WO2021132634A1 - 合金 - Google Patents
合金 Download PDFInfo
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- WO2021132634A1 WO2021132634A1 PCT/JP2020/048927 JP2020048927W WO2021132634A1 WO 2021132634 A1 WO2021132634 A1 WO 2021132634A1 JP 2020048927 W JP2020048927 W JP 2020048927W WO 2021132634 A1 WO2021132634 A1 WO 2021132634A1
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 218
- 239000000956 alloy Substances 0.000 title claims abstract description 218
- 239000000126 substance Substances 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 76
- 229910052719 titanium Inorganic materials 0.000 claims description 39
- 229910052758 niobium Inorganic materials 0.000 claims description 37
- 229910052720 vanadium Inorganic materials 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 238000012360 testing method Methods 0.000 description 80
- 239000010955 niobium Substances 0.000 description 62
- 239000010936 titanium Substances 0.000 description 51
- 238000005260 corrosion Methods 0.000 description 43
- 230000007797 corrosion Effects 0.000 description 43
- 239000010949 copper Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 238000005096 rolling process Methods 0.000 description 22
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 19
- 239000011575 calcium Substances 0.000 description 16
- 239000011651 chromium Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- 238000005728 strengthening Methods 0.000 description 14
- 229910001374 Invar Inorganic materials 0.000 description 13
- 239000011701 zinc Substances 0.000 description 12
- 238000005098 hot rolling Methods 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000005482 strain hardening Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 229910003271 Ni-Fe Inorganic materials 0.000 description 7
- 238000009776 industrial production Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001192 hot extrusion Methods 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 239000003949 liquefied natural gas Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000012925 reference material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
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- 238000004513 sizing Methods 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
Definitions
- the present disclosure relates to alloys, and more particularly to alloys having a low coefficient of thermal expansion.
- Austenitic stainless steel which does not easily become brittle even at low temperatures, is used as a material for transportation pipes and storage tanks for low-temperature substances such as LNG (liquefied natural gas).
- LNG liquefied natural gas
- the temperature drops when the cryogenic substances are flowing, and when the cryogenic substances are stored, and when the cryogenic substances are not flowing, and when the cryogenic substances are stored.
- the temperature rises when not stored.
- the above-mentioned austenitic stainless steel material has a high coefficient of thermal expansion. Therefore, thermal expansion and contraction due to temperature changes occur in the piping for transporting low-temperature substances and the tank for storage. Therefore, as a mechanism for absorbing such thermal expansion and contraction, loop pipes are arranged at predetermined lengths in the pipes for transporting low-temperature substances.
- the loop piping absorbs deformation of the transportation piping due to thermal expansion and contraction.
- the loop piping increases the total length of the piping and increases the manufacturing cost. Therefore, alloys having a lower coefficient of thermal expansion than austenitic stainless steel are required as materials for transportation pipes and storage tanks for low-temperature substances.
- Invar alloy is known as an alloy with a small coefficient of thermal expansion.
- the Invar alloy can maintain a low coefficient of thermal expansion against temperature changes due to spontaneous volume magnetostriction (Invar effect). Therefore, the dimensions are unlikely to change even under the influence of heat.
- the coefficient of thermal expansion of Invar alloy is much smaller than the coefficient of thermal expansion of austenitic stainless steel. Therefore, if Invar alloy is used as a material for transportation pipes and storage tanks for low-temperature substances, deformation of the transportation pipes and storage tanks due to thermal expansion and contraction can be suppressed.
- Patent Document 1 Invar alloys used for transportation pipes and storage tanks for low-temperature substances represented by LNG are disclosed in Japanese Patent Application Laid-Open No. 2017-512899 (Patent Document 1).
- the alloys disclosed in Patent Document 1 are 35 wt% ⁇ Ni ⁇ 37 wt%, Mn ⁇ 0.6 wt%, C ⁇ 0.07 wt%, Si ⁇ 0.35 wt%, Cr ⁇ 0.5 wt%, Co ⁇ 0.
- Patent Document 1 states that the alloys disclosed in this document are used in tanks or pipes for receiving liquefied gas.
- the Invar alloy has a low coefficient of thermal expansion, but its strength is low. If the strength of the alloy having a low coefficient of thermal expansion is high, the thickness of the transportation pipe can be reduced, and the structural stability of the transportation pipe and the storage tank is also improved. Therefore, an Invar alloy having high strength is required.
- the Inver alloy disclosed in Patent Document 2 has C: 0.015 to 0.10%, Si: 0.35% or less, Mn: 1.0% or less, P: 0.015% or less in terms of weight ratio. , S: 0.0010% or less, Cr: 0.3% or less, Ni: 35 to 37%, Mo: 0 to 0.5%, V: 0 to 0.05%, Al: 0.01% or less, It is characterized by containing Nb: 0.15% or more and less than 1.0%, Ti: 0.003% or less, N: 0.005% or less, and the balance consisting of Fe and unavoidable impurities. As a result, Patent Document 2 describes that a high-strength Invar alloy having excellent hot workability can be obtained.
- the method for producing an amber alloy disclosed in Patent Document 3 is a method for producing an Fe—Ni-based amber alloy containing Ni: 30 to 45% and C: 0.001 to 0.04% in weight%.
- the alloy was heated to 900 ⁇ 1150 ° C., at T R ° C. below the temperature shown by the following equation (1), and performing hot rolling of more than 5% cumulative rolling reduction.
- T R (°C) 2,500 ⁇ C% + 750 ⁇ (1)
- the strength of the Invar alloy can be increased by the techniques disclosed in Patent Documents 2 and 3 described above.
- the coefficient of thermal expansion may increase. Therefore, there is a demand for an alloy having a sufficiently high strength and a sufficiently low coefficient of thermal expansion.
- An object of the present disclosure is to provide an alloy having high strength and a low coefficient of thermal expansion.
- the alloys according to the present disclosure are The chemical composition is mass%, C: 0.10% or less, Si: 0.50% or less, Mn: 0.15 to 0.60%, P: 0.015% or less, S: 0.0030% or less, Ni: 30.0-40.0%, Cr: 0.50% or less, Mo: 0.50% or less, Co: 0.250% or less, Al: 0.0150% or less, Ca: 0.0050% or less, Mg: 0.0300% or less, N: 0.0100% or less, O: 0.0300% or less, Pb: 0.0040% or less, Zn: 0.020% or less, Total of one or more selected from the group consisting of Nb: 0 to less than 0.145%, Ti: 0 to less than 0.145%, and V: 0 to less than 0.145%: 0.015 to 0.
- the alloy according to the present disclosure has high strength and a low coefficient of thermal expansion.
- FIG. 1A is a transmission electron microscope (TEM) photograph of the alloy of test number 4.
- FIG. 1B is a schematic view of the TEM photograph of FIG. 1A.
- FIG. 2 is a diagram showing the relationship between the equation (1) and the coefficient of thermal expansion.
- the present inventors investigated and examined an alloy having high strength and a low coefficient of thermal expansion.
- Precipitation strengthening is one of the methods for increasing the strength of alloys.
- carbides, nitrides and / or carbonitrides are precipitated to strengthen the alloy.
- the coefficient of thermal expansion of the alloy increases due to the thermal expansion of the precipitates.
- Ni—Fe-based alloys having a Ni content of 30.0 to 40.0% by mass it has been studied to increase the strength while suppressing the coefficient of thermal expansion, so that the increase in strength due to precipitation strengthening can be avoided. I came. Therefore, conventionally, it has been attempted to increase the strength of the alloy by solid solution strengthening, fine graining of crystal grain size, or cold working instead of precipitation strengthening.
- Patent Document 2 the strength is increased by containing 0.15% or more of Nb as an alloy element in the alloy (paragraphs [0012] and [0023] of Patent Document 2).
- the C content in the alloy is kept low. Therefore, in Patent Document 2, a large amount of Nb is dissolved in a solid solution, and the strength of the alloy is increased by solid solution strengthening.
- Patent Document 3 the residual strain of the alloy is adjusted by adjusting the rolling conditions to increase the strength of the alloy (paragraph [0011] of Patent Document 3). That is, in Patent Document 2 and Patent Document 3, the strength of the alloy is increased by a method other than precipitation strengthening.
- FIG. 1A is a transmission electron microscope (TEM) photograph of the alloy of test number 4 (example of the present invention) in the examples described later.
- FIG. 1B is a schematic view of the TEM photograph of FIG. 1A.
- the precipitate contained 86.3% of Nb in the composition excluding C. That is, the black spots in the TEM photograph of FIG. 1 are precipitates (carbonitrides) containing Nb.
- the TEM photograph of FIG. 1 is a transmission electron microscope
- nanocarbonitrides by precipitating nano-sized fine carbonitrides (hereinafter, also simply referred to as nanocarbonitrides), a lower coefficient of thermal expansion can be obtained while increasing the strength. Nanocarbonitrides fix dislocations. Therefore, the alloy can be strengthened. Nanocarbonitrides are also very small in volume, so their volume expansion with temperature changes is small. Therefore, the present inventors have considered that the strength of the Ni—Fe-based alloy should be increased by precipitation strengthening of nanocarbon nitrides instead of solid solution strengthening by solid solution Nb. It is considered that this makes it possible to reduce the amount of solid solution Nb and further reduce the coefficient of thermal expansion.
- carbonitride includes carbides, nitrides and / or carbonitrides.
- the present inventors have studied to specify the size and number density of nanocarbonitrides that can achieve both low coefficient of thermal expansion and high strength of the alloy.
- the nanocarbonitride is very small, and it is difficult to accurately specify the appropriate size and number density. Therefore, the present inventors have investigated the chemical composition of a Ni—Fe-based alloy capable of finely dispersing such nanocarbonitrides.
- the present inventors can precipitate nanocarbonitrides as long as they contain one or more of Nb, Ti and V that form carbonitrides and have a chemical composition with an increased C content and N content. I thought it might be.
- C 0.10% or less
- Si 0.50% or less
- Mn 0.15 to 0.60%
- P 0.015% or less
- S 0.0030%
- Cr 0.50% or less
- Mo 0.50% or less
- Co 0.250% or less
- Al 0.0150% or less
- Ca 0.0050
- Mg 0.0300% or less
- N 0.0100% or less
- O 0.0300% or less
- Pb 0.0040% or less
- Sn 0 to 0.100%
- W 0 to 0.200%
- B 0 to 0.0040%
- the balance is an alloy composed of Fe and impurities, in place of a part of Fe.
- Nb 0 to less than 0.145%
- Ti 0 to less than 0.145%
- V 0 to less than 0.145%. It was considered that if the alloy contains less than .145%, nanocarbon nitride can be precipitated, and as a result, the coefficient of thermal expansion can be further reduced while increasing the strength.
- the present inventors investigated the cause in detail. As a result, it was found that the carbonitride may be excessively precipitated only by having the above chemical composition. Therefore, the present inventors further investigated an alloy capable of precipitating nanocarbonitride in an appropriate amount. As a result, the following findings were obtained.
- FIG. 2 is a diagram showing the relationship between the equation (1) and the coefficient of thermal expansion.
- FIG. 2 shows the relationship between the formula (1) and the coefficient of thermal expansion in an alloy in which the content of each element in the chemical composition is within the above range in the examples described later.
- the content of each element in the chemical composition of the alloy is substituted in% by mass for each element symbol.
- the vertical axis of FIG. 2 is the coefficient of thermal expansion of the alloy. The coefficient of thermal expansion of the alloy was measured by the measuring method described later.
- Formula (1) is a formula that defines the relationship between the contents of Nb, Ti and V forming nanocarbonitrides and C and N. If the total content of Nb, Ti and V is limited to less than 0.145% and Fn1 is 6.00 or less, the nanocarbonitride is finely dispersed and excess nanocarbonitride is precipitated. Can be suppressed. Therefore, the coefficient of thermal expansion of the alloy can be further reduced while increasing the strength.
- the total amount of one or more selected from the group consisting of Nb: 0 to less than 0.145%, Ti: 0 to less than 0.145%, and V: 0 to less than 0.145% is 0. Limit to less than 015 to 0.145%.
- the Nb content, the Ti content and the V content, and the C content and the N content are adjusted so as to satisfy the formula (1).
- the equation (1) is as shown below. (Nb + 3 ⁇ Ti + V) / (C + N) ⁇ 6.00 (1)
- the content of each element in the chemical composition of the alloy is substituted in% by mass for each element symbol in the formula (1).
- the alloy according to this embodiment was completed based on an idea completely different from the conventional technology.
- the alloy according to this embodiment has the following constitution.
- the chemical composition is mass%, C: 0.10% or less, Si: 0.50% or less, Mn: 0.15 to 0.60%, P: 0.015% or less, S: 0.0030% or less, Ni: 30.0-40.0%, Cr: 0.50% or less, Mo: 0.50% or less, Co: 0.250% or less, Al: 0.0150% or less, Ca: 0.0050% or less, Mg: 0.0300% or less, N: 0.0100% or less, O: 0.0300% or less, Pb: 0.0040% or less, Zn: 0.020% or less, Total of one or more selected from the group consisting of Nb: 0 to less than 0.145%, Ti: 0 to less than 0.145%, and V: 0 to less than 0.145%: 0.015 to 0.
- the alloy of [1] has high strength and a lower coefficient of thermal expansion.
- the alloy according to [1] contains 0.020% or more in total of one or more selected from the group consisting of Cu: 0 to 0.300%, Sn: 0 to 0.100%, and W: 0 to 0.200%. alloy.
- the alloy of [2] has high strength, a low coefficient of thermal expansion, and further has excellent corrosion resistance.
- the alloy is either a pipe material, a plate material, or a bar material.
- % in the chemical composition means mass% unless otherwise specified.
- C 0.10% or less Carbon (C) is inevitably contained. That is, the C content is more than 0%. C deoxidizes the alloy in the steelmaking process. C further increases the strength of the alloy. If C is contained even in a small amount, the above effect can be obtained to some extent. However, if the C content exceeds 0.10%, the corrosion resistance of the alloy is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the C content is 0.10% or less.
- the upper limit of the C content is preferably 0.09%, more preferably 0.08%, still more preferably 0.06%, still more preferably 0.05%.
- the lower limit of the C content is preferably 0.01%, more preferably 0.02%.
- Si Silicon
- Si Silicon
- the upper limit of the Si content is preferably 0.40%, more preferably 0.30%, still more preferably 0.25%, still more preferably 0.20%.
- the lower limit of the Si content is preferably 0.01%, more preferably 0.05%.
- Mn 0.15 to 0.60%
- Mn Manganese
- S sulfur
- Mn content 0.15 to 0.60%
- Mn content is 0.15 to 0.60%.
- the preferable lower limit of the Mn content is 0.16%, more preferably 0.17%, still more preferably 0.19%, still more preferably 0.20%, still more preferably 0.21. %.
- the preferred upper limit of the Mn content is 0.55%, more preferably 0.50%, still more preferably 0.45%.
- Phosphorus (P) is an impurity that is inevitably contained. That is, the P content is more than 0%. P lowers the weldability and hot workability of the alloy. If the P content exceeds 0.015%, the weldability and hot workability of the alloy will be significantly reduced even if the content of other elements is within the range of the present embodiment. Therefore, the P content is 0.015% or less.
- the preferred upper limit of the P content is 0.012%, more preferably 0.010%, still more preferably 0.008%.
- the P content is preferably as low as possible. However, excessive reduction of P content increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the P content is 0.001%, and more preferably 0.002%.
- S 0.0030% or less Sulfur (S) is an impurity that is inevitably contained. That is, the S content is more than 0%. S lowers the weldability and hot workability of the alloy. If the S content exceeds 0.0030%, the weldability and hot workability of the alloy will be significantly reduced even if the content of other elements is within the range of the present embodiment. Therefore, the S content is 0.0030% or less.
- the preferred upper limit of the S content is 0.0025%, more preferably 0.0020%, still more preferably 0.0015%, still more preferably 0.0010%.
- the S content is preferably as low as possible. However, excessive reduction of S content increases manufacturing cost. Therefore, when industrial production is taken into consideration, the preferable lower limit of the S content is 0.0001%, and more preferably 0.0002%.
- Ni 30.0-40.0%
- Nickel (Ni) increases the spontaneous volume magnetostriction of the alloy, resulting in a decrease in the coefficient of thermal expansion of the alloy.
- Ni also enhances the corrosion resistance of the alloy. If the Ni content is less than 30.0%, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the Ni content exceeds 40.0%, the coefficient of thermal expansion of the alloy will rather increase even if the content of other elements is within the range of this embodiment. Therefore, the Ni content is 30.0 to 40.0%.
- the lower limit of the Ni content is preferably 31.0%, more preferably 32.0%, still more preferably 33.0%, still more preferably 34.0%.
- the preferred upper limit of the Ni content is 39.0%, more preferably 38.0%, still more preferably 37.0%.
- Chromium (Cr) is inevitably contained. That is, the Cr content is more than 0%. Cr enhances the corrosion resistance of the alloy. If even a small amount of Cr is contained, the above effect can be obtained to some extent. However, if the Cr content exceeds 0.50%, the hot workability of the alloy is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the Cr content is 0.50% or less.
- the preferred upper limit of the Cr content is 0.45%, more preferably 0.40%, still more preferably 0.35%, still more preferably 0.30%, still more preferably 0.25. %, More preferably 0.20%, still more preferably 0.15%, still more preferably 0.10%.
- the preferable lower limit of the Cr content is 0.01%.
- Mo Molybdenum
- Mo Molybdenum
- the preferred upper limit of the Mo content is 0.45%, more preferably 0.40%, still more preferably 0.35%, still more preferably 0.30%, still more preferably 0.25. %, More preferably 0.20%, still more preferably 0.15%, still more preferably 0.10%.
- the preferable lower limit of the Mo content is 0.01%.
- Co 0.250% or less Cobalt (Co) is inevitably contained. That is, the Co content is more than 0%. Co, like Ni, increases the strength of the alloy. If even a small amount of Co is contained, the above effect can be obtained to some extent. However, if the Co content exceeds 0.250%, the coefficient of thermal expansion of the alloy will rather increase even if the content of other elements is within the range of this embodiment. Therefore, the Co content is 0.250% or less.
- the preferred upper limit of the Co content is 0.200%, more preferably 0.150%, still more preferably 0.100%, still more preferably 0.080%.
- the lower limit of the Co content is preferably 0.001%, more preferably 0.005%, still more preferably 0.010%, still more preferably 0.020%.
- Al 0.0150% or less
- Aluminum (Al) is inevitably contained. That is, the Al content is more than 0%. Al deoxidizes the alloy. If Al is contained even in a small amount, the above effect can be obtained to some extent. However, if the Al content exceeds 0.0150%, the spontaneous volume magnetostriction of the alloy will decrease even if the other element content is within the range of this embodiment. As a result, the coefficient of thermal expansion of the alloy increases. Therefore, the Al content is 0.0150% or less.
- the preferred upper limit of the Al content is 0.0120%, more preferably 0.0100%, still more preferably 0.0090%, still more preferably 0.0080%, still more preferably 0.0070.
- the Al content is the total Al (Total-Al) content.
- Ca 0.0050% or less Calcium (Ca) is inevitably contained. That is, the Ca content is more than 0%. Ca refines MnS and enhances the hot workability of the alloy. If even a small amount of Ca is contained, the above effect can be obtained to some extent. However, if the Ca content exceeds 0.0050%, even if the content of other elements is within the range of the present embodiment, an excessively large amount of coarse inclusions are generated, and the hot workability of the alloy is improved. descend. Therefore, the Ca content is 0.0050% or less.
- the preferred upper limit of the Ca content is 0.0040%, more preferably 0.0030%, still more preferably 0.0020%.
- the preferable lower limit of the Ca content is 0.0001%, more preferably 0.0003%, still more preferably 0.0005%.
- Mg 0.0300% or less Magnesium (Mg) is inevitably contained. That is, the Mg content is more than 0%. Similar to Ca, Mg refines MnS and enhances the hot workability of the alloy. If even a small amount of Mg is contained, the above effect can be obtained to some extent. However, if the Mg content exceeds 0.0300%, even if the content of other elements is within the range of this embodiment, an excessively large amount of coarse inclusions are generated, and the hot workability of the alloy is improved. descend. Therefore, the Mg content is 0.0300% or less.
- the preferred upper limit of the Mg content is 0.0200%, more preferably 0.0100%, even more preferably 0.0050%, even more preferably 0.0020%, still more preferably 0.0010. %.
- the preferable lower limit of the Mg content is 0.0001%, more preferably 0.0002%.
- N 0.0100% or less Nitrogen (N) is an impurity that is inevitably contained. That is, the N content is more than 0%. N lowers the hot workability of the alloy. When the N content exceeds 0.0100%, even if the content of other elements is within the range of the present embodiment, an excessively large amount of nitride is formed, the coefficient of thermal expansion of the alloy increases, and the coefficient of thermal expansion of the alloy increases. The corrosion resistance of the alloy is reduced. Therefore, the N content is 0.0100% or less.
- the preferred upper limit of the N content is 0.0095%, more preferably 0.0090%.
- the N content is preferably as low as possible. However, excessive reduction of N increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the N content is 0.0001%, more preferably 0.0003%, still more preferably 0.0005%.
- Oxygen (O) is an impurity that is inevitably contained. That is, the O content is more than 0%. O produces coarse inclusions and reduces the hot workability of the alloy. If the O content exceeds 0.0300%, the hot workability of the alloy will be significantly reduced even if the content of other elements is within the range of the present embodiment. Therefore, the O content is 0.0300% or less.
- the preferred upper limit of the O content is 0.0200%, more preferably 0.0180%, still more preferably 0.0150%.
- the O content is preferably as low as possible. However, excessive reduction of O content increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the O content is 0.0001%, and more preferably 0.0005%.
- Pb 0.0040% or less
- Lead (Pb) is an impurity that is inevitably contained. That is, the Pb content is more than 0%.
- Pb is a metal having a low melting point, which lowers the hot workability of the alloy. If the Pb content exceeds 0.0040%, the hot workability of the alloy will be significantly reduced even if the content of other elements is within the range of the present embodiment. Therefore, the Pb content is 0.0040% or less.
- the preferred upper limit of the Pb content is 0.0030%, more preferably 0.0025%, even more preferably 0.0020%, even more preferably 0.0015%, even more preferably 0.0010. %.
- the Pb content is preferably as low as possible. However, excessive reduction of Pb content increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the Pb content is 0.0001%.
- Zinc (Zn) is an impurity that is inevitably contained. That is, the Zn content is more than 0%. Zn is a metal having a low melting point, which lowers the hot workability of the alloy. If the Zn content exceeds 0.020%, the hot workability of the alloy will be significantly reduced even if the other element content is within the range of the present embodiment. Therefore, the Zn content is 0.020% or less.
- the preferred upper limit of the Zn content is 0.018%, more preferably 0.016%, even more preferably 0.015%, still more preferably 0.010%.
- the Zn content is preferably as low as possible. However, excessive reduction of Zn content increases the manufacturing cost. Therefore, when industrial production is taken into consideration, the preferable lower limit of the Zn content is 0.001%.
- Niobium (Nb), Titanium (Ti) and Vanadium (V) all increase the strength of the alloy.
- Nb, Ti and V form nano-level carbonitrides.
- the strength of the alloy is increased by the fine dispersion precipitation of nano-level carbonitrides.
- the total content of one or more selected from the group consisting of Nb: 0 to less than 0.145%, Ti: 0 to less than 0.145%, and V: 0 to less than 0.145% is 0.015%. If it is less than, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, the total content of one or more selected from the group consisting of Nb: 0 to less than 0.145%, Ti: 0 to less than 0.145%, and V: 0 to less than 0.145% is 0. If it is 145% or more, nano-level carbonitrides are excessively produced even if the content of other elements is within the range of this embodiment.
- the total content of one or more selected from the group consisting of Nb: 0 to less than 0.145%, Ti: 0 to less than 0.145%, and V: 0 to less than 0.145% is 0. It is 015 to less than 0.145%.
- the preferable lower limit of the total content of Nb, Ti and V is 0.016%, more preferably 0.017%, further preferably 0.020%, still more preferably 0.030%.
- the preferred upper limit of the total content of Nb, Ti and V is 0.140%, more preferably 0.135%, still more preferably 0.120%.
- the rest of the chemical composition of the alloy of this embodiment is Fe and impurities.
- the impurities are those mixed from ore, scrap, or the manufacturing environment as a raw material when the alloy is industrially manufactured, and are allowed as long as they do not adversely affect the alloy of the present embodiment. Means what is done.
- the chemical composition of the low thermal expansion alloy of the present embodiment may further contain one or more selected from the group consisting of Cu, Sn, and W instead of a part of Fe. All of these elements enhance the corrosion resistance of the alloy.
- Cu 0 to 0.300% Copper (Cu) is an optional element and may not be contained. That is, the Cu content may be 0%. When Cu is contained, that is, when the Cu content is more than 0%, Cu enhances the corrosion resistance of the alloy. If even a small amount of Cu is contained, the above effect can be obtained to some extent. However, if the Cu content exceeds 0.300%, the hot workability of the alloy is lowered even if the content of other elements is within the range of this embodiment. Therefore, the Cu content is 0 to 0.300%.
- the lower limit of the Cu content is preferably 0.001%, more preferably 0.005%, still more preferably 0.010%.
- the preferred upper limit of the Cu content is 0.250%, more preferably 0.200%, still more preferably 0.150%, still more preferably 0.120%, still more preferably 0.100. %, More preferably 0.070%.
- Tin (Sn) is an optional element and may not be contained. That is, the Sn content may be 0%.
- Sn When Sn is contained, that is, when the Sn content is more than 0%, Sn enhances the corrosion resistance of the alloy. If Sn is contained even in a small amount, the above effect can be obtained to some extent. However, if the Sn content exceeds 0.100%, the hot workability of the alloy is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the Sn content is 0 to 0.100%.
- the preferred lower limit of the Sn content is 0.001%, more preferably 0.002%, still more preferably 0.003%.
- the preferred upper limit of the Sn content is 0.080%, more preferably 0.070%, still more preferably 0.050%, still more preferably 0.030%, still more preferably 0.020. %.
- W 0 to 0.200%
- Tungsten (W) is an optional element and may not be contained. That is, the W content may be 0%.
- W When W is contained, that is, when the W content is more than 0%, W enhances the corrosion resistance of the alloy. If W is contained even in a small amount, the above effect can be obtained to some extent. However, if the W content exceeds 0.200%, the hot workability of the alloy is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the W content is 0 to 0.200%.
- the lower limit of the W content is preferably 0.001%, more preferably 0.003%, still more preferably 0.005%.
- the preferable upper limit of the W content is 0.150%, more preferably 0.100%, further preferably 0.050%, still more preferably 0.030%, still more preferably 0.020. %.
- Preferable total content of Cu, Sn and W Preferable total content of Cu, Sn and W
- Cu, Sn and W all enhance the corrosion resistance of the alloy.
- the total content of one or more selected from the group consisting of Cu: 0 to 0.300%, Sn: 0 to 0.100%, and W: 0 to 0.200% is 0.020% or more.
- the corrosion resistance of the alloy is significantly increased.
- the preferable lower limit of the total content of Cu, Sn and W is 0.025%, more preferably 0.030%, still more preferably 0.040%.
- the preferable upper limit of the total content of Cu, Sn and W is 0.600, more preferably 0.300%, further preferably 0.250%, still more preferably 0.200%, and further. It is preferably 0.180%.
- the chemical composition of the low thermal expansion alloy of the present embodiment may further contain B instead of a part of Fe.
- B 0 to 0.0040%
- Boron (B) is an optional element and may not be contained. That is, the B content may be 0%. When it is contained, that is, when the B content is more than 0%, B enhances the hot workability of the alloy. If B is contained even in a small amount, the above effect can be obtained to some extent. However, if the B content exceeds 0.0040%, the hot workability of the alloy is rather lowered even if the content of other elements is within the range of the present embodiment. Therefore, the B content is 0 to 0.0040%.
- the preferable lower limit of the B content is 0.0001%, more preferably 0.0002%, still more preferably 0.0008%, still more preferably 0.0012%.
- the preferred upper limit of the B content is 0.0035%, more preferably 0.0030.
- Fn1 (Nb + 3 ⁇ Ti + V) / (C + N).
- the chemical composition satisfies the content of each of the above-mentioned elements and the total content of Nb, Ti and V is less than 0.015 to 0.145%, and Fn1 When is 6.00 or less, the nanocarbonitride is finely dispersed in the alloy in an appropriate amount. Therefore, high strength can be obtained and the coefficient of thermal expansion can be maintained low.
- Fn1 is 6.00 or less.
- the upper limit of Fn1 is preferably 5.20, more preferably 4.20, and even more preferably 3.20.
- the lower limit of Fn1 is not particularly limited, but is, for example, 0.13.
- the shape of the alloy of this embodiment is not particularly limited.
- the shape of the alloy is, for example, a pipe material, a plate material, and a bar material.
- the alloy is used as a material for a pipe for transporting a low-temperature substance represented by LNG and a tank for storing a low-temperature substance.
- alloy pipes, alloy plates, and alloy rods are used as materials to be incorporated into piping for transporting low-temperature substances and tanks for storing low-temperature substances by welding or the like.
- the alloy of the present embodiment having the above constitution has the content of each element in the chemical composition within the above range, and the total content of one or more selected from the group consisting of Nb, Ti, and V.
- the amount is 0.015 to less than 0.145%, and the formula (1) is satisfied. Therefore, the alloy of the present embodiment can have both a sufficiently low coefficient of thermal expansion and high strength.
- the alloy of this embodiment further has a total content of one or more selected from the group consisting of Cu, Sn and W of 0.020% or more. In this case, the alloy of the present embodiment has a low coefficient of thermal expansion and high strength, and further has excellent corrosion resistance.
- the alloy manufacturing method of the present embodiment includes a material preparation step, a hot working step, a cold working step carried out as necessary (that is, an arbitrary step), and a cold working step as needed. It is provided with a heat treatment step to be performed (that is, an arbitrary step).
- a material preparation step that is, a hot working step
- a cold working step carried out as necessary that is, an arbitrary step
- a cold working step as needed. It is provided with a heat treatment step to be performed (that is, an arbitrary step).
- a heat treatment step to be performed that is, an arbitrary step.
- a material having the above-mentioned chemical composition is prepared.
- the material may be supplied by a third party or may be manufactured.
- the material may be ingot, slab, bloom, billet.
- the material is manufactured by the following method.
- a molten alloy having the above-mentioned chemical composition is produced.
- An ingot is manufactured by a lump formation method using the manufactured molten alloy.
- the slab, bloom, and billet (cylindrical material) may be produced by a continuous casting method using the produced molten alloy.
- the billets may be manufactured by performing hot working on the manufactured ingots, slabs, and blooms.
- the ingot may be hot forged to produce a cylindrical billet, and this billet may be used as a material (cylindrical material).
- the temperature of the material immediately before the start of hot forging is not particularly limited, but is, for example, 900 to 1300 ° C.
- the method of cooling the material after hot forging is not particularly limited.
- the material prepared in the material preparing step is hot-worked to produce an intermediate material.
- the intermediate material may be, for example, a pipe material, a plate material, or a bar material.
- the intermediate material is a pipe material (alloy pipe)
- the following processing is performed in the hot processing process.
- An intermediate material (alloy tube) is manufactured by performing hot extrusion represented by the Eugene Sejurne method on a cylindrical material having through holes.
- the temperature of the material immediately before hot extrusion is not particularly limited.
- the temperature of the material immediately before hot extrusion is, for example, 900 to 1300 ° C.
- a hot punching pipe manufacturing method may be carried out.
- perforation rolling by the Mannesmann method may be carried out to manufacture an alloy tube.
- the columnar material is drilled and rolled by a drilling machine.
- the perforated round billet is further hot-rolled by a mandrel mill, reducer, sizing mill or the like to produce an intermediate material (alloy tube).
- the cumulative surface reduction rate in the hot working process is not particularly limited, but is, for example, 20 to 80%.
- the hot working process uses, for example, one or a plurality of rolling mills provided with a pair of work rolls.
- An alloy plate is manufactured by hot rolling a material such as a slab using a rolling mill.
- the temperature of the material immediately before hot rolling is, for example, 800 to 1300 ° C.
- the hot working process includes, for example, a rough rolling process and a finish rolling process.
- the material is hot-processed to produce billets.
- a bulk rolling mill is used for the rough rolling process. Billets are manufactured by performing slab rolling on the material with a slab rolling mill.
- a continuous rolling mill is installed downstream of the ingot rolling mill, hot rolling is further performed on the billet after the ingot rolling using the continuous rolling mill to produce a smaller billet. You may.
- a continuous rolling mill for example, horizontal stands having a pair of horizontal rolls and vertical stands having a pair of vertical rolls are alternately arranged in a row.
- the material temperature immediately before the rough rolling step is not particularly limited, but is, for example, 900 to 1300 ° C.
- the finish rolling process the billet is first heated.
- the billet after heating is hot-rolled using a continuous rolling mill to produce a bar.
- the heating temperature in the heating furnace in the finish rolling step is not particularly limited, but is, for example, 800 to 1300 ° C.
- the cold working process is carried out as needed. That is, the cold working process is an arbitrary process and does not have to be carried out.
- the intermediate material is descaled and then cold-worked.
- the descale treatment is, for example, shot blasting and / or pickling.
- the intermediate material is a pipe or bar
- the cold working is, for example, cold drawing or cold Pilger rolling.
- the intermediate material is a plate material
- the cold working is, for example, cold rolling.
- strain is applied to the intermediate material before the heat treatment step. As a result, recrystallization and sizing can be performed during the heat treatment step.
- the surface reduction rate in the cold working process is not particularly limited, but is, for example, 10 to 70%.
- the heat treatment step is carried out as needed. That is, the heat treatment step is an arbitrary step and does not have to be carried out.
- heat treatment for the purpose of recrystallization is carried out on the intermediate material after the hot working step or the cold working step.
- the heat treatment temperature is 750 to 950 ° C.
- the holding time at the heat treatment temperature is not particularly limited, but is, for example, 5 to 30 minutes. After the holding time has elapsed, the intermediate material is water-cooled to produce an alloy as a product.
- the alloy of this embodiment can be manufactured by the above manufacturing process.
- the method for producing the alloy is not particularly limited as long as the chemical composition of the present embodiment is satisfied.
- the effects of the alloy of this embodiment will be described more specifically by way of examples.
- the conditions in the following examples are one condition example adopted for confirming the feasibility and effect of the alloy of this embodiment. Therefore, the alloy of this embodiment is not limited to this one condition example.
- the molten alloys of each test number in Table 1 were produced by vacuum melting, and the columnar ingots having the chemical compositions shown in Table 1 were produced using the molten alloys.
- the outer diameter of the ingot was 250 mm.
- a blank column in Table 1 means that the corresponding element content was below the detection limit. That is, the blank portion means that the minimum digit of the corresponding element content was below the detection limit. For example, in the case of Ti content in Table 1, the smallest digit is the third decimal place. Therefore, the Ti content of test number 1 means that it was not detected in the number of digits up to the third decimal place (the significant figure was 0% in the content up to the third decimal place).
- the ingot was heated to 1200 ° C. Hot forging was carried out on the heated ingot to produce a material having a thickness of 40 mm and a width of 100 mm.
- the material was hot-rolled to produce an intermediate material (alloy plate).
- the heating temperature of the material in hot rolling was 1200 ° C.
- Cold rolling was carried out on the intermediate material to obtain an intermediate material (alloy plate) having a thickness of 15 mm and a width of 100 mm.
- the intermediate material after cold rolling was heat-treated at a heat treatment temperature of 850 ° C.
- the holding time at the heat treatment temperature was 30 minutes. After the holding time had elapsed, the intermediate material was water-cooled to produce alloys (alloy plates) of each test number.
- the surface reduction rate in hot rolling and the surface reduction rate in cold rolling were the same for all test numbers.
- Table 2 shows the drawing values (%) of the intermediate materials of each test number at 900 ° C. When the drawing value at 900 ° C. was less than 70%, it was determined that the hot workability was low. For intermediate materials with test numbers that had low hot workability, the following evaluation tests (coefficient of thermal expansion evaluation test, tensile strength evaluation test, corrosion resistance evaluation test) were performed without performing the steps after the hot work process. Not performed (indicated by "-" in the "linear expansion coefficient” column, "tensile strength” column, and “corrosion rate” column in Table 2).
- Test piece was taken from the center position of the plate width of the alloy of each test number and the center position of the plate thickness.
- the test piece was a tensile test piece having a parallel portion length of 65 mm and a parallel portion diameter of 6 mm.
- the length of the parallel part was parallel to the longitudinal direction of the alloy.
- the central axis of the tensile test piece almost coincided with the center position of the thickness of the alloy plate.
- a tensile test was carried out in the air at room temperature in accordance with JIS Z 2241 (2011) to determine the tensile strength (MPa).
- Table 2 shows the tensile strength (MPa) of the alloy of each test number.
- the test piece was immersed in a 6% ferric chloride solution. The temperature of the solution during immersion was 35 ⁇ 1 ° C. After soaking for 24 hours, the test piece was removed from the solution. After removing the corrosion products adhering to the test piece, the test piece was washed and dried. The mass of the test piece after drying was measured, and the weight loss was determined. Based on the obtained weight loss, the corrosion rate (mg / cm 2 / h)) was determined. Based on the determined corrosion rate, the corrosion resistance of the alloys of each test number was evaluated as follows.
- Evaluation A Corrosion rate is 0.90 times or less of the corrosion rate of the reference material
- Evaluation B Corrosion rate is more than 0.90 times to 1.00 times the corrosion rate of the reference material
- Evaluation X Corrosion rate is the reference material When the evaluation A was more than 1.00 times the corrosion rate of A, it was judged that particularly excellent corrosion resistance was obtained. The obtained evaluation results are shown in the "corrosion rate" column in Table 2.
- the corrosion rate of test number 12 (reference material) was 6.5 mg / cm 2 / h.
- test numbers 1 to 11 test numbers 1 to 3, 5, 7, 9 and 11 further had a total content of Nb, Ti and V of 0.030% or more. Therefore, the tensile strength was 504 MPa or more, and further excellent strength was obtained as compared with Test Nos. 4, 6, 8 and 10 in which the total content of Nb, Ti and V was less than 0.030%.
- the total content of Cu, Sn and W was 0.020% or more. Therefore, not only high strength and a lower coefficient of thermal expansion were obtained, but also the corrosion resistance was evaluated as A, and excellent corrosion resistance was obtained ( corrosion rate of 5.9 mg / cm 2 / h or less).
- test number 12 the total content of Nb, Ti and V was less than 0.015%. Therefore, the strength was too low.
- test number 13 the Nb content was too high. Therefore, the total content of Nb, Ti and V exceeded 0.145%. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test number 14 the Ti content was too high. Therefore, the total content of Nb, Ti and V exceeded 0.145%. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test number 15 the V content was too high. Therefore, the total content of Nb, Ti and V exceeded 0.145%. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test numbers 16 to 18 the total content of Nb, Ti and V was less than 0.015%. Therefore, the strength was too low.
- test number 19 the V content was too high. Therefore, the total content of Nb, Ti and V exceeded 0.145%. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test number 20 the Nb content was too high. Therefore, the total content of Nb, Ti and V exceeded 0.145%. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test number 21 the Sn content was too high. Therefore, cracks were confirmed in the intermediate material after hot rolling, and the hot workability was low.
- test number 22 the Ti content was high, and the total content of Nb, Ti, and V exceeded 0.145%. In addition, the N content was too high. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test number 23 the Pb content was too high. Therefore, cracks were confirmed in the intermediate material after hot rolling, and the hot workability was low.
- test number 24 the B content was too high. Therefore, cracks were confirmed in the intermediate material after hot rolling, and the hot workability was low.
- test number 25 the Cu content was too high. Therefore, cracks were confirmed in the intermediate material after hot rolling, and the hot workability was low.
- test number 26 the W content was too high. Therefore, cracks were confirmed in the intermediate material after hot rolling, and the hot workability was low.
- test number 27 the Nb content and Ti content were too high. Therefore, the total content of Nb, Ti and V exceeded 0.145%. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
- test number 30 the total content of Nb, Ti and V was 0.145% or more. Therefore, the coefficient of thermal expansion was too high. In addition, the corrosion resistance was low.
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Abstract
Description
TR(℃)=2,500×C%+750・・・(1)
化学組成が、質量%で、
C:0.10%以下、
Si:0.50%以下、
Mn:0.15~0.60%、
P:0.015%以下、
S:0.0030%以下、
Ni:30.0~40.0%、
Cr:0.50%以下、
Mo:0.50%以下、
Co:0.250%以下、
Al:0.0150%以下、
Ca:0.0050%以下、
Mg:0.0300%以下、
N:0.0100%以下、
O:0.0300%以下、
Pb:0.0040%以下、
Zn:0.020%以下、
Nb:0~0.145%未満、Ti:0~0.145%未満、及び、V:0~0.145%未満からなる群から選択される1種以上の合計:0.015~0.145%未満、
Cu:0~0.300%、
Sn:0~0.100%、
W:0~0.200%、及び、
B:0~0.0040%、を含有し、
残部はFe及び不純物からなり、
式(1)を満たす。
(Nb+3×Ti+V)/(C+N)≦6.00 (1)
ここで、式(1)中の各元素記号には、合金の化学組成中の各元素の含有量が質量%で代入される。
(Nb+3×Ti+V)/(C+N)≦6.00 (1)
ここで、式(1)中の各元素記号には、合金の化学組成中の各元素の含有量が質量%で代入される。
化学組成が、質量%で、
C:0.10%以下、
Si:0.50%以下、
Mn:0.15~0.60%、
P:0.015%以下、
S:0.0030%以下、
Ni:30.0~40.0%、
Cr:0.50%以下、
Mo:0.50%以下、
Co:0.250%以下、
Al:0.0150%以下、
Ca:0.0050%以下、
Mg:0.0300%以下、
N:0.0100%以下、
O:0.0300%以下、
Pb:0.0040%以下、
Zn:0.020%以下、
Nb:0~0.145%未満、Ti:0~0.145%未満、及び、V:0~0.145%未満からなる群から選択される1種以上の合計:0.015~0.145%未満、
Cu:0~0.300%、
Sn:0~0.100%、
W:0~0.200%、及び、
B:0~0.0040%、を含有し、
残部はFe及び不純物からなり、
式(1)を満たす、合金。
(Nb+3×Ti+V)/(C+N)≦6.00 (1)
ここで、式(1)中の各元素記号には、合金の化学組成中の各元素の含有量が質量%で代入される。
[1]に記載の合金であって、
前記化学組成は、
Cu:0~0.300%、Sn:0~0.100%、及び、W:0~0.200%からなる群から選択される1種以上を合計で0.020%以上含有する、
合金。
前記合金は、管材、板材、及び棒材のいずれかである、
[1]又は[2]に記載の合金。
本実施形態の合金の化学組成は、次の元素を含有する。
炭素(C)は不可避に含有される。つまり、C含有量は0%超である。Cは、製鋼工程において、合金を脱酸する。Cはさらに、合金の強度を高める。Cが少しでも含有されれば、上記効果がある程度得られる。しかしながら、C含有量が0.10%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の耐食性が低下する。したがって、C含有量は0.10%以下である。C含有量の好ましい上限は0.09%であり、さらに好ましくは0.08%であり、さらに好ましくは0.06%であり、さらに好ましくは0.05%である。C含有量の好ましい下限は0.01%であり、さらに好ましくは0.02%である。
シリコン(Si)は不可避に含有される。つまり、Si含有量は0%超である。Siは製鋼工程において、合金を脱酸する。Siが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Si含有量が0.50%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の自発体積磁歪が減少し、合金の熱膨張係数が高まる。Si含有量が0.50%を超えればさらに、合金の熱間加工性が低下する。Si含有量が0.50%を超えればさらに、介在物が過剰に多く生成して合金の耐食性が低下する。したがって、Si含有量は0.50%以下である。Si含有量の好ましい上限は0.40%であり、さらに好ましくは0.30%であり、さらに好ましくは0.25%であり、さらに好ましくは0.20%である。Si含有量の好ましい下限は0.01%であり、さらに好ましくは0.05%である。
マンガン(Mn)は、製鋼工程において、合金を脱酸する。Mnはさらに、硫黄(S)と結合してMnSを形成し、合金の熱間加工性を高める。Mn含有量が0.15%未満であれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Mn含有量が0.60%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の自発体積磁歪が減少する。その結果、合金の熱膨張係数が高まる。したがって、Mn含有量は0.15~0.60%である。Mn含有量の好ましい下限は0.16%であり、さらに好ましくは0.17%であり、さらに好ましくは0.19%であり、さらに好ましくは0.20%であり、さらに好ましくは0.21%である。Mn含有量の好ましい上限は0.55%であり、さらに好ましくは0.50%であり、さらに好ましくは0.45%である。
燐(P)は不可避に含有される不純物である。つまり、P含有量は0%超である。Pは合金の溶接性及び熱間加工性を低下する。P含有量が0.015%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の溶接性及び熱間加工性が顕著に低下する。したがって、P含有量は0.015%以下である。P含有量の好ましい上限は0.012%であり、さらに好ましくは0.010%であり、さらに好ましくは0.008%である。P含有量はなるべく低い方が好ましい。しかしながら、P含有量の過剰な低減は製造コストを高める。したがって、工業生産を考慮した場合、P含有量の好ましい下限は0.001%であり、さらに好ましくは0.002%である。
硫黄(S)は不可避に含有される不純物である。つまり、S含有量は0%超である。Sは合金の溶接性及び熱間加工性を低下する。S含有量が0.0030%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の溶接性及び熱間加工性が顕著に低下する。したがって、S含有量は0.0030%以下である。S含有量の好ましい上限は0.0025%であり、さらに好ましくは0.0020%であり、さらに好ましくは0.0015%であり、さらに好ましくは0.0010%である。S含有量はなるべく低い方が好ましい。しかしながら、S含有量の過剰な低減は製造コストを高める。したがって、工業生産を考慮した場合、S含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0002%である。
ニッケル(Ni)は、合金の自発体積磁歪を高め、その結果、合金の熱膨張係数を低下する。Niはさらに、合金の耐食性を高める。Ni含有量が30.0%未満であれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Ni含有量が40.0%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱膨張係数がかえって増大する。したがって、Ni含有量は30.0~40.0%である。Ni含有量の好ましい下限は31.0%であり、さらに好ましくは32.0%であり、さらに好ましくは33.0%であり、さらに好ましくは34.0%である。Ni含有量の好ましい上限は39.0%であり、さらに好ましくは38.0%であり、さらに好ましくは37.0%である。
クロム(Cr)は不可避に含有される。つまり、Cr含有量は0%超である。Crは合金の耐食性を高める。Crが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Cr含有量が0.50%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が低下する。したがって、Cr含有量は0.50%以下である。Cr含有量の好ましい上限は0.45%であり、さらに好ましくは0.40%であり、さらに好ましくは0.35%であり、さらに好ましくは0.30%であり、さらに好ましくは0.25%であり、さらに好ましくは0.20%であり、さらに好ましくは0.15%であり、さらに好ましくは0.10%である。Cr含有量の好ましい下限は0.01%である。
モリブデン(Mo)は不可避に含有される。つまり、Mo含有量は0%超である。Moは合金の強度を高める。Moが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Mo含有量が0.50%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が低下する。したがって、Mo含有量は0.50%以下である。Mo含有量の好ましい上限は0.45%であり、さらに好ましくは0.40%であり、さらに好ましくは0.35%であり、さらに好ましくは0.30%であり、さらに好ましくは0.25%であり、さらに好ましくは0.20%であり、さらに好ましくは0.15%であり、さらに好ましくは0.10%である。Mo含有量の好ましい下限は0.01%である。
コバルト(Co)は不可避に含有される。つまり、Co含有量は0%超である。Coは、Niと同様に、合金の強度を高める。Coが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Co含有量が0.250%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱膨張係数がかえって高まってしまう。したがって、Co含有量は0.250%以下である。Co含有量の好ましい上限は0.200%であり、さらに好ましくは0.150%であり、さらに好ましくは0.100%であり、さらに好ましくは0.080%である。Co含有量の好ましい下限は0.001%であり、さらに好ましくは0.005%であり、さらに好ましくは0.010%であり、さらに好ましくは0.020%である。
アルミニウム(Al)は不可避に含有される。つまり、Al含有量は0%超である。Alは合金を脱酸する。Alが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Al含有量が0.0150%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の自発体積磁歪が減少する。その結果、合金の熱膨張係数が高まる。したがって、Al含有量は0.0150%以下である。Al含有量の好ましい上限は0.0120%であり、さらに好ましくは0.0100%であり、さらに好ましくは0.0090%であり、さらに好ましくは0.0080%であり、さらに好ましくは0.0070%であり、さらに好ましくは0.0060%であり、さらに好ましくは0.0035%未満である。Al含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0005%であり、さらに好ましくは0.0010%であり、さらに好ましくは0.0012%である。本実施形態において、Al含有量とは、全Al(Total-Al)の含有量である。
カルシウム(Ca)は不可避に含有される。つまり、Ca含有量は0%超である。CaはMnSを微細化して、合金の熱間加工性を高める。Caが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Ca含有量が0.0050%を超えれば、他の元素含有量が本実施形態の範囲内であっても、粗大な介在物が過剰に多く生成して、合金の熱間加工性を低下する。したがって、Ca含有量は0.0050%以下である。Ca含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0030%であり、さらに好ましくは0.0020%である。Ca含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0005%である。
マグネシウム(Mg)は不可避に含有される。つまり、Mg含有量は0%超である。MgはCaと同様に、MnSを微細化して、合金の熱間加工性を高める。Mgが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Mg含有量が0.0300%を超えれば、他の元素含有量が本実施形態の範囲内であっても、粗大な介在物が過剰に多く生成して、合金の熱間加工性が低下する。したがって、Mg含有量は0.0300%以下である。Mg含有量の好ましい上限は0.0200%であり、さらに好ましくは0.0100%であり、さらに好ましくは0.0050%であり、さらに好ましくは0.0020%であり、さらに好ましくは0.0010%である。Mg含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0002%である。
窒素(N)は不可避に含有される不純物である。つまり、N含有量は0%超である。Nは、合金の熱間加工性を低下する。N含有量が0.0100%を超えれば、他の元素含有量が本実施形態の範囲内であっても、窒化物を過剰に多く形成して、合金の熱膨張係数が増大し、かつ、合金の耐食性が低下する。したがって、N含有量は0.0100%以下である。N含有量の好ましい上限は0.0095%であり、さらに好ましくは0.0090%である。N含有量はなるべく低い方が好ましい。しかしながら、Nの過剰な低減は製造コストを高める。したがって、工業生産を考慮した場合、N含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0005%である。
酸素(O)は不可避に含有される不純物である。つまり、O含有量は0%超である。Oは粗大な介在物を生成し、合金の熱間加工性を低下する。O含有量が0.0300%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が顕著に低下する。したがって、O含有量は0.0300%以下である。O含有量の好ましい上限は0.0200%であり、さらに好ましくは0.0180%であり、さらに好ましくは0.0150%である。O含有量はなるべく低い方が好ましい。しかしながら、O含有量の過剰な低減は、製造コストを高める。したがって、工業生産を考慮した場合、O含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0005%である。
鉛(Pb)は不可避に含有される不純物である。つまり、Pb含有量は0%超である。Pbは低融点の金属であり、合金の熱間加工性を低下する。Pb含有量が0.0040%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が顕著に低下する。したがって、Pb含有量は0.0040%以下である。Pb含有量の好ましい上限は0.0030%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%であり、さらに好ましくは0.0015%であり、さらに好ましくは0.0010%である。Pb含有量はなるべく低い方が好ましい。しかしながら、Pb含有量の過剰な低減は製造コストを高くする。したがって、工業生産を考慮した場合、Pb含有量の好ましい下限は0.0001%である。
亜鉛(Zn)は不可避に含有される不純物である。つまり、Zn含有量は0%超である。Znは低融点の金属であり、合金の熱間加工性を低下する。Zn含有量が0.020%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が顕著に低下する。したがって、Zn含有量は0.020%以下である。Zn含有量の好ましい上限は0.018%であり、さらに好ましくは0.016%であり、さらに好ましくは0.015%であり、さらに好ましくは0.010%である。Zn含有量はなるべく低い方が好ましい。しかしながら、Zn含有量の過剰な低減は製造コストを高くする。したがって、工業生産を考慮した場合、Zn含有量の好ましい下限は0.001%である。
ニオブ(Nb)、チタン(Ti)及びバナジウム(V)はいずれも、合金の強度を高める。合金の化学組成中の各元素の含有量が上述の範囲内であり、かつ、後述する式(1)を満たす場合、Nb、Ti及びVはいずれも、ナノレベルの炭窒化物を形成し、ナノレベルの炭窒化物の微細分散析出により、合金の強度を高める。Nb:0~0.145%未満、Ti:0~0.145%未満、及び、V:0~0.145%未満からなる群から選択される1種以上の合計含有量が0.015%未満であれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Nb:0~0.145%未満、Ti:0~0.145%未満、及び、V:0~0.145%未満からなる群から選択される1種以上の合計含有量が0.145%以上であれば、他の元素含有量が本実施形態の範囲内であっても、ナノレベルの炭窒化物が過剰に生成する。この場合、合金の熱膨張係数が高まり、かつ、合金の耐食性が低下する。したがって、Nb:0~0.145%未満、Ti:0~0.145%未満、及び、V:0~0.145%未満からなる群から選択される1種以上の合計含有量は0.015~0.145%未満である。Nb、Ti及びVの合計含有量の好ましい下限は0.016%であり、さらに好ましくは0.017%であり、さらに好ましくは0.020%であり、さらに好ましくは0.030%である。Nb、Ti及びVの合計含有量の好ましい上限は0.140%であり、さらに好ましくは0.135%であり、さらに好ましくは0.120%である。
[任意元素第1群(Cu、Sn、W)]
本実施形態の低熱膨張合金の化学組成はさらに、Feの一部に代えて、Cu、Sn、及び、Wからなる群から選択される1種以上を含有してもよい。これらの元素はいずれも、合金の耐食性を高める。
銅(Cu)は任意元素であり、含有されなくてもよい。つまり、Cu含有量は0%であってもよい。Cuが含有される場合、つまり、Cu含有量が0%超である場合、Cuは、合金の耐食性を高める。Cuが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Cu含有量が0.300%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が低下する。したがって、Cu含有量は0~0.300%である。Cu含有量の好ましい下限は0.001%であり、さらに好ましくは0.005%であり、さらに好ましくは0.010%である。Cu含有量の好ましい上限は0.250%であり、さらに好ましくは0.200%であり、さらに好ましくは0.150%であり、さらに好ましくは0.120%であり、さらに好ましくは0.100%であり、さらに好ましくは0.070%である。
錫(Sn)は任意元素であり、含有されなくてもよい。つまり、Sn含有量は0%であってもよい。Snが含有される場合、つまり、Sn含有量が0%超である場合、Snは、合金の耐食性を高める。Snが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Sn含有量が0.100%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が低下する。したがって、Sn含有量は0~0.100%である。Sn含有量の好ましい下限は0.001%であり、さらに好ましくは0.002%であり、さらに好ましくは0.003%である。Sn含有量の好ましい上限は0.080%であり、さらに好ましくは0.070%であり、さらに好ましくは0.050%であり、さらに好ましくは0.030%であり、さらに好ましくは0.020%である。
タングステン(W)は任意元素であり、含有されなくてもよい。つまり、W含有量は0%であってもよい。Wが含有される場合、つまり、W含有量が0%超である場合、Wは、合金の耐食性を高める。Wが少しでも含有されれば、上記効果がある程度得られる。しかしながら、W含有量が0.200%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性が低下する。したがって、W含有量は0~0.200%である。W含有量の好ましい下限は0.001%であり、さらに好ましくは0.003%であり、さらに好ましくは0.005%である。W含有量の好ましい上限は0.150%であり、さらに好ましくは0.100%であり、さらに好ましくは0.050%であり、さらに好ましくは0.030%であり、さらに好ましくは0.020%である。
好ましくは、本実施形態の合金の化学組成では、Cu:0~0.300%、Sn:0~0.100%、及び、W:0~0.200%からなる群から選択される1種以上を合計で0.020%以上含有する。
本実施形態の低熱膨張合金の化学組成はさらに、Feの一部に代えて、Bを含有してもよい。
ボロン(B)は任意元素であり、含有されなくてもよい。つまり、B含有量は0%であってもよい。含有される場合、つまり、B含有量が0%超である場合、Bは合金の熱間加工性を高める。Bが少しでも含有されれば、上記効果がある程度得られる。しかしながら、B含有量が0.0040%を超えれば、他の元素含有量が本実施形態の範囲内であっても、合金の熱間加工性がかえって低下する。したがって、B含有量は0~0.0040%である。B含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0002%であり、さらに好ましくは0.0008%であり、さらに好ましくは0.0012%である。B含有量の好ましい上限は0.0035%であり、さらに好ましくは0.0030である。
本実施形態の合金の化学組成は、式(1)を満たす。
(Nb+3×Ti+V)/(C+N)≦6.00 (1)
ここで、式(1)中の各元素記号には、合金の化学組成中の各元素の含有量が質量%で代入される。
本実施形態の合金の形状は特に限定されない。合金の形状はたとえば、管材、板材、及び棒材である。合金は、LNGに代表される低温物質の輸送用配管、及び、低温物質の貯蔵用タンクの素材として使用される。具体的には、合金管、合金板、合金棒は、低温物質の輸送用配管及び低温物質の貯蔵用タンクに、溶接等により組み込まれる素材として使用される。
本実施形態の合金の製造方法の一例を以下に説明する。なお、本実施形態の合金は、以下の製造方法に限定されない。以下に説明する製造方法は、本実施形態の合金の製造方法の好ましい一例である。
素材準備工程では、上述の化学組成を有する素材を準備する。素材は第三者から供給されてもよいし、製造してもよい。素材はインゴットであってもよいし、スラブ、ブルーム、ビレットであってもよい。素材を製造する場合、次の方法により、素材を製造する。上述の化学組成を有する溶融合金を製造する。製造された溶融合金を用いて、造塊法によりインゴットを製造する。製造された溶融合金を用いて、連続鋳造法によりスラブ、ブルーム、ビレット(円柱素材)を製造してもよい。製造されたインゴット、スラブ、ブルームに対して熱間加工を実施して、ビレットを製造してもよい。たとえば、インゴットに対して熱間鍛造を実施して、円柱状のビレットを製造し、このビレットを素材(円柱素材)としてもよい。この場合、熱間鍛造開始直前の素材の温度は特に限定されないが、たとえば、900~1300℃である。熱間鍛造後の素材の冷却方法は特に限定されない。
熱間加工工程では、素材準備工程において準備された素材に対して熱間加工を実施して、中間材を製造する。中間材はたとえば管材であってもよいし、板材であってもよいし、棒材であってもよい。
冷間加工工程は必要に応じて実施する。つまり、冷間加工工程は任意の工程であり、実施しなくてもよい。実施する場合、中間材に対して、脱スケール処理を実施した後、冷間加工を実施する。脱スケール処理はたとえば、ショットブラスト及び/又は酸洗である。中間材が管材又は棒材である場合、冷間加工はたとえば、冷間抽伸又は冷間ピルガー圧延である。中間材が板材である場合、冷間加工はたとえば、冷間圧延である。冷間加工工程を実施することにより、熱処理工程前に、中間材に歪を付与する。これにより、熱処理工程時において再結晶の発現及び整粒化を行うことができる。冷間加工工程における減面率は特に限定されないが、たとえば、10~70%である。
熱処理工程は必要に応じて実施する。つまり、熱処理工程は任意の工程であり、実施しなくてもよい。実施する場合、熱間加工工程後又は冷間加工工程後の中間材に対して、再結晶を目的とした熱処理を実施する。熱処理温度は750~950℃である。熱処理温度での保持時間は特に限定されないが、たとえば、5~30分である。保持時間経過後の中間材を水冷して、製品である合金を製造する。
[グリーブル試験]
各試験番号の合金の熱間加工性を、グリーブル試験によって評価した。各試験番号の熱間鍛造後のインゴットから、外径10mm、長さ130mmの棒状試験片を採取し、900℃の絞り値を求めた。具体的には、グリーブル試験機(DYNAMIC SYSTEM Inc.社製 Gleeble 3500-GTC)に棒状試験片を設置した。棒状試験片を、直接通電により1200℃に加温して1分間保持した。その後、1分間で900℃まで降温し、歪み速度10/秒で破断まで引っ張り、断面の絞り値(試験後の棒状試験片の破断面積/試験前の棒状試験片の長手方向に垂直な断面積)を算出した。各試験番号の中間材の900℃での絞り値(%)を表2に示す。なお、900℃での絞り値が70%未満であった場合、熱間加工性が低いと判定した。熱間加工性が低かった試験番号の中間材については、熱間加工工程以降の工程を実施せず、以下に示す評価試験(熱膨張係数評価試験、引張強さ評価試験、耐食性評価試験)を実施しなかった(表2中の「線膨張係数」欄、「引張強さ」欄、「腐食速度」欄において「-」で表記)。
各試験番号の合金板の板幅中央位置であって、板厚中心位置から、直径5mm、長さ20mmの試験片を採取した。試験片の長手方向は、合金板の長手方向と平行であった。試験片の中心軸は、合金板の板厚中心位置とほぼ一致した。試験片を用いて、JIS Z 2285(2003)に基づいて、熱膨張係数を求めた。熱膨張係数の測定には、水平型示差膨張式機械分析装置(NETZSCH社 DIL402 Expedis Supreme)を用いた。具体的には、試験片を5℃/minの速度で昇温し、30~100℃の熱膨張係数を1℃ピッチで求めた。求めた熱膨張係数の平均を、線膨張係数(×10-6/K)とした。各試験番号の合金の線膨張係数(×10-6/K)を表2に示す。
各試験番号の合金の板幅中央位置であって、板厚中心位置から、試験片を採取した。試験片は、平行部長さ65mm、平行部の直径6mmの引張試験片とした。平行部長さは、合金の長手方向と平行であった。引張試験片の中心軸は、合金板の板厚中心位置とほぼ一致した。得られた試験片を用いて、JIS Z 2241(2011)に準拠して、常温大気中にて、引張試験を実施して、引張強さ(MPa)を求めた。各試験番号の合金の引張強さ(MPa)を表2に示す。
各試験番号の合金の板幅中央位置であって、板厚中心位置から、厚さ1mm、幅10mm、長さ55mmの試験片を採取した。試験片の長手方向は、合金板の長手方向と平行であった。試験片の長手方向に垂直な断面の中心位置は、合金板の板厚中心位置とほぼ一致した。試験片を用いて、JIS G 0578(2000)に準拠した塩化第二鉄腐食試験を実施した。具体的には、試験片を表面研磨した。表面研磨後の試験片を脱脂した後、乾燥した。試験前の試験片の質量を測定した。質量を測定後、試験片を、6%塩化第二鉄溶液中へ浸漬した。浸漬中の溶液の温度は35±1℃とした。24時間浸漬した後、試験片を溶液から取り出した。試験片に付着している腐食生成物を除去した後、試験片を洗浄及び乾燥した。乾燥後の試験片の質量を測定し、減量を求めた。求めた減量に基づいて、腐食速度(mg/cm2/h))を求めた。求めた腐食速度に基づいて、各試験番号の合金の耐食性を次のとおり評価した。
評価A:腐食速度が、基準材の腐食速度の0.90倍以下
評価B:腐食速度が、基準材の腐食速度の0.90倍超~1.00倍
評価X:腐食速度が、基準材の腐食速度の1.00倍超
評価Aの場合、特に優れた耐食性が得られたと判断した。得られた評価結果を表2中の「腐食速度」欄に示す。なお、試験番号12(基準材)の腐食速度は、6.5mg/cm2/hであった。
表1及び表2を参照して、試験番号1~11の合金の化学組成は適切であり、かつ、Nb、Ti及びVの合計含有量が0.015~0.145%未満であり、式(1)を満たした。そのため、試験番号1~11の合金の引張強さは472MPa以上であった。また、試験番号1~11の合金の熱膨張係数は1.00×10-6/K以下であった。なお、試験番号1~11の合金の900℃での絞り値は70%以上であった。
Claims (3)
- 化学組成が、質量%で、
C:0.10%以下、
Si:0.50%以下、
Mn:0.15~0.60%、
P:0.015%以下、
S:0.0030%以下、
Ni:30.0~40.0%、
Cr:0.50%以下、
Mo:0.50%以下、
Co:0.250%以下、
Al:0.0150%以下、
Ca:0.0050%以下、
Mg:0.0300%以下、
N:0.0100%以下、
O:0.0300%以下、
Pb:0.0040%以下、
Zn:0.020%以下、
Nb:0~0.145%未満、Ti:0~0.145%未満、及び、V:0~0.145%未満からなる群から選択される1種以上の合計:0.015~0.145%未満、
Cu:0~0.300%、
Sn:0~0.100%、
W:0~0.200%、及び、
B:0~0.0040%、を含有し、
残部はFe及び不純物からなり、
式(1)を満たす、合金。
(Nb+3×Ti+V)/(C+N)≦6.00 (1)
ここで、式(1)中の各元素記号には、合金の化学組成中の各元素の含有量が質量%で代入される。 - 請求項1に記載の合金であって、
前記化学組成は、
Cu:0~0.300%、Sn:0~0.100%、及び、W:0~0.200%からなる群から選択される1種以上を合計で0.020%以上含有する、
合金。 - 前記合金は、管材、板材、及び棒材のいずれかである、
請求項1又は請求項2に記載の合金。
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CA3159934A CA3159934A1 (en) | 2019-12-27 | 2020-12-25 | Alloy |
EP20907786.6A EP4083249A4 (en) | 2019-12-27 | 2020-12-25 | ALLOY |
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