CN102985570A - 由扁钢制品制造经热成型且淬火的、具有金属抗腐蚀涂层的钢制零件的方法 - Google Patents
由扁钢制品制造经热成型且淬火的、具有金属抗腐蚀涂层的钢制零件的方法 Download PDFInfo
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- CN102985570A CN102985570A CN2011800293670A CN201180029367A CN102985570A CN 102985570 A CN102985570 A CN 102985570A CN 2011800293670 A CN2011800293670 A CN 2011800293670A CN 201180029367 A CN201180029367 A CN 201180029367A CN 102985570 A CN102985570 A CN 102985570A
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- coating
- band steel
- steel goods
- aforementioned
- metal
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 136
- 239000010959 steel Substances 0.000 title claims abstract description 136
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000576 coating method Methods 0.000 title claims description 57
- 239000011248 coating agent Substances 0.000 title claims description 55
- 238000005260 corrosion Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 67
- 238000000137 annealing Methods 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 24
- 238000003856 thermoforming Methods 0.000 claims description 23
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910018134 Al-Mg Inorganic materials 0.000 claims description 4
- 229910018467 Al—Mg Inorganic materials 0.000 claims description 4
- 229910018125 Al-Si Inorganic materials 0.000 claims description 3
- 229910018520 Al—Si Inorganic materials 0.000 claims description 3
- 229910009369 Zn Mg Inorganic materials 0.000 claims description 2
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 2
- 229910007573 Zn-Mg Inorganic materials 0.000 claims description 2
- 229910007567 Zn-Ni Inorganic materials 0.000 claims description 2
- 229910007614 Zn—Ni Inorganic materials 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000012797 qualification Methods 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- 229910018464 Al—Mg—Si Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000005488 sandblasting Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229910000734 martensite Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 239000012792 core layer Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 239000011253 protective coating Substances 0.000 abstract 1
- 239000011241 protective layer Substances 0.000 abstract 1
- 238000005121 nitriding Methods 0.000 description 29
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
- C21D8/0457—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种由扁钢制品制造涂覆有金属保护涂层的钢制零件的方法，该扁钢制品具有至少0.4重量%的Mn含量。为了以经济的方式制造高坚固性的钢制零件，同时使生成金属诱导缝隙的风险降到最低，根据本发明，扁钢制品在连续炉中退火，退火气氛含有达25体积%的H2、0.1-10体积%的NH3、H2O和余量的N2以及由于技术条件限制无法避免的杂质，该退火气氛具有在-50℃和-5℃之间的露点，在400-1100℃的维持温度下保持5-600秒。经退火处理的扁钢制品具有厚度为5-200μm的渗氮层（N），该渗氮层的晶粒尺寸小于位于扁钢制品内部的内核层（K）的晶粒尺寸。在扁钢制品经过金属保护层涂层之后，由经退火的扁钢制品分割出板材，该板材在可选的预成型后加热到780-950℃的奥氏体化温度、热成型为钢制零件然后这样快速地冷却，从而在扁钢制品中形成淬火组织。
Description
技术领域
本发明涉及一种由扁钢制品制造经热成型且淬火的、涂覆有金属抗腐蚀保护涂层的钢制零件的方法，该扁钢制品具有至少0.4重量%的锰含量。
背景技术
于2005年9月15日至25日在法兰克福举办的第61届国际车展中，发表在蒂森克虏伯汽车股份公司的展报内的文章《轻巧的汽车车身的潜力》中报道过，在实践中特别是由硼合金钢材制造高强度车身零件中应用热成型淬火。此处提到的硼合金钢材的典型例子是标号为22MnB5的钢，该钢可以在钢手册2004中以材料号1.5528找到。
与钢22MnB5类似的钢在JP 2006104526 A中已知。该已知钢除了铁和不可避免的杂质还含有（重量%）0.05-0.55%的C，最大2%的Si，0.1-3%的Mn，最大0.1%的P和最大0.03%的S。为了改善淬硬性，可以额外在钢内增加0.0002-0.005%含量的B和0.001-0.1%含量的Ti。各个Ti含量作用为使钢内存在的氮固化。钢内存在的硼可以以这种方式尽可能完全地发挥其提升坚固性的作用。
根据JP 2006104526 A，首先由这类型的钢制成板材，该板材稍后在高于Ac3-温度，典型位于850-950℃范围内的温度中进行预热。接下来在冲压工具中进行的、从该温度区域迅速的冷却过程中，在由各个板材毛坯挤压成型的零件中形成保障了所追求的高强度的马氏体结构。有利的是，加热到所述温度水平的板材能够通过相对较小的变形力变形成复杂形状的零件。这特别适用于这类板材，其由高坚固性的钢制成并且设计有抗腐蚀涂层。
镀锌的扁钢制品热成型为高坚固性或者最高坚固性的钢制零件存在一个特别的困难。具有金属抗腐蚀涂层的钢片由于热成型和接下来进行的或者与热成型同时进行的淬火中必须加热到这样一个温度，该温度位于保护涂层的金属的熔化温度之上，由此存在所谓的“液化金属脆裂”风险。当镀层的熔化成液态的金属渗入到在成型过程中在各个扁钢制品表面形成的缺口内，发生钢的脆裂。液态金属到达钢基底并在那里的晶界汇集由此降低可承受的最大拉力和压力。
由较高坚固性和高坚固性含锰钢制成的扁钢制品的液化金属脆裂的危险性经证明是特别关键的。这类钢只具有有限的延展性所以在其变形过程中趋向于形成靠近表面的、靠近晶界的裂缝。
由DE-OS 18 13 808中已知，钢板的抗腐蚀性和抗氧化性可通过渗氮处理进行改善，通过该渗氮处理产生一个靠近表面的、厚2.5-19μm的具有与钢板的内核区域相比提高的氮含量的边缘层。渗氮层具有较好的粘附性。
由DE 691 07 931 T2进一步已知，通过渗碳处理或者渗氮处理可以在由低碳钢组成的、用于机动车车身制造的扁钢制品的靠近表面的区域产生较高的碳含量或者氮含量，用来改善相关扁钢制品的可处理性。
在现有技术中该措施没有与较高坚固性的或者高坚固性的、具有至少0.4重量%的锰含量的钢联系在一起，其中根据本发明处理加工的钢的典型锰含量位于0.4-0.6重量%内，特别位于0.6-3.0重量%范围内。
根据本发明处理加工的扁钢制品的碳含量典型为多于0.06重量%和少于0.8重量%，特别少于0.45重量%。
为了调整根据本发明处理加工的钢的各项性质，可以使其含有达0.2重量%的Ti、达0.005重量%的B、达0.5重量%的Cr、达0.1重量%的V或者达0.03重量%的Nb。
氮化或者内部渗氮的前提是具有渗透性的氮。当氮处于原初状态（statu nascendi）时该前提条件得到满足。
通常，渗氮处理通过在含氨的H2-N2-退火气氛内使各个的扁钢制品退火完成。这里的氨和氮作为氮的供体。氨气在气压和高于400℃的温度下***成两倍于其体积的氮和氢。氮气的分解可以通过下述反应方程式描述：
2NH3->2[N]+3H2
发明内容
在前述现有技术的背景下本发明的目的在于，提供一种方法，以经济的方式允许，在将金属诱导的裂缝风险减到最低的同时制造高坚固性的钢制零件。
该目的根据本发明由此实现，即，在制造高坚固性的钢制零件过程中，施行权利要求1披露的工作步骤。
本发明的具有优势的设计方案在各个独立权利要求的从属权利要求中给出，并且下面以细节阐述一般性的发明理念。
根据本发明的用于制造具有金属抗腐蚀涂层的钢制零件的方法，由该想法出发，在对扁钢制品进行热成型之前在其表面实施渗氮处理，通过该处理在扁钢制品中制造精细结构的边缘层。在一方面，该边缘层为热成型改善了表面磨光的钢制产品的成型性质。
另一方面，经证实，根据本发明的方法在扁钢制品的渗氮边缘区域，出乎预料地有益于防止热成型过程中钢制精细板材的金属脆裂。渗氮区导致晶界面/相界面（Phasengranzflaechen）在热成型过程中的显著提高，该提高抵制了由镀膜金属材料渗入钢基底导致的裂缝问题。此外在涂层内存在一个不寻常的高的铁渗透。其结果是，特别是基于锌的涂层的处理过程中，涂层在热学方面更加稳定。
为了能够利用前述总结的根据本发明实施的边缘层渗氮的有利影响，根据本发明的方法包含下述处理步骤：
-制备一块由钢制成的扁钢制品，其具有至少0.4重量%的锰含量。此处所说的扁钢制品指的是钢片、钢带、钢板或者同类型产品。这样的扁钢制品可以在热轧或者冷轧状态以本发明的方式进行处理。还可能，将不同的钢板组合形成一个扁钢制品，该扁钢制品在接下来根据本发明的方式中进行处理，其中钢板由具有权利要求1给出的类型的钢制成。
-扁钢制品在连续炉中退火，退火气氛含有达25体积%的H2、0.1-10体积%的NH3、H2O和余量的N2以及由于技术条件限制无法避免的杂质，该退火气氛具有在-50℃和-5℃之间的露点。维持温度为400-1000℃，扁钢制品在该维持温度下维持5-600秒。最终通过该渗氮-退火处理在扁钢制品表面存在厚度为5-200μm的、限定在扁钢制品的游离表面的可延展的渗氮层，该渗氮层的晶粒尺寸小于位于内部的、由边缘层覆盖的、由扁钢制品的基本材料构成的内核层的晶粒尺寸。
-在产生渗氮层后，以前述方式退火的扁钢制品经金属保护层涂层。此处本发明利用了这样的认识，液化金属脆裂的风险可以由此降低，即，可以通过有目的地调整扁钢制品的邻近表面区域来改变对于液化金属脆裂无抵抗力的温度范围，从而使该温度范围与对于热成型典型的温度范围不发生重叠。
-由金属保护层涂层的扁钢制品分割成板材。
-如果成型需要两个或者多个步骤，板材可以在该步骤中可选地预成型。预成型可以到这个程度，在预成型后板材的形状几乎完全等同于零件的最终形状。典型地，预成型在一块冷的或者加热到低于奥氏体化温度的半热的板材上进行。只通过热成型一步完成的成型可以不使用预成型。
-用于热成型的板材加热到780-950℃的奥氏体化温度。
-然后将加热后的板材热成型为最终的钢制零件。
-然后将得到的钢制零件进行冷却，此处由奥氏体化温度出发进行加速冷却。钢制零件的冷却这样进行，从而在扁钢制品中形成淬火组织。
热成型和淬火可以在同一个步骤中完成。这种情况下，热成型和淬火共同在一个工具中一步进行。与此相反，两步式的过程中分开进行工作步骤“成型”和“生成调制组织或淬火组织”。
令人惊讶的是，利用根据本发明给出的退火条件，即使在很短的时间内也可以达到所希望的渗氮深度。所以根据本发明的方法的优势在于，以一种非常经济的方式应用连续炉实行本方法。这实现了，根据本发明的方法结合到以高速传送带速度为前提的、连续进行的制造过程中，例如在火焰涂层设备中，钢带在连续的运行中进行热处理并热浸镀抗腐蚀涂层。
在反应腔内存在的铁表面在催化上有利于分解过程。在氮原子分离的瞬间，一部分氮原子渗入到铁材料中。
氮的转移发生在若干个步骤中：
●转移到工件表面
●吸附在表面
●渗透表面（吸收）
●渗透到工件内部
由于在奥氏体中提高的氮溶解度，进行两相热处理（即在两相区域α/γ-Fe）是实用的。无论接下来的金属保护层涂层是连续进行还是逐件进行，通常，在实践中在给出的条件下可以这样以特别经济和环保的方式优化渗氮处理的效果，即，至少遵守下述条件的其中一条：
-退火气氛的H2含量不超过10体积%，
-退火气氛的NH3含量不超过5体积%，
-退火气氛的露点在-40℃至-15℃，
-退火温度在680℃至840℃，
-退火维持时间为30-120秒。
对于本发明的效果起决定作用的是，在根据本发明的退火处理中对渗氮边缘层进行调整，使其晶粒尺寸远远小于扁钢制品的未在退火过程中进行渗氮的内核层晶粒尺寸。实际测试已经给出，根据DINEN ISO 643渗氮层的晶粒尺寸特性数值比板材加热和热成型前的经退火的扁钢制品的基本材料（内核层）的晶粒尺寸特性数值至少小2。
在根据本发明的方法中对渗氮边缘层进行有目的地调整。该精细结构的、同样只是部分再结晶的渗氮层的厚度由根据DIN 50190-3得出的渗氮硬化厚度决定。此处的渗氮硬化厚度是从表面到钢基底之间的距离，在钢基底处，硬度对应于+50HV的核心硬度。以这种方式在扁钢制品的经过渗氮的、靠近表面的边缘层区域调整出这样一个硬度，该硬度比内核区域的硬度高至少25%，即HV（渗氮）/HV(内核区域)≥1.25。
典型地，根据本发明处理的扁钢制品中，在退火处理后的渗氮边缘层的厚度大于5μm并且小于200μm。
本发明在实践中特别具有优势的设计方案的特征在于，具有金属保护层的扁钢制品涂层通过热浸镀涂层进行，该热浸镀涂层在接续在退火处理之后的工作步骤中连续地进行。在这种情况下，根据本发明进行的退火处理与为接下来的表面磨光而进行的、通过异相的退火气-金属-反应进行的表面调节同时进行。
特别具有优势的是，根据本发明的方法在火焰涂层设备中进行，因为在该情况下的退火处理可以包含基本原理的边缘渗氮、表面调节和重结晶，并且接下来的热浸镀可以在退火处理之后连续地在线（inline）进行。在此，原则上可以考虑，使含有NH3的气体流过扁钢制品穿过的炉子的整个长度。为了不使连续炉的全部零件都处于渗氮气体中，有利的是，将炉子的一个部分与炉子其它部分分离，并且含有NH3的气体只对这个分离出的部分进行进气冲击。
为了保证经退火后的扁钢制品的作为火焰涂层实行的热浸镀情况下优化的钢基底涂层粘附性，可以在火焰涂层前进行扁钢制品的表面氧化。
在根据本发明制造的扁钢制品的优选通过热浸镀进行的表面磨光过程中，可以在钢基底上引入已知的涂层***，该***由Zn、Al、Zn-Al、Zn-Mg、Zn-Ni、Zn-Fe、Al-Mg、Al-Si、Zn-Al-Mg或Zn-Al-Si构成。在热浸镀之后可以进行热处理步骤，为了使金属保护层以特定的方式形成。如果有需求，还可以在热浸镀后连续进行渗透退火，例如锌镀层退火处理。
作为在线（in line）进行的热浸镀的替代或者补充，扁钢制品（根据本发明的方式在连续退火中在该扁钢制品上形成一个精细结构化的渗氮层）可以具有一个金属的、金属-无机的或者金属-有机的涂层，该涂层中例如通过Zn涂层、ZnNi涂层或者ZnFe涂层借助PVD析出或CVD析出或借助其他金属-无机的或者金属-有机的涂层方法进行电解地涂层。
为了进一步优化机械性质，可以在根据本发明的退火处理之后以常规方式进行一个过时效处理。
由根据本发明进行处理后的扁钢制品经热成型然后经淬火得到的零件具有800-2000MPa，特别是900-2000MPa的抗拉强度。
根据本发明制造的渗氮涂层允许了，根据本发明的扁钢制品顺利地加热到奥氏体化温度，在该温度的扁钢制品具有完整的奥氏体结构。如果扁钢制品设有金属涂层，该涂层的熔点低于或等于加热温度，在如此高的加热温度还是使脆裂风险降到最低。通过本发明的渗氮实现的边缘层的精细晶粒避免了裂缝的形成并且保证了，涂层金属不能渗入内核区域或者钢基底的基本材料中。
通过根据本发明制造的精细结构化的、经渗氮的渗氮层避免了在优选直接即没有板材预成型的情况下进行的热成型过程中，由金属涂层特别是锌涂层，或者是由涂层金属渗透引起的进入到晶界的固体金属脆裂。同样地，根据本发明的方法由渗氮引起的、鉴于铁/涂层金属的比例具有优势的涂层的形成避免了焊缝的形成并且抑制了液态金属脆裂。
附图说明
下面根据实施例进一步阐述本发明。图中：
图1：根据本发明的经渗氮退火的钢质样品的垂直磨片；
图2：未经退火的、轧硬的对比样品的垂直磨片；
图3：图1和图2所示的样品的氮含量的GDOES-深度曲线；
图4：由图1所示的钢制样品形成的钢制零件的拉伸区域的垂直磨片；
图5：由图2所示的轧硬的钢制样品形成的钢制零件的拉伸区域的垂直磨片。
具体实施方式
为了验证根据本发明的方法所能达到的效果，分别制造一个多相钢“MP”和通常用于热成型的钢“WU”的轧硬的冷带样品。钢MP和WU的成分在表格1中给出。
两个由钢MP和WU制成的样品投入到用于边缘层渗氮的连续炉中进行根据本发明的退火处理。此处使用的退火参数在表格2中给出。
为了便于比较，将两个由钢MP和WU制成的样品投入到连续炉中进行传统退火，如同通常为热浸镀锌做准备所进行的步骤。
图1中示出了由钢WU制成并根据本发明进行退火处理后的样品的显微图。很明显可以看出，作为根据本发明的处理步骤的结果，靠近表面处调整出一个精细结构的结构区域（渗氮区域N）
与此相反，同样由钢WU制成经过冷轧的样品的显微图没有这样的渗氮区域N（图2）。
此外测量了由钢WU制成经过根据本发明的退火处理和冷轧的样品的渗氮含量的GDOES。GDOES（“GDOES”=Glow Discharge OpticalEmission Spectrometer）测量法指的是快速获得涂层浓度情况的标准方法。其在由Hubert
VDI-Verlag GmbH于杜塞尔多夫，1993年出版的VDI-词典“Werkstofftechnik”（材料技术）中有所描述。
GDOES测量的结果在图3中给出，其中虚线示出了轧硬样品的氮分布，而实线示出了根据本发明处理的样品的氮分布。
图3也明确示出了，根据本发明处理的样品具有明显的氮化的渗氮层N，其厚度约为20μm。
鉴于显微硬度测量可以证明，由钢WU制成、经过根据本发明的热处理的样品中的氮化的渗氮层N具有340HV的显微硬度而没有经过氮化的内核区域（基本材料）K具有180HV的硬度。氮化的渗氮层N的硬度
与内核区域K的硬度
的比值约为1.9，由此远大于根据本发明的预先给出的该比值1.25。
退火之后是样品的表面磨光，该过程中将厚度为10μm的锌层电解地涂覆在样品上。
接下来由由钢WU制成的样品借助所谓的一步式或者直接热成型方法成型并且压制硬化成钢制零件。为此样品经6分钟的奥氏体化时间加热到880℃的奥氏体化温度然后在热压变形工具中热成型为用于机动车车身的零件。
在热成型之后得到的零件以已知方式如此迅速冷却，从而形成淬火组织。
通过图4和5的对比很明显，根据本发明的方法制造的零件的拉伸区域内丝毫没有裂缝形成，而传统方式制造的零件明显地存在晶体间的裂缝。
由钢MP制成的经过退火处理、镀锌和变形的样品对于根据本发明的和传统方式的退火处理后的样品可以给出类似的结果。
根据本发明的方法改善了热成型中表面磨光的扁钢制品的成型性能。为此在表面磨光之前、以连续进行的或者逐件进行的方式通过退火过程中有目的地气体-金属-反应来制造边缘氮化，其结果是调节出一个精细结构化的含氮的渗氮层N。该氮化的边缘层N一方面提高了涂层中的铁渗透，并且在热成型之前进行的退火过程中阻止了脆化剂“涂层金属”，特别是锌传递到结晶界限。
最终获得这样的零件，其钢基底完全没有裂缝。
剩余的铁及无可避免的杂质
表格1
表格2
Claims (15)
1.一种由扁钢制品制造涂覆有金属抗腐蚀保护涂层的钢制零件的方法，所述扁钢制品具有至少0.4重量%的Mn含量，所述方法包含以下步骤：
-制备所述扁钢制品；
-使所述扁钢制品在连续炉中退火；
-退火气氛含有达25体积%的H2、0.1-10体积%的NH3、H2O和余量的N2以及由于技术条件限制无法避免的杂质，所述退火气氛具有在-50℃和-5℃之间的露点，
-维持温度为400-1100℃
-维持时间为5-600秒，
-经退火处理的所述扁钢制品具有厚度为5-200μm的渗氮层（N），所述渗氮层的晶粒尺寸小于位于所述扁钢制品内部的内核层（K）的晶粒尺寸；
-用金属保护层对所述经过退火的扁钢制品进行涂层；
-由所述扁钢制品分割出板材；
-所述板材可选地进行预成型；
-将所述板材加热到780-950℃的奥氏体化温度，
-将经过加热的板材热成型为钢制零件，
-所述钢制零件这样进行加速冷却，从而在所述扁钢制品中形成淬火组织。
2.根据权利要求1所述的方法，其特征在于，所述退火气氛的H2含量最高为10体积%。
3.根据前述权利要求的任意一项所述的方法，其特征在于，所述退火气氛的NH3含量最高为5体积%。
4.根据前述权利要求的任意一项所述的方法，其特征在于，所述退火气氛的露点为-40℃至-15℃。
5.根据前述权利要求的任意一项所述的方法，其特征在于，所述退火的维持温度为680-840℃。
6.根据前述权利要求的任意一项所述的方法，其特征在于，所述退火的维持时间为30-120秒。
7.根据前述权利要求的任意一项所述的方法，其特征在于，在板材加热和热成型前的所述经退火的扁钢制品的渗氮层（N）的根据DIN EN ISO 643得出晶粒尺寸特性数值比基本原料（K）的晶粒尺寸特性数值至少小2。
8.根据前述权利要求的任意一项所述的方法，其特征在于，用金属保护层对所述扁钢制品进行的涂层通过热浸镀进行，所述热浸镀在连续进行的工作流程中、在退火处理后进行。
9.根据权利要求8所述的方法，其特征在于，在所述热浸镀前进行所述扁钢制品的表面氧化。
10.根据权利要求8或9所述的方法，其特征在于，所述扁钢制品在所述热浸镀处理后连续地进行渗透退火。
11.根据权利要求1至7的任意一项所述的方法，其特征在于，所述具有金属的、金属-有机的或者金属-无机的保护涂层的扁钢制品的涂层通过电解涂层或借助PVD析出或CVD析出进行。
12.根据前述权利要求的任意一项所述的方法，其特征在于，所述金属涂层是Zn涂层、Al涂层、Zn-Al涂层、Zn-Mg涂层、Zn-Ni涂层、Al-Mg涂层、Al-Si涂层、Zn-Al-Mg涂层或Zn-Al-Mg-Si涂层。
13.根据前述权利要求的任意一项所述的方法，其特征在于，在所述加热过程中调整得到的奥氏体化温度为860-950℃。
14.根据前述权利要求的任意一项所述的方法，其特征在于，所述经过热成型获得的零件的热成型和冷却过程在一个步骤中进行。
15.根据前述权利要求的任意一项所述的方法，其特征在于，对所述获得的零件进行喷砂处理。
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| DE102010017354.1 | 2010-06-14 | ||
| DE102010017354A DE102010017354A1 (de) | 2010-06-14 | 2010-06-14 | Verfahren zum Herstellen eines warmgeformten und gehärteten, mit einer metallischen Korrosionsschutzbeschichtung überzogenen Stahlbauteils aus einem Stahlflachprodukt |
| PCT/EP2011/059808 WO2011157690A1 (de) | 2010-06-14 | 2011-06-14 | Verfahren zum herstellen eines warmgeformten und gehärteten, mit einer metallischen korrosionsschutzbeschichtung überzogenen stahlbauteils aus einem stahlflachprodukt |
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| CN115287444B (zh) * | 2022-09-08 | 2024-02-06 | 西部超导材料科技股份有限公司 | 一种Bi-2212超导线材热处理方法 |
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| JP2013534971A (ja) | 2013-09-09 |
| CN102985570B (zh) | 2016-03-30 |
| EP2580358A1 (de) | 2013-04-17 |
| DE102010017354A1 (de) | 2011-12-15 |
| WO2011157690A1 (de) | 2011-12-22 |
| BR112012030991A2 (pt) | 2016-11-08 |
| KR20130085410A (ko) | 2013-07-29 |
| DE102010017354A9 (de) | 2012-04-05 |
| US20130206284A1 (en) | 2013-08-15 |
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