CN113544295A - 超级奥氏体材料 - Google Patents
超级奥氏体材料 Download PDFInfo
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- CN113544295A CN113544295A CN201980092769.1A CN201980092769A CN113544295A CN 113544295 A CN113544295 A CN 113544295A CN 201980092769 A CN201980092769 A CN 201980092769A CN 113544295 A CN113544295 A CN 113544295A
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- superaustenitic
- nitrogen
- limit
- chromium
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- 239000000463 material Substances 0.000 title claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 40
- 239000000956 alloy Substances 0.000 claims abstract description 40
- 239000011651 chromium Substances 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000010955 niobium Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 7
- 239000011574 phosphorus Substances 0.000 claims abstract 7
- 238000005260 corrosion Methods 0.000 claims description 28
- 230000007797 corrosion Effects 0.000 claims description 28
- 238000001514 detection method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 238000003754 machining Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 17
- 238000005266 casting Methods 0.000 claims 1
- 238000010273 cold forging Methods 0.000 claims 1
- 229910000734 martensite Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 description 21
- 239000010959 steel Substances 0.000 description 21
- 238000001556 precipitation Methods 0.000 description 5
- 238000005482 strain hardening Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 229910001199 N alloy Inorganic materials 0.000 description 3
- GJPVPJBNBCITNZ-UHFFFAOYSA-N [N].[Mn].[Cr] Chemical compound [N].[Mn].[Cr] GJPVPJBNBCITNZ-UHFFFAOYSA-N 0.000 description 3
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical group [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910019932 CrNiMo Inorganic materials 0.000 description 1
- JXMHJWIFEMFZDH-UHFFFAOYSA-N [Mn].[Mo].[Cr] Chemical compound [Mn].[Mo].[Cr] JXMHJWIFEMFZDH-UHFFFAOYSA-N 0.000 description 1
- MPQIMOMLTNCGNB-UHFFFAOYSA-N [N].[Mn].[Ni].[Cr] Chemical compound [N].[Mn].[Ni].[Cr] MPQIMOMLTNCGNB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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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
- C22C38/18—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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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C21D6/00—Heat treatment of ferrous alloys
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- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/10—Modifying the physical properties of iron or steel by deformation by cold working of the whole cross-section, e.g. of concrete reinforcing bars
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- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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Abstract
本发明涉及一种超级奥氏体材料,由具有以下成分的合金组成(所有值均以wt%表示):元素碳(C)0.01‑0.50,硅(Si)<0.5,锰(Mn)0.1‑5.0,磷(P)<0.05,硫(S)<0.005,铁(Fe)残余量,铬(Cr)23.0‑33.0,钼(Mo)2.0‑5.0,镍(Ni)10.0‑20.0,钒(V)<0.5,钨(W)<0.5,铜(Cu)0.50‑5.0,钴(Co)<5.0,钛(Ti)<0.1,铝(Al)<0.2,铌(Nb)<0.1,硼(B)<0.01,氮(N)0.40‑0.90。
Description
技术领域
本发明涉及一种超级奥氏体材料及其制造方法。
背景技术
这种材料可以用于例如化工厂建设、海洋环境、油田或气田技术中。
然而,这种材料的一个要求是它们还必须抗腐蚀,特别是抗在氯化物浓度高的介质中或者硫酸条件下的腐蚀。
这种材料可以例如从CN 107876562 A、CN 104195446 A或DE 43 42 188中知晓。
EP 1 069 202 A1公开了一种具有高屈服强度、高强度和延展性的顺磁耐腐蚀奥氏体钢,其应耐腐蚀,特别是在具有氯化物浓度高的介质中;该钢应含有0.6wt%至1.4wt%的氮、17wt%至24wt%的铬,以及锰和氮。
WO 02/02837 A1公开了一种用于油田技术中在高氯化物浓度的介质中使用的耐腐蚀材料。在这种情况下,它是铬-镍-钼超级奥氏体,其具有相对较低的氮浓度,但具有非常高的铬浓度和非常高的镍浓度。
与前面提到的铬-锰-氮钢相比,这些铬-镍-钼钢通常具有更好的腐蚀行为。总的来说,铬-锰-氮钢构成了一种相当便宜的合金成分,但它提供了强度、韧性和耐腐蚀性的优异组合。上述铬-镍-钼钢的耐腐蚀性能明显高于铬-锰-氮钢,但由于镍含量非常高,因此成本也高得多。
耐腐蚀性的特征值包括所谓的PREN16值;也习惯上通过MARC来定义所谓的点蚀当量数;超级奥氏体被确定为具有α>42的PREN16,其中PREN=%Cr+3.3x%Mo+16x%N。
用于描述此类钢的耐点蚀的已知MARC公式如下:MARC=%Cr+3.3x%Mo+20x%N+20x%C–0.25x%Ni–0.5x%Mn。
类似的钢种也可用作潜艇的造船钢;在这种情况下,这些是铬-镍-锰-氮钢,它们也与铌合金化以稳定碳,但这会降低缺口杆的韧性。基本上,这些钢含有更少的锰,因此具有相对好的耐腐蚀性,但它们还没有达到纯高氮合金CrMnN钢的强度。
为实现高耐腐蚀性,已知的常见超级奥氏体的钼浓度>4%。但是钼会增加偏析可能性,从而增加对沉淀的敏感性(特别是sigma相或chi相),这会导致这些合金需要均质化退火,并且钼含量高于6%时,需要重熔减少偏析。
发明内容
本发明的目的是制造一种超级奥氏体、高强度和坚韧的材料,该材料可以以相对简单和廉价的方式生产并且特别适用于腐蚀性的硫酸环境。
所述目的是通过具有权利要求1的特征的材料来实现的。在从属权利要求中公开了有利的改进。
本发明的另一个目的是创造一种制造该材料的方法。
所述目的是通过权利要求18的特征来实现的。在引用独立权利要求的从属权利要求中公开了有利的改进。
当下文给出%值时,它们总是以wt%(重量百分比)表示。
根据本发明,所述材料旨在用于造船和化工厂建设或两者的结合,在这种情况下特别是用于海船的烟道气脱硫系统中。它还可以用于所有其他可能会发生腐蚀的区域,特别是由于硫酸或酸性气体而引起的腐蚀。在这方面,即使在可选的冷成型之后,所述材料也具有完全奥氏体结构。在应变硬化后,屈服强度应当是Rp0.2>1000MPa。
根据本发明的合金尤其包含以下元素(所有值以wt%表示):
利用这种合金,不同已知钢种的积极性能以协同和惊人的方式结合在一起。。
基本上,根据本发明的钢应该以无沉淀状态存在,因为沉淀对韧性和耐腐蚀性有负面影响。在根据本发明的合金中,碳含量特别限于0.50%。同时,在合金中特意添加了铜含量。
使用根据本发明的合金,特别令人惊讶的是可以建立非常高的氮值,这对强度来说是非常好的;这些氮值令人惊讶地高于我们从技术文献中尽可能找出的值。根据经验方法,在没有PESR的情况下,根据本发明的合金的高氮浓度根本无法添加到合金中,参见图4。
下面详细描述各元素以及适当的其他合金组分。所有与合金成分有关的指标均以重量百分比(wt%)表示。各个合金元素的上限和下限可以在权利要求的范围内自由组合。
碳可以以高达0.50%的浓度存在于根据本发明的钢合金中。碳是一种奥氏体促进剂,并且在高机械特性值方面具有有益效果。为了避免碳化物沉淀,碳含量应设定在0.01-0.25%之间,优选0.01-0.10%之间。
硅以高达0.5%的浓度提供,主要用于对钢进行脱氧。所述指定的上限可靠地避免了金属间相的形成。由于硅也是铁氧体促进剂,因此在这点上也是在安全范围内选择上限。特别地,可以以0.1-0.4%的浓度提供硅。
锰的浓度为0.1-5%。与根据现有技术的材料相比,这是极低的值。到目前为止,已经假定高氮溶解度需要大于19%,优选大于20%的锰浓度。使用本合金,令人惊讶地发现,即使使用根据本发明的非常低的锰浓度,也能实现大于根据专家普遍共识可能达到的氮溶解度。此外,到目前为止,已经假定良好的耐腐蚀性伴随着非常高的锰浓度,但是根据本发明,其结果表明,由于无法解释的协同效应,上述假定对于本合金显然是不必要的。锰的下限可以选择为0.1%、0.5%、1.0%、2.0%或2.5%。锰的上限可以选择为3.0%、3.5%、4.0%、4.5%或5.0%。
在17%或更高的浓度下,铬对于更高的耐腐蚀性是必要的。根据本发明,需要至少23%且至多33%的铬浓度。到目前为止,由于铬是铁氧体稳定元素之一,因此假设浓度高于23%会对磁导率产生不利影响。相比之下,在根据本发明的合金中,已经确定即使在高于23%的非常高的铬浓度下也不会对本合金的磁导率产生负面影响,而是如上已知的以最佳方式影响耐点蚀性和应力裂纹腐蚀性。铬的下限可以选择为23%、24%、25%或26%。铬的上限可以选择为28%、29%、30%、31%或32%。
钼是一种通常对耐腐蚀性有显著贡献的元素,特别是对耐点蚀性有显著贡献;镍的作用加强了钼的作用。根据本发明,添加2.0%-5.0%的钼。还证明>5%和特别是>6%的Mo浓度会导致强烈的偏析行为,这会增加sigma相沉淀的敏感性,从而反过来会降低耐腐蚀性。钼的下限可选择为2.0%、2.2%、2.3%、2.4%、2.5%、3.0%、3.2%、3.3%、3.4或3.5%。钼的上限可选择为4.4%、4.5%、4.6%、4.7%、4.8%、4.9%或5.0%。
根据本发明,钨的浓度小于0.5%并且有助于提高耐腐蚀性。钨的上限可以选择为0.5%、0.4%、0.3%、0.2%、0.1%或低于检测限(即没有任何有意添加到合金中的含量)。
根据本发明,镍的浓度为10%至20%,这在含有氯化物的介质中实现了高应力裂纹耐腐蚀性。镍的下限可以选择为10%、11%、12%、13%、14%或15%。镍的上限可以选择为17%、18%或19%。
众所周知,在合金中加入Cu>0.5%能使奥氏体不锈钢产品的耐硫酸性提高。同时,文献还提到,Cu增加了对不需要的Cr2N沉淀的析出的敏感性,这大大降低了腐蚀性能,尤其是在高氮合金钢中。根据本发明,即使Cu浓度>0.5,优选>1.0,以及>0.40%的高N浓度,也可以产生无Cr2N的结构。然而,这种效果在一定量后达到饱和。根据本发明,铜的上限被选择为<5%,优选<3%或<2.5%,特别是<2%。铜的下限可选择为0.6%、0.7%、0.8%、0.9%、1%或1.1%。尤其适合的一种应用领域是烟气洗涤,尤其是在例如远洋船舶中。使用这些浓度,一方面可以实现对硫酸和酸性气体腐蚀的良好耐受性,另一方面,可以通过如上所述的整个合金基本上防止上述氮化铬的沉淀。
钴可以以高达5%的浓度存在,特别是为了代替镍。钴的上限可以选择为5%、3%、1%、0.5%、0.4%、0.3%、0.2%、0.1%或低于检测限(即没有任何有意添加到合金中的含量)。
所包含的氮浓度为0.40%-0.90%,以确保高强度。氮也有助于改进耐腐蚀性,并且是一种强大的奥氏体促进剂,这就是为什么其浓度大于0.40%是有益的。为了避免含氮沉淀,特别是氮化铬,氮的上限设定为0.90%;事实证明,尽管锰含量非常低,但与已知合金相比,可以实现合金中的这些高氮浓度。一方面由于良好的氮溶解度,由较高氮浓度(尤其是高于0.90%的氮浓度)导致的缺点,作为PESR路线的一部分的由压力引起的氮含量增加,实际上已不是问题。由于根据本发明的通过铬和氮补偿的低钼含量,该路线也是不必要的。如果氮与碳的比大于15,则特别有利。氮的下限可以选择为0.40%或0.45%。氮的上限可选择为0.90%、0.80%、0.70%、0.65%或0.60%。
根据一般现有技术(V.G.Gavriljuk和H.Berns的“High Nitrogen Steels(高氮钢)”,第264页,1999),像现在这样在大气压下熔化的CrNiMn(Mo)奥氏体钢达到0.2%到0.5%的氮浓度。只有铬-锰-钼奥氏体能达到0.5%到1%的氮浓度。
根据本发明,有利的是,与所有预期相反,无需压力引起的氮含量增加,这通常是实现这种浓度所必需的,即可实现所述高氮浓度。
其结果是,根据本发明的方法也是廉价的,因为不需要昂贵的压力引起的氮含量增加,这也使得可以省略与之相关的重熔过程。
此外,可以包含硼、铝和硫作为额外的合金成分,但它们只是可选的。本发明钢合金不一定含有合金成分钒和钛。尽管这些元素确实能对氮的溶解度作出积极贡献,但是即使在它们不存在的情况下也可以提供根据本发明的高氮溶解度。
根据本发明的合金不应含有铌,因为它会降低韧性,并且历史上仅用于结合碳,这对于根据本发明的合金来说不是必需的。高达0.1%的铌的浓度仍然可以容忍,但不应超过不可避免的杂质的浓度。
附图说明
以下将基于附图以示例的方式阐述本发明。在附图中:
图1:合金元素表;
图2:示出了生产路线及其替代方案的示意图;
图3是根据本发明的概念内的三种不同合金的表格,以及氮含量的所得实际值与根据流行学派的这种合金的理论氮溶解度相比较的表格。
图4:示出了图3中提到的示例在可能的应变硬化之前的强度。
具体实施方式
将各组分在大气条件下熔化,然后进行二次冶金处理。然后,铸造块,然后立即热锻。在本发明的上下文中,“之后立即”表示不进行额外的重熔过程,例如电渣重熔(ESR)或压力电渣重熔(PESR)。
根据本发明,如果适用以下关系是有利的:
MARCopt:40<%Cr+3.3x%Mo+20x%C+20x%N–0.5x%Mn
优化MARC公式实现以下效果,即已经发现,镍的其他惯用扣除不适用于根据本发明的系统并且40的极限值是必要的。
然后根据需要进行冷成型步骤,其中发生应变硬化,然后是机械加工,特别是可以是车削、铣削或磨削。
图2示出了用于生产根据本发明的合金组合物的可能加工路线的示例。下面将通过示例的方式描述一种可能的路线。在真空感应熔炼装置(VID)中,熔融金属同时进行熔化和二次冶金处理。然后将熔融金属倒入铸锭模具中,并在其中凝固成块。然后在多个步骤中热成型。例如,它们在旋锻机中预锻,并在多线轧机中达到最终尺寸,或在两辊轧机机架中轧制成板状。根据要求,还可以进行热处理步骤。
为了进一步提高强度,还可以进行冷成型步骤。
根据本发明的超奥氏体材料不仅可以通过所描述的生产路线(特别是图2所示)来生产,根据本发明的合金的有利性能也可以通过使用粉末冶金的生产路线来实现。
图3示出了根据本发明的合金组合物内的三种不同变型,它们具有分别测量的氮值,这些变型是用与根据本发明的合金相关的根据本发明的方法生产的。这些非常高的氮浓度与在右列中显示的根据来自“On restricting aspects in the production of non-magnetic Cr-Mn-N-alloy steels,Saller,2005”的Stein、Satir、Kowandar和Medovar的氮溶解度形成对比。在Medovar中,指示了不同的温度。然而,很明显,所述的高氮值远远超过了理论预期值。
这甚至更令人惊讶,因为对于根据本发明的合金,所采用的路线实际上不能证明高氮溶解度的预期是合理的,特别是因为对氮溶解度具有非常积极影响的锰含量与已知的相应合金相比急剧降低。
因此,本发明的优点在于,已生产出具有提高的耐腐蚀性和低镍含量的奥氏体高强度材料,其同时表现出高强度和顺磁性行为。即使在冷成型后,仍存在完全奥氏体结构,因此可以成功地将廉价的CrMnN钢的积极性能与CrNiMo钢的技术优异的腐蚀相关性能成功结合起来。
本发明的一个特殊特征在于,由于氮含量高,应变硬化速率高于其他超级奥氏体,从而能够达到2000MPa的抗拉强度(Rm)。因此,作为最后的生产步骤,可以通过冷轧或其他具有高变形率的冷成型工艺实现高应变硬化。
根据本发明的材料的典型应用领域是造船和化工厂建设或两者的组合,在这种情况下特别是在海船的烟气脱硫系统中,但也可以用于尤其预期存在硫酸腐蚀的所有其他领域中。
特别是在需要非常高强度的应用中,如上所述,可以通过冷变形进一步提高强度。
Claims (22)
1.一种超级奥氏体材料,其由具有以下合金元素(所有值以wt%表示)以及不可避免的杂质的合金组成:
元素
碳 (C) 0.01 - 0.50
硅 (Si) < 0.5
锰 (Mn) 01 - 5.0
磷 (P) < 0.05
硫 (S) < 0.005
铁 (Fe) 残余量
铬 (Cr) 23.0 - 33.0
钼 (Mo) 2.0 - 5.0
镍 (Ni) 10.0 - 20.0
钒 (V) < 0.5
钨 (W) < 0.5
铜 (Cu) 0.50 - 5.0
钴 (Co) < 5.0
钛 (Ti) < 0.1
铝 (Al) < 0.2
铌 (Nb) < 0.1
硼 (B) < 0.01
氮 (N) 0.40 - 0.90。
2.根据权利要求1所述的超级奥氏体材料,
其特征在于,所述合金由以下元素以及不可避免的杂质组成(所有值均以wt%表示):
元素
碳 (C) 0.01 - 0.30
硅 (Si) < 0.5
锰 (Mn) 0.5 - 4.0
磷 (P) < 0.05
硫 (S) < 0.005
铁 (Fe) 残余量
铬 (Cr) 24.0 - 30.0
钼 (Mo) 3.0 - 5.0
镍 (Ni) 14.0 - 19.0
钒 (V) < 0.3
钨 (W) < 0.1
铜 (Cu) 0.75 - 3.5
钴 (Co) < 0.5
钛 (Ti) < 0.05
铝 (Al) < 0.1
铌 (Nb) < 0.025
硼 (B) < 0.005
氮 (N) 0.40 - 0.70。
3.根据权利要求1或2所述的超级奥氏体材料,
其特征在于,所述合金由以下元素以及不可避免的杂质组成(所有值均以wt%表示):
元素
碳 (C) 0.01 - 0.10
硅 (Si) < 0.5
锰 (Mn) 1.0 - 4.0
磷 (P) < 0.05
硫 (S) < 0.005
铁 (Fe) 残余量
铬 (Cr) 26.0 - 29.0
钼 (Mo) 3.5 - 4.5
镍 (Ni) 15.0 - 18.0
钒 (V) 低于检测限
钨 (W) 低于检测限
铜 (Cu) 1.0 - 2.0
钴 (Co) 低于检测限
钛 (Ti) 低于检测限
铝 (Al) < 0.1
铌 (Nb) 低于检测限
硼 (B) < 0.005
氮 (N) 0.45 - 0.60。
4.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
所述材料的生产为通过对熔融金属进行二次冶金处理、浇铸成块、热成型、可能地冷锻,以及如果需要,进一步进行机械加工。
5.根据前述权利要求任一项所述的超级奥氏体材料,其特征在于,
屈服强度Rp0.2为> 500 MPa。
6.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
室温下纵向缺口杆冲击功Av为 > 300 J。
7.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
冷变形后,材料是完全奥氏体的,即没有变形诱导的马氏体。
8.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
锰的上限为 3.0%、3.5%、4.0%、4.5% 或 5.0%,以及
下限为0.1%、0.5%、1.0%、2.0%或2.5%。
9.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
铬的上限为 28%、29%、29.8 或 31.5%,以及
下限为23.2%、24%、25%或26%。
10.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
钼的上限为 4.4%、4.5%、4.6%、4.7%、4.8%、4.9%或 5.0%,以及
下限为 2.05%、2.1%、2.2%、2.3%、2.4%、2.5%、3.0%、3.2%、3.3%、3.4% 或 3.5%。
11.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
镍的上限为 16.8%、17%、18% 或 19%,以及
下限为10.2%、11%、12%、13%、14%或15%。
12.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
氮的上限为 0.60%、0.65%、0.70%、0.75%、0.80%、0.85% 或 0.88%,以及
下限为0.46%、0.50%或0.55%。
13.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
钴以< 5%、< 1%、< 0.5%、< 0.4%、< 0.3%、< 0.2%、< 0.1% 或低于检测限存在。
14.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
铜的上限为5%、4.5%、4.0%、3.5%、3.0%、2.5% 或 2%,以及
下限为0.60%、0.70%、0.80%、0.90%、1.0 %或1.1 %。
15.根据前述权利要求任一项所述的超级奥氏体材料,
其特征在于,
钨以< 0.5%、< 0.3%、< 0.2%、< 0.1% 或低于检测限存在。
16.一种用于制造根据前述权利要求之一所述的材料的方法,
其特征在于,
所述合金由以下元素以及不可避免的杂质组成(所有值均以wt%表示):
元素
碳 (C) 0.01 - 0.50
硅 (Si) < 0.5
锰 (Mn) 0.1 - 5.0
磷 (P) < 0.05
硫 (S) < 0.005
铁 (Fe) 残余量
铬 (Cr) 23.0 - 33.0
钼 (Mo) 2.0 - 5.0
镍 (Ni) 10.0 - 20.0
钒 (V) < 0.5
钨 (W) < 0.5
铜 (Cu) 0.50 - 5.0
钴 (Co) < 5.0
钛 (Ti) < 0.1
铝 (Al) < 0.2
铌 (Nb) < 0.1
硼 (B) < 0.01
氮 (N) 0.40 - 0.90,
以上被熔融,然后进行二次冶金加工,然后将所得合金浇铸成块并使其凝固,之后立即加热并进行热成型,产品优选经历额外的冷成型和后续机械加工。
17.根据权利要求18所述的制造材料的方法,
其特征在于,
所述合金由以下元素以及不可避免的杂质组成(所有值均以wt%表示):
元素
碳 (C) 0.01 - 0.30
硅 (Si) < 0.5
锰 (Mn) 0.5 - 4.0
磷 (P) < 0.05
硫 (S) < 0.005
铁 (Fe) 残余量
铬 (Cr) 24.0 - 30.0
钼 (Mo) 3.0 - 5.0
镍 (Ni) 14.0 - 19.0
钒 (V) < 0.3
钨 (W) < 0.1
铜 (Cu) 0.75 - 3.5
钴 (Co) < 0.5
钛 (Ti) < 0.05
铝 (Al) < 0.1
铌 (Nb) < 0.025
硼 (B) < 0.005
氮 (N) 0.40 - 0.70。
18.根据权利要求18或19所述的制造材料的方法,
其特征在于,
所述合金由以下元素以及不可避免的杂质组成(所有值均以wt%表示):
元素
碳 (C) 0.01 - 0.10
硅 (Si) < 0.5
锰 (Mn) 1.0 - 4.0
磷 (P) < 0.05
硫 (S) < 0.005
铁 (Fe) 残余量
铬 (Cr) 26.0 - 29.0
钼 (Mo) 3.5 - 4.5
镍 (Ni) 15.0 - 18.0
钒 (V) 低于检测限
钨 (W) 低于检测限
铜 (Cu) 1.0 - 2.0
钴 (Co) 低于检测限
钛 (Ti) 低于检测限
铝 (Al) < 0.1
铌 (Nb) 低于检测限
硼 (B) < 0.005
氮 (N) 0.45 - 0.60。
19.根据权利要求16-18任一项所述的方法,
其特征在于,
热变形分成几个子步骤进行。
20.根据权利要求16-19任一项所述的方法,
其特征在于,
在热变形子步骤之间,所述产品被重新加热,并且在最后的热变形步骤之后,根据需要进行固溶退火。
21.根据权利要求16-20任一项所述的方法,
其特征在于,
在最后的热变形步骤和任选的固溶退火之后,进行冷成形步骤,以实现抗拉强度Rm >1000 MPa,特别是Rm > 2000 MPa。
22.根据权利要求1至15中任一项所述的材料的用途,所述材料特别是采用根据权利要求16至21中任一项所述的方法生产,用于暴露于硫酸腐蚀的系统和系统部件,尤其是在烟道气脱硫系统中。
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CN115992330A (zh) * | 2023-02-17 | 2023-04-21 | 东北大学 | 一种高氮低钼超级奥氏体不锈钢及其合金成分优化设计方法 |
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CN115261718B (zh) * | 2022-03-28 | 2023-06-06 | 江西宝顺昌特种合金制造有限公司 | 一种超级奥氏体不锈钢s34565板材及其制备方法 |
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Application publication date: 20211022 |