CN117488068A - 汽车面板用热镀锌板的制备方法 - Google Patents
汽车面板用热镀锌板的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 54
- 239000010959 steel Substances 0.000 claims abstract description 54
- 239000011701 zinc Substances 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 238000007747 plating Methods 0.000 claims abstract description 23
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- 238000003618 dip coating Methods 0.000 claims description 7
- 238000010924 continuous production Methods 0.000 claims description 6
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- 238000005096 rolling process Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002310 reflectometry Methods 0.000 claims description 5
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
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- 239000010936 titanium Substances 0.000 claims description 4
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- 239000012535 impurity Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 8
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- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
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- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract
本发明公开了汽车面板用热镀锌板的制备方法，通过调控钢基板组织成分、组织性能、表面状态及热镀锌工艺，成功制备出无锌花热镀锌板，产品表面无任何肉眼可见缺陷；其锌液与钢基之间具有良好浸润性，锌液在基板表面形核及生长阻力较大，较现有产品，锌花数量更少，锌花尺寸更为细小；脱脂清洗后带钢表面清洁度较高，钢基与镀液之间反应活性高，对热浸镀锌反应更有利；锌液对钢板的的平衡浸润力较大，带钢在锌液中具有良好润湿性和粘附性；热浸镀后通过添加晶核长大抑制剂VC和控制冷却速度，晶核无法快速长大。本方法制备的无锌花热镀锌板表面质量、致密性和均匀性较高，耐腐蚀性好，具有优良成形性能和涂装性能，在汽车板领域具有广泛应用前景。
Description
技术领域
本发明属于钢铁冶金生产技术领域，具体涉及汽车面板用热镀锌板的制备方法。
背景技术
热镀锌产品按表面状态可分为大锌花、小锌花、无锌花及光整表面产品。汽车面板用镀锌板不仅要有良好的耐腐蚀性、可涂装性，而且对产品表面质量的要求也极为严格。带锌花钢板镀层易产生晶间腐蚀、其耐腐蚀性不如无锌花钢板；热镀锌钢板涂装时，锌花引起的钢板表面凹凸不平在涂装后仍然清晰可见，影响产品的外观质量。因此，汽车面板用镀锌板不仅要无锌花、镀层表面光洁、无缺陷，镀层厚度均匀，且具有一定的粗糙度，以保证与漆膜之间具有良好的附着性，以及涂装后具有良好的耐腐蚀性和美观性。目前国内的镀锌机组主要生产大锌花、小锌花热镀锌板、无锌花镀锌板，其中无锌花镀锌板是通过增加晶核数量，抑制晶核长大，从而控制锌花尺寸大小，并非严格意义上的无锌花板，性能和表面状态均难于满足生产高端汽车外板生产要求。
发明内容
为克服上述现有技术的缺陷，本发明通过调控钢基板组织成分、组织性能、表面状态及热镀锌工艺等，成功制备出高端无锌花热镀锌板汽车外板，产品表面无任何肉眼可见缺陷。
为了实现上述发明目的，本发明提供了汽车面板用热镀锌板的制备方法，，所述制备方法包括如下步骤：
①汽车面板用镀锌板的原料钢为钛、铌稳定化的超低碳钢，原料钢化学组成以质量百分比计，C≤0.004%；Si≤0.020%；Mn：0.10~0.20%；P≤0.015%；S≤0.010%；Als：0.015~0.045%；N≤0.004%；Nb：0.006~0.010%；Ti：0.010~0.014%。冷硬卷在连续生产线上进行热浸镀锌，其中冷硬卷基板粗糙度为：0.6µm≤冷硬卷基板粗糙度算术平均值Ra≤0.8µm，60≤波峰数Rpc≤80，表面粗糙度最大值Rmax≤3 Ra，冷硬卷厚度为0.4~0.8mm。
精轧机工作辊经激光毛化后还需使用抛光机对辊面进行抛光。轧制后基板表面粗糙度应为：0.6µm≤冷硬卷基板粗糙度算术平均值Ra≤0.8µm，60≤波峰数Rpc≤80，表面粗糙度最大值Rmax≤3 Ra，在该条件下，锌液与钢基之间具有良好的的浸润性，锌液在基板表面形核及生长阻力较大、形核数量较少。
②冷硬卷在连续生产线上进行热浸镀锌，采用阴极电解脱脂方式对带钢进行除污处理，脱脂清洗后带钢反射率达到80%以上，在线连续退火炉采用全辐射加热，退火炉均热段温度750~850℃，均热时间50~100s，退火炉内采用15%H2和85%N2的混合气体，氧气含量≤10ppm，还原加热时间≥30s，露点-60~-30℃。
所述的脱脂清洗后带钢反射率≥80%，因为带钢清洗不净时，退火后，部分油脂未挥发就被碳化，在带钢表面碳化形成黑斑，影响带钢表面质量。
③热镀锌炉鼻子需安装抽真空装置，清除热镀锌炉鼻子内锌灰及抑制热镀锌炉鼻子内锌灰形成。
④热浸镀温度为450~520℃，带钢入锌锅温度高于锌液温度5~10℃，锌液中晶核长大抑制剂VC的质量百分数为0.01%~0.02%，抑制锌花的快速长大。
⑤采用气体喷吹强制冷却方式对热浸镀后的试样进行快速冷却，冷却速度≥30℃/s，防止锌花快速长大。
⑥光整辊经激光毛化处理及抛光处理，光整辊表面粗糙度：1.0µm≤轧辊表面粗糙度算术平均值Ra≤1.5µm，100≤波峰数Rpc≤120，表面粗糙度最大值Rmax≤3Ra，光整压下量≥2%，在较大的压下量下，不仅确保镀锌板具有一定的粗糙度，还能进一步破坏表面锌花结构。
进一步的，步骤②中，连续退火后钢板表面氧化膜厚度≤16nm，（1 1 1）晶面占比≥85%。由于氧化膜过厚不仅影响镀液与钢基之间的润湿性，还抑制热浸镀锌初始阶段的铁锌反应。Fe（1 1 1）晶面不仅与镀液之间反应活性高，而且比其他结晶方位有更大的溶解度，相比对热浸镀锌反应更有利。
进一步的，步骤③中，所述的热镀锌炉鼻子需安装抽真空装置，真空度≤10-2Pa，避免炉鼻子内锌蒸气过饱和附着在带钢表面引起表面质量缺陷。
进一步的，热浸镀温度优选为460~480℃；镀液成份以质量百分数计为，0.1%≤Al≤0.2%，0.1%≤RE≤0.2%，0.01%≤VC≤0.02%，杂质元素（Pb、Sb、Sn等）的和≤0.05%，其余为Zn，锌液对钢板的的平衡浸润力≥0.6 N/m，该条件下不仅带钢在锌液中具有良好的润湿性，而且镀层还具有良好粘附性，镀层厚度为60~120 g/m2，热浸镀时间为3~5s，气刀压力为200~230bar。此外，锌锅内还需安装自动除渣装置。
与现有技术相比，本发明的有益效果：
本发明通过调控钢基板组织成分、组织性能、表面状态及热镀锌工艺等，成功制备出无锌花热镀锌板，产品表面无任何肉眼可见缺陷，能够满足汽车面板用镀锌板要求。其锌液与钢基之间具有良好的浸润性，锌液在基板表面形核及生长阻力较大，形核数量很少；脱脂清洗后带钢表面清洁度较高，钢基与镀液之间反应活性高，而且比其他结晶方位有更大的溶解度，对热浸镀锌反应更有利；锌液对钢板的的平衡浸润力较大，带钢在锌液中具有良好的润湿性和粘附性；热浸镀后冷却速度较大，晶核无法快速长大。综上，本发明专利制备的无锌花热镀锌板表面质量、致密性和均匀性较高，耐腐蚀性好，具有优良的成形性能和涂装性能，在汽车板领域具有广泛的应用前景。
具体实施方式
以下结合具体实施例对本发明作进一步说明，但不以任何方式限制本发明。为免赘述，以下实施例中原材料若无特别说明则均为市售产品，所用方法若无特别说明则均为常规方法。
实施例1
汽车面板用热镀锌板的制备方法，所述制备方法包括如下步骤：
①选取钛、铌稳定化的超低碳钢，化学成分（质量分数，%） C 0.004；Si 0.002；Mn0.20； P 0.009；S 0.008；Als 0.030；N 0.003；Nb 0.006；Ti 0.010。采用激光毛化及抛光机抛光后的冷轧精轧机工作辊对所述钢的热轧产品进行轧制，所得冷硬卷基板粗糙度Ra为0.8µm，波峰数Rpc为80，表面粗糙度最大值Rmax为2.0µm，冷硬卷厚度为0.5mm。
②将所得冷硬卷在连续生产线上进行热浸镀锌，带钢首先经阴极电解脱脂30s，脱脂清洗后带钢反射率为82%，将脱脂清洗后的带钢进行退火处理，退火温度为800℃，退火炉内气氛为15%氢气和85%氮气的混合气体，氧气含量为3ppm，还原加热时间30s，露点-55℃，连续退火后钢板表面氧化膜厚度约为6nm，（1 1 1）晶面占比为85%。
③热镀锌炉鼻子安装抽真空装置，真空度0.8×10-2Pa。
④退火后的带钢经炉鼻子进入锌锅，进行热浸镀，带钢入锌锅温度为480℃，热浸镀镀液温度为470℃，镀液成份以质量百分数计：Al 0.2%，RE 0.2%，Pb 0.015%，Sb 0.01%，Sn 0.01%，VC 0.01%，其余为Zn，锌液对钢板的的平衡浸润力为0.96 N/m。热浸镀时间为5s，气刀压力为200 bar，镀层厚度80 g/m2。
⑤采用气体喷吹强制冷却方法对热浸镀后的试样进行快速冷却，冷却速度为30℃/s。
⑥采用激光毛化及抛光处理的光整辊对其进行光整处理，光整辊表面粗糙度算术平均值Ra为1.5µm，波峰数Rpc为110，表面粗糙度最大值Rmax为3.5µm，光整压下量 2.5%。
上述制备方法得到镀锌成品表面无肉眼可见锌花，镀层表面无任何锌粒、条纹和缩孔等影响表面质量的缺陷，磷化后，磷化膜的膜重2~3 g/m2，磷化膜的晶粒尺寸为3~5µm，磷化膜的P比在85%以上，满足了汽车板生产要求。
实施例2
汽车面板用热镀锌板的制备方法，所述制备方法包括如下步骤：
选取钛、铌稳定化的超低碳钢，化学成分（质量分数， %） C 0.002；Si 0.001；Mn：0.14；P 0.006；S 0.005；Als 0.045；N 0.003；Nb 0.010；Ti 0.014。采用激光毛化及抛光机抛光后的冷轧精轧机工作辊对所述钢的热轧产品进行轧制，所得冷硬卷基板粗糙度Ra为0.6µm，波峰数Rpc为60，表面粗糙度最大值Rmax为1.5µm，冷硬卷厚度为0.6mm。
将所得冷硬卷在连续生产线上进行热浸镀锌，带钢首先经阴极电解脱脂30s，脱脂清洗后带钢反射率为85% ，将脱脂清洗后的带钢进行退火处理，退火温度为750℃，退火炉内气氛为15%氢气和85%氮气的混合气体，氧气含量为5ppm，露点-35℃，连续退火后钢板表面氧化膜厚度约为15nm，（1 1 1）晶面占比约为88%。
退火后的带钢经炉鼻子进入锌锅，进行热浸镀，带钢入锌锅温度为470℃，热浸镀镀液温度为460，镀液成份（质量百分数，%）Al 0.1，RE 0.1，Pb 0.010， Sb 0.01， Sn 0.01，VC 0.01，其余为Zn，锌液对钢板的的平衡浸润力为0.90 N/m。热浸镀时间为5s，气刀压力为230bar，镀层厚度110g/m2。 采用气体喷吹强制冷却方法对热浸镀后的试样进行快速冷却，冷却速度为40℃/s。采用激光毛化及抛光处理的光整辊对其进行光整处理、光整压下量3%。
得到镀锌成品表面无锌花，镀层表面无任何锌粒、条纹和缩孔等影响表面质量缺陷，磷化后，磷化膜的膜重2~3 g/m2，磷化膜的晶粒尺寸为3~5µm，磷化膜的P比在85%以上，满足了板生产要求。
对于任何熟悉本领域的技术人员而言，在不脱离本发明技术方案范围情况下，都可利用上述揭示的技术内容对本发明技术方案作出许多可能的变动和修饰，或修改为等同变化的等效实施例。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰，均应仍属于本发明技术方案保护的范围内。
Claims (5)
1.汽车面板用热镀锌板的制备方法，其特征在于，所述制备方法包括如下步骤：
①汽车面板用镀锌板的原料钢为钛、铌稳定化的超低碳钢，原料钢化学组成以质量百分比计，C≤0.004%；Si≤0.020%；Mn：0.10~0.20%；P≤0.015%；S≤0.010%；Als：0.015~0.045%；N≤0.004%；Nb：0.006~0.010%；Ti：0.010~0.014%；冷硬卷在连续生产线上进行热浸镀锌，其中冷硬卷基板粗糙度为：0.6µm≤冷硬卷基板粗糙度算术平均值Ra≤0.8µm，60≤波峰数Rpc≤80，表面粗糙度最大值Rmax≤3 Ra，冷硬卷厚度为0.4~0.8mm；
②冷硬卷在连续生产线上进行热浸镀锌，采用阴极电解脱脂方式对带钢进行除污处理，脱脂清洗后带钢反射率达到80%以上，在线连续退火炉采用全辐射加热，退火炉均热段温度750~850℃，均热时间50~100s，退火炉内采用15%H2和85%N2的混合气体，氧气含量≤10ppm，还原加热时间≥30s，露点-60~-30℃；
③热镀锌炉鼻子安装抽真空装置；
④热浸镀温度为450~520℃，带钢入锌锅温度高于锌液温度5~10℃；
⑤采用气体喷吹强制冷却方法对热浸镀后的试样进行快速冷却，冷却速度≥30℃/s；
⑥光整辊经激光毛化处理及抛光处理，光整辊表面粗糙度：1.0µm≤轧辊表面粗糙度算术平均值Ra≤1.5µm，100≤波峰数Rpc≤120，表面粗糙度最大值Rmax≤3Ra，光整压下量≥2%。
2. 根据权利要求1所述的制备方法，其特征在于，步骤②中，连续退火后钢板表面氧化膜厚度≤16nm，（1 1 1）晶面占比≥85%。
3.根据权利要求2所述的制备方法，其特征在于，步骤③中，所述的热镀锌炉鼻子安装抽真空装置，真空度≤10-2Pa。
4.根据权利要求3所述的制备方法，其特征在于，步骤④中，热浸镀温度优选为460~480℃。
5. 根据权利要求4所述的制备方法，其特征在于，步骤④中，镀液成份以质量百分数计为：0.1%≤Al≤0.2%，0.1%≤RE≤0.2%，0.01%≤VC≤0.02%，杂质元素Pb、Sb、Sn的和≤0.05%，其余为Zn，锌液对钢板的的平衡浸润力≥0.6 N/m；镀层厚度为60~120 g/m2，热浸镀时间为3~5s。
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