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WO2024185746A1 - Élément en alliage résistant à la chaleur à base d'austénite - Google Patents

Élément en alliage résistant à la chaleur à base d'austénite Download PDF

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Publication number
WO2024185746A1
WO2024185746A1 PCT/JP2024/008081 JP2024008081W WO2024185746A1 WO 2024185746 A1 WO2024185746 A1 WO 2024185746A1 JP 2024008081 W JP2024008081 W JP 2024008081W WO 2024185746 A1 WO2024185746 A1 WO 2024185746A1
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content
creep rupture
mass
alloy
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PCT/JP2024/008081
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Japanese (ja)
Inventor
友彰 浜口
奈央 大瀧
克樹 田中
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Nippon Steel Corp
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Nippon Steel Corp
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Priority to KR1020257032405A priority Critical patent/KR20250154483A/ko
Priority to JP2025505330A priority patent/JPWO2024185746A1/ja
Priority to CN202480016802.3A priority patent/CN120835936A/zh
Publication of WO2024185746A1 publication Critical patent/WO2024185746A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the present invention relates to austenitic heat-resistant alloy members.
  • Patent Document 1 discloses an austenitic heat-resistant alloy component that achieves both excellent hot workability and creep rupture strength by strictly controlling the S content in relation to the Ca, Mg, and REM contents.
  • Patent Document 2 also discloses an austenitic heat-resistant alloy that, by performing heat treatment under appropriate conditions, reduces the variation in mechanical properties depending on the part, and exhibits sufficient 0.2% yield strength and tensile strength at room temperature as well as creep rupture strength at high temperatures for use as a large structural component, and a method for manufacturing the alloy.
  • Patent Document 3 discloses an austenitic heat-resistant alloy member having a thickness of over 30 mm, which has improved creep strength and crack resistance during multi-layer welding by controlling the average crystal grain size in the center of the thickness of the member according to the B, Ti, and W contents.
  • Patent Document 4 discloses an austenitic stainless steel that has improved high-temperature strength and fatigue resistance by increasing the W content, which is effective in increasing strength, and creating a metal structure in which the austenite crystal grains are coarse and have little variation.
  • the present invention aims to solve the above problems and provide an austenitic heat-resistant alloy component that has excellent creep rupture strength and creep rupture ductility.
  • the present invention was completed based on the above findings, and is summarized as the following austenitic heat-resistant alloy members.
  • each symbol is defined as follows, and each element symbol in the above formula represents the content (mass %) of each element contained in the alloy member.
  • the chemical composition is, in mass%, replacing a part of the Fe, Ca: 0.0100% or less, Mg: 0.0500% or less, REM: 0.1000% or less, Co: 1.000% or less, Cu: 1.00% or less, Mo: 1.000% or less; and V: 0.500% or less; It contains one or more selected from The austenitic heat-resistant alloy member according to (1) above.
  • the austenitic heat-resistant alloy member of the present invention has excellent creep rupture strength and creep rupture ductility.
  • C 0.010-0.150% C stabilizes austenite and forms fine carbides at grain boundaries, improving creep rupture strength at high temperatures. To fully obtain this effect, the C content is set to 0.010% or more. However, if C is contained in an excessive amount, the carbides become coarse and precipitate in large quantities, which reduces the ductility of the grain boundaries and further reduces the toughness and creep rupture strength. Therefore, the C content is set to 0.010 to 0.150%.
  • the C content is preferably 0.030% or more, and more preferably 0.050% or more. It is preferably 0.120% or less, and more preferably 0.100% or less.
  • Si 2.00% or less Si is an element that has a deoxidizing effect and is effective in improving corrosion resistance and oxidation resistance at high temperatures. However, if Si is contained in excess, the stability of austenite decreases, leading to a decrease in toughness and creep rupture strength. Therefore, the Si content is set to 2.00% or less. The Si content is preferably 1.50% or less, and more preferably 1.00% or less.
  • the Si content is preferably 0.02% or more, and more preferably 0.05% or more.
  • Mn 2.00% or less Mn, like Si, is an element that not only has a deoxidizing effect but also contributes to the stabilization of austenite. However, excessive Mn content leads to embrittlement, and furthermore, the toughness and creep rupture ductility are reduced. Therefore, the Mn content is set to 2.00% or less.
  • the Mn content is preferably 1.80% or less, and more preferably 1.50% or less.
  • the Mn content is preferably 0.005% or more, and more preferably 0.010% or more.
  • P 0.0400% or less P is contained in the alloy as an impurity, and if contained in a large amount, it significantly reduces hot workability and weldability, and further reduces creep rupture ductility after long-term use. Therefore, the P content is set to 0.0400% or less.
  • the P content is preferably 0.0300% or less, and more preferably 0.0250% or less.
  • the P content is preferably 0.0005% or more, and more preferably 0.0008% or more.
  • S 0.0100% or less S has the effect of improving creep rupture properties by being present in crystal grains. However, if a large amount of S is contained, hot workability and weldability are significantly reduced, and creep rupture ductility after long-term use is also reduced. Therefore, the S content is set to 0.0100% or less.
  • the S content is preferably 0.0095% or less, and more preferably 0.0090% or less.
  • the S content is preferably 0.0015% or more, more preferably 0.0018% or more, and even more preferably 0.0020% or more.
  • Cr:20.00 ⁇ 28.00% Cr is an element that dissolves in the matrix and contributes greatly to improving creep rupture strength at high temperatures. Cr is also an essential element for ensuring oxidation resistance and corrosion resistance at high temperatures. In order to obtain the above effect, the Cr content must be 20.00% or more. However, if the Cr content exceeds 28.00%, the stability of austenite at high temperatures is deteriorated, and creep rupture failure is increased. This leads to a decrease in strength. Therefore, the Cr content is set to 20.00 to 28.00%. The Cr content is preferably 21.00% or more, and more preferably 22.00% or more. Also, the Cr content is preferably 27.00% or less, and more preferably 26.00% or less.
  • Ni 35.00-50.00%
  • Ni is an element that dissolves in the matrix and contributes greatly to improving creep rupture strength at high temperatures.
  • Ni is also an effective element for obtaining austenite, and improves structural stability during long-term use.
  • the Ni content needs to be 35.00% or more.
  • Ni is an expensive element, and if it is contained in a large amount, it will lead to an increase in costs. Therefore, the Ni content is set to 35.00 to 50.00%.
  • the Ni content is preferably 37.00% or more.
  • the Ni content is preferably 39.00% or more, and more preferably 48.00% or less, and more preferably 46.00% or less.
  • W 4.00-10.00%
  • W is an element that dissolves in the matrix and contributes greatly to improving creep rupture strength at high temperatures. To fully exert this effect, the W content must be 4.00% or more. However, even if W is added in excess, the effect is saturated and the creep rupture strength is actually reduced. Furthermore, since W is an expensive element, adding it in excess leads to an increase in costs. Therefore, the W content
  • the W content is set to 4.00 to 10.00%.
  • the W content is preferably 5.00% or more, and more preferably 6.00% or more.
  • the W content is set to 9.00%. It is preferably equal to or less than 8.00%, and more preferably equal to or less than 8.00%.
  • Ti 0.01 ⁇ 1.20% Ti precipitates within grains as fine carbonitrides and contributes to improving creep rupture strength at high temperatures. To obtain this effect, the Ti content must be 0.01% or more. However, if the Ti content is excessive, a large amount of carbonitrides will precipitate, which will lead to a decrease in creep rupture ductility and toughness. Therefore, the Ti content is set to 0.01 to 1.20%.
  • the Ti content is preferably 0.03% or more, and more preferably 0.05% or more.
  • the Ti content is preferably 1.00% or less, and more preferably 0.80% or less. .
  • Nb 0.01 ⁇ 1.00% Nb combines with C or C and N to precipitate within grains as fine carbides or carbonitrides, and contributes to improving creep rupture strength at high temperatures. To obtain this effect, the Nb content must be However, if the Nb content is excessive, a large amount of carbides or carbonitrides will precipitate, which will lead to a decrease in creep rupture ductility and toughness. Therefore, the Nb content should be 0.01% or more.
  • the Nb content is preferably 0.05% or more, and more preferably 0.10% or more.
  • the Nb content is preferably 0.80% or less. It is preferable that the content of C is 0.60% or less, and more preferable that the content of C is 0.60% or less.
  • N 0.0200% or less
  • N is an effective element for stabilizing austenite, if it is contained in excess, a large amount of fine nitrides will precipitate in the grains during use at high temperatures, resulting in a decrease in creep rupture ductility and toughness. Therefore, the N content is set to 0.0200% or less.
  • the N content is preferably 0.0180% or less, and more preferably 0.0150% or less.
  • the N content is preferably 0.0005% or more, and more preferably 0.0008% or more.
  • Al 0.010-0.300% Since Al is an element having a deoxidizing effect, the Al content must be 0.010% or more. However, if the Al content is excessive, the cleanliness of the alloy is significantly deteriorated, and the hot working is difficult. The strength and ductility of the steel will decrease. Therefore, the Al content is set to 0.010 to 0.300%.
  • the Al content is preferably 0.030% or more, and more preferably 0.050% or more.
  • the Al content is preferably 0.250% or less, and more preferably 0.200% or less.
  • B 0.0005-0.0400%
  • B is an element necessary for improving creep rupture strength by segregating to grain boundaries during use at high temperatures to strengthen the grain boundaries and finely disperse grain boundary carbides. For this reason, the B content must be 0.0005% or more. However, if the B content is excessive, not only the weldability but also the hot workability deteriorates. Therefore, the B content
  • the B content is set to 0.0005 to 0.0400%.
  • the B content is preferably 0.0010% or more, and more preferably 0.0020% or more.
  • the B content is set to 0.0300% or less. It is preferable that the content of C is 0.0200% or less, and more preferable that the content of C is 0.0200% or less.
  • O 0.0100% or less
  • O (oxygen) is contained in the alloy as an impurity, and if its content is excessive, it reduces hot workability and further deteriorates toughness and ductility. Therefore, the O content is set to 0.0100% or less.
  • the O content is preferably 0.0080% or less, and more preferably 0.0050% or less.
  • the O content is preferably 0.0005% or more, and more preferably 0.0008% or more.
  • the balance is Fe and impurities.
  • impurities refers to components that are mixed in when the alloy is industrially produced due to various factors in the raw materials such as ores and scraps, and in the manufacturing process, and are acceptable within the range that does not adversely affect the present invention.
  • the austenitic heat-resistant alloy of the present invention may further contain one or more elements selected from Ca, Mg, REM, Co, Cu, Mo, and V in the ranges shown below. Note that these elements are not necessarily essential for the components, so the lower limit of the content is 0%. The reasons for limiting each element are explained below.
  • Ca 0.0100% or less Ca may be contained as necessary because it has the effect of forming a compound with S to reduce the amount of S in the matrix and improving hot workability.
  • the Ca content is 0.0100% or less.
  • the Ca content is preferably 0.0080% or less.
  • the Ca content is preferably 0.0001% or more, more preferably 0.0002% or more, and even more preferably 0.0003% or more.
  • Mg 0.0500% or less Mg, like Ca, forms a compound with S to reduce the amount of S in the matrix and improve hot workability, so it may be included as necessary.
  • the Mg content is set to 0.0500% or less.
  • the Mg content is preferably set to 0.0450% or less.
  • the Mg content is preferably set to 0.0001% or more, more preferably set to 0.0002% or more, and even more preferably set to 0.0003% or more.
  • REM 0.1000% or less REM, like Ca, forms a compound with S to reduce the amount of S in the matrix and improve hot workability, so it may be contained as necessary.
  • the REM content is set to 0.1000% or less.
  • the REM content is preferably 0.0800% or less.
  • the REM content is preferably 0.0001% or more, more preferably 0.0002% or more, and even more preferably 0.0003% or more.
  • REM is a general term for 17 elements in total: Sc, Y, and lanthanides, and the REM content refers to the total content of one or more REM elements.
  • REM is generally contained in misch metal. For this reason, for example, it may be added in the form of misch metal, and the amount of REM may be adjusted to be within the above range.
  • Co 1.000% or less
  • Co has the effect of improving creep rupture strength. That is, Co is an austenite generating element like Ni, and enhances phase stability and contributes to improving creep rupture strength. Therefore, Co may be contained. However, since Co is an extremely expensive element, excessive Co content leads to a significant increase in cost. Therefore, the Co content is set to 1.000% or less.
  • the Co content is preferably 0.800% or less, and more preferably 0.600% or less.
  • the Co content is preferably 0.010% or more, and more preferably 0.050% or more.
  • Cu 1.00% or less
  • Cu has the effect of improving creep rupture strength. That is, Cu, like Ni and Co, is an austenite forming element, and contributes to improving creep rupture strength by increasing phase stability. Therefore, Cu may be contained. However, excessive Cu content leads to a decrease in hot workability. Therefore, the Cu content is set to 1.00% or less.
  • the Cu content is preferably 0.80% or less, and more preferably 0.60% or less.
  • the Cu content is preferably 0.01% or more, and more preferably 0.05% or more.
  • Mo 1.000% or less Mo has the effect of improving creep rupture strength. That is, Mo has the effect of improving creep rupture strength at high temperatures by dissolving in the matrix. Therefore, Mo may be contained. However, if Mo is contained in excess, the stability of austenite decreases, which leads to a decrease in creep rupture strength. Therefore, the Mo content is set to 1.000% or less.
  • the Mo content is preferably 0.800% or less, and more preferably 0.700% or less.
  • the Mo content is preferably 0.010% or more, and more preferably 0.050% or more.
  • V 0.500% or less
  • V has the effect of improving creep rupture strength. That is, like Nb, V combines with C or C and N to form fine carbides or carbonitrides, and has the effect of improving creep rupture strength. Therefore, V may be contained. However, if V is contained in excess, a large amount of carbides or carbonitrides will precipitate, resulting in a decrease in creep rupture ductility. Therefore, the V content is set to 0.500% or less.
  • the V content is preferably 0.400% or less, and more preferably 0.300% or less. On the other hand, if it is desired to obtain the above effect, the V content is preferably 0.010% or more, and more preferably 0.050% or more.
  • each symbol is defined as follows, and each element symbol in the above formula represents the content (mass %) of each element contained in the alloy member.
  • CrER Cr content (mass%) in the precipitate obtained by extraction residue analysis
  • W ER W content (mass%) in the precipitate obtained by extraction residue analysis
  • FeER Fe content (mass%) in the precipitate obtained by extraction residue analysis
  • NiER Ni content (mass%) in the precipitate obtained by extraction residue analysis
  • the value on the right hand side of equation (i) is less than 97.50, the amount of Cr, W, Fe, and Ni dissolved in solid solution is insufficient, and creep rupture strength cannot be improved. Therefore, the value on the right hand side of equation (i) must be 97.50 or more. It is preferable that the value on the right hand side of equation (i) is 98.00 or more, and more preferably 98.50 or more.
  • the content (mass%) of each element in the precipitate analyzed as the electrolytic extraction residue in the above formula can be measured by the following procedure. Specifically, about 0.4 g of a sample is electrolyzed at a current value of 20 mA/ cm2 using 10% acetylacetone-1% tetramethylammonium chloride/methanol. The electrolyzed sample solution is then filtered through a 0.2 ⁇ m filter, and the residue is decomposed with an acid. Then, the amount (mass%) of the above elements analyzed as the electrolytic extraction residue is calculated using an ICP (inductively coupled plasma) emission spectrometer.
  • ICP inductively coupled plasma
  • t is defined as the thickness (mm) of the alloy part
  • D is defined as the average grain size at the center of the thickness of the alloy part.
  • the average grain size D is preferably 6.0 or less, and more preferably 5.0 or less.
  • the average grain size D is preferably -2.0 or more, more preferably -1.0 or more, and even more preferably 0 or more.
  • the average grain size D is measured in accordance with ASTM E112 (2013). Specifically, a test piece for microstructure observation is taken so that the cross section perpendicular to the longitudinal direction of the alloy member is the observation surface, and the observation surface is mirror-polished. After polishing, the test piece is corroded with mixed acid and observed under an optical microscope. Ten fields of view are observed so that the center of the thickness of the alloy member is the center of the field of view. Then, the grain size of each field of view is obtained by the comparison method specified in ASTM E112, and the average value is taken as the average grain size D. In this case, the standard observation magnification is 100 times, and depending on the grain size, it is 200 times or 400 times.
  • a correction value Q defined by the following formula (I) is used to perform correction in accordance with ASTM E112 (2013).
  • Q 6.64log 10 (M/100)...(I)
  • M is the observation magnification.
  • the austenitic heat-resistant alloy member of the present invention may be, for example, an alloy pipe or an alloy plate.
  • the wall thickness is preferably 1 mm or more, or 5 mm or more, and is preferably 100 mm or less, 80 mm or less, 65 mm or less, or 55 mm or less.
  • the plate thickness is preferably 1 to 100 mm.
  • Manufacturing method There is no particular limitation on the manufacturing method of the austenitic heat-resistant alloy member of the present invention, but for example, a steel ingot or slab having the above-mentioned chemical composition is subjected to hot working, and then, if necessary, further subjected to a different hot working method such as hot extrusion, followed by a solution heat treatment. Furthermore, if necessary, cold working may be performed.
  • the solution heat treatment conditions must be strictly controlled, taking into account the thickness of the component. Specifically, the solution heat treatment temperature T must be 1180-1250°C, and the following formulas (iii) and (iv) must be satisfied. After solution heat treatment, it is desirable to water-cool the alloy component.
  • the solution heat treatment temperature T is less than 1180°C, recrystallization does not occur, so the strain caused by processing cannot be eliminated and creep rupture ductility deteriorates. In addition, Cr, W, Fe, and Ni cannot be fully dissolved, making it impossible to ensure good creep rupture strength. On the other hand, if the solution heat treatment temperature T is more than 1250°C, the creep rupture ductility deteriorates due to the coarsening of austenite grains. For this reason, the solution heat treatment temperature T is set to 1180-1250°C.
  • the solution heat treatment time tr is set to 10 min or more.
  • Austenitic heat-resistant alloys 1 to 38 having the chemical compositions shown in Tables 1 and 2 were melted in a laboratory to produce ingots. The ingots were then formed by hot forging and rolling, and then subjected to solution heat treatment under the conditions shown in Tables 3 and 4 to obtain alloy pipes with the wall thicknesses shown in Tables 3 and 4 (Test Nos. 1 to 50).
  • ⁇ About electrolytic extraction residue The contents (mass%) of Cr, W, Fe, and Ni in the precipitate analyzed as the electrolytic extraction residue were measured by the following procedure. Specifically, about 0.4 g of the sample was electrolyzed at a current value of 20 mA/ cm2 using 10% acetylacetone-1% tetramethylammonium chloride/methanol. The electrolyzed sample solution was then filtered through a 0.2 ⁇ m filter, and the residue was decomposed with an acid. The amounts (mass%) of the above elements analyzed as the electrolytic extraction residue were then calculated using an ICP emission spectrometer.
  • the average grain size D was measured in accordance with ASTM E112 (2013). Specifically, a test piece for microstructure observation was taken so that the cross section perpendicular to the longitudinal direction of the alloy pipe was the observation surface, and the observation surface was mirror-polished. After polishing, the test piece was corroded with mixed acid and observed under an optical microscope. Ten fields of view were observed so that the center of the thickness of the alloy pipe was the center of the field of view. Then, the grain size of each field of view was obtained by the comparison method specified in ASTM E112, and the average value was taken as the average grain size D. In this case, the standard observation magnification was 100 times, and depending on the grain size, it was 200 times or 400 times.
  • Test Nos. 1 to 43 which satisfy all the provisions of the present invention, showed good results in both creep rupture strength and creep rupture ductility.
  • the solution heat treatment temperature T was low, so recrystallization did not occur and creep rupture ductility deteriorated.
  • the LMP was less than the left side value of formula (iii), Cr, W, Fe, and Ni could not be fully dissolved, and creep rupture strength deteriorated.
  • the austenitic heat-resistant alloy member of the present invention is excellent in both long-term creep rupture strength and creep rupture ductility, and is therefore suitable for use as a material for superheater tubes and reheater tubes of power generation boilers.

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Abstract

Cet élément en alliage résistant à la chaleur à base d'austénite a une composition chimique contenant, en % en masse, 0,010 à 0,150 % de C, 2,00 % ou moins de Si, 2,00 % ou moins de Mn, 0,0400 % ou moins de P, 0,0100 % ou moins de S, 20,00 à 28,00 % de Cr, 35,00 à 50,00 % de Ni, 4,00 à 10,00 % de W, 0,01 à 1,20 % de Ti, 0,01 à 1,00 % de Nb, 0,0200 % ou moins de N, 0,010 à 0,300 % de Al, 0,01 à 1,20 % de B, et 0,0100 % ou moins de O, la partie restante étant Fe et des impuretés, et l'élément satisfait à 97,50 ≤ (Cr+W+Fe+Ni)-(CrER+WER+FeER+NiER) et -2.2×10-5×t3+2,1 ≤ D.
PCT/JP2024/008081 2023-03-07 2024-03-04 Élément en alliage résistant à la chaleur à base d'austénite Pending WO2024185746A1 (fr)

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KR1020257032405A KR20250154483A (ko) 2023-03-07 2024-03-04 오스테나이트계 내열 합금 부재
JP2025505330A JPWO2024185746A1 (fr) 2023-03-07 2024-03-04
CN202480016802.3A CN120835936A (zh) 2023-03-07 2024-03-04 奥氏体系耐热合金构件

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JP2016037664A (ja) * 2014-08-06 2016-03-22 新日鐵住金株式会社 オーステナイト系耐熱合金部材

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JP5998950B2 (ja) 2013-01-24 2016-09-28 新日鐵住金株式会社 オーステナイト系耐熱合金部材
JP6736964B2 (ja) 2016-05-16 2020-08-05 日本製鉄株式会社 オーステナイト系耐熱合金部材
US20200232081A1 (en) 2017-02-09 2020-07-23 Nippon Steel Corporation Austenitic Heat Resistant Alloy and Method for Producing Same

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JP2014001437A (ja) * 2012-06-20 2014-01-09 Nippon Steel & Sumitomo Metal オーステナイト系耐熱部材
JP2014034725A (ja) * 2012-08-10 2014-02-24 Nippon Steel & Sumitomo Metal オーステナイト系耐熱合金部材
JP2014145109A (ja) * 2013-01-29 2014-08-14 Nippon Steel & Sumitomo Metal オーステナイト系耐熱合金部材およびオーステナイト系耐熱合金素材
JP2016037664A (ja) * 2014-08-06 2016-03-22 新日鐵住金株式会社 オーステナイト系耐熱合金部材

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