WO2018193810A1 - 高強度低熱膨張合金線 - Google Patents
高強度低熱膨張合金線 Download PDFInfo
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- 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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Images
Classifications
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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
Description
(1)質量%で、C:0.1%以上0.4%以下、Si:0.1%以上2.0%以下、Mn:0%超2.0%以下、Ni:25%以上40%以下、V:0.5%以上3.0%以下、Mo:0.4%以上1.9%以下、Cr:0%以上3.0%以下、Co:0%以上3.0%以下、B:0%以上0.05%以下、Ca:0%以上0.05%以下、Mg:0%以上0.05%以下、Al:0%以上1.5%以下、Ti:0%以上1.5%以下、Nb:0%以上1.5%以下、Zr:0%以上1.5%以下、Hf:0%以上1.5%以下、Ta:0%以上1.5%以下、W:0%以上1.5%以下、Cu:0%以上1.5%以下、O:0%以上0.005%以下、及びN:0%以上0.03%以下を含み、残部がFe及び不可避的不純物からなる高強度低熱膨張合金線であって、
前記合金線の結晶粒内には、Mo及びVの両方を含む(Mo,V)C系複合炭化物が存在し、
前記合金線に含まれるMo、V及びCの量をそれぞれ[Mo]、[V]及び[C]としたとき、([Mo]+2.8[V])/[C]の値が9.6以上21.7以下であり、
前記(Mo,V)C系複合炭化物に含まれるMo及びVの量をそれぞれ{Mo}及び{V}としたとき、{Mo}/{V}の値が0.2以上4.0以下である、前記高強度低熱膨張合金線。
(2)前記結晶粒において、前記(Mo,V)C系複合炭化物の密度が10個/μm2以上であり、かつ、前記(Mo,V)C系複合炭化物の総個数に対する直径150nm以下の前記(Mo,V)C系複合炭化物の個数の割合が50%以上である、(1)に記載の高強度低熱膨張合金線。
(3)質量%で、Cr:0%超3.0%以下を含み、
前記合金線に含まれるMo、V及びCrの量をそれぞれ[Mo]、[V]及び[Cr]としたとき、([Mo]+[V])/[Cr]の値が1.2以上である、(1)又は(2)に記載の高強度低熱膨張合金線。
(4)質量%で、Co:0%超3.0%以下を含み、
前記合金線に含まれるCo及びNiの量をそれぞれ[Co]及び[Ni]としたとき、[Co]+[Ni]が35%以上40%以下である、(1)~(3)のいずれかに記載の高強度低熱膨張合金線。
(5)質量%で、B:0%超0.05%以下、Ca:0%超0.05%以下、及び、Mg:0%超0.05%以下のうちの1種又は2種以上を含む、(1)~(4)のいずれかに記載の高強度低熱膨張合金線。
(6)質量%で、Al:0%超1.5%以下、Ti:0%超1.5%以下、Nb:0%超1.5%以下、Zr:0%超1.5%以下、Hf:0%超1.5%以下、Ta:0%超1.5%以下、W:0%超1.5%以下、及び、Cu:0%超1.5%以下のうちの1種又は2種以上を含む、(1)~(5)のいずれかに記載の高強度低熱膨張合金線。
(7)質量%で、N:0%超0.03%以下を含む、(1)~(6)のいずれかに記載の高強度低熱膨張合金線。
(8)引張強さが1400MPa以上である、(1)~(7)のいずれかに記載の高強度低熱膨張合金線。
(9)前記合金線の最終線径の100倍の標点間距離で測定される捻回値が、20回以上である、(1)~(8)のいずれかに記載の高強度低熱膨張合金線。
(10)伸びが0.8%以上である、(1)~(9)のいずれかに記載の高強度低熱膨張合金線。
(11)15℃から100℃までの2点間における平均線熱膨張係数が3×10-6/℃以下(15~100℃)、15℃から230℃までの2点間における平均線熱膨張係数が4×10-6/℃以下(15~230℃)、100℃から240℃までの2点間における平均線熱膨張係数が4×10-6/℃以下(100~240℃)、かつ、230℃から290℃までの2点間における平均線熱膨張係数が11×10-6/℃以下(230~290℃)である、(1)~(10)のいずれかに記載の高強度低熱膨張合金線。
(12)(1)~(11)のいずれかに記載の高強度低熱膨張合金線と、前記高強度低熱膨張合金線の表面に形成されたAl被覆層又はZn被覆層とを備える高強度低熱膨張被覆合金線。
以下、本発明の合金線の組成について説明する。なお、本明細書において、「%」は別段規定される場合を除き、質量%を意味する。
Cは、本発明の合金線の必須元素である。Cは、固溶の強化、並びに、炭化物形成による析出硬化及びその強化に有効である。このようなCの効果を有効に発揮させる観点から、Cの含有量は、0.1%以上、好ましくは0.13%以上、さらに好ましくは0.15%以上に調整される。一方、Cの含有量が過剰であると、延性が低下するとともに、線熱膨張係数が増大する。したがって、Cの含有量は、0.4%以下、好ましくは0.38%以下、さらに好ましくは0.36%以下に調整される。
Siは、本発明の合金線の必須元素である。Siは、固溶の強化に有効である。このようなSiの効果を有効に発揮させる観点から、Siの含有量は、0.1%以上、好ましくは0.2%以上、さらに好ましくは0.3%以上に調整される。一方、Siの含有量が過剰であると、線熱膨張係数が増大する。したがって、Siの含有量は、2.0%以下、好ましくは1.7%以下、さらに好ましくは1.3%以下に調整される。
Mnは、本発明の合金線の必須元素である。Mnは、脱酸剤として作用するとともに、固溶の強化に有効である。このようなMnの効果を有効に発揮させる観点から、Mnの含有量は、0%超、好ましくは0.1%以上、さらに好ましくは0.2%以上に調整される。一方、Mnの含有量が過剰であると、線熱膨張係数が増大する。したがって、Mnの含有量は、2.0%以下、好ましくは1.8%以下、さらに好ましくは1.3%以下に調整される。
Niは、本発明の合金線の必須元素である。Niは、低い線熱膨張係数の実現に有効である。このようなNiの効果を有効に発揮させる観点から、Niの含有量は、25%以上、好ましくは30%以上、さらに好ましくは34%以上に調整される。一方、Niの含有量が過剰であると、低い線熱膨張係数の実現が困難となるとともに、合金線コストが増加する。したがって、Niの含有量は、40%以下、好ましくは39%以下、さらに好ましくは38%以下に調整される。
Vは、本発明の合金線の必須元素である。Vは、炭化物形成による析出硬化及びその強化に有効であるとともに、結晶粒内炭化物の粗大化抑制及び結晶粒内炭化物の微細析出促進を通じた延性劣化回避に有効である。このようなVの効果を有効に発揮させる観点から、Vの含有量は、0.5%以上、好ましくは0.6%以上、さらに好ましくは0.7%以上に調整される。一方、Vの含有量が過剰であると、上記効果が飽和し、含有量の増加に見合う効果の増加が得られないとともに、線熱膨張係数が増大する。したがって、Vの含有量は、3.0%以下、好ましくは2.8%以下、さらに好ましくは2.6%以下に調整される。
Moは、本発明の合金線の必須元素である。Moは、炭化物形成による析出硬化及びその強化に有効であるとともに、結晶粒内炭化物の粗大化抑制及び結晶粒内炭化物の微細析出促進を通じた延性劣化回避に有効である。このようなMoの効果を有効に発揮させる観点から、Moの含有量は、0.4%以上、好ましくは0.5%以上、さらに好ましくは0.7%以上に調整される。一方、Moの含有量が過剰であると、上記効果が飽和し、含有量の増加に見合う効果の増加が得られないとともに、線熱膨張係数が増大する。したがって、Moの含有量は、1.9%以下、好ましくは1.7%以下、さらに好ましくは1.5%以下に調整される。
本発明の合金線に含まれるMo、V及びCの量をそれぞれ[Mo]、[V]及び[C]としたとき、([Mo]+2.8[V])/[C]の値は、9.6以上21.7以下である。([Mo]+2.8[V])/[C]の値が9.6未満であると、Cの含有量が相対的に過剰となり、延性が低下する。したがって、([Mo]+2.8[V])/[C]の値は、9.6以上、好ましくは10.0以上、さらに好ましくは10.8以上に調整される。([Mo]+2.8[V])/[C]の値が9.6以上であると、炭化物形成による析出硬化及びその強化を実現できるとともに、延性を最適化できる。一方、([Mo]+2.8[V])/[C]の値が21.7を超えると、Vの含有量及びMoの含有量が相対的に過剰となり、V及びMoの効果が飽和し、含有量の増加に見合う効果の増加が得られないとともに、線熱膨張係数が増大する。したがって、([Mo]+2.8[V])/[C]の値は、21.7以下、好ましくは21.3以下、さらに好ましくは21.0以下に調整される。
Crは、本発明の合金線の任意元素である。Crは、固溶の強化に有効である。このようなCrの効果を有効に発揮させることが望まれる場合、Crの含有量は、0%超、好ましくは0.1%以上、さらに好ましくは0.3%以上に調整される。一方、Crの含有量が過剰であると、粗大な炭化物の形成により強度及び延性が低下するとともに、線熱膨張係数が増大する。したがって、Crの含有量は、3.0%以下、好ましくは2.5%以下、さらに好ましくは2.0%以下に調整される。
Coは、本発明の合金線の任意元素である。Coは、Niと同様の効果を有するとともに、キュリー点の上昇による線熱膨張係数の安定化に有効である。このようなCoの効果を有効に発揮させることが望まれる場合、Coの含有量は、0%超、好ましくは0.1%以上、さらに好ましくは0.3%以上に調整される。一方、Coの含有量が過剰であると、合金線コストが増加するとともに、線熱膨張係数が増大する。したがって、Coの含有量は、3.0以下、好ましくは2.8以下、さらに好ましくは2.5%以下に調整される。
Bは、本発明の合金線の任意元素である。Bは、粒界強化による熱間加工性の向上及び耐粒界酸化性の強化に有効である。このようなBの効果を有効に発揮させることが望まれる場合、Bの含有量は、0%超、好ましくは0.001%以上、さらに好ましくは0.002%以上に調整される。一方、Bの含有量が過剰であると、熱間加工性が低下する。したがって、Bの含有量は、0.05%以下、好ましくは0.03%以下、さらに好ましくは0.01%以下に調整される。
Caは、本発明の合金線の任意元素である。Caは、S固定による熱間加工性の向上に有効である。このようなCaの効果を有効に発揮させることが望まれる場合、Caの含有量は、0%超、好ましくは0.005%以上、さらに好ましくは0.01%以上に調整される。一方、Caの含有量が過剰であると、熱間加工性が低下する。したがって、Caの含有量は、0.05%以下、好ましくは0.04%以下、さらに好ましくは0.03%以下に調整される。
Mgは、本発明の合金線の任意元素である。Mgは、S固定による熱間加工性の向上に有効である。このようなMgの効果を有効に発揮させることが望まれる場合、Mgの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.015%以上に調整される。一方、Mgの含有量が過剰であると、熱間加工性が低下する。したがって、Mgの含有量は、0.05%以下、好ましくは0.045%以下、さらに好ましくは%0.04以下に調整される。
Alは、本発明の合金線の任意元素である。Alは、脱酸効果による酸化物系介在物の除去、固溶の強化、並びに、析出硬化及びその強化に有効である。このようなAlの効果を有効に発揮させることが望まれる場合、Alの含有量は、0%超、好ましくは0.005%以上、さらに好ましくは0.01%以上に調整される。一方、Alの含有量が過剰であると、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Alの含有量は、1.5%以下、好ましくは1.3%以下、さらに好ましくは1.0%以下に調整される。
Tiは、本発明の合金線の任意元素である。Tiは、析出硬化及びその強化に有効であり、V又はMoの代替元素として使用可能である。このようなTiの効果を有効に発揮させることが望まれる場合、Tiの含有量は、0%超、好ましくは0.001%以上、さらに好ましくは0.005%以上に調整される。一方、Tiの含有量が過剰であると、時効硬化能の低下、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Tiの含有量は、1.5%以下、好ましくは1.3%以下、さらに好ましくは1.0%以下に調整される。
Nbは、本発明の合金線の任意元素である。Nbは、析出硬化及びその強化に有効であり、V又はMoの代替元素として使用可能である。このようなNbの効果を有効に発揮させることが望まれる場合、Nbの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.02%以上に調整される。一方、Nbの含有量が過剰であると、時効硬化能の低下、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Nbの含有量は、1.5%以下、好ましくは1.3%以下、さらに好ましくは1.0%以下に調整される。
Zrは、本発明の合金線の任意元素である。Zrは、析出硬化及びその強化に有効であり、V又はMoの代替元素として使用可能である。このようなZrの効果を有効に発揮させることが望まれる場合、Zrの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.02%以上に調整される。一方、Zrの含有量が過剰であると、時効硬化能の低下、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Zrの含有量は、1.5%以下、好ましくは1.3%以下、さらに好ましくは1.0%以下に調整される。
Hfは、本発明の合金線の任意元素である。Hfは、析出硬化及びその強化に有効であり、V又はMoの代替元素として使用可能である。このようなHfの効果を有効に発揮させることが望まれる場合、Hfの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.02%以上に調整される。一方、Hfの含有量が過剰であると、時効硬化能の低下、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Hfの含有量は、1.5%以下、好ましくは1.4%以下、さらに好ましくは1.3%以下に調整される。
Taは、本発明の合金線の任意元素である。Taは、析出硬化及びその強化に有効であり、V又はMoの代替元素として使用可能である。このようなTaの効果を有効に発揮させることが望まれる場合、Taの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.02%以上に調整される。一方、Taの含有量が過剰であると、時効硬化能の低下、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Taの含有量は、1.5%以下、好ましくは1.4%以下、さらに好ましくは1.3%以下に調整される。
Wは、本発明の合金線の任意元素である。Wは、析出硬化及びその強化に有効であり、V又はMoの代替元素として使用可能である。このようなWの効果を有効に発揮させることが望まれる場合、Wの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.02%以上に調整される。一方、Wの含有量が過剰であると、時効硬化能の低下、延性の低下、熱膨張係数の増加及び合金線コストの増加が生じる。したがって、Wの含有量は、1.5%以下、好ましくは1.4%以下、さらに好ましくは1.3%以下に調整される。
Cuは、本発明の合金線の任意元素である。Cuは、Cu粒子形成により析出硬化及びその強化に有効であるとともに、キュリー点を上昇させる。このようなCuの効果を有効に発揮させることが望まれる場合、Cuの含有量は、0%超、好ましくは0.01%以上、さらに好ましくは0.02%以上に調整される。一方、Cuの含有量が過剰であると、熱間加工性の低下、合金線コストの増加が生じる。したがって、Cuの含有量は、1.5%以下、好ましくは1.3%以下、さらに好ましくは1.0%以下に調整される。
Oは、本発明の合金線の不純物である。Oは、酸化物形成により延性を低下させる。したがって、Oの含有量は、0.005%以下、好ましくは0.003%以下、さらに好ましくは0.001%以下に調整される。
Nは、本発明の合金線の任意元素である。Nは、固溶の強化等、Cと同様の効果を有する。このようなNの効果を有効に発揮させることが望まれる場合、Nの含有量は、0%超、好ましくは0.01%以上に調整される。一方、Nの含有量が過剰であると、窒化物形成により延性が低下する。したがって、Nの含有量は、0.03%以下、好ましくは0.025%以下に調整される
以下、本発明の合金線の組織について説明する。
本発明の合金線は、Mo及びVの両方を含む(Mo,V)C系複合炭化物(以下「複合炭化物」という場合がある)が内部に存在する結晶粒を有する。
本発明の合金線の引張強さ(TS)は、好ましくは1300MPa以上、さらに好ましくは1400MPa以上、更に一層好ましくは1500MPa以上である。本発明の合金線の伸び(EL)は、好ましくは0.8%以上、さらに好ましくは1.0%以上である。TS及びELは、合金線から作製した試験片に対して、JIS Z 2241に従って引張試験を実施することにより測定される。
本発明の合金線の形態は、線状である限り特に限定されない。本発明の合金線の形態としては、例えば、丸線、平線、角線等が挙げられる。本発明の合金線の線径は特に限定されないが、例えば2.0~3.8mmである。なお、「線径」の意義は上記の通りである。
本発明の合金線は、例えば、次の方法により製造することができる。本発明の合金組成を有する鋼を溶製し、造塊又は連続鋳造により鋼塊やブルームを製造した後、熱間鍛造又は熱間圧延にて丸棒、角材等の目的の形状を有した鋼材へ成形する。その後、鋼材に対して、溶体化処理、伸線加工及び時効熱処理を順次実施することにより、本発明の合金線を製造することができる。例えば、溶体化処理は加熱温度1200℃、加熱時間30分間で実施することができる。なお、溶体化処理は、熱間鍛造又は熱間圧延での鋼材製造工程の後、即座に水冷等の急冷を行えば省略することができる。時効熱処理は、例えば、加熱温度625℃、加熱時間2時間で実施することができる。溶体化処理の後であって時効熱処理の前に、鋼材に冷間加工を施すことが好ましい。
本発明の被覆合金線は、本発明の合金線と、本発明の合金線の表面に形成されたAl被覆層(Al皮膜)又はZn被覆層(Zn皮膜)とを備える。本発明の被覆合金線は、本発明の合金線と同様の効果に加えて、Al被覆層又はZn被覆層に起因する耐食性を有する。Al被覆層は、例えば、コンフォーム押出等の公知の方法で形成することができる。Zn被覆層は、例えば、めっき処理等の公知の方法で形成することができる。
表1(本発明例No.1~30)及び表2(比較例No.31~55)に示す成分組成を有する50kgの合金を真空誘導溶解炉(VIM)で溶製してインゴットを得た。このインゴットを1200℃で1時間加熱し、直径20mmの棒鋼に鍛伸した。この棒鋼に対して、加熱温度1200℃、加熱時間30分間の条件で溶体化処理を実施した。溶体化処理後の棒鋼を直径15mmまで旋削し、次いで、室温下、伸線加工を施し、線径8mmの合金線を製造した。なお、表1及び表2中、[Mo]、[V]及び[C]は、それぞれ、合金に含まれるMo、V及びCの量を表す。
線径8mmの合金線から作製した試験片(長さ10mm)を、加熱温度500~1000℃、加熱時間30分間~24時間の条件で時効熱処理した。
線径8mmの合金線から作製した試験片(長さ100mm)に対して、加熱時間を6時間に固定し、加熱温度を610~650℃の間で変化させて時効熱処理を行った。時効処理前と時効熱処理後の試験片に対して、機械加工にてJIS14A号試験片を作製し、引張試験機(100kN万能試験機、島津製作所社製)を使用して、JIS Z 2241に従って引張試験を実施し、引張強さ(TS)を測定した。横軸を時効温度、縦軸を引張強さとする曲線を作成し(図1参照)、この曲線に基づいて、最大引張強さ(MAX6hr)の96%以上の引張強さを確保できる温度範囲を求めた。最大引張強さ(MAX6hr)の96%以上の引張強さを確保できる温度範囲が30℃以上である場合を「A:熱的時効安定性が良好」、30℃未満である場合を「F:熱的時効安定性が不良」と評価した。結果を表5(本発明例No.1~30)及び表6(比較例No.31~55)に示す。なお、図1は、加熱時間を6時間に固定し、加熱温度を610~650℃の間で変化させて時効熱処理を行った場合の、横軸を時効温度、縦軸を引張強さとする曲線の一例であり、この曲線では、最大引張強さ(MAX6hr)の96%以上の引張強さを確保できる温度範囲が32℃である。
線径8mmの合金線から作製した試験片(長さ100mm)に対して、加熱温度を650℃に固定し、加熱時間を30分~9時間の間で変化させて時効熱処理を行った。時効処理前と時効熱処理後の試験片に対して、機械加工にてJIS14A号試験片を作製し、引張試験機(500kN万能試験機、島津製作所社製)を使用して、JIS Z 2241に従って引張試験を実施し、引張強さ(TS)を測定した。横軸を時効温度、縦軸を引張強さとする曲線を作成し(図2参照)、この曲線に基づいて、最大引張強さ(MAX650℃)の97%以上の引張強さを確保できる時間範囲を求めた。最高引張強さ(MAX650℃)の97%以上の引張強さを確保できる時間範囲が3時間以上である場合を「A:経時的時効安定性が良好」、3時間未満である場合を「F:経時的時効安定性が不良」と評価した。結果を表5(本発明例No.1~30)及び表6(比較例No.31~55)に示す。なお、図2は、加熱温度を650℃に固定し、加熱時間を30分~9時間の間で変化させて時効熱処理を行った場合の、横軸を時効温度、縦軸を引張強さとする曲線の一例であり、この曲線では、最大引張強さ(MAX650℃)の97%以上の引張強さを確保できる時間範囲が3.8時間である。
線径8mmの合金線から作製した試験片(長さ300mm)に対して、加熱温度500~1000℃、加熱時間30分間~24時間の条件で時効熱処理を実施した。時効熱処理後の試験片に対して、室温下、伸線加工を施し、線径3.1mmの試験片(長さ400mm以上)を作製した。線径3.1mm、ゲージ長さ250mmの引張試験片に対して、引張試験機(100kN万能試験機、島津製作所社製)を使用して、室温で20mm/min以下のストローク速度にて引張試験を実施し、引張強さ(TS)及び伸び(EL)を測定した。TSが1500MPa以上、かつ、ELが0.8%以上である場合を「A:引張特性がきわめて良好」、TSが1500MPa未満、1400MPa以上、かつELが0.8%以上である場合を「B:引張特性が良好」、TSが1400MPa未満、1300MPa以上、かつELが0.8%以上である場合を「C:引張特性が概ね良好」、TSが1300MPa未満、又は、ELが0.8%未満である場合を「F:引張特性が不良」と評価した。結果を表5(本発明例No.1~30)及び表6(比較例No.31~55)に示す。ここでA又はB又はCと評価された場合には以下の評価を行ったが、ここでFと評価された場合には以下の評価は行わなかった。
上記と同様にして作製した線径3.1mmの試験片(長さ310mm)の捻回値を測定した。捻回値の測定は、次の通り実施した。試験片の一端を固定し、試験片の他端を捻じり、試験片が破断するまでの捻じり回数を捻回値として測定した。標点間距離は100D(Dは試験片の最終線径を表す)とし、捻じり速度は60rpmとした。捻回値が60回以上である場合を「A:捻回値がきわめて良好」、捻回値が20~59回である場合を「B:捻回値が良好」、捻回値が20回未満である場合を「F:捻回値が不良」と評価した。結果を表5(本発明例No.1~30)及び表6(比較例No.31~55)に示す。ここでA又はBと評価された場合には以下の評価を行ったが、ここでFと評価された場合には以下の評価は行わなかった。
上記と同様にして作製した線径3.1mmの試験片の線熱膨張係数を測定した。線熱膨張係数の測定は、次の通り実施した。フォーマスター試験機(Formastor―EDP、富士電波工機社製)にて、昇温過程における試験片の変位を計測し、15℃から100℃までの2点間における平均線熱膨張係数、15℃から230℃までの2点間における平均線熱膨張係数、100℃から240℃までの2点間における平均線熱膨張係数、及び、230℃から290℃までの2点間における平均線熱膨張係数を測定した。15℃から100℃までの2点間における平均線熱膨張係数が3.0×10-6/℃以下である場合を「A:線熱膨張係数がきわめて低い」、3.0×10-6/℃を超えて3.5×10-6/℃未満の場合を「B:線熱膨張係数が低い」、3.5×10-6/℃以上の場合を「F:線熱膨張係数が高い」と評価した。また、15℃から230℃までの2点間における平均線熱膨張係数が4.0×10-6/℃以下である場合を「A:線熱膨張係数がきわめて低い」、4.0×10-6/℃を超えて4.5×10-6/℃未満の場合を「B:線熱膨張係数が低い」、4.5×10-6/℃以上の場合を「F:線熱膨張係数が高い」と評価した。また、100℃から240℃までの2点間における平均線熱膨張係数が4.0×10-6/℃以下である場合を「A:線熱膨張係数がきわめて低い」、4.0×10-6/℃を超えて4.5×10-6/℃未満の場合を「B:線熱膨張係数が低い」、4.5×10-6/℃以上の場合を「F:線熱膨張係数が高い」と評価した。さらに、230℃から290℃までの2点間における平均線熱膨張係数が11.0×10-6/℃以下である場合を「A:線熱膨張係数がきわめて低い」、11.0×10-6/℃を超えて11.5×10-6/℃未満の場合を「B:線熱膨張係数が低い」、11.5×10-6/℃以上の場合を「F:線熱膨張係数が高い」と評価した。以上の4つの温度範囲を測定および評価した結果から、さらに各試験片の線熱膨張係数の総合評価を行った。15℃から230℃の平均線熱膨張係数、100℃~240℃の平均線熱膨張係数、及び15℃~290℃の平均線熱膨張係数の評価において、全てA評価あるいはB評価が1つであとの3つがA評価の場合の総合評価は「A:線熱膨張係数がきわめて低い」、B評価が2つであとの2つがA評価の場合の総合評価は「B:線熱膨張係数が低い」1つはA評価であとの3つがB評価の場合の総合評価は「C:線熱膨張係数が概ね低い」、F評価が1つ以上の場合の総合評価は「F:線熱膨張係数が高い」と評価した。結果を表5(本発明例No.1~30)及び表6(比較例No.31~55)に示す。
条件a:本発明の合金組成を満たす、
条件b:結晶粒内部に(Mo,V)C系複合炭化物が存在する、
条件c:([Mo]+2.8[V])/[C]の値が9.6以上21.7以下である、 条件d:{Mo}/{V}の値が0.2以上4.0以下である、
条件e:結晶粒において、(Mo,V)C系複合炭化物の密度が10個/μm2以上であり、かつ、(Mo,V)C系複合炭化物の総個数に対する直径150nm以下の(Mo,V)C系複合炭化物の個数の割合が50%以上である、
条件f:Crの含有量が0%超である場合、([Mo]+[V])/[Cr]の値が1.2以上である、
条件g:Coの含有量が0%超である場合、[Co]+[Ni]が35%以上40%以下である、
を全て満たし、高強度低熱膨張合金線として必要な特性が全てA又はB評価であり、すなわち、高強度、高捻回値、良好な延性及び低い熱膨張率を兼ね備えていた。また、本発明例No.1~No.26は、時効安定性(熱的時効安定性及び経時的時効安定性)に優れていた。
Claims (12)
- 質量%で、
C:0.1%以上0.4%以下、
Si:0.1%以上2.0%以下、
Mn:0%超2.0%以下、
Ni:25%以上40%以下、
V:0.5%以上3.0%以下、
Mo:0.4%以上1.9%以下、
Cr:0%以上3.0%以下、
Co:0%以上3.0%以下、
B:0%以上0.05%以下、
Ca:0%以上0.05%以下、
Mg:0%以上0.05%以下、
Al:0%以上1.5%以下、
Ti:0%以上1.5%以下、
Nb:0%以上1.5%以下、
Zr:0%以上1.5%以下、
Hf:0%以上1.5%以下、
Ta:0%以上1.5%以下、
W:0%以上1.5%以下、
Cu:0%以上1.5%以下、
O:0%以上0.005%以下、及び
N:0%以上0.03%以下
を含み、残部がFe及び不可避的不純物からなる高強度低熱膨張合金線であって、
前記合金線の結晶粒内には、Mo及びVの両方を含む(Mo,V)C系複合炭化物が存在し、
前記合金線に含まれるMo、V及びCの量をそれぞれ[Mo]、[V]及び[C]としたとき、([Mo]+2.8[V])/[C]の値が9.6以上21.7以下であり、
前記(Mo,V)C系複合炭化物に含まれるMo及びVの量をそれぞれ{Mo}及び{V}としたとき、{Mo}/{V}の値が0.2以上4.0以下である、前記高強度低熱膨張合金線。 - 前記結晶粒において、前記(Mo,V)C系複合炭化物の密度が10個/μm2以上であり、かつ、前記(Mo,V)C系複合炭化物の総個数に対する直径150nm以下の前記(Mo,V)C系複合炭化物の個数の割合が50%以上である、請求項1に記載の高強度低熱膨張合金線。
- 質量%で、Cr:0%超3.0%以下を含み、
前記合金線に含まれるMo、V及びCrの量をそれぞれ[Mo]、[V]及び[Cr]としたとき、([Mo]+[V])/[Cr]の値が1.2以上である、請求項1又は2に記載の高強度低熱膨張合金線。 - 質量%で、Co:0%超3.0%以下を含み、
前記合金線に含まれるCo及びNiの量をそれぞれ[Co]及び[Ni]としたとき、[Co]+[Ni]が35%以上40%以下である、請求項1~3のいずれか一項に記載の高強度低熱膨張合金線。 - 質量%で、B:0%超0.05%以下、Ca:0%超0.05%以下、及び、Mg:0%超0.05%以下のうちの1種又は2種以上を含む、請求項1~4のいずれか一項に記載の高強度低熱膨張合金線。
- 質量%で、Al:0%超1.5%以下、Ti:0%超1.5%以下、Nb:0%超1.5%以下、Zr:0%超1.5%以下、Hf:0%超1.5%以下、Ta:0%超1.5%以下、W:0%超1.5%以下、及び、Cu:0%超1.5%以下のうちの1種又は2種以上を含む、請求項1~5のいずれか一項に記載の高強度低熱膨張合金線。
- 質量%で、N:0%超0.03%以下を含む、請求項1~6のいずれか一項に記載の高強度低熱膨張合金線。
- 引張強さが1400MPa以上である、請求項1~7のいずれか一項に記載の高強度低熱膨張合金線。
- 前記合金線の最終線径の100倍の標点間距離で測定される捻回値が、20回以上である、請求項1~8のいずれか一項に記載の高強度低熱膨張合金線。
- 伸びが0.8%以上である、請求項1~9のいずれか一項に記載の高強度低熱膨張合金線。
- 15℃から100℃までの2点間における平均線熱膨張係数が3×10-6/℃以下(15~100℃)、15℃から230℃までの2点間における平均線熱膨張係数が4×10-6/℃以下(15~230℃)、100℃から240℃までの2点間における平均線熱膨張係数が4×10-6/℃以下(100~240℃)、かつ、230℃から290℃までの2点間における平均線熱膨張係数が11×10-6/℃以下(230~290℃)である、請求項1~10のいずれか一項に記載の高強度低熱膨張合金線。
- 請求項1~11のいずれか一項に記載の高強度低熱膨張合金線と、前記高強度低熱膨張合金線の表面に形成されたAl被覆層又はZn被覆層とを備える高強度低熱膨張被覆合金線。
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