WO2018193810A1 - Câble en alliage à faible dilatation thermique et haute résistance - Google Patents

Câble en alliage à faible dilatation thermique et haute résistance Download PDF

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Publication number
WO2018193810A1
WO2018193810A1 PCT/JP2018/013316 JP2018013316W WO2018193810A1 WO 2018193810 A1 WO2018193810 A1 WO 2018193810A1 JP 2018013316 W JP2018013316 W JP 2018013316W WO 2018193810 A1 WO2018193810 A1 WO 2018193810A1
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less
alloy wire
thermal expansion
strength
low
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PCT/JP2018/013316
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English (en)
Japanese (ja)
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孝 細田
中間　一夫
知哉 松岡
美里 草刈
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山陽特殊製鋼株式会社
住友電気工業株式会社
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Priority to JP2018560237A priority Critical patent/JP6812461B2/ja
Priority to KR1020197030872A priority patent/KR102509847B1/ko
Priority to CN201880026074.9A priority patent/CN110546292B/zh
Publication of WO2018193810A1 publication Critical patent/WO2018193810A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention it is desired to avoid changes in size and shape due to thermal expansion.
  • the present invention can be used for core materials for low-slack power transmission lines, wires for precision mechanical parts, etc. that may increase in temperature during use.
  • the present invention relates to a high strength low thermal expansion alloy wire and a high strength low thermal expansion coated alloy wire.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-228947
  • C 0.1 to 0.4%
  • Si 0.2 to 1.5%
  • Mn 0.1 to 1.5%
  • Ni 33-42%
  • Co 5.0% or less
  • Cr 0.75-3.0%
  • V 0.2-3.0%
  • B 0.003% or less
  • O 0.003% or less
  • Al 0.1% or less
  • Mg 0.1% or less
  • Ti 0.1% or less
  • Ca 0.1% or less
  • a high-strength, low-thermal-expansion alloy wire characterized by having a relationship of 1.0% ⁇ V + Cr ⁇ 5.0%.
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-256395
  • C 0.1 to 0.4%
  • V more than 0.5% to 3.0%
  • Ni 25 to 50% by mass.
  • the high-strength low thermal expansion alloy wire contains one or more of Al, Mo, Ti, Nb, Ta, Zr, Hf, W, and Cu in a total amount of 5% or less. It is disclosed that
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2003-82439 discloses that by weight, C: 0.20 to 0.40%, Si: ⁇ 0.8%, Mn: ⁇ 1.0%, P: ⁇ 0.050%, S: ⁇ 0.015%, Cu: ⁇ 1.0%, Ni: 35-40%, Cr: ⁇ 0.5%, Mo: 1.5-6.0%, V: 0.05 to 1.0%, O: ⁇ 0.015%, N: ⁇ 0.03%, Mo / V ⁇ 1.0 and (0.3Mo + V) ⁇ 4C, and the balance Fe
  • the average coefficient of linear thermal expansion from 20 to 230 ° C. and from 230 to 290 ° C. is 3.7 ⁇ 10 ⁇ 6 or less and 10.8 ⁇ 10 ⁇ 6 or less, respectively.
  • Patent Documents 1 to 3 are hardened by precipitation hardening by aging heat treatment, but the optimum conditions for aging heat treatment (temperature and holding time of the temperature) ) Range, for example, the optimum range for obtaining the maximum hardness is narrow, and it is difficult to obtain the desired hardness.
  • the present invention is an alloy wire having characteristics (for example, high strength, high twist value, good ductility, low coefficient of thermal expansion, etc.) necessary as a high strength low thermal expansion alloy wire,
  • An object of the present invention is to provide an alloy wire capable of using a wide range of conditions for heat treatment to obtain a desired hardness.
  • the present inventors By appropriately controlling the composition of the alloy wire, the composition of the carbides present in the crystal grains, the dispersion state of the carbides present in the crystal grains, the present inventors have obtained the characteristics necessary as a high-strength low thermal expansion alloy wire. (For example, high strength, high twist value, good ductility, low coefficient of thermal expansion, etc.)
  • a wide range of conditions can be used for heat treatment to obtain the desired hardness
  • the present inventors have found that an alloy wire can be realized.
  • the present invention provides the following high-strength low thermal expansion alloy wires and high-strength low thermal expansion coated alloy wires.
  • C 0.1% to 0.4%
  • Si 0.1% to 2.0%
  • Mn more than 0% to 2.0%
  • Ni 25% to 40%
  • % V: 0.5% to 3.0%
  • Mo 0.4% to 1.9%
  • Cr 0% to 3.0%
  • Co 0% to 3.0%
  • B 0% to 0.05%
  • Ca 0% to 0.05%
  • Mg 0% to 0.05%
  • Al 0% to 1.5%
  • Ti 0% or more 1.5% or less
  • Nb 0% to 1.5%
  • Zr 0% to 1.5%
  • Hf 0% to 1.5%
  • Ta 0% to 1.5%
  • W 0% to 1.5%
  • Cu 0% to 1.5%
  • O 0% to 0.005%
  • N 0% to 0.03%
  • the high-strength, low-thermal-expansion alloy wire according to (1) wherein a ratio of the number of the (Mo, V) C-based composite carbide is 50% or more.
  • the amounts of Mo, V and Cr contained in the alloy wire are [Mo], [V] and [Cr], respectively, the value of ([Mo] + [V]) / [Cr] is 1.2 or more.
  • Co more than 0%, including 3.0% or less, Any one of (1) to (3), wherein [Co] + [Ni] is 35% or more and 40% or less when the amounts of Co and Ni contained in the alloy wire are [Co] and [Ni], respectively.
  • the high-strength low thermal expansion alloy wire according to any one of (1) to (4), comprising: (6) In mass%, Al: more than 0% and 1.5% or less, Ti: more than 0% and 1.5% or less, Nb: more than 0% and 1.5% or less, Zr: more than 0% and 1.5% or less Hf: more than 0% and 1.5% or less, Ta: more than 0% and 1.5% or less, W: more than 0% and 1.5% or less, and Cu: more than 0% and 1.5% or less.
  • the high-strength low-thermal-expansion alloy wire according to any one of (1) to (5), comprising seeds or two or more kinds.
  • to 100 ° C. is 3 ⁇ 10 ⁇ 6 / ° C. or less (15 to 100 ° C.), average linear thermal expansion between two points from 15 ° C. to 230 ° C.
  • the high strength according to any one of (1) to (10), wherein an average linear thermal expansion coefficient between two points from 230 ° C. to 290 ° C. is 11 ⁇ 10 ⁇ 6 / ° C.
  • a high-strength and low-heat comprising the high-strength low-thermal expansion alloy wire according to any one of (1) to (11) and an Al coating layer or a Zn coating layer formed on the surface of the high-strength low-thermal expansion alloy wire Expanded coated alloy wire.
  • an alloy wire having characteristics necessary for a high-strength low thermal expansion alloy wire for example, high strength, high twist value, good ductility, low thermal expansion coefficient, etc.
  • Alloy wires and coated alloy wires are provided that can be used in a wide range of conditions for heat treatment to obtain the desired hardness.
  • the alloy wire and the coated alloy wire of the present invention are desired to avoid dimensional and shape changes due to thermal expansion. However, there is a possibility that the temperature rises during use. It is useful as a high-strength, low-thermal expansion alloy wire used in
  • Fig. 1 shows an example of a curve in which the horizontal axis is the aging temperature and the vertical axis is the tensile strength when aging heat treatment is performed with the heating time fixed at 6 hours and the heating temperature varied between 610 and 650 ° C.
  • FIG. FIG. 2 shows a curve in which the horizontal axis is the aging temperature and the vertical axis is the tensile strength when the heating temperature is fixed at 650 ° C. and the heating time is changed between 30 minutes and 9 hours. It is a conceptual diagram which shows an example.
  • composition of the alloy wire of the present invention will be described.
  • “%” means mass% unless otherwise specified.
  • C 0.1% or more and 0.4% or less C is an essential element of the alloy wire of the present invention.
  • C is effective for strengthening solid solution, precipitation hardening due to carbide formation, and strengthening thereof. From the viewpoint of effectively exhibiting such C effects, the C content is adjusted to 0.1% or more, preferably 0.13% or more, and more preferably 0.15% or more. On the other hand, when the content of C is excessive, ductility is lowered and the linear thermal expansion coefficient is increased. Therefore, the C content is adjusted to 0.4% or less, preferably 0.38% or less, and more preferably 0.36% or less.
  • Si 0.1% or more and 2.0% or less Si is an essential element of the alloy wire of the present invention. Si is effective for strengthening solid solution. From the viewpoint of effectively exhibiting the effect of Si, the Si content is adjusted to 0.1% or more, preferably 0.2% or more, and more preferably 0.3% or more. On the other hand, if the Si content is excessive, the linear thermal expansion coefficient increases. Accordingly, the Si content is adjusted to 2.0% or less, preferably 1.7% or less, and more preferably 1.3% or less.
  • Mn more than 0% and not more than 2.0% Mn is an essential element of the alloy wire of the present invention. Mn acts as a deoxidizer and is effective for strengthening solid solution. From the viewpoint of effectively exhibiting such an effect of Mn, the content of Mn is adjusted to more than 0%, preferably 0.1% or more, and more preferably 0.2% or more. On the other hand, if the Mn content is excessive, the linear thermal expansion coefficient increases. Therefore, the Mn content is adjusted to 2.0% or less, preferably 1.8% or less, and more preferably 1.3% or less.
  • Ni 25% or more and 40% or less
  • Ni is an essential element of the alloy wire of the present invention.
  • Ni is effective for realizing a low linear thermal expansion coefficient. From the viewpoint of effectively exhibiting such an effect of Ni, the Ni content is adjusted to 25% or more, preferably 30% or more, and more preferably 34% or more. On the other hand, if the Ni content is excessive, it is difficult to achieve a low linear thermal expansion coefficient, and the alloy wire cost increases. Therefore, the Ni content is adjusted to 40% or less, preferably 39% or less, and more preferably 38% or less.
  • V 0.5% to 3.0%
  • V is an essential element of the alloy wire of the present invention.
  • V is effective for precipitation hardening due to carbide formation and its strengthening, and is effective for avoiding ductile deterioration through suppressing coarsening of carbides in crystal grains and promoting fine precipitation of carbides in crystal grains.
  • the V content is adjusted to 0.5% or more, preferably 0.6% or more, and more preferably 0.7% or more.
  • the content of V is adjusted to 3.0% or less, preferably 2.8% or less, and more preferably 2.6% or less.
  • Mo 0.4% or more and 1.9% or less Mo is an essential element of the alloy wire of the present invention. Mo is effective for precipitation hardening by carbide formation and its strengthening, and is effective for preventing ductility deterioration through suppressing coarsening of carbides in crystal grains and promoting fine precipitation of carbides in crystal grains. From the viewpoint of effectively exhibiting such an effect of Mo, the Mo content is adjusted to 0.4% or more, preferably 0.5% or more, and more preferably 0.7% or more. On the other hand, when the content of Mo is excessive, the above effect is saturated, an increase in the effect commensurate with the increase in content cannot be obtained, and the linear thermal expansion coefficient increases. Therefore, the Mo content is adjusted to 1.9% or less, preferably 1.7% or less, and more preferably 1.5% or less.
  • the alloy wire of the present invention contains the above essential elements, and the balance consists of Fe and unavoidable impurities, but can contain one or more of the following optional elements and impurities as necessary.
  • Cr 0% to 3.0% Cr is an optional element of the alloy wire of the present invention. Cr is effective for strengthening solid solution. When it is desired to effectively exhibit such an effect of Cr, the Cr content is adjusted to more than 0%, preferably 0.1% or more, more preferably 0.3% or more. On the other hand, when the content of Cr is excessive, the formation of coarse carbides decreases the strength and ductility, and increases the linear thermal expansion coefficient. Therefore, the Cr content is adjusted to 3.0% or less, preferably 2.5% or less, and more preferably 2.0% or less.
  • the value of ([Mo] + [V]) / [Cr] is preferably Is 1.2 or more.
  • the value of ([Mo] + [V]) / [Cr] is adjusted to 1.2 or more, preferably 1.3 or more, and more preferably 1.5 or more.
  • the upper limit of the value of ([Mo] + [V]) / [Cr] is not particularly limited, but is preferably 8.0 or less, more preferably 6.0 or less.
  • Co is an optional element of the alloy wire of the present invention.
  • Co has the same effect as Ni and is effective in stabilizing the linear thermal expansion coefficient due to an increase in the Curie point.
  • the Co content is adjusted to more than 0%, preferably 0.1% or more, and more preferably 0.3% or more.
  • the Co content is adjusted to 3.0 or less, preferably 2.8 or less, and more preferably 2.5% or less.
  • [Co] + [Ni] is preferably 35% or more and 40% or less, when the amounts of Co and Ni contained in the alloy wire of the present invention are [Co] and [Ni], respectively.
  • [Co] + [Ni] is less than 35%, it is difficult to realize a low linear thermal expansion coefficient. Therefore, [Co] + [Ni] is adjusted to preferably 35% or more, more preferably 36% or more, and still more preferably 37% or more.
  • [Co] + [Ni] is 35% or more, a low linear thermal expansion coefficient can be realized.
  • [Co] + [Ni] exceeds 40%, it is difficult to realize a low coefficient of linear thermal expansion, and the alloy wire cost increases. Therefore, [Co] + [Ni] is adjusted to preferably 40% or less, more preferably 39.5% or less, and still more preferably 39% or less.
  • B 0% to 0.05%
  • B is an optional element of the alloy wire of the present invention.
  • B is effective for improving hot workability by strengthening grain boundaries and strengthening resistance to grain boundary oxidation.
  • the B content is adjusted to more than 0%, preferably 0.001% or more, more preferably 0.002% or more.
  • the B content is adjusted to 0.05% or less, preferably 0.03% or less, and more preferably 0.01% or less.
  • Ca 0% to 0.05%
  • Ca is an optional element of the alloy wire of the present invention. Ca is effective in improving hot workability by S fixation. When it is desired to effectively exhibit such an effect of Ca, the Ca content is adjusted to more than 0%, preferably 0.005% or more, and more preferably 0.01% or more. On the other hand, when the content of Ca is excessive, hot workability is lowered. Therefore, the Ca content is adjusted to 0.05% or less, preferably 0.04% or less, and more preferably 0.03% or less.
  • Mg 0% to 0.05%
  • Mg is an optional element of the alloy wire of the present invention.
  • Mg is effective in improving hot workability by S fixation.
  • the content of Mg is adjusted to more than 0%, preferably 0.01% or more, more preferably 0.015% or more.
  • the Mg content is adjusted to 0.05% or less, preferably 0.045% or less, and more preferably% 0.04 or less.
  • Al 0% to 1.5%
  • Al is an optional element of the alloy wire of the present invention.
  • Al is effective for removal of oxide inclusions due to the deoxidation effect, strengthening of solid solution, precipitation hardening, and strengthening thereof.
  • the Al content is adjusted to more than 0%, preferably 0.005% or more, and more preferably 0.01% or more.
  • the Al content is adjusted to 1.5% or less, preferably 1.3% or less, and more preferably 1.0% or less.
  • Ti 0% or more and 1.5% or less
  • Ti is an optional element of the alloy wire of the present invention. Ti is effective for precipitation hardening and strengthening thereof, and can be used as an alternative element for V or Mo.
  • the Ti content is adjusted to more than 0%, preferably 0.001% or more, and more preferably 0.005% or more.
  • the Ti content is adjusted to 1.5% or less, preferably 1.3% or less, and more preferably 1.0% or less.
  • Nb 0% to 1.5%
  • Nb is an optional element of the alloy wire of the present invention.
  • Nb is effective for precipitation hardening and strengthening thereof, and can be used as an alternative element for V or Mo.
  • the content of Nb is adjusted to more than 0%, preferably 0.01% or more, more preferably 0.02% or more.
  • the Nb content is adjusted to 1.5% or less, preferably 1.3% or less, and more preferably 1.0% or less.
  • Zr 0% to 1.5%
  • Zr is an optional element of the alloy wire of the present invention.
  • Zr is effective for precipitation hardening and strengthening thereof, and can be used as an alternative element for V or Mo.
  • the Zr content is adjusted to be more than 0%, preferably 0.01% or more, more preferably 0.02% or more.
  • the Zr content is adjusted to 1.5% or less, preferably 1.3% or less, and more preferably 1.0% or less.
  • Hf 0% to 1.5%
  • Hf is an optional element of the alloy wire of the present invention.
  • Hf is effective for precipitation hardening and strengthening thereof, and can be used as an alternative element for V or Mo.
  • the content of Hf is adjusted to more than 0%, preferably 0.01% or more, more preferably 0.02% or more.
  • the content of Hf is adjusted to 1.5% or less, preferably 1.4% or less, and more preferably 1.3% or less.
  • Ta 0% to 1.5% Ta is an optional element of the alloy wire of the present invention.
  • Ta is effective for precipitation hardening and strengthening thereof, and can be used as an alternative element for V or Mo.
  • the content of Ta is adjusted to more than 0%, preferably 0.01% or more, more preferably 0.02% or more.
  • the Ta content is adjusted to 1.5% or less, preferably 1.4% or less, and more preferably 1.3% or less.
  • W 0% to 1.5%
  • W is an optional element of the alloy wire of the present invention.
  • W is effective for precipitation hardening and strengthening thereof, and can be used as an alternative element for V or Mo.
  • the W content is adjusted to more than 0%, preferably 0.01% or more, more preferably 0.02% or more.
  • the W content is adjusted to 1.5% or less, preferably 1.4% or less, and more preferably 1.3% or less.
  • Cu 0% to 1.5%
  • Cu is an optional element of the alloy wire of the present invention.
  • Cu is effective for precipitation hardening and its strengthening by forming Cu particles and raises the Curie point.
  • the Cu content is adjusted to more than 0%, preferably 0.01% or more, more preferably 0.02% or more.
  • the Cu content is adjusted to 1.5% or less, preferably 1.3% or less, and more preferably 1.0% or less.
  • O 0% or more and 0.005% or less
  • O is an impurity of the alloy wire of the present invention.
  • O reduces ductility due to oxide formation. Therefore, the content of O is adjusted to 0.005% or less, preferably 0.003% or less, and more preferably 0.001% or less.
  • N is an optional element of the alloy wire of the present invention.
  • N has the same effects as C, such as solid solution strengthening.
  • the N content is adjusted to more than 0%, preferably 0.01% or more.
  • the N content is adjusted to 0.03% or less, preferably 0.025% or less.
  • the alloy wire according to an embodiment of the present invention includes B: more than 0% and less than 0.05%, Ca: more than 0% and less than 0.05%, and Mg: more than 0% and less than 0.05%. Includes seeds or two or more.
  • the alloy wire according to another embodiment of the present invention includes Al: more than 0% and 1.5% or less, Ti: more than 0% and 1.5% or less, Nb: more than 0% and 1.5% or less, Zr: 0% More than 1.5%, Hf: more than 0% and 1.5% or less, Ta: more than 0% and 1.5% or less, W: more than 0% and 1.5% or less, and Cu: more than 0% 1.5 % Or less of 1 type or 2 types or more.
  • the alloy wire of the present invention has crystal grains in which (Mo, V) C-based composite carbide containing both Mo and V (hereinafter sometimes referred to as “composite carbide”) exists.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ is 0.2 or more and 4.0 or less. If the value of ⁇ Mo ⁇ / ⁇ V ⁇ is less than 0.2, Mo-deficient carbides are formed, hardness and strength are reduced, and intragranular carbides are formed and grown quickly in aging heat treatment, resulting in high hardness. In addition, the temperature range of aging heat treatment that can maintain high strength is narrowed, and high hardness and high strength cannot be obtained under aging conditions in a wide temperature range.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ is adjusted to 0.2 or more, preferably 0.3 or more, and more preferably 0.4 or more.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ is 0.2 or more, precipitation hardening and its strengthening can be optimized.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ exceeds 4.0, V-deficient carbides are formed, the hardness and strength are reduced, and the formation and growth of intragranular carbides occur early in the aging heat treatment.
  • the temperature range of aging heat treatment that can maintain hardness and high strength is narrowed, and high hardness and high strength cannot be obtained under aging conditions in a wide temperature range.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ is adjusted to 4.0 or less, preferably 3.7 or less, and more preferably 3.4 or less.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ is 4.0 or less, precipitation hardening and its strengthening can be optimized.
  • the value of ⁇ Mo ⁇ / ⁇ V ⁇ is obtained as follows.
  • a specimen is taken from the alloy wire and the cross section of the specimen is polished.
  • the composition of carbides present inside the crystal grains is analyzed using a transmission electron microscope (TEM) and an energy dispersive X-ray fluorescence analyzer (EDX).
  • TEM transmission electron microscope
  • EDX energy dispersive X-ray fluorescence analyzer
  • TEM transmission electron microscope
  • EDX energy dispersive X-ray fluorescence analyzer
  • the density of (Mo, V) C-based composite carbide in the crystal grains is preferably 10 pieces / ⁇ m 2 or more. If the density of the (Mo, V) C-based composite carbide in the crystal grains is less than 10 pieces / ⁇ m 2 , the precipitates are few and the strength may be reduced, but the (Mo, V) C in the crystal grains may be low. When the density of the system composite carbide is 10 pieces / ⁇ m 2 or more, precipitation hardening and its strengthening can be optimized.
  • Ratio of the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less to the total number of (Mo, V) C-based composite carbides in the crystal grains (the presence of (Mo, V) C-based composite carbides having a diameter of 150 nm or less
  • the ratio is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more.
  • the ratio of the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less to the total number of (Mo, V) C-based composite carbides in the crystal grains is less than 50%, a large number of coarse particles are formed, although there is a risk of low strength, the ratio of the number of (Mo, V) C composite carbide having a diameter of 150 nm or less to the total number of (Mo, V) C composite carbide in the crystal grains is 50% or more. Precipitation hardening and its strengthening can be optimized.
  • the density of the (Mo, V) C-based composite carbide in the crystal grains and the abundance of the (Mo, V) C-based composite carbide having a diameter of 150 nm or less are measured as follows using TEM and EDX.
  • TEM the microstructure of the cross section of the polished specimen is observed, and (Mo, V) C-based composite carbide existing in the crystal grains is identified by composition analysis using electron diffraction and EDX.
  • the total number of (Mo, V) C-based composite carbides is counted from the TEM bright field images observed and photographed at a magnification of 5,000 to 200,000 according to the size of the carbides present in the crystal grains.
  • the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less existing in the field image is counted. Based on the observation area of the TEM bright field image and the total number of (Mo, V) C composite carbides present in the TEM bright field image, the density of (Mo, V) C composite carbide (pieces / ⁇ m). 2 ).
  • the total number of (Mo, V) C-based composite carbides counted by the above method Based on the total number of (Mo, V) C-based composite carbides counted by the above method and the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less, the total number of (Mo, V) C-based composite carbides The ratio of the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less to the number (the presence ratio of (Mo, V) C-based composite carbides of 150 nm or less) is determined.
  • the major axis of the (Mo, V) C-based composite carbide is defined as the diameter of the (Mo, V) C-based composite carbide.
  • the tensile strength (TS) of the alloy wire of the present invention is preferably 1300 MPa or more, more preferably 1400 MPa or more, and even more preferably 1500 MPa or more.
  • the elongation (EL) of the alloy wire of the present invention is preferably 0.8% or more, more preferably 1.0% or more. TS and EL are measured by carrying out a tensile test according to JIS Z 2241 on a test piece prepared from an alloy wire.
  • the twist value of the alloy wire of the present invention measured at a distance between the gauge points 100 times the final wire diameter of the alloy wire of the present invention is preferably 20 times or more, more preferably 60 times or more.
  • the twist value is measured as follows. One end of a test piece prepared from an alloy wire is fixed, the other end of the test piece is twisted, and the number of twists until the test piece breaks is measured as a twist value.
  • the distance between the gauge points is 100 ⁇ D (D represents the final wire diameter of the test piece), and the twisting speed is 60 rpm.
  • wire diameter means the diameter of a circle when the cross section of the test piece is a circle, and the equivalent circle diameter converted from the area of the cross section when the cross section of the test piece is not a circle.
  • equivalent circle diameter means the diameter of a circle having the same area as the cross-sectional area of the test piece.
  • the average linear thermal expansion coefficient between two points from 15 ° C. to 100 ° C. of the alloy wire of the present invention is preferably 3.4 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 3.0 ⁇ 10 ⁇ 6 / ° C. or less. It is.
  • the average linear thermal expansion coefficient between two points from 15 ° C. to 230 ° C. of the alloy wire of the present invention is preferably 4.4 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 4.0 ⁇ 10 ⁇ 6 / ° C. or less. It is.
  • the average linear thermal expansion coefficient between two points from 100 ° C. to 240 ° C. of the alloy wire of the present invention is preferably 4.4 ⁇ 10 ⁇ 6 / ° C.
  • the average linear thermal expansion coefficient between two points from 230 ° C. to 290 ° C. of the alloy wire of the present invention is preferably. It is 11.4 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 11.0 ⁇ 10 ⁇ 6 / ° C. or less.
  • the linear thermal expansion coefficient is measured as follows. Measure the displacement of the test piece in the temperature rising process with a Formaster tester (Formaster-EDP, manufactured by Fuji Electric Koki Co., Ltd.).
  • the form of the alloy wire of the present invention is not particularly limited as long as it is linear.
  • Examples of the form of the alloy wire of the present invention include a round wire, a flat wire, and a square wire.
  • the wire diameter of the alloy wire of the present invention is not particularly limited, but is, for example, 2.0 to 3.8 mm. The meaning of “wire diameter” is as described above.
  • the alloy wire of the present invention can be produced, for example, by the following method.
  • a steel material having a desired shape such as a round bar or square bar by hot forging or hot rolling after melting the steel having the alloy composition of the present invention and producing a steel ingot or bloom by ingot forming or continuous casting.
  • the alloy wire of the present invention can be manufactured by sequentially performing solution treatment, wire drawing and aging heat treatment on the steel material.
  • the solution treatment can be performed at a heating temperature of 1200 ° C. and a heating time of 30 minutes.
  • the solution treatment can be omitted if rapid cooling such as water cooling is performed immediately after the steel material manufacturing process by hot forging or hot rolling.
  • the aging heat treatment can be performed, for example, at a heating temperature of 625 ° C. and a heating time of 2 hours. It is preferable to cold work the steel after the solution treatment and before the aging heat treatment.
  • the alloy wire having the alloy composition of the present invention has a wide range of aging heat treatment conditions (temperature and holding time of the temperature) for obtaining high hardness. Therefore, when imparting hardness by aging heat treatment, it is possible to avoid a decrease in hardness due to a change in manufacturing conditions (for example, material, heating temperature, heating time, etc.), poor control, and the like. In addition, in the aging heat treatment, even when an excessive heat treatment is performed, a significant decrease in hardness due to the excessive heat treatment can be avoided. Such stability is caused by precipitation of (Mo, V) C-based composite carbide having a value of ⁇ Mo ⁇ / ⁇ V ⁇ of 0.2 or more and 4.0 or less in the crystal grains in the aging heat treatment. It is an effect.
  • the coated alloy wire of the present invention includes the alloy wire of the present invention and an Al coating layer (Al coating) or a Zn coating layer (Zn coating) formed on the surface of the alloy wire of the present invention.
  • the coated alloy wire of the present invention has corrosion resistance due to the Al coating layer or the Zn coating layer in addition to the same effects as the alloy wire of the present invention.
  • the Al coating layer can be formed by a known method such as conform extrusion.
  • the Zn coating layer can be formed by a known method such as plating.
  • Ingots were obtained by melting 50 kg of alloys having the composition shown in Table 1 (Invention Examples No. 1 to 30) and Table 2 (Comparative Examples No. 31 to 55) in a vacuum induction melting furnace (VIM). .
  • the ingot was heated at 1200 ° C. for 1 hour and forged into a steel bar having a diameter of 20 mm.
  • the steel bar was subjected to a solution treatment under the conditions of a heating temperature of 1200 ° C. and a heating time of 30 minutes.
  • the steel bar after solution treatment was turned to a diameter of 15 mm, and then drawn at room temperature to produce an alloy wire with a wire diameter of 8 mm.
  • [Mo], [V] and [C] represent the amounts of Mo, V and C contained in the alloy, respectively.
  • test piece (length: 10 mm) prepared from an alloy wire having a wire diameter of 8 mm was subjected to an aging heat treatment under the conditions of a heating temperature of 500 to 1000 ° C. and a heating time of 30 minutes to 24 hours.
  • the test piece after the aging heat treatment was analyzed for the composition of carbides present in the crystal grains using a transmission electron microscope (TEM) and an energy dispersive X-ray fluorescence analyzer (EDX). Analysis by TEM and EDX was performed as follows. Using TEM, the microstructure of the cross section of the polished specimen is observed, and using EDX, (Mo, V) C-based composite carbide existing in the crystal grains is identified, and (Mo, V) C-based is identified. The amount of Mo and V contained in the composite carbide was measured, and the value of ⁇ Mo ⁇ / ⁇ V ⁇ was determined. The results are shown in Table 3 (Invention Examples No. 1 to 30) and Table 4 (Comparative Example Nos. 31 to 55). In Tables 3 and 4, ⁇ Mo ⁇ and ⁇ V ⁇ represent the amounts of Mo and V contained in the (Mo, V) C-based composite carbide, respectively.
  • TEM transmission electron microscope
  • EDX energy dispersive X-ray fluorescence analyzer
  • the density of the (Mo, V) C type complex carbide which exists in a crystal grain was analyzed using TEM and EDX. Analysis by TEM and EDX was performed as follows. Using TEM, the microstructure of the cross section of the polished specimen was observed, and (Mo, V) C-based composite carbide existing inside the crystal grains was identified by composition analysis using electron diffraction and EDX. And the amount of Mo and V contained in the (Mo, V) C-based composite carbide was measured, and the value of ⁇ Mo ⁇ / ⁇ V ⁇ was determined. The value of ⁇ Mo ⁇ / ⁇ V ⁇ of the composite carbide targeted in the present invention is 0.2 to 4.0.
  • the total number of (Mo, V) C-based composite carbides is counted from a TEM bright field image observed and photographed at a magnification of 5,000 to 200,000 according to the size of carbides present in the crystal grains.
  • the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less present in the TEM bright field image was counted.
  • the density of (Mo, V) C composite carbide (pieces / ⁇ m). 2 ) was obtained.
  • the total number of (Mo, V) C-based composite carbides counted by the above method and the number of (Mo, V) C-based composite carbides having a diameter of 150 nm or less, the total number of (Mo, V) C-based composite carbides The ratio of the number of (Mo, V) C-based composite carbide having a diameter of 150 nm or less to the number (the presence ratio of (Mo, V) C-based composite carbide having a diameter of 150 nm or less) was determined.
  • the major axis of the (Mo, V) C-based composite carbide was defined as the diameter of the (Mo, V) C-based composite carbide.
  • the horizontal axis is the aging temperature and the vertical axis is the tensile strength when the aging heat treatment is performed with the heating time fixed at 6 hours and the heating temperature varied between 610 ° C. and 650 ° C.
  • the temperature range in which 96% or more of the maximum tensile strength (MAX 6 hr) can be secured is 32 ° C.
  • the horizontal axis represents the aging temperature and the vertical axis represents the tensile strength. It is an example of a curve. In this curve, the time range in which a tensile strength of 97% or more of the maximum tensile strength (MAX 650 ° C.) can be secured is 3.8 hours.
  • test piece (length: 300 mm) produced from an alloy wire having a wire diameter of 8 mm under the conditions of a heating temperature of 500 to 1000 ° C. and a heating time of 30 minutes to 24 hours.
  • the test piece after the aging heat treatment was drawn at room temperature to prepare a test piece (length 400 mm or more) having a wire diameter of 3.1 mm.
  • a tensile tester 100 kN universal testing machine, manufactured by Shimadzu Corporation
  • a tensile test piece having a wire diameter of 3.1 mm and a gauge length of 250 mm
  • a tensile test at a stroke speed of 20 mm / min or less at room temperature.
  • tensile strength (TS) and elongation (EL) were measured.
  • twist value after aging heat treatment The twist value of a test piece (length: 310 mm) having a wire diameter of 3.1 mm produced in the same manner as described above was measured. The twist value was measured as follows. One end of the test piece was fixed, the other end of the test piece was twisted, and the number of twists until the test piece was broken was measured as a twist value. The distance between the gauge points was 100 D (D represents the final wire diameter of the test piece), and the twisting speed was 60 rpm. When the twist value is 60 times or more, “A: The twist value is very good”, and when the twist value is 20 to 59 times, “B: The twist value is good”, and the twist value is 20 times.
  • the linear thermal expansion coefficient of a test piece having a wire diameter of 3.1 mm produced in the same manner as above was measured.
  • the linear thermal expansion coefficient was measured as follows. Measure the displacement of the test piece in the temperature rising process with a Formaster tester (Formaster-EDP, manufactured by Fuji Electric Koki Co., Ltd.). Average linear thermal expansion coefficient between two points from 15 ° C to 100 ° C, 15 ° C Average linear thermal expansion coefficient between two points from 1 to 230 ° C, average linear thermal expansion coefficient between two points from 100 ° C to 240 ° C, and average linear thermal expansion coefficient between two points from 230 ° C to 290 ° C was measured. When the average linear thermal expansion coefficient between two points from 15 ° C.
  • the average linear thermal expansion coefficient from 15 ° C to 230 ° C In the evaluation of the average linear thermal expansion coefficient from 15 ° C to 230 ° C, the average linear thermal expansion coefficient from 100 ° C to 240 ° C, and the average linear thermal expansion coefficient from 15 ° C to 290 ° C, all have one A or B evaluation.
  • the overall evaluation when the other three are A evaluations is “A: The linear thermal expansion coefficient is very low”, and the two B evaluations are two, and the overall evaluation is “B: linear thermal expansion coefficient is The overall evaluation when the “low” one is A evaluation and the three are B evaluation is “C: linear thermal expansion coefficient is generally low”, and the overall evaluation when one or more F evaluations is “F: linear thermal expansion” The coefficient is high. " The results are shown in Table 5 (Invention Examples No. 1 to 30) and Table 6 (Comparative Example Nos. 31 to 55).
  • Condition a satisfying the alloy composition of the present invention
  • Condition b (Mo, V) C-based composite carbide exists inside the crystal grains.
  • Condition c The value of ([Mo] +2.8 [V]) / [C] is 9.6 or more and 21.7 or less
  • Condition d The value of ⁇ Mo ⁇ / ⁇ V ⁇ is 0.2 or more and 4 0.0 or less
  • Condition e (Mo, V) C-based composite carbide has a density of 10 pieces / ⁇ m 2 or more in crystal grains and has a diameter of 150 nm or less (Mo, V) with respect to the total number of (Mo, V) C-based composite carbides.
  • V The ratio of the number of C-based composite carbides is 50% or more.
  • Condition f When the Cr content is more than 0%, the value of ([Mo] + [V]) / [Cr] is 1.2 or more.
  • Condition g When the content of Co is more than 0%, [Co] + [Ni] is 35% or more and 40% or less. All the characteristics required for a high-strength, low-thermal-expansion alloy wire were A or B evaluations, that is, high strength, high twist value, good ductility, and low thermal expansion coefficient.
  • Invention Example No. 1-No. No. 26 was excellent in aging stability (thermal aging stability and aging stability over time).
  • Invention Example No. 27-No. 30 satisfies all the conditions a to d and is generally excellent in wear resistance, high strength, good ductility, low thermal expansion coefficient and aging stability (thermal aging stability and aging stability over time). There is C evaluation which does not satisfy any one of the conditions e to g and is slightly inferior to B evaluation in any one of them.
  • Comparative Example No. 31-No. 55 does not satisfy any one or more of conditions a to d, and is at least one of strength, twisting characteristics, ductility, thermal expansion coefficient, and aging stability (thermal aging stability and aging stability over time)
  • the species was F rated and lacked the necessary properties.

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Abstract

L'invention concerne un câble en alliage qui possède les caractéristiques indispensables à un câble en alliage à faible dilatation thermique et haute résistance. Plus précisément, l'invention a pour objet de fournir un câble en alliage qui permet la mise en œuvre d'une large plage de conditions dans un traitement thermique destiné à obtenir la dureté souhaitée lors de la fabrication de câbles en alliage. À cet effet, l'invention fournit un câble en alliage à faible dilatation thermique et haute résistance qui possède une composition d'alliage prédéfinie, et des particules cristallines dans la partie interne desquelles un carbure composite à base de (Mo, V) C est présent. Lorsque les quantités de Mo, V et C contenues dans ledit câble en alliage sont respectivement représentées par ［Ｍｏ］, ［Ｖ］ et ［Ｃ］, la valeur de （［Ｍｏ］＋２．８［Ｖ］）／［Ｃ］ est supérieure ou égale à 9,6 et inférieure ou égale à 21,7. Lorsque les quantités de Mo et V contenues dans ledit carbure composite à base de (Mo, V) C sont respectivement représentées par ｛Ｍｏ｝ et ｛Ｖ｝, la valeur de ｛Ｍｏ｝／｛Ｖ｝ est supérieure ou égale à 0,2 et inférieure ou égale à 4,0.
PCT/JP2018/013316 2017-04-19 2018-03-29 Câble en alliage à faible dilatation thermique et haute résistance WO2018193810A1 (fr)

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CN112962020A (zh) * 2019-12-12 2021-06-15 全球能源互联网研究院有限公司 一种架空导线用合金材料及其制备方法
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CN113718182B (zh) * 2021-08-30 2022-06-17 无锡华能电缆有限公司 锌铝镀层殷钢单线及其制备方法
CN116043127A (zh) * 2022-12-08 2023-05-02 宝武特冶航研科技有限公司 一种热膨胀系数低的因瓦合金材料
CN117144263B (zh) * 2023-08-09 2024-03-19 无锡市蓝格林金属材料科技有限公司 倍容导线用高强度低热膨胀因瓦合金丝材及其制备方法

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