CN101809182B - 通过dff调节制造锌镀层退火的钢片材的方法 - Google Patents
通过dff调节制造锌镀层退火的钢片材的方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 94
- 239000010959 steel Substances 0.000 title claims abstract description 94
- 239000011701 zinc Substances 0.000 title claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 24
- 238000000576 coating method Methods 0.000 title claims abstract description 24
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- 230000001105 regulatory effect Effects 0.000 title description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 20
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- 150000001875 compounds Chemical class 0.000 claims abstract description 14
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- 235000013980 iron oxide Nutrition 0.000 claims abstract description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 229910001566 austenite Inorganic materials 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
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- 229910000859 α-Fe Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910001563 bainite Inorganic materials 0.000 claims description 8
- 229910000734 martensite Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
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- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
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- 239000011572 manganese Substances 0.000 description 29
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910000794 TRIP steel Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 7
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- 230000006866 deterioration Effects 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000635 Spelter Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 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 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
- C21D1/52—Methods of heating with flames
-
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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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
- 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
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/561—Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
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- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23C2/0224—Two or more thermal pretreatments
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- 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
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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Abstract
本发明涉及一种制备热浸锌镀层退火的钢片材的方法，该钢片材具有TRIP显微组织并且按重量％计包含如下元素：0.01≤C≤0.22％，0.50≤Mn≤2.0％，0.5＜Si≤2.0％，0.005≤Al≤2.0％，Mo＜0.01％，Cr≤1.0％，P＜0.02％，Ti≤0.20％，V≤0.40％，Ni≤1.0％，Nb≤0.20％，组成的余量是铁和来自熔炼的不可避免的杂质，所述方法包括如下步骤：-氧化所述钢片材以便在钢片材的表面上形成铁氧化物层，以及形成选自下组中至少一种氧化物的内部氧化物：Si氧化物、Mn氧化物、Al氧化物、包含Si和Mn的复合氧化物、包含Si和Al的复合氧化物、包含Al和Mn的复合氧化物以及包含Si、Mn和Al的复合氧化物；-还原所述氧化的钢片材，以便还原铁氧化物层；-对所述还原的钢片材进行热浸镀锌以形成锌基涂覆的钢片材；和-使所述锌基涂覆的钢片材经受合金化处理从而形成锌镀层退火的钢片材。
Description
技术领域
本发明涉及制造具有TRIP显微组织的热浸锌镀层退火的钢片材的方法。
背景技术
为了满足使动力驱动的陆地车辆的结构减轻的需要，已知使用TRIP钢(术语TRIP代表转变诱发塑性)，该TRIP钢兼具有很高的机械强度以及很高变形水平的可能性。TRIP钢具有包含铁素体、残余奥氏体和任选的马氏体和/或贝氏体的显微组织，这允许它们获得600-1000MPa的拉伸强度。这类钢广泛用于生产能量吸收零件，例如结构和安全零件如纵向部件和增强件。
在送交给汽车制造商之前，通常通过热浸镀锌使钢片材涂覆有锌基涂层，以便提高抗腐蚀性。在离开锌浴之后，通常使镀锌的钢片材经受退火，这促进锌涂层与钢中的铁的合金化(所谓的锌镀层退火)。这种由锌-铁合金制成的涂层提供了比锌涂层更好的可焊性。
大多数TRIP钢片材是通过向钢中添加大量的硅获得的。在室温下，硅使铁素体和奥氏体稳定化，并抑制残余奥氏体分解形成碳化物。然而，含有多于0.2重量％硅的TRIP钢片材难以镀锌，因为在恰好发生在涂覆之前的退火期间，在钢片材的表面上形成了硅氧化物。这些硅氧化物显示出对熔融锌的不良润湿性，从而使钢片材的镀覆性能劣化。
为解决这个问题，已知使用具有低硅含量(低于0.2重量％)的TRIP钢。然而，这具有如下的主要缺陷：只有当碳含量提高时才能获得高水平的拉伸强度，即约800MPa。但是，这具有降低焊接点的机械抗性(mechanical resistance)的效应。
另一方面，在锌镀层退火处理期间，不论TRIP钢的组成如何，合金化速度强烈降低，因为外部选择性氧化充当了对铁的扩散屏障，从而必须提高锌镀层退火的温度。由于残余奥氏体在高温下的分解，所以锌镀层退火温度的提高对TRIP效应的保持是有害的。为了保持TRIP效应，必须将大量的钼(多于0.15重量％)添加到钢中，使得可以延迟碳化物的析出。然而，这对钢片材的成本产生影响。
实际上，当TRIP钢片材变形时，随着残余奥氏体在变形影响下转变成马氏体，观察到TRIP效应，并且TRIP钢片材的强度提高。
发明内容
因此，本发明的目的是弥补上述缺陷并且提出一种对钢片材进行热浸锌镀层退火的方法，该钢片材具有高硅含量(大于0.5重量％)和显示出高机械特性的TRIP显微组织，该方法确保了钢片材表面的良好润湿性并且没有未镀覆部分，因而确保了钢片材上的锌合金涂层的良好附着性和美好的表面外观，且保留了TRIP效应。
本发明的第一个主题是制备具有TRIP显微组织的热浸锌镀层退火的钢片材的方法，所述TRIP显微组织包含铁素体、残余奥氏体和任选的马氏体和/或贝氏体，所述方法包括以下步骤：
-提供重量比组成包含如下元素的钢片材：
0.01≤C≤0.22％
0.50≤Mn≤2.0％
0.5＜Si≤2.0％
0.005≤Al≤2.0％
Mo＜0.01％
Cr≤1.0％
P＜0.02％
Ti≤0.20％
V≤0.40％
Ni≤1.0％
Nb≤0.20％，
组成的余量是铁和来自熔炼的不可避免的杂质，
-氧化所述钢片材以便在钢片材的表面上形成铁氧化物层，以及形成选自下组中至少一种氧化物的内部氧化物：Si氧化物、Mn氧化物、Al氧化物、包含Si和Mn的复合氧化物、包含Si和Al的复合氧化物、包含Al和Mn的复合氧化物以及形成包含Si、Mn和Al的复合氧化物。
-还原所述氧化的钢片材，以便还原铁氧化物层，
-对所述还原的钢片材进行热浸镀锌以形成锌基涂覆的钢片材，和
-使所述锌基涂覆的钢片材经受合金化处理从而形成锌镀层退火的钢片材。
为了获得根据本发明的具有TRIP显微组织的热浸锌镀层退火的钢片材，提供了包含以下元素的钢片材：
-含量为0.01-0.22重量％的碳。该元素对于获得良好的机械性能是必要的，但其不能以过大量存在以便不损害可焊性。为了促进淬硬性并获得足够的屈服强度Re以及为了形成稳定的残余奥氏体，碳含量必须不小于0.01重量％。从在高温下形成的奥氏体显微组织发生贝氏体转变，并且形成铁素体/贝氏体层片。由于与奥氏体相比，碳在铁素体中的溶解度非常低，因此奥氏体中的碳在层片之间排出。由于硅和锰，因而存在极少的碳化物析出。因此，层片间奥氏体逐渐富集碳而无任何碳化物析出。这种富集使奥氏体稳定化，换言之，在冷却到室温时，不发生该奥氏体的马氏体转变。
-含量为0.50-2.0重量％的锰。锰促进淬硬性，使得能够获得高的屈服强度Re。锰促进奥氏体的形成，有助于降低马氏体转变开始温度Ms并使奥氏体稳定化。然而，必须避免钢具有过高锰含量以便抑制偏析，这可在钢片材的热处理期间得到验证。此外，过量添加锰导致形成引起脆性的厚的内部锰氧化物层，且锌基涂层的附着性将不足。
-含量为大于0.5重量％，优选大于0.6重量％，并且小于或等于2.0重量％的硅。硅改善钢的屈服强度Re。该元素使铁素体和残余奥氏体在室温下稳定。在冷却时，硅抑制渗碳体从奥氏体的析出，显著延缓碳化物的生长。这源自于硅在渗碳体中的溶解度很低且硅提高奥氏体中碳的活性。因此，形成的任何渗碳体核将被富硅的奥氏体区域所包围，且被排出到析出物-基质界面。该富硅奥氏体还较富集碳，并且由于渗碳体和相邻的奥氏体区域之间的降低的碳活性梯度所致的减少的扩散，渗碳体的生长减缓。因此，这种硅添加有助于使足够量的残余奥氏体稳定从而获得TRIP效应。在用以改善钢片材润湿性的退火步骤期间，内部硅氧化物以及包含硅和/或锰和/或铝的复合氧化物形成并且分散在片材表面下方。然而，过量添加硅导致形成厚的内部硅氧化物层以及可能的包含硅和/或锰和/或铝的复合氧化物，该复合氧化物引起脆性并且锌基涂层的附着性将不足。
-含量为0.005-2.0重量％的铝。与硅相似，铝使铁素体稳定且随钢片材冷却而增加铁素体的形成。它在渗碳体中不太可溶且在此方面可用于在保持钢处于贝氏体转变温度时避免渗碳体的析出以及用于使残余奥氏体稳定。需要最小量的铝以便使钢脱氧。
-含量小于0.01重量％的钼，且优选不超过0.006重量％。常规方法要求添加Mo以便防止碳化物在镀锌之后的再加热期间析出。这里，得益于硅、锰和铝的内部氧化，可以在比不包含内部氧化物的常规镀锌钢片材的温度更低的温度下进行镀锌钢片材的合金化处理。因此，可以降低钼含量且少于0.01重量％，因为它对于延迟贝氏体转变不是必需的，在常规镀锌钢片材的合金化处理期间正是如此。
-含量不超过1.0重量％的铬。必须限制铬含量以便在对钢进行镀锌时避免表面外观问题。
-含量不超过0.02重量％、且优选小于0.010重量％的磷。磷与硅结合通过抑制碳化物的析出而提高残余奥氏体的稳定性。
-含量不超过0.20重量％的钛。钛改善屈服强度Re，但必须将其含量限制到0.20重量％以便避免劣化韧性。
-含量不超过0.40重量％的钒。钒通过晶粒细化改善屈服强度Re，且改善钢的可焊性。然而，高于0.40重量％时，钢的韧性劣化且具有在焊接区域中出现裂纹的风险。
-含量不超过1.0重量％的镍。镍增加屈服强度Re。由于其高成本，因此通常将其含量限制在1.0重量％。
-含量不超过0.20重量％的铌。铌促进碳氮化物的析出，由此提高屈服强度Re。然而，高于0.20重量％时，使可焊性和热成形性劣化。
组成的余量由铁和通常预期发现的其它元素以及来自钢熔炼的杂质(其比例不会对所需性能产生影响)组成。
在熔融锌浴中进行热浸镀锌并热处理以形成所述锌镀层退火钢片材之前，首先使具有上述组成的钢片材经受氧化随后还原。
目的是形成具有受控厚度的铁氧化物外层的氧化的钢片材，当在热浸镀锌之前对钢片材进行退火时，所述铁氧化物外层将保护钢免于发生硅、锰和铝的选择性外部氧化。
在允许于钢片材的表面上形成铁氧化层的条件下进行钢片材的所述氧化，该铁氧化层不包含选自下组中的表层氧化物：硅氧化物、锰氧化物、铝氧化物、包含硅和/或锰和/或铝的复合氧化物。在这个步骤期间，硅、锰和铝的内部选择性氧化将在铁氧化物层下方发展，并导致深的金属硅、锰和铝贫化区，当实施进一步还原时这将使表层选择性氧化的风险最小化。因而形成选自下组中至少一种氧化物的内部氧化物层：硅氧化物、锰氧化物、铝氧化物、包含Si和Mn的复合氧化物、包含Si和Al的复合氧化物、包含Mn和Al的复合氧化物以及包含Si、Mn和Al的复合氧化物。
优选地，通过在直焰炉中将所述钢片材从环境温度加热到680-800℃之间的加热温度T1来进行该氧化，该直焰炉中的气氛包含空气和燃料，且空气与燃料之比优选为1至1.2。
当温度T1高于800℃时，形成于钢片材表面上的铁氧化物层将含有来自钢中的锰，从而润湿性将受损。如果温度T1低于680℃，则将不利于硅、锰和铝的内部氧化，且钢片材的可镀锌性将不足。
空气与燃料之比小于1的气氛导致形成硅、锰和铝的表层氧化，且因而形成可能与铁氧化物结合的选自下组中的浅表氧化物层：硅氧化物、锰氧化物、铝氧化物、以及包含硅和/或锰和/或铝的复合氧化物，从而润湿性受到损害。然而，当空气与燃料之比大于1.2时，铁氧化物层过厚，且将不会被完全还原，润湿性也将受到损害。
当离开直焰炉时，在允许实现铁氧化物完全还原成铁的条件下使氧化的钢片材还原。可在辐射型管式炉中或在电阻炉中进行该还原步骤。因而在包含如下成分的气氛中热处理所述的氧化的钢片材：优选大于15体积％的氢气，余量为氮气和不可避免的杂质。实际上，如果气氛中的氢气含量小于15体积％，那么铁氧化物层可能被不充分还原并且润湿性受到损害。
将所述氧化的钢片材从加热温度T1加热到均热温度T2，然后在所述均热温度T2下将其均热并持续均热时间t2，最后从所述均热温度T2冷却到冷却温度T3。
所述均热温度T2优选为770-850℃。当钢片材处于温度T2时，形成由铁素体和奥氏体构成的双相显微组织。当T2高于850℃时，奥氏体的体积比率增长过多，并且在钢表面上发生外部选择性氧化。但当T2低于770℃时，形成足够体积比率的奥氏体所需的时间过长。
为了获得所需的TRIP效应，在均热步骤期间必须形成充足的奥氏体以便在冷却步骤期间保持足够的残余奥氏体。进行均热并持续时间t2，该时间t2优选为20-180s。如果时间t2长于180s，则奥氏体晶粒粗化且成形之后的钢的屈服强度Re将是有限的。此外，钢的淬硬性是低的。然而，如果将钢片材均热持续小于20s的时间t2，则形成的奥氏体比例将不足，且在冷却时将不形成充足的残余奥氏体和贝氏体。
最后在与熔融锌浴的温度接近的冷却温度T3下将还原的钢片材冷却，以便避免所述浴的冷却或再加热。因而，T3优选为460-510℃。因此，可以获得具有均匀显微组织的锌基涂层。
当钢片材冷却时，在优选为450-500℃温度的熔融锌浴中对其进行热浸。该浴可含有0.08-0.135重量％的溶解铝，余量为锌和不可避免的杂质。将铝加入浴中以便使熔融锌脱氧，并且使得更易于控制锌基涂层的厚度。在该条件下，在钢和锌基涂层的界面处引起δ相(FeZn7)的析出。
当离开浴时，通过喷射气体扫拭钢片材以便调节锌基涂层的厚度。根据所需的耐腐蚀性确定该厚度，其通常为3-10μm。
最后对热浸镀锌的钢片材进行热处理，以便通过铁从钢扩散到涂层的锌而获得由锌-铁合金制成的涂层。通过将所述钢片材保持在460-510℃的温度T4并持续10-30s的均热时间t4来进行该合金化处理。得益于不存在硅、锰和铝的外部选择性氧化，该温度T4低于常规合金化温度。由于此原因，对于钢不需要大量的钼，并且可将钢中的钼含量限制在低于0.01重量％。如果温度T4低于460℃，则铁和锌的合金化是不可能的。如果温度T4高于510℃，则因不希望的碳化物析出而难以形成稳定的奥氏体，并且不能获得TRIP效应。调节时间t4使得合金中的平均铁含量为8-12重量％，这对于改善涂层的可焊接性和在成型时限制粉末化是良好的折衷。
具体实施方式
现在将通过以非限制性表述且参照图1和2而提供的实施例来说明本发明。
使用来自0.8mm厚的片材的样品A和B进行试验，该片材是由组成如表I所示的钢片材制成。
在直焰炉中将样品A和B从环境温度(20℃)预热到750℃，在辐射型管式炉中对它们进行后续且连续的退火，在该炉中将它们从750℃加热到800℃，然后在800℃将它们均热60s，最后将它们冷却到460℃。辐射型管式炉中的气氛包含30体积％的氢气，余量为氮气和不可避免的杂质。
在冷却后，在熔融锌基浴中对样品A和B进行热浸镀锌，所述浴包含0.12重量％铝，余量为锌和不可避免的杂质。所述浴的温度为460℃。在用氮气扫拭并冷却锌基涂层之后，该锌基涂层的厚度为7μm。
首先，目标是当直焰炉中的空气与燃料之比波动时，比较这些样品的润湿性和附着性。根据本发明，样品A的空气与燃料之比为0.90，而样品B的空气与燃料之比为1.05。结果显示在表II中。
润湿性由操作者目视对比。在样品的180°弯曲测试之后还目视对比涂层的附着性。
表I：样品A和B的以重量％计的钢化学组成，组成的余量为铁和不可避免的杂质(样品A和B)。
表I
| C | Mn | Si | Al | Mo | Cr | P | Ti | V | Ni | Nb |
| 0.20 | 1.73 | 1.73 | 0.01 | 0.005 | 0.02 | 0.01 | 0.005 | 0.005 | 0.01 | 0.005 |
表II
| 润湿性 | 附着性 | 表面外观 | |
| 样品A** | 坏 | 坏 | 坏 |
| 样品B* | 好 | 好 | 好 |
*根据本发明
**根据常规方法
图1是样品A在预热步骤之后且在退火步骤之前的照片，而图2是样品B在预热步骤之后且在退火步骤之前的照片。
然而，目的是显示硅和锰的内部选择性氧化对合金化温度的影响。因此，将施用于样品B以便获得本发明的锌镀层退火钢片材的合金化处理的温度与样品A的合金化温度进行比较。
然后，通过将已经热浸镀锌的样品B加热到480℃且将其保持在这个温度下19s，对其进行合金化处理。发明人检测到根据本发明所得热浸锌镀层退火的钢片材的TRIP显微组织没有因该合金化处理而丧失。
为了实现样品A锌基涂层的合金化，必须将其加热到540℃，且将其保持在该温度下20s。通过这样的处理，发明人检测到发生碳化物析出，在冷却到室温期间残余奥氏体不再保持且TRIP效应消失。
Claims (8)
1.制备具有TRI P显微组织的热浸锌镀层退火的钢片材的方法，所述TRIP显微组织包含铁素体、残余奥氏体和任选的马氏体和/或贝氏体，所述方法包括以下步骤：
-提供重量比组成包含如下元素的钢片材：
0.01≤C≤0.22％
0.50≤Mn≤2.0％
0.5＜Si≤2.0％
0.005≤Al≤2.0％
Mo＜0.01％
Cr≤1.0％
P＜0.02％
Ti≤0.20％
V≤0.40％
Ni≤1.0％
Nb≤0.20％，
组成的余量是铁和来自熔炼的不可避免的杂质，
-通过在直焰炉中将钢片材从环境温度加热到680-800℃的温度T1来氧化所述钢片材以便在钢片材的表面上形成铁氧化物层，以及形成选自下组中至少一种氧化物的内部氧化物：Si氧化物、Mn氧化物、Al氧化物、包含Si和Mn的复合氧化物、包含Si和Al的复合氧化物、包含Al和Mn的复合氧化物以及包含Si、Mn和Al的复合物，所述直焰炉中的气氛包含空气和燃料，且空气与燃料之比为1.0至1.2，
-还原所述氧化的钢片材，以便还原铁氧化物层，所述还原由在下述气氛中进行的热处理构成，该气氛包含大于15体积％的氢气，余量为氮气和不可避免的杂质；所述热处理包括：从温度T1到770-850℃的均热温度T2的加热阶段，在所述均热温度T2下持续20-180s的均热时间t2的均热阶段，和从所述均热温度T2冷却到冷却温度T3的冷却阶段，
-对所述还原的钢片材进行热浸镀锌以形成锌基涂覆的钢片材，和
-在460-510℃的温度T4下使所述锌基涂覆的钢片材经受合金化处理从而形成锌镀层退火的钢片材。
2.根据权利要求1的方法，其中所述钢片材以重量％计包含＜0.010％的P。
3.根据权利要求1的方法，其中所述钢片材以重量％计包含≤0.006％的Mo。
4.根据权利要求1-3中任一项的方法，其中所述冷却温度T3为460-510℃。
5.根据权利要求1-3中任一项的方法，其中在辐射型管式炉或电阻炉中进行所述还原。
6.根据权利要求1-3中任一项的方法，其中通过在包含如下成分的熔融浴中热浸所述还原的钢片材来进行热浸镀锌：0.08-0.135重量％的铝，余量为锌和不可避免的杂质。
7.根据权利要求6的方法，其中所述熔融浴的温度为450-500℃。
8.根据权利要求1-3中任一项的方法，其中通过加热所述锌基涂覆的钢片材持续10-30s的均热时间t 4来进行所述合金化处理。
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| CN (1) | CN101809182B (zh) |
| AR (1) | AR067339A1 (zh) |
| AT (1) | ATE521726T1 (zh) |
| BR (1) | BRPI0813687B1 (zh) |
| CA (1) | CA2701091C (zh) |
| ES (1) | ES2371985T3 (zh) |
| PL (1) | PL2171116T3 (zh) |
| RU (1) | RU2451107C2 (zh) |
| WO (1) | WO2009004425A1 (zh) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9068255B2 (en) | 2009-12-29 | 2015-06-30 | Posco | Zinc-plated steel sheet for hot pressing having outstanding surface characteristics, hot-pressed moulded parts obtained using the same, and a production method for the same |
| KR20120075260A (ko) * | 2010-12-28 | 2012-07-06 | 주식회사 포스코 | 도금밀착성이 우수한 용융도금강판 및 그 제조방법 |
| BR112014007530B1 (pt) * | 2011-09-30 | 2018-12-11 | Nippon Steel & Sumitomo Metal Corporation | chapa de aço galvanizada por imersão a quente de alta resistência e processo para produção da mesma |
| KR20130076589A (ko) * | 2011-12-28 | 2013-07-08 | 주식회사 포스코 | 도금표면 품질 및 도금밀착성이 우수한 고강도 용융아연도금강판 및 그 제조방법 |
| EP2840161B1 (en) * | 2012-04-17 | 2018-09-12 | JFE Steel Corporation | Method for producing alloyed hot-dip galvanized steel sheet having excellent adhesion to plating and excellent sliding properties |
| WO2014037627A1 (fr) | 2012-09-06 | 2014-03-13 | Arcelormittal Investigación Y Desarrollo Sl | Procede de fabrication de pieces d'acier revêtues et durcies a la presse, et tôles prerevêtues permettant la fabrication de ces pieces |
| CN103805840B (zh) * | 2012-11-15 | 2016-12-21 | 宝山钢铁股份有限公司 | 一种高成形性热镀锌超高强度钢板及其制造方法 |
| JP5920249B2 (ja) * | 2013-03-05 | 2016-05-18 | Ｊｆｅスチール株式会社 | めっき密着性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 |
| WO2014135753A1 (fr) | 2013-03-06 | 2014-09-12 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de réalisation d'une tôle à revêtement znal avec un essorage optimisé, tôle, pièce et véhicule correspondants |
| TWI613325B (zh) * | 2013-05-17 | 2018-02-01 | Ａｋ鋼鐵資產公司 | 供壓模淬火（ｐｒｅｓｓ ｈａｒｄｅｎｉｎｇ）應用之鍍鋅鋼及製造方法 |
| WO2015001367A1 (en) * | 2013-07-04 | 2015-01-08 | Arcelormittal Investigación Y Desarrollo Sl | Cold rolled steel sheet, method of manufacturing and vehicle |
| JP5799996B2 (ja) * | 2013-09-12 | 2015-10-28 | Ｊｆｅスチール株式会社 | 外観性とめっき密着性に優れる溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板ならびにそれらの製造方法 |
| RU2647419C2 (ru) | 2013-12-10 | 2018-03-15 | Арселормиттал | Способ отжига листовой стали |
| WO2017006144A1 (en) | 2015-07-09 | 2017-01-12 | Arcelormittal | Steel for press hardening and press hardened part manufactured from such steel |
| WO2018138791A1 (ja) * | 2017-01-25 | 2018-08-02 | 新日鐵住金株式会社 | 鋼板 |
| WO2018234839A1 (en) | 2017-06-20 | 2018-12-27 | Arcelormittal | ZINC COATED STEEL SHEET HAVING HIGH STRENGTH POINTS WELDABILITY |
| WO2019092467A1 (en) * | 2017-11-08 | 2019-05-16 | Arcelormittal | A galvannealed steel sheet |
| CN108165892A (zh) * | 2017-11-23 | 2018-06-15 | 南阳汉冶特钢有限公司 | 一种低温压力容器用35-50mm厚Q420R高强钢及其生产方法 |
| CN113969336B (zh) * | 2020-07-23 | 2023-03-28 | 宝山钢铁股份有限公司 | 一种热镀锌钢板的制造方法、钢板及车用构件 |
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| JP2970445B2 (ja) * | 1994-12-14 | 1999-11-02 | 住友金属工業株式会社 | Ｓｉ添加高張力鋼材の溶融亜鉛めっき方法 |
| RU2128719C1 (ru) * | 1997-03-05 | 1999-04-10 | Научно-производственный институт АО "Новолипецкий металлургический комбинат" | Способ производства горячеоцинкованного металла высших категорий вытяжки с тончайшим цинковым покрытием с превосходной штампуемостью |
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| JP4464720B2 (ja) * | 2003-04-10 | 2010-05-19 | 新日本製鐵株式会社 | 高強度溶融亜鉛めっき鋼板およびその製造方法 |
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2008
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- 2008-06-06 WO PCT/IB2008/001462 patent/WO2009004425A1/en active Application Filing
- 2008-06-06 BR BRPI0813687A patent/BRPI0813687B1/pt active IP Right Grant
- 2008-06-06 AT AT08762800T patent/ATE521726T1/de active
- 2008-06-06 EP EP08762800A patent/EP2171116B1/en active Active
- 2008-06-06 KR KR1020107001332A patent/KR101273308B1/ko active IP Right Grant
- 2008-06-06 JP JP2010514160A patent/JP5713673B2/ja active Active
- 2008-06-06 US US12/666,702 patent/US20100193081A1/en not_active Abandoned
- 2008-06-06 CN CN200880025372.2A patent/CN101809182B/zh active Active
- 2008-06-06 ES ES08762800T patent/ES2371985T3/es active Active
- 2008-06-06 PL PL08762800T patent/PL2171116T3/pl unknown
- 2008-06-06 CA CA2701091A patent/CA2701091C/en active Active
- 2008-06-27 AR ARP080102782A patent/AR067339A1/es active IP Right Grant
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2014
- 2014-11-07 JP JP2014227461A patent/JP2015078438A/ja active Pending
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| US3925579A (en) * | 1974-05-24 | 1975-12-09 | Armco Steel Corp | Method of coating low alloy steels |
| US3936543A (en) * | 1974-08-22 | 1976-02-03 | Armco Steel Corporation | Method of coating carbon steel |
| EP0448351A1 (en) * | 1990-03-20 | 1991-09-25 | Kawasaki Steel Corporation | Method of producing hot-dip galvannealed steel sheet |
| BE1014997A3 (fr) * | 2001-03-28 | 2004-08-03 | Ct Rech Metallurgiques Asbl | Procede de recuit en continu de bandes en acier en vue de leur galvanisation au trempe et four pour sa mise en oeuvre. |
| CN1771344A (zh) * | 2003-04-10 | 2006-05-10 | 新日本制铁株式会社 | 高强度熔融镀锌钢板及其制造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| AR067339A1 (es) | 2009-10-07 |
| CA2701091C (en) | 2012-04-17 |
| JP2015078438A (ja) | 2015-04-23 |
| ES2371985T3 (es) | 2012-01-12 |
| CA2701091A1 (en) | 2009-01-08 |
| CN101809182A (zh) | 2010-08-18 |
| BRPI0813687A8 (pt) | 2015-12-15 |
| US20100193081A1 (en) | 2010-08-05 |
| ATE521726T1 (de) | 2011-09-15 |
| JP5713673B2 (ja) | 2015-05-07 |
| EP2009129A1 (en) | 2008-12-31 |
| JP2010532820A (ja) | 2010-10-14 |
| EP2171116B1 (en) | 2011-08-24 |
| WO2009004425A1 (en) | 2009-01-08 |
| BRPI0813687B1 (pt) | 2018-10-30 |
| PL2171116T3 (pl) | 2012-01-31 |
| BRPI0813687A2 (pt) | 2014-12-30 |
| KR20100055389A (ko) | 2010-05-26 |
| RU2010102924A (ru) | 2011-08-10 |
| KR101273308B1 (ko) | 2013-06-11 |
| RU2451107C2 (ru) | 2012-05-20 |
| EP2171116A1 (en) | 2010-04-07 |
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