CN103764388A - 冶金结合的不锈钢 - Google Patents
冶金结合的不锈钢 Download PDFInfo
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- CN103764388A CN103764388A CN201280041804.5A CN201280041804A CN103764388A CN 103764388 A CN103764388 A CN 103764388A CN 201280041804 A CN201280041804 A CN 201280041804A CN 103764388 A CN103764388 A CN 103764388A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 144
- 239000010935 stainless steel Substances 0.000 title claims abstract description 141
- 239000011651 chromium Substances 0.000 claims abstract description 131
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 130
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 129
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000000203 mixture Substances 0.000 claims abstract description 94
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 25
- 239000010959 steel Substances 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 57
- 108010041952 Calmodulin Proteins 0.000 claims description 49
- 102000000584 Calmodulin Human genes 0.000 claims description 46
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 238000004080 punching Methods 0.000 claims description 28
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- 239000010962 carbon steel Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- 238000000151 deposition Methods 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000005498 polishing Methods 0.000 description 9
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- 239000002245 particle Substances 0.000 description 7
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- 238000009792 diffusion process Methods 0.000 description 5
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- 239000011573 trace mineral Substances 0.000 description 5
- 235000013619 trace mineral Nutrition 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000005254 chromizing Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005244 galvannealing Methods 0.000 description 1
- -1 industry is typical Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
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- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/001—Interlayers, transition pieces for metallurgical bonding of workpieces
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
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- B23K35/0266—Rods, electrodes, wires flux-cored
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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- B23K35/308—Fe as the principal constituent with Cr as next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B23K35/3053—Fe as the principal constituent
- B23K35/308—Fe as the principal constituent with Cr as next major constituent
- B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- General Chemical & Material Sciences (AREA)
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Abstract
一种具有不锈钢外部的钢模;所述钢模包括含有至少55重量%铁的核心区域,所述核心区域冶金结合到由不锈钢区域和结合区域构成的不锈钢涂层。所述不锈钢区域可以具有约1微米至约250微米的厚度和跨越所述不锈钢区域厚度的大约一致的不锈钢组合物。所述不锈钢组合物包括铁和约10重量%至约30重量%铬的掺合物。所述结合区域位于所述不锈钢区域和所述核心区域之间,具有大于1微米并且小于所述不锈钢区域厚度的厚度,并且具有结合组合物。所述结合组合物包括铁和铬的掺合物,具有大约等于所述不锈钢区域铬浓度的、邻近不锈钢区域的铬浓度,并且具有含有小于约5重量%铬的、邻近核心区域的铬浓度。
Description
技术领域
本公开内容涉及冶金结合到并负载不锈钢外层的非不锈钢产品。
背景技术
钢是世界上最普遍存在的结构材料之一。遗憾的是,钢易于氧化及因而导致的结构性和装饰性失效。已经开发了多种技术以尝试提供用于钢的防护涂层,这些技术包括镀锌、镀锌退火(galvannealing)、铬化处理(chromizing)、包层(cladding)、涂漆等。
一个保护钢的好的方法是在钢产品的外部提供不锈钢组合物。铬化处理是一种在钢的表面生产铬-铁合金及由此形成的不锈钢的常见方法。对铁铬化处理包括热沉积-扩散法,铬通过热沉积-扩散法扩散到钢中并在钢基体中产生变化的铬浓度。通常地,所述基体的表面具有最高的铬浓度并且铬浓度随着进入基体的距离的增加而减小。铬浓度通常遵循典型的扩散函数,也就是说,铬浓度随离开基体的距离而指数地降低。其它的铬化处理产品,如描述于美国专利3,312,546中的那些,包括具有20%以上的铬浓度的扩散涂层,该铬浓度随进入基体的距离而线性地降低(参见图1)。这些高铬含量的涂层看来是包含由主体基体(bulk substrate)负载的含铬材料的箔或层。
随进入基体的深度而增长的铬浓度可以影响材料的耐腐蚀性。也就是说,表面的磨损连续地产生具有更低的铬浓度的新层,容易理解的是,所述新层具有比初始表面小的耐腐蚀性。由于铬化的表面中可变的铬浓度引起的这种不期望的效果,已经由***复合的出现克服了。
将不锈钢***焊接或***复合到碳钢上产生了冶金结合到碳钢基体上的具有一致组合物的不锈钢层。该技术克服了与铬化处理相关的可变的浓度,但是其严重地受限于飞层(flying layer)的厚度、烈性***的使用以及形成的冶金结合。在***焊接的金属中已经观察到了两种类型的冶金结合:在烈性***载荷下,横截面由基层和飞层的波状混合而组成,并且在较低的***载荷下,横截面包括飞层的颗粒向基层的注入。例如,参见Explosive welding of stainless steel-carbon steel coaxial pipes,J.Mat.Sci.,2012,47-2,685-695;和Microstructure of Austenitic stainless SteelExplosively Bonded to low Carbon-Steel,J.Electron Microsc.(Tokyo),1973,22-1,13-18。
现有技术没有教导包括扩散结合到碳钢基体的具有一致组合物的不锈钢层的材料。理想地,这样的材料将包括与***焊接的不锈钢相关的耐腐蚀性和在典型的铬化处理应用中观察到的深度扩散结合。
发明概述
第一实施方案是冶金结合在钢模(steel form)上的不锈钢,所述钢模包括含有至少55重量%铁的核心区域并负载有不锈钢涂层。所述不锈钢涂层由不锈钢区域和结合区域构成。所述不锈钢区域具有约1微米至约250微米的厚度,并具有跨越不锈钢区域的厚度的大约一致的不锈钢组合物。所述不锈钢组合物包括铁和铬的掺合物,并且包括约10重量%至约30重量%的铬浓度。所述结合区域位于所述不锈钢区域和所述核心区域之间,具有大于1微米并且小于所述不锈钢区域厚度的厚度,并具有结合组合物。所述结合组合物包括铁和铬的掺合物,并且所述结合组成具有大约等于所述不锈钢区域铬浓度的、邻近所述不锈钢区域的铬浓度,以及所述结合组合物具有含有小于约5重量%铬的、邻近所述核心区域的铬浓度。
第二实施方案是钢板,所述钢板包括:第一不锈钢区域,所述第一不锈钢区域具有约1微米至约250微米的厚度;第一结合区域,所述第一结合区域位于所述第一不锈钢区域和核心区域之间,所述第一结合区域具有大于1微米并且小于所述第一不锈钢区域厚度的厚度;所述核心区域,所述核心区域具有约100微米至约4毫米的厚度,所述核心区域具有含有至少85重量%铁的核心组合物;第二结合区域,所述第二结合区域位于所述核心区域和第二不锈钢区域之间;以及所述第二不锈钢区域,所述第二不锈钢区域具有约1微米至约250微米的厚度。所述第二结合区域具有大于1微米并且小于所述第二不锈钢区域厚度的厚度。所述第一和第二不锈钢区域具有跨越各自的不锈钢区域厚度的大约一致的不锈钢组合物。独立地,所述不锈钢组合物包括铁和铬的掺合物,以及约10重量%至约30重量%的铬浓度。所述第一和第二结合区域具有结合组合物,所述结合组合物独立地包括铁和铬的掺合物,具有大约等于所述不锈钢区域铬浓度的、邻近所述不锈钢区域的铬浓度,并且具有含有小于约5重量%铬的、邻近所述核心区域的铬浓度。
附图的简要说明
为了更完全地理解所述公开内容,应参考以下详细说明和附图,其中:
图1是铬浓度随铬化钢(现有技术)的深度而变化的曲线图;
图2是铬浓度和铁浓度随300系列产品的前体的深度而变化的曲线图;
图3是300系列产品的前体的横截面的SEM图;
图4是铬浓度随300系列产品的深度而变化的曲线图,(实线)测得的能量-色散X射线光谱(EDX)数据,(虚线)为核心中的铬浓度而标准化的EDX数据;
图5是300系列产品的横截面的SEM图;
图6是铬浓度、镍浓度和铁浓度随400系列产品的前体的深度而变化的曲线图;
图7是400系列产品的前体的横截面的SEM图;
图8是铬浓度和镍浓度随400系列产品的深度而变化的曲线图;
图9是400系列产品的横截面的SEM图;和
图10是本文中描述的一个实施方案的示意图。
虽然附图中说明了具体的实施方案,应当理解所述公开内容是说明性的,这些实施方案并非意在用来限制本文中描述和说明的发明。
发明详述
术语“掺合物”涉及多种金属,优选为过渡金属,是指所述金属在给定区域中是混合的。掺合物可以进一步描述为固溶体、合金、均质掺合物、异质掺合物、金属相或还包括金属间的或不溶的结构、晶体或微晶的前述中的一个。重要地,本文中使用的术语“掺合物”清楚地排除了混合的颗粒或晶体或互溶的材料。也就是说,本文中描述的掺合物不包括可区分的组合物颗粒,该组合物颗粒例如通过将所述掺合物加热到组合物颗粒可以相互扩散的温度下,可以形成固溶体、单一金属相等。显著地,掺合物可包括金属间的种类,因为这些金属间的种类在“溶质”或主体金属相中是不可溶的。另外,混合的-互溶材料的排除没有限制样品的同质性;异质的掺合物可以包括掺合物中的至少一种金属的浓度梯度,但不包括一种相或组合物的可区分的颗粒或晶体,所述可区分的颗粒或晶体与具有第二相的组合物的颗粒或晶体混合,或混合在具有第二相的组合物的溶质中,所述第一相的组合物在所述第二相的组合物中是可溶的。
名词“合金”涉及金属掺合物,是指金属,优选为过渡金属的特定组合物,在整个掺合物中具有窄的金属浓度变化。合金的一个实例为304不锈钢,其具有包括约18-20重量%Cr、约8-10.5重量%Ni和约2重量%Mn的铁组合物。如本文中使用的,占比容的合金不包括浓度梯度。包括浓度梯度的比容将包括诸如掺合物,多个或一系列合金。
本文中术语“浓度梯度”指的是掺合物中的至少一种元素浓度的有规律的增加或减少。通常地,浓度梯度是在掺合物中观察到的,其中掺合物中的至少一种元素从设定值增加或减小到更高/更低的设定值。所述增加或减少可以是线性的、抛物线的、高斯的或它们的混合。通常地,浓度梯度不是阶梯函数。阶梯函数变化更好地描述为多个相邻的掺合物。
本文中描述的材料的层和/或区域被提及为“冶金结合的”。也就是说,提供所述层和/或区域的组合物的金属、合金或掺合物是通过晶格结构的一致性(a conformance of lattice structures)连接的。不包含如粘合剂或钎缝金属(braze metal)的中间层。结合区域是这样的区域:其中的两种或多种金属、合金或掺合物之间的冶金结合显示出晶格结构的一致性。所述晶格结构的一致性是从一种金属、合金或掺合物的晶格向冶金结合的金属、合金或掺合物的晶格的逐渐变化。
虽然本文中使用的术语对于钢工业是典型的,但是本文中所公开的组合物或区域可以由一种或多种元素组成或基本上由一种或多种元素组成。显著地,认为钢是碳钢,所述碳钢是至少铁和碳的混合物,并且通常含有最高达2%的总的合金元素,包括碳、铬、钴、铌、钼、镍、钛、钨、钒、锆或其它金属。因此,钢或碳钢不是由一种或多种元素组成的,也不是基本上由一种或多种元素组成的,但可以是在铁中受支持(supported)的多种元素的任意组合物。当组合物或区域描述为由一种或多种元素组成或基本上由一种或多种元素组成时,所述组合物或区域中的未公开的元素的浓度不能通过能量-色散X射线光谱(EDX)(例如,EDX具有低至约0.5至1原子百分率的水平的典型灵敏度)检测的。当组合物或区域描述为由一种或多种元素组成时,所述组合物或区域中未公开的元素的浓度是不可检测的或在例如通过IPC直接元素分析的计量误差之内。
本文中描述的材料包括多种冶金结合的金属、合金或掺合物。所述金属、合金或掺合物中过渡金属的组合物或浓度是本文中描述的材料的重要特征。所述组合物或浓度随着穿过所述材料的深度或距离而产生的变化是同样重要的。因此,在本文中,所描述的金属、合金或掺合物中的成分金属的组合物或浓度是通过EDX测定的。另外,在本文中,当组合物被称为越过一段距离内、在层中或在区域中是“大约一致的”时,术语“大约一致的”是指在该距离、层或区域内的金属的相对百分率在通过EDX测量的标准误差内是一致的。优选地,当标绘成浓度(y-轴)相对于距离(x-轴)的函数时,移动平均数在越过“大约一致的”距离、层或区域上具有约为零的斜率。更优选地,所述组合物中的单个元素的浓度(或相对百分率)在越过所述距离上的变化小于约5重量%、4重量%、3重量%、2重量%或1重量%。
第一实施方案是钢模,所述钢模具有不锈钢外部。所述钢模包括核心区域,所述核心区域负载有不锈钢涂层;也就是说,所述钢模包括核心区域、结合区域和不锈钢区域,其中所述结合区域将所述核心区域冶金结合到所述不锈钢区域。本文中,所述钢模是由包括至少55重量%铁的层或区域限定的,显著地,所述钢模可以由诸如有机或无机涂层涂覆,但是,这些涂层在本文中不是所述钢模的部分。所述钢模的核心区域包括铁,优选地包括至少55重量%的铁。更优选地,所述核心区域中的铁浓度大于98重量%、99重量%或99.5重量%。甚至更优选地,所述核心区域是具有小于约0.5重量%的碳浓度的碳钢。又优选地,所述核心区域是具有小于约0.25重量%的碳浓度的碳钢。甚至又优选地,所述核心区域基本不含铬和/或基本不含镍。
所述核心区域负载的不锈钢涂层由不锈钢区域和结合区域构成,所述结合区域邻近于所述核心区域和包括所述不锈钢外部的所述不锈钢区域。所述不锈钢区域,优选地,具有约1微米至约250微米、约5微米至约250微米、约10微米至约250微米、约25微米至约250微米、约50至约250微米、约10微米至约200微米或约10至约100微米的厚度。
所述不锈钢区域具有不锈钢组合物。本文中,不锈钢组合物是指所述不锈钢区域包括铁和铬的掺合物,特别地,所述不锈钢组合物包括约10重量%至约30重量%的铬浓度,例如,所述铬浓度可以为约10重量%、约12重量%、约14重量%、约16重量%、约18重量%、约20重量%、约22重量%、约24重量%、约26重量%、约28重量%或约30重量%。优选地,所述不锈钢组合物在跨越所述不锈钢区域的厚度上是大约一致的。
所述不锈钢组合物包括铁和铬的掺合物,并且还可以包括选自镍、钼、钛、铌、钽、钒、钨、铜和它们的混合物的过渡金属。在一个实例中,所述不锈钢组合物包括铁、铬和镍的掺合物,并且包括约5重量%至约20重量%的镍浓度。在该实例中,所述结合组合物(如以下描述的)基本上由铁、铬和镍组成。
在一个优选实例中,所述不锈钢组合物具有约16重量%至约25重量%的铬浓度和约6重量%至约14重量%的镍浓度。在另一优选实例中,所述不锈钢组合物基本上由铁、铬和镍组成。
在另一实例中,所述不锈钢组合物可以具有约10.5重量%至约18重量%的铬浓度。在又一优选的实例中,所述不锈钢组合物基本上由铁和铬组成,并且所述结合组合物基本上由铁和铬组成。
如上所述的,所述不锈钢涂层包括所述不锈钢区域和位于所述不锈钢区域和所述核心区域之间的所述结合区域。所述结合区域,优选地,具有大于1微米并且小于所述不锈钢区域厚度的厚度。更优选地,所述结合区域具有约5微米至约200微米、约5至约100微米或约10微米至约50微米的厚度。
所述结合区域具有结合组合物,所述结合组合物包括铁和铬的掺合物。所述结合组合物还包括大约等于所述不锈钢区域铬浓度的、邻近所述不锈钢区域的铬浓度,并且具有含有小于约5重量%、约4重量%、约3重量%、约2重量%、约1重量%或约0.5重量%铬的、所述邻近核心区域的铬浓度。也就是说,穿过所述结合区,所述铬浓度下降到小于所述不锈钢区域的浓度一半的浓度,优选地下降到大约等于所述核心区域中的铬浓度的浓度。所述结合区域内的铬浓度梯度可以包括铬浓度的线性降低或铬浓度的反曲线降低(sigmoidal decrease),优选为反曲线降低。
另一实施方案是钢板,所述钢板包括多个区域,包括第一不锈钢区域、位于所述第一不锈钢区域和核心区域之间的第一结合区域、所述核心区域、位于所述核心区域和第二不锈钢区域之间的第二结合区域和所述第二不锈钢区域(例如,参见图10)。在该实施方案中,所述第一不锈钢区域具有约1微米至约250微米的厚度;所述第一结合区域具有大于1微米并且小于所述第一不锈钢区域厚度的厚度;所述核心区域具有约100微米至约4毫米的厚度;所述第二不锈钢区域具有约1微米至约250微米的厚度;以及所述第二结合区域具有大于1微米并且小于所述第二不锈钢区域厚度的厚度。
优选地,所述核心区域具有包括至少85重量%铁的核心组合物。更优选地,所述核心区域中的铁浓度大于98重量%、99重量%或99.5重量%。甚至更优选地,所述核心区域为具有小于约0.5重量%的碳浓度的碳钢。又优选地,所述核心区域是具有小于约0.25重量%的碳浓度的碳钢。甚至又优选地,所述核心区域基本不含铬。
所述第一和第二不锈钢区域具有跨越各自的不锈钢区域的厚度的大约一致的不锈钢组合物。这些不锈钢组合物,独立地,包括铁和铬的掺合物,其具有约10重量%至约30重量%的铬浓度,例如,所述铬浓度可以为约10重量%、约12重量%、约14重量%、约16重量%、约18重量%、约20重量%、约22重量%、约24重量%、约26重量%、约28重量%或约30重量%。
所述第一和第二结合区域具有包括铁和铬的掺合物的结合组合物。独立地,所述结合区域具有大约等于所述不锈钢区域铬浓度的、邻近各自的不锈钢区域的铬浓度,并且具有含有小于约5重量%、约4重量%、约3重量%、约2重量%、约1重量%或约0.5重量%铬的、邻近所述核心区域的铬浓度,优选地,邻近所述核心区域的铬浓度大约等于所述核心区域的铬浓度。也就是说,单独的结合区域各自具有铬浓度梯度。所述结合区域中的铬浓度梯度可以包括铬浓度的线性降低或铬浓度的反曲线降低(sigmoidal decrease),优选反曲线降低。
在一个实例中,所述第一和第二不锈钢组合物,独立地,包括铁、铬和镍的掺合物,具有约5重量%至约20重量%的镍浓度。在该实例中,各自的第一和第二结合组合物也包括镍。
在另一实例中,所述第一和第二不锈钢组合物独立地包括铁、铬和选自镍、钼、钛、铌、钽、钒、钨、铜和它们的混合物的过渡金属的掺合物。在该实例中,各自的结合组合物也将包括所选择的过渡金属。
优选地,包括以上所述区域的钢板具有约0.1毫米至约4毫米的厚度。所述厚度是材料的高度、长度或宽度中较小的。对于典型的板,长度和宽度比高度(或厚度)大多个数量级。例如,所述钢板可以是具有约1米至约4米的宽度和大于50米的宽度的钢卷。
所述单独的不锈钢区域可以具有相同或不同的厚度,优选地,所述第一和第二不锈钢区域具有大约相同的厚度(例如,±5%)。在一个实例中,所述第一不锈钢区域具有约10微米至约100微米的厚度。在另一实例中,所述第二不锈钢区域具有约10微米至约100微米的厚度。单独的结合区域可以具有相同或不同的厚度,优选地,所述第一和第二结合区域具有大约相同的厚度(例如,±5%)。在另一实例中,所述第一结合区域具有约5微米至约100微米的厚度。在又一实例中,所述第二结合区域具有约5微米至约100微米的厚度。
又一实施方案是包括由不锈钢区域负载的拉丝不锈钢(brushedstainless steel)表面的钢模。在该实施方案中,所述不锈钢区域可以具有约5微米至约200微米的厚度,具有包括铁和铬的掺合物的大约一致的不锈钢组合物,并且可以具有约10重量%至约30重量%的铬浓度。所述不锈钢区域是由结合区域负载的。优选地,所述结合区域具有约5微米至约200微米,但是小于所述不锈钢区域厚度的厚度。所述结合区域将所述不锈钢区域冶金结合到核心区域。所述核心区域具有包括至少85重量%铁的核心组合物。所述结合区域还包括结合组合物,所述结合组合物包括铁和铬的掺合物,和结合区域浓度梯度,该浓度梯度从大约等于所述不锈钢区域铬浓度的、邻近所述不锈钢区域的铬浓度向小于约1重量%的、邻近所述核心区域的铬浓度降低。
除了以上提供的实施方式方案的描述,本文中描述的产品优选地没有塑性应变。塑性应变是由金属或掺合物的变形形变带来引起的所述金属或掺合物中颗粒的伸长或拉伸。例如,冷轧钢将在轧制的方向上显示出塑性形变应变。钢中的塑性形变应变是通过研究所述钢的横截面是容易观察和计量的。本文中,所述产品优选地基本上没有塑性形变应变,也就是说,所述产品包括小于15%、10%或5%的塑性应变塑性形变。更优选地,本文中描述的产品基本上没有塑性形变,也就是说,所述产品包括小于1%的塑性形变。甚至更优选地,本文中描述的产品没有塑性应变形变,也就是说,所描述的产品的塑性形变是不可通过研究产品的横截面是不可观察的。
本文描述的包括由钢或碳钢基体或核心负载的不锈钢层或区域的产品可以通过铬到起始基体上的低温沉积制备,所述起始基体成为核心区域。用于铬到所述起始基体上的沉积的可用技术包括但不限于:物理气相沉积、化学气相沉积、金属-有机化学气相沉积、溅射、离子注入、电镀、化学镀、包埋渗、ONERA法、盐浴法、铬-冰晶石法(chromium-cryoliteprocesses)、Alphatising法等。在一个优选实例中,铬沉积在所述起始基体上的非致密层中。在另一优选实例中,铬沉积为基本上由铬组成的层。图2和3显示了在所述碳钢基体上所沉积的铬层的EDX和扫描电子显微镜(SEM)数据。图2显示了在所述碳钢基体中所沉积的铬和铁的近似重量百分率。图3显示了沉积在所述碳钢基体上的铬的横截面SEM图。在又一优选实例中,铬沉积为铁和铬的掺合物。在再一优选实例中,铬沉积为铬和选自镍、钼、钛、铌、钽、钒、钨、铜和它们的混合物的元素的掺合物。在又另一优选实例中,铬和选自镍、钼、钛、铌、钽、钒、钨、铜和它们的混合物的元素的多个层沉积到所述起始基体上。图6和7显示了在所述碳钢基体上所沉积的镍和铬层的EDX和SEM数据。图6显示了在所述碳钢基体中所沉积的铬、所沉积的镍和铁的近似重量百分率。图7显示了由所述碳钢基体负载的铬和镍的横截面SEM图。
铬沉积到所述起始基体上之后,将沉积的铬和任何其它沉积的金属加热到约800℃至约1200℃或约1000℃的温度。图4和5显示了通过加热例如图2和3中所示的沉积的铬制备的由碳钢核心负载的400系列不锈钢的EDX和SEM数据。图4显示了随深度而变化的(所测量和标准化的)铬的近似重量百分率。所述不锈钢区域可以与选自403SS、405SS、409SS、410SS、414SS、416SS、420SS和422SS的不锈钢组合物牌号相媲美。所述不锈钢层的组合物牌号可以受到所述碳钢基体中微量元素的浓度(例如,镍、碳、锰、硅、磷、硫和氮),一种或多种微量元素向所沉积的铬中的添加,或通过所沉积的铬的后处理(例如,通过溶液、沉积或离子注入的方法)的一种或多种微量元素的添加的影响。图5显示了显著地省略了各自区域之间的任何可观察到的区别(例如,界面)的所述不锈钢区域、结合区域和核心区域的SEM横截面。
图8和9显示了通过加热例如图6和7中所示的沉积的铬制备的由碳钢核心负载的300系列不锈钢的EDX和SEM数据。图8显示了作为随深度而变化的的函数的铬和镍的近似大约的重量百分率。所述不锈钢区域可以与选自301SS、302SS、303SS和304SS的不锈钢组合物牌号相媲美比较。另外,所述不锈钢层组成的组合物牌号可以受到所述碳钢基体中微量元素的浓度的影响(例如,碳、锰、硅、磷、硫和氮),受到一种或多种微量元素向所述沉积后的铬中的添加的影响,或受到通过所述沉积后的铬的后处理(例如,通过溶液、沉积或离子注入)的添加一种或多种微量元素的添加的影响。此外,所述不锈钢组合物的牌号受到所述不锈钢层中的铬和镍的浓度影响,这些浓度可以独立地增加或降低。图9显示了显著地省略了各自区域之间的任何可观察到的区别(例如,界面)的所述不锈钢区域、结合区域和核心区域的SEM横截面。
所述不锈钢区域、结合区域和任选地所述核心区域的厚度和组合物的测定是通过本文中描述的产品的样品的横截面分析测定的。优选地,所述样品是由产品表面的1厘米×1厘米区域限定的。然后,穿过所述1厘米×1厘米区域的中心切割样品,将切割暴露的表面在Buehler EcoMet 250磨削抛光机(ginder-polisher)上抛光。5步抛光工艺包括:使用Buehler 180Grit盘在6lbs.的力下的5分钟,使用Hercules S盘和6微米的抛光悬浮液(polishing suspension)在6lbs.的力下的4分钟,使用Trident3/6微米盘和6微米的抛光悬浮液在6lbs.的力下的3分钟,使用Trident3/6微米盘和3微米的抛光悬浮液在6lbs.的力下的2分钟,以及然后使用微布盘(microcloth disk)和0.05微米的抛光悬浮液在6lbs.的力下的1.5分钟。然后将切割并抛光的表面放入有能量-色散X射线光谱(EDX)功能的设备中。以上提供的磨削抛光工艺(grinding-polishing procedure)可能交叉污染不同的层,不出所料的是所述污染跨越抛光的表面可以是一致的。因此,不含第一元素的区域的基线测量可能显示出比EDX测得的所述第一元素的基线浓度更大的值(参见,例如图4)。基线的提高依赖于抛光区域的面积和在抛光表面中各自元素的浓度。
Claims (14)
1.一种具有不锈钢外部的钢模,所述钢模包括:
核心区域、第一结合区域和第一不锈钢区域;
所述核心区域通过所述第一结合区域冶金结合到所述第一不锈钢区域;所述核心区域包括至少55重量%铁,优选地,至少85重量%铁;
所述第一不锈钢区域具有约1微米至约250微米的厚度,具有不锈钢组合物,并且包括所述不锈钢外部,所述不锈钢组合物跨越所述不锈钢区域的厚度是大约一致的,所述不锈钢组合物包括铁和铬的掺合物,并且所述不锈钢组合物包括约10重量%至约30重量%的铬浓度;以及
所述第一结合区域位于所述不锈钢区域和所述核心区域之间,所述结合区域具有大于1微米并且小于所述不锈钢区域厚度的厚度,并具有结合组合物,所述结合组合物包括铁和铬的掺合物,并且所述结合组合物具有大约等于所述不锈钢区域铬浓度的、邻近所述不锈钢区域的铬浓度并且具有含有小于约5重量%铬的、邻近所述核心区域的铬浓度。
2.根据权利要求1所述的钢模,其中所述钢模是具有约100微米至约4毫米的厚度的钢板,并且其中所述核心区域具有约100微米至约4毫米的厚度。
3.根据前述权利要求中任一项所述的钢模,所述钢模还包括通过第二结合区域冶金结合到所述核心区域的第二不锈钢区域。
4.根据前述权利要求中任一项所述的钢模,其中所述核心区域基本上不含铬。
5.根据前述权利要求中任一项所述的钢模,其中所述核心区域为具有小于约0.5重量%的碳浓度,优选地为小于约0.25重量%的碳浓度的碳钢。
6.根据前述权利要求中任一项所述的钢模,其中所述不锈钢区域具有约10微米至约100微米的厚度。
7.根据前述权利要求中任一项所述的钢模,其中所述结合区域具有约5微米至约100微米的厚度,优选地,约10微米至约50微米的厚度。
8.根据前述权利要求中任一项所述的钢模,其中所述不锈钢组合物包括铁、铬和过渡金属的掺合物,所述过渡金属选自镍、钼、钛、铌、钽、钒、钨、铜和它们的混合物。
9.根据前述权利要求中任一项所述的钢模,其中所述不锈钢组合物包括铁、铬和镍的掺合物;其中所述不锈钢组合物包括约5重量%至约20重量%的镍浓度;并且其中所述结合组合物基本上由铁、铬和镍组成。
10.根据权利要求9所述的钢模,其中所述不锈钢组合物包括约16重量%至约25重量%的铬浓度和约6重量%至约14重量%的镍浓度。
11.根据权利要求9所述的钢模,其中所述不锈钢组合物基本上由铁、铬和镍组成。
12.根据权利要求1至8中任一项所述的钢模,其中所述不锈钢组合物包括约10.5重量%至约18重量%的铬浓度。
13.根据权利要求12所述的钢模,其中所述不锈钢组合物基本上由铁和铬组成;并且其中所述结合组合物基本上由铁和铬组成。
14.制备前述权利要求中任一项所述的钢模的方法,所述方法基本上由以下步骤构成:
提供碳钢基体;
沉积铬和任选地选自镍、钼、钛、铌、钽、钒、钨、铜和它们的混合物的过渡金属作为沉积层;以及然后
加热所述碳钢基体到约800℃至约1200℃的温度,从而通过将铁从所述碳钢基体扩散入所述沉积层和将铬扩散入所述碳钢基体而形成所述核心区域、所述第一结合区域和所述第一不锈钢区域。
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US20140037987A1 (en) | 2014-02-06 |
US8784997B2 (en) | 2014-07-22 |
CN103764388B (zh) | 2016-08-17 |
US20130252022A1 (en) | 2013-09-26 |
US8628861B2 (en) | 2014-01-14 |
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