% or less, a solid solution of rhenium and tungsten can be formed. If the rhenium content exceeds 26 wt%, a solid solution cannot be formed, and the strength of the tungsten alloy wire 1 may decrease and become brittle.
　［耐屈曲性］
　続いて、本実施の形態に係るタングステン合金線１の耐屈曲性について、図３及び図４を用いて説明する。 [Bending resistance]
Next, the bending resistance of the tungsten alloy wire 1 according to the present embodiment will be explained using FIGS. 3 and 4.
　図３は、本実施の形態に係るタングステン合金線の熱影響を受けた後の耐屈曲性を示す図である。図３に示す実施例１～８は、線径及び成分の少なくとも一方が異なるタングステン合金線である。各実施例に係るタングステン合金線１の線径は、０．０２ｍｍ以上１．００ｍｍ以下の範囲内である。また、各実施例に係るタングステン合金線１におけるレニウムの含有量は、５ｗｔ％以上２６ｗｔ％以下の範囲内である。また、各実施例に係るタングステン合金線１におけるタングステンの含有量は、７４ｗｔ％以上９５ｗｔ％以下である。 FIG. 3 is a diagram showing the bending resistance of the tungsten alloy wire according to the present embodiment after being affected by heat. Examples 1 to 8 shown in FIG. 3 are tungsten alloy wires that differ in at least one of wire diameter and composition. The wire diameter of the tungsten alloy wire 1 according to each example is within the range of 0.02 mm or more and 1.00 mm or less. Further, the content of rhenium in the tungsten alloy wire 1 according to each example is within the range of 5 wt% or more and 26 wt% or less. Moreover, the content of tungsten in the tungsten alloy wire 1 according to each example is 74 wt% or more and 95 wt% or less.
　また、図３には、比較例１～７に係るタングステン線の耐屈曲性についても図示している。比較例１～３は、レニウムを含むタングステン合金線である。比較例１～３に係るタングステン合金線におけるレニウムの含有量は、１ｗｔ％又は３ｗｔ％以下である。比較例１～３に係るタングステン合金線の線径は、０．１０ｍｍ又は０．５０ｍｍである。比較例４～６は、カリウムを含むタングステン線（カリウムドープタングステン線）である。比較例４～６に係るカリウムドープタングステン線におけるカリウムの含有量は、０．００７ｗｔ％である。比較例４～６に係るカリウムドープタングステン線の線径は、０．０４ｍｍ、０．１０ｍｍ又は０．５０ｍｍである。比較例７は、添加物を含んでいない純タングステン線である。なお、各実施例及び各比較例では、製造上避けられない不可避的な不純物が微量に含まれている。 Further, FIG. 3 also illustrates the bending resistance of the tungsten wires according to Comparative Examples 1 to 7. Comparative Examples 1 to 3 are tungsten alloy wires containing rhenium. The content of rhenium in the tungsten alloy wires according to Comparative Examples 1 to 3 is 1 wt% or 3 wt% or less. The wire diameter of the tungsten alloy wires according to Comparative Examples 1 to 3 is 0.10 mm or 0.50 mm. Comparative Examples 4 to 6 are tungsten wires containing potassium (potassium-doped tungsten wires). The potassium content in the potassium-doped tungsten wires according to Comparative Examples 4 to 6 is 0.007 wt%. The wire diameter of the potassium-doped tungsten wires according to Comparative Examples 4 to 6 is 0.04 mm, 0.10 mm, or 0.50 mm. Comparative Example 7 is a pure tungsten wire containing no additives. In addition, each Example and each Comparative Example contain a trace amount of unavoidable impurities that cannot be avoided during manufacturing.
　本願発明者らは、実施例１～８に係るタングステン合金線、並びに、比較例１～７に係るタングステン合金線、カリウムドープタングステン線及び純タングステン線に対して、所定の温度で熱処理を行った。各実施例及び各比較例について５本ずつサンプルを作成し、各サンプルに対して異なる温度（１１００℃、１３００℃、１５００℃、１７００℃、２０００℃）で熱処理を行った。熱処理時間は、特に影響を与えるものがないが、例えば、１分程度である。 The inventors of the present application heat-treated the tungsten alloy wires according to Examples 1 to 8, and the tungsten alloy wires, potassium-doped tungsten wires, and pure tungsten wires according to Comparative Examples 1 to 7 at a predetermined temperature. . Five samples were prepared for each example and each comparative example, and each sample was heat treated at different temperatures (1100°C, 1300°C, 1500°C, 1700°C, 2000°C). The heat treatment time has no particular influence, but is, for example, about 1 minute.
　熱処理後、各実施例及び各比較例の各サンプルに対して、コイリング試験を行った。図４は、本実施の形態に係るタングステン合金線１のコイリング試験の概要を示す図である。 After the heat treatment, a coiling test was conducted on each sample of each Example and each Comparative Example. FIG. 4 is a diagram showing an outline of a coiling test of the tungsten alloy wire 1 according to the present embodiment.
　コイリング試験では、断面形状が円形で均一な径の棒状の芯材２０に対して、タングステン合金線１を巻き付け、タングステン合金線１の破断又は表面剥離が生じるか否かを確認した。コイリング試験に用いる芯材２０の断面の径Ｒは、対象となるタングステン合金線１の線径φと同じにした。すなわち、タングステン合金線１の線径が小さい程、小さい曲率半径（大きい曲率）で屈曲（コイリング）が行われるようにしている。例えば、実施例１に係る線径１．００ｍｍのタングステン合金線１の場合、線径１．００ｍｍの円柱状の芯材２０を利用した。実施例７に係る線径０．０４ｍｍのタングステン合金線１の場合、線径０．０４ｍｍの円柱状の芯材２０を利用した。比較例１～７に係るタングステン合金線、カリウムドープタングステン線及び純タングステン線についても同様である。 In the coiling test, the tungsten alloy wire 1 was wound around a rod-shaped core material 20 with a circular cross-sectional shape and a uniform diameter, and it was confirmed whether the tungsten alloy wire 1 would break or the surface would peel off. The diameter R of the cross section of the core material 20 used in the coiling test was made the same as the wire diameter φ of the tungsten alloy wire 1 to be tested. That is, the smaller the wire diameter of the tungsten alloy wire 1 is, the smaller the radius of curvature (larger curvature) is bent (coiling). For example, in the case of the tungsten alloy wire 1 with a wire diameter of 1.00 mm according to Example 1, a cylindrical core material 20 with a wire diameter of 1.00 mm was used. In the case of the tungsten alloy wire 1 with a wire diameter of 0.04 mm according to Example 7, a cylindrical core material 20 with a wire diameter of 0.04 mm was used. The same applies to the tungsten alloy wire, potassium-doped tungsten wire, and pure tungsten wire according to Comparative Examples 1 to 7.
　図３の実施例１～８に係るタングステン合金線１では、いずれの温度においても破断又は表面剥離が生じなかった（図中“ＯＫ”で表している）。すなわち、線径によらず、レニウムの含有量が５ｗｔ％以上２６ｗｔ％以下の範囲では、１１００℃以上の熱影響を受けたとしても、折り曲げに対して強い（耐屈曲性に優れた）タングステン合金線１が実現できている。 In the tungsten alloy wires 1 according to Examples 1 to 8 in FIG. 3, no breakage or surface peeling occurred at any temperature (represented by "OK" in the figure). In other words, regardless of the wire diameter, if the rhenium content is in the range of 5 wt% or more and 26 wt% or less, the tungsten alloy is strong against bending (has excellent bending resistance) even when subjected to heat effects of 1100°C or more. Line 1 has been realized.
　これに対して、比較例１～３に示されるように、レニウムの含有量が１ｗｔ％又は３ｗｔ％である場合、比較例３の１１００℃の熱影響を受けた場合を除いて、いずれも破断又は表面剥離が生じた（図中“ＮＧ”で表している）。比較例３では、線径が０．１０ｍｍであって細いので、低い温度（１１００℃）では結晶粒界に取り込まれる酸素が少なく破断にまでは至らなかったと想定される。 On the other hand, as shown in Comparative Examples 1 to 3, when the rhenium content is 1wt% or 3wt%, all cases break except for the case where the rhenium content was affected by heat at 1100°C in Comparative Example 3. Or surface peeling occurred (represented by "NG" in the figure). In Comparative Example 3, the wire diameter was 0.10 mm, which was small, so it is assumed that at a low temperature (1100° C.), less oxygen was taken into the grain boundaries and the wire did not break.
　また、比較例４～６に示されるように、カリウムドープタングステン線の場合、線径が小さく、かつ、熱処理の温度が低い場合（比較例５の１１００℃、並びに、比較例６の１１００℃及び１３００℃）を除いて、いずれも破断又は表面剥離が生じた。なお、カリウムは、レニウムとは異なり、結晶粒界に存在し、酸素を取り込む効果がない。 In addition, as shown in Comparative Examples 4 to 6, in the case of potassium-doped tungsten wire, when the wire diameter is small and the heat treatment temperature is low (1100 ° C in Comparative Example 5, 1100 ° C and Breakage or surface peeling occurred in all cases except at 1300°C. Note that, unlike rhenium, potassium exists at grain boundaries and has no effect of taking in oxygen.
　比較例７に示されるように、純タングステン線の場合、熱影響による酸素が結晶粒界に入り込むので、破断又は表面剥離が生じた。 As shown in Comparative Example 7, in the case of pure tungsten wire, oxygen entered the grain boundaries due to the influence of heat, resulting in breakage or surface peeling.
　［効果など］
　以上のように、本実施の形態に係るタングステン合金線１は、１１００℃以上の熱影響を少なくとも１回受ける環境下で使用されるタングステン合金線であって、レニウムを５ｗｔ％以上２６ｗｔ％以下の含有量で含む。 [Effects etc.]
As described above, the tungsten alloy wire 1 according to the present embodiment is a tungsten alloy wire used in an environment where it is subjected to heat effects of 1100° C. or higher at least once, and contains rhenium in a proportion of 5 wt% or more and 26 wt% or less. Included in content.
　これにより、タングステン合金線１は、レニウムを５ｗｔ％以上含有することによって、熱影響を受けた場合に結晶粒界に入る酸素をレニウムが取り込むことができ、結晶粒界を起点とする亀裂の発生を抑制することができる。よって、熱影響を受けたとしても、断線などが発生しにくく、耐屈曲性に優れたタングステン合金線１を実現することができる。また、レニウムの含有量が２６ｗｔ％以下であることで、レニウムとタングステンとの合金（固溶体）を形成することができるので、タングステン合金線１の強度を高めることができる。 As a result, since the tungsten alloy wire 1 contains 5 wt% or more of rhenium, rhenium can take in oxygen that enters the grain boundaries when affected by heat, and cracks occur starting from the grain boundaries. can be suppressed. Therefore, it is possible to realize a tungsten alloy wire 1 that is less likely to be disconnected even if it is affected by heat and has excellent bending resistance. Further, since the rhenium content is 26 wt% or less, an alloy (solid solution) of rhenium and tungsten can be formed, so that the strength of the tungsten alloy wire 1 can be increased.
　また、本実施の形態に係る金属製品は、タングステン合金線１を備える。例えば、金属製品は、棒１１、電極１２又は撚り線１３である。 Further, the metal product according to this embodiment includes a tungsten alloy wire 1. For example, the metal products are rods 11, electrodes 12 or strands 13.
　これにより、金属製品の製造時又は使用時に熱影響を受けたとしても、タングステン合金線１は折り曲げに強い。このため、金属製品の品質の低下を抑制することができる。 As a result, the tungsten alloy wire 1 is resistant to bending even if it is affected by heat during manufacturing or use of the metal product. Therefore, deterioration in the quality of metal products can be suppressed.
　［製造方法］
　本実施の形態に係るタングステン合金線１は、例えば、次のような方法で製造することができる。 [Production method]
The tungsten alloy wire 1 according to this embodiment can be manufactured, for example, by the following method.
　まず、タングステン粉末とレニウム粉末とを混合し、プレス成型して焼結してインゴット化する。タングステン粉末とレニウム粉末との混合比を調整することで、レニウムの含有量を５ｗｔ％以上２６ｗｔ％以下に調整することができる。 First, tungsten powder and rhenium powder are mixed, press-molded, and sintered to form an ingot. By adjusting the mixing ratio of tungsten powder and rhenium powder, the content of rhenium can be adjusted to 5 wt% or more and 26 wt% or less.
　次に、インゴット化したタングステン塊に対して、周囲から鍛造圧縮して伸展するスエージング加工を施すことによりワイヤ状にする。その後、伸線ダイスを用いた線引き（伸線）を行う。線引きは、孔径が互いに異なる複数の伸線ダイスを、孔径が漸次小さくなる順番で用いることで行われる。 Next, the ingot-shaped tungsten lump is made into a wire shape by performing a swaging process in which the ingot is forged and compressed from the periphery and then expanded. Thereafter, wire drawing is performed using a wire drawing die. Wire drawing is performed by using a plurality of wire drawing dies having different hole diameters in order of decreasing hole diameter.
　伸線ダイスの孔径を適宜調整することによって、図３に示したような０．０２ｍｍから１．００ｍｍの範囲のタングステン合金線１を製造することができる。なお、線引き時には、所定の温度での加熱が行われてもよい。また、線引き後のタングステン合金線１に対して、電解研磨などの表面処理が行われてもよい。 By appropriately adjusting the hole diameter of the wire drawing die, it is possible to manufacture a tungsten alloy wire 1 having a diameter ranging from 0.02 mm to 1.00 mm as shown in FIG. Note that during wire drawing, heating may be performed at a predetermined temperature. Further, the tungsten alloy wire 1 after drawing may be subjected to surface treatment such as electrolytic polishing.
　（その他）
　以上、本発明に係るタングステン合金線及び金属製品について、上記の実施の形態などに基づいて説明したが、本発明は、上記の実施の形態に限定されるものではない。 (others)
Although the tungsten alloy wire and metal product according to the present invention have been described above based on the above-described embodiments, the present invention is not limited to the above-described embodiments.
　例えば、タングステン合金線は、レニウムの代わりに、ルテニウム（Ｒｕ）又はコバルト（Ｃｏ）を含んでもよい。例えば、タングステン合金線は、タングステンの含有量が９９．８ｗｔ％であり、ルテニウムの含有量が０．２ｗｔ％であり、微量の不純物を含んでもよい。当該タングステン合金線に対して熱処理を行った後、コイリング試験を行った結果、熱処理の温度が１１００℃、１３００℃、１５００℃、１７００℃、２０００℃のいずれの場合も、耐屈曲性の悪化が見られなかった。 For example, the tungsten alloy wire may contain ruthenium (Ru) or cobalt (Co) instead of rhenium. For example, the tungsten alloy wire has a tungsten content of 99.8 wt%, a ruthenium content of 0.2 wt%, and may contain trace amounts of impurities. After heat-treating the tungsten alloy wire, a coiling test was conducted, and it was found that the bending resistance deteriorated regardless of the heat treatment temperature of 1100°C, 1300°C, 1500°C, 1700°C, or 2000°C. I couldn't see it.
　その他、各実施の形態に対して当業者が思いつく各種変形を施して得られる形態や、本発明の趣旨を逸脱しない範囲で各実施の形態における構成要素及び機能を任意に組み合わせることで実現される形態も本発明に含まれる。 In addition, forms obtained by applying various modifications to each embodiment that those skilled in the art can think of, or by arbitrarily combining the constituent elements and functions of each embodiment without departing from the spirit of the present invention. The form is also included in the present invention.
１　タングステン合金線
１１　棒
１２　電極
１３　撚り線 1 Tungsten alloy wire 11 Rod 12 Electrode 13 Twisted wire

Claims (3)

  1. 　１１００℃以上の熱影響を少なくとも１回受ける環境下で使用されるタングステン合金線であって、
    　レニウムを５ｗｔ％以上２６ｗｔ％以下の含有量で含む、
    　タングステン合金線。     A tungsten alloy wire used in an environment where it is subjected to thermal effects of 1100°C or more at least once,
    Contains rhenium in a content of 5 wt% or more and 26 wt% or less,
    Tungsten alloy wire.
  2. 　請求項１に係るタングステン合金線を備える金属製品。 A metal product comprising the tungsten alloy wire according to claim 1.
  3. 　前記金属製品は、棒、電極又は撚り線である、
    　請求項２に記載の金属製品。     the metal product is a rod, an electrode or a stranded wire;
    The metal product according to claim 2.
PCT/JP2023/019619 2022-06-06 2023-05-26 Tungsten alloy wire and metal products WO2023238699A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022091886A JP2023178898A (en) 2022-06-06 2022-06-06 Tungsten alloy wire and metal product
JP2022-091886 2022-06-06

Publications (1)

Publication Number Publication Date
WO2023238699A1 true WO2023238699A1 (en) 2023-12-14

Family

ID=89118134

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/019619 WO2023238699A1 (en) 2022-06-06 2023-05-26 Tungsten alloy wire and metal products

Country Status (3)

Country Link
JP (1) JP2023178898A (en)
TW (1) TW202348810A (en)
WO (1) WO2023238699A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022076997A (en) * 2020-11-10 2022-05-20 株式会社東芝 Tungsten wire rope and endoscope snare using the same
WO2022113525A1 (en) * 2020-11-27 2022-06-02 パナソニックＩｐマネジメント株式会社 Metal wire
WO2022191026A1 (en) * 2021-03-09 2022-09-15 株式会社 東芝 Rhenium tungsten wire rod and thermocouple using this

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022076997A (en) * 2020-11-10 2022-05-20 株式会社東芝 Tungsten wire rope and endoscope snare using the same
WO2022113525A1 (en) * 2020-11-27 2022-06-02 パナソニックＩｐマネジメント株式会社 Metal wire
WO2022191026A1 (en) * 2021-03-09 2022-09-15 株式会社 東芝 Rhenium tungsten wire rod and thermocouple using this

Also Published As

Publication number Publication date
TW202348810A (en) 2023-12-16
JP2023178898A (en) 2023-12-18

Similar Documents

Publication Publication Date Title
WO2020218058A1 (en) Tungsten wire and tungsten product
KR20170041164A (en) Copper alloy wire, stranded copper alloy wire, coated electric wire, and terminal-equipped electric wire
JP2012509998A (en) New metal fiber yarn with improved strength and workability
CN109518499B (en) 1860 MPa-level prestressed steel strand and manufacturing method thereof
JP2011146352A (en) Cu-Ag ALLOY WIRE
WO2023153089A1 (en) Tungsten wire and metal mesh
WO2022113525A1 (en) Metal wire
WO2023238699A1 (en) Tungsten alloy wire and metal products
CN101004995A (en) Method for producing thorium-tungsten wire
JP5611589B2 (en) Method for manufacturing filament cathode member for magnetron and filament cathode member for magnetron
WO2021033500A1 (en) Wire for electric discharge machining and manufacturing method thereof
WO2023228833A1 (en) Tungsten wire
JP2022521950A (en) Steel cord for rubber reinforcement
JP2012045580A (en) Method for manufacturing steel wire for reinforcement of rubber article, device for manufacturing the same, steel cord for reinforcement of the rubber article, and pneumatic tire
JP4986522B2 (en) Wires for automobile wires and electric wires for automobiles
CN103137254A (en) Novel aviation cable protecting cover
WO2024171770A1 (en) Composite wire and robot
WO2024162034A1 (en) Stranded wire and robot
WO2023228832A1 (en) Hydrogen-permeable filter
JP2022182462A (en) Metal material for foil yarn and foil yarn as well as twist yarn and cloth formed with foil yarn
JP6997354B1 (en) Medical Pt alloy wire and medical Pt alloy coil
JP5264248B2 (en) Steel cord for reinforcing rubber structures
CN109826031B (en) Layered alternate twisting steel wire cord
WO2023204036A1 (en) Wire, stranded wire, cable, and method for producing wire
JP2018141209A (en) Method for manufacturing aluminum alloy wire

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23819681

Country of ref document: EP

Kind code of ref document: A1