CN105792980B - 热冲压制品的制造方法 - Google Patents
热冲压制品的制造方法 Download PDFInfo
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- CN105792980B CN105792980B CN201480065830.0A CN201480065830A CN105792980B CN 105792980 B CN105792980 B CN 105792980B CN 201480065830 A CN201480065830 A CN 201480065830A CN 105792980 B CN105792980 B CN 105792980B
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- galvanized steel
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- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 87
- 239000008397 galvanized steel Substances 0.000 claims abstract description 87
- 239000011701 zinc Substances 0.000 claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 32
- 238000012545 processing Methods 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 37
- 239000010452 phosphate Substances 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910000831 Steel Inorganic materials 0.000 description 31
- 239000010959 steel Substances 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 18
- 239000013078 crystal Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000005480 shot peening Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
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- 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
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
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- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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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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- 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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- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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Abstract
热冲压制品的制造方法包括:成形工序,对其上形成有镀锌层(12)的镀锌钢板(1)进行加热并通过热冲压将经加热的镀锌钢板(1)成形;除去工序,在成形工序后对形成于镀锌层(12)的表面上的氧化膜(13)照射激光以除去氧化膜(13);涂装工序,在除去工序后在通过热冲压成形的镀锌钢板(1)上进行涂装处理。
Description
发明领域
本发明涉及一种可合适在通过热冲压成形的热冲压制品上进行涂装处理的热冲压制品的制造方法。
背景技术
近来,在汽车工业中,高抗拉强度钢板已普遍用于改进碰撞安全性和减少车辆的重量以改进燃料效率。但是,当待使用的钢的强度增加时,在压制成形期间可能发生钢板的擦伤或断裂,或者成形品的形状因回弹现象而可能不稳定。
作为制造高强度制品的技术,采用了热压成形(热冲压),其中不是简单对高强度钢板进行压制(冷压),而是在低强度状态(例如加热状态)下对高强度钢板进行压制成形。
在热冲压中,在将钢板加热至800℃或更高的奥氏体转变温度范围以将其软化的状态下对钢板进行压制。同时,通过与模具接触所获得的冷却效果(接触冷却)来强化钢板的淬火。作为结果,由于改进了压制品的强度并减小了其残余应力,因此还减小了作为高抗拉强度钢板的问题的季节性开裂、延迟断裂等的敏感性。
但是,镀锌退火(galvannealed)钢板在强度、焊接性、涂装性质等方面优异,并由此用作用于车身的钢板。当使用这样的镀锌退火钢板时,在其表面进行涂装处理。
在该涂装处理中,作为表面处理实施例如磷酸盐处理,并在磷酸盐晶体膜上形成涂膜。为了进行磷酸盐处理,从确保涂膜的优异的涂装性能(例如粘合性和耐蚀性)的观点考虑,形成优异的磷酸盐晶体膜是重要的。特别地,镀锌退火钢板由与磷酸盐处理溶液强烈反应的Zn-Fe合金形成,并且基本上不含杂质等。因此,可形成优异的磷酸盐晶体膜。
但是,即使在该情况下,由于通常在大气中进行热冲压,因此也在钢板的表面上形成氧化物。以锌基氧化膜的形式形成该氧化物。当形成该氧化膜时,涂膜的粘合性(特别地磷酸盐晶体膜的粘合性)可能降低。
鉴于该观点,例如公开了一种热冲压制品的制造方法,该方法包括:热压成形工序,在其上形成有镀锌层的镀锌钢板上进行热压成形(热冲压);和氧化锌层除去工序,通过喷丸除去经由加热工序而形成于镀锌钢板表面上的镀锌层的氧化锌层(例如,参考日本专利申请公开No.2012-25977(JP 2012-25977A))。
这样,通过除去氧化锌层(氧化膜)可改进涂膜的粘合性。但是,根据基于本发明人后述的实验,可能存在这种情况:即使进行了上述的喷丸以除去氧化膜,部分氧化膜被压破并残留在钢板中。由此,涂膜的粘合性可能不足。另外,部分镀膜可能被剥离,且镀膜的防蚀性能可能降低。另外,通过弹丸颗粒之间的碰撞而向产品施加了压缩残余应力,这可能使产品变形。
发明内容
本发明提供一种热冲压制品的制造方法,其中可通过有效地除去氧化膜来改进涂膜的粘合性。
在此,作为深入研究的结果,本发明人已发现如下涂膜粘合性降低的原因。具体地,为了从镀锌钢板制造热冲压制品,在将镀锌钢板加热至作为母材的钢材的奥氏体转变温度范围(800℃或更高)之后将镀锌钢板成形。此时,如图9A所示,在镀锌钢板9的镀锌层92的表面上形成氧化膜93。
接着,如图9B所示,在成形之后冷却的镀锌钢板9中,因氧化膜93和镀锌层92之间的体积膨胀系数的不同而在氧化膜93和镀锌层92之间形成空隙C。
在此,特别地,在进行化学转化处理的情况下,在氧化膜93的表面上形成结晶化的化学转化膜94。但是,与其中未形成氧化膜93的情况相比,构成化学转化膜94的晶体的附着量减少。当使用镀锌退火钢板(例如Galvalume钢板)时,在氧化膜中形成Al氧化物,其引起晶体的上述附着量的减少以及涂膜粘合性的降低。
接着,如图9B所示,即使通过电沉积涂装等进一步形成涂膜95,在氧化膜93和涂膜95之间也保持粘合力,但在氧化膜93和镀锌层92之间仍存在空隙C。
接着,在使用环境下,如图9C所示,含有盐成分的水W等透过氧化膜93并侵入氧化膜93和镀锌层92之间的空隙C。由此,在该空间中腐蚀发展。进一步,空隙C周围的区域被碱化,并且涂膜的剥离自空隙C扩展。
考虑到这点,优选确切地除去在其与镀锌层之间形成空隙的氧化膜,并且作为用于除去氧化膜的手段,本发明人已关注于利用激光加热来使氧化膜升华的技术。
根据本发明的一方面,提供了一种热冲压制品的制造方法,该方法包括:成形工序,对其上形成有镀锌层的镀锌钢板进行加热并通过热冲压将经加热的镀锌钢板成形;除去工序,在成形工序后对形成于镀锌层表面上的氧化膜照射激光以除去氧化膜;和涂装工序,在除去工序后,在通过热冲压成形的镀锌钢板上进行涂装处理。
根据本发明的该方面,利用激光来使在通过热冲压将镀锌钢板成形时形成于镀锌钢板表面的氧化膜升华(蒸发)。因此,可从镀锌钢板的表面更有效地除去氧化膜。特别地,通过激光将热量迅速地输入浮于空隙上方的部分的氧化膜。因此,可容易地除去氧化膜。
由此,在热冲压期间,即使因氧化膜和镀锌层之间的体积膨胀系数的不同而将界面剥离并形成空隙,也可通过利用激光除去作为形成空隙的原因的氧化膜来消除空隙。
另外,根据本发明的该方面,利用照射激光来使氧化膜蒸发(升华),并由此不像利用喷丸或机械抛光的氧化膜除去那样,氧化膜可被均匀除去而不被压破。另外,由于通过激光除去氧化膜,因此镀锌钢板的表面被快速加热和冷却。由此,可使激光对镀锌钢板的母材的影响最小化。
在涂装工序中,可在除去了氧化膜的镀锌层的表面上进行磷酸盐化学转化处理,并且可在进行了磷酸盐化学转化处理的表面上形成涂膜。作为结果,由于利用激光照射来除去氧化膜,因此可增加镀锌层上构成化学转化膜的磷酸盐晶体的附着量。
根据本发明的该方面,可通过有效地除去氧化膜来改进涂膜的粘合性。
附图说明
以下将参考附图描述本发明示例性实施方案的特征、优点及技术和产业重要性,其中相同的附图标记表示相同的元件,并且其中:
图1是说明根据本发明的实施方案的热冲压制品的制造方法的图;
图2A是说明在图1的工序b即成形工序之后镀锌钢板的示意性截面图;
图2B是说明在图1的工序e即氧化膜除去工序之后镀锌钢板的示意性截面图;
图2C是说明在图1的工序f即涂装工序之后镀锌钢板的示意性截面图;
图3是说明根据实施例1的镀锌钢板在热冲压之后(在加热之后)的截面照片;
图4是说明根据实施例1的镀锌钢板在除去氧化膜之前和之后的表面的照片;
图5A是说明除去氧化膜之前的元素分析的结果的曲线图;
图5B是说明除去氧化膜之后的元素分析的结果的曲线图;
图6A是除去氧化膜之前的截面照片;
图6B是除去氧化膜之后的截面照片;
图7是说明镀锌钢板在除去氧化膜之前和之后的维氏硬度的测定结果的曲线图;
图8A是说明根据比较例1的镀锌钢板在除去氧化膜之后的截面照片;
图8B是说明根据比较例2的镀锌钢板的截面照片;
图8C是说明根据比较例3的镀锌钢板的截面照片;
图9A是说明在相关技术的热冲压制品的制造方法中的利用热冲压的成形工序的图;
图9B是说明在相关技术的热冲压制品的制造方法中的涂装工序的图;和
图9C是说明在相关技术的热冲压制品的制造方法中的镀锌钢板在涂装工序之后的状态的图。
具体实施方式
以下,将参考附图并基于实施方案来说明本发明。图1是说明根据本发明的实施方案的热冲压制品的制造方法的图,其中工序a是准备作为镀锌钢板的材料的工序,工序b是将镀锌钢板切割为板材的工序,工序c是对镀锌钢板进行加热的工序,工序d是成形工序,工序e是氧化膜除去工序,并且工序f是涂装工序。
图2A是说明在图1的工序d即成形工序之后的镀锌钢板的截面示意图;图2B是说明在图1的工序e即氧化膜除去工序之后的镀锌钢板的截面示意图;并且图2C是说明在图1的工序f即涂装工序之后的镀锌钢板的截面示意图。
如图1的工序a所示,首先,准备由其中在钢板(例如硼钢板)上形成有镀锌层的镀锌钢板制成的卷材10。作为镀锌钢板1,例如可使用热浸镀锌钢板或电解镀锌钢板。例如,作为热浸镀锌钢板,可使用例如包括Galvalume钢板的热浸铝—锌合金镀覆钢板的镀锌退火钢板。
如图1的工序b所示,从卷材10切割出板状镀锌钢板1。接着,如图1的工序c所示,将镀锌钢板1加热至奥氏体转变温度范围(800℃或更高)。
之后,如图1的工序d所示,使用包括上模41和下模42的成形装置4,通过热冲压将经加热的镀锌钢板1成形(成形工序)。在热冲压期间,在被软化的状态下使用成形装置4对镀锌钢板1进行压制。同时,可利用与上模41和下模42接触而获得的冷却效果(接触冷却)来强化镀锌钢板1的淬火。
此时,如图2A所示,在大气中经加热的镀锌层12的表面上形成氧化膜13。在成形之后冷却的镀锌钢板1中,因氧化膜13和镀锌层12之间的体积膨胀系数的不同而在氧化膜13和镀锌层12之间形成上述空隙C。
因此,如图1的工序e和图2B所示,在对镀锌钢板1进行后述的涂装处理之前,对在成形工序中形成于镀锌层12的表面上的氧化膜13照射激光5以除去氧化膜13。
由此,利用激光使在通过热冲压将镀锌钢板1成形时形成于镀锌层12表面上的氧化膜13升华(蒸发)。因此,可从镀锌钢板1的表面更有效地除去氧化膜13。
这样,如图2C所示,在热冲压期间,即使由于氧化膜13和镀锌层12之间的体积膨胀系数的不同而将界面剥离并形成空隙C,也可通过利用激光5除去作为形成空隙C的原因的氧化膜来消除空隙C。
在此,如从本发明人后述的实施例中可清晰看到的那样,当通过机械手段(例如喷丸或抛光)来除去氧化膜时,氧化膜可能被压破且包括空隙的氧化膜的一部分可能残留在钢板中。另外,当通过化学手段(例如使用蚀刻溶液的蚀刻)来除去氧化膜时,难以仅有效地除去氧化膜。特别地,由于优先除去镀锌钢板表面上的微小凸起部,因此难以均匀除去氧化膜。
但是,根据本实施方案,通过激光5的照射使氧化膜13蒸发(升华),并且由此不像基于机械手段或化学手段的氧化膜除去那样,氧化膜可被均匀除去而不被压破。另外,由于通过激光5除去氧化膜13,因此镀锌钢板1的母材11的表面被快速地加热和冷却。由此,可使激光5对镀锌钢板1的母材的影响最小化。另外,通过恰当地控制激光5的功率,可减小激光5对母材的影响。
接着,如图1的工序f和图2C所示,在除去了氧化膜13的镀锌层12的表面上实施磷酸盐化学转化处理(涂装用表面处理),并在其上形成磷酸盐化学转化膜14。然后,通过电沉积涂装在磷酸盐化学转化膜14的表面形成涂膜15,由此制造热冲压制品。
当使用上述方法制造热冲压制品时,利用激光5照射氧化膜13来除去氧化膜13。因此,可增加镀锌层上构成磷酸盐化学转化膜14的磷酸盐晶体的附着量。
另外,由于在镀锌钢板1中不存在空隙C,因此涂膜15(具体为磷酸盐化学转化膜14)和镀锌层12变得彼此紧密接触。由此,含有盐成分的水等不侵入到空隙C中,且腐蚀不发展。
另外,通过除去引起电不均匀性的氧化膜的元素,钢板在电学方面稳定,且可改进耐蚀性。另外,与形成氧化膜13的情况相比,可增加构成磷酸盐化学转化膜14的磷酸盐晶体的附着量,并可改进涂膜15的粘合性。
(实施例1)
<热冲压>
作为镀锌钢板,准备了在22MnB5钢的表面上形成有镀锌退火涂层的钢板(涂层重量:50g/m2)。在此,利用ICP对根据JIS H 401的涂层重量测定中得到的溶液进行分析,并测定Zn的重量。结果发现Zn的重量为30g/m2。将该镀锌钢板在900℃的加热温度下保持10秒,且在700℃或更低(具体为20℃的模具温度)的成形及淬火温度下进行淬火。
<氧化膜的除去>
图3是说明根据实施例1的镀锌钢板在热冲压之后(在加热之后)的截面照片。如图3所示,在镀锌层(Zn-Fe合金层)的表面上形成氧化膜(20μm或更小)。在氧化膜和镀锌层之间形成空隙。在镀锌层下方形成Fe-Zn固溶体层。接着,在如表2所示的300MW/cm2的条件下利用激光照射其上形成有氧化膜的镀锌钢板的表面以除去氧化膜。
图4是说明根据实施例1的镀锌钢板在除去氧化膜之前和之后的表面的照片。其上形成有氧化膜的镀锌钢板的表面呈现出从黄色到棕色的颜色,这些为氧化膜的颜色(上侧照片)。另一方面,在除去氧化膜之后,镀锌钢板的表面呈现出白色,其为镀锌层的颜色。
在图4中所示的测定位置,利用高频辉光放电光谱(GDS)分析元素含量。图5A是说明除去氧化膜之前的元素分析的结果的曲线图,且图5B是说明除去氧化膜之后的元素分析的结果的曲线图。由上述结果发现,通过照射激光,氧含量从15质量%减少至5质量%。进一步,利用X射线能谱(EDX),对镀锌钢板除去氧化膜之前和之后的表面进行元素分析。
[表1]
如上述结果清楚地所示,发现了通过照射激光,氧含量从15质量%减少至约3质量%。
图6A是除去氧化膜之前的截面照片,且图6B在除去氧化膜之后的截面照片。如图6A和6B所示,通过照射激光除去了氧化膜。因此可认为,在除去氧化膜之后,氧为激光照射期间含有的氧。
图7是说明镀锌钢板在除去氧化膜之前和之后的维氏硬度的测定结果的曲线图。从镀锌层和母材之间的界面向母材的内部测定维氏硬度。从上述结果可认为,在除去氧化膜之后,钢板的表面因激光照射而被轻微软化,但是对钢板强度基本上没影响。
<磷酸盐化学转化处理>
在除去了氧化膜的镀锌钢板的镀锌层的表面上实施磷酸盐化学转化处理,并随后测定磷酸盐化学转化膜的涂层重量。通过基于JIS K 0119的X射线荧光光谱法来测定磷酸盐化学转化膜的涂层重量。结果示于表2。
<涂膜的形成和剥离试验>
在得到的其上形成有磷酸盐化学转化膜的镀锌钢板上进行阳离子电沉积涂装(目标厚度:10μm),由此制备试样。使用盐水浸渍试验机,将镀锌钢板浸入具有0.1%或更高的盐浓度及40℃或更高温度的温水中持续200小时或更长,使用胶带评价涂膜的粘合性。结果示于表2。在此,通过用涂膜剥离部分的面积除以试样的面积来得到表2所示的剥离面积率。
[表2]
(实施例2和3)
采用与实施例1相同的方法制备相当于热冲压制品的镀锌钢板。在各镀锌钢板的表面上实施磷酸盐化学转化处理,并在其上形成涂膜,由此制备试样。使用试样的涂膜进行剥离试验。实施例2和3与实施例1的区别在于,如表2所示改变了激光的照射强度。采用与实施例1相同的方法,在涂装之前测定磷酸盐化学转化膜的涂层重量,并在涂装之后测定其剥离面积。结果示于表2。
(比较例1)
采用与实施例1相同的方法制备相当于热冲压制品的镀锌钢板。在镀锌钢板的表面上实施磷酸盐化学转化处理,并在其上形成涂膜,由此制备试样。使用试样的涂膜进行剥离试验。比较例1与实施例1的区别在于,没有利用激光除去氧化膜。采用与实施例1相同的方法,在涂装之前测定磷酸盐化学转化膜的涂层重量,并在涂装之后测定其剥离面积。结果示于表2。
(比较例2)
采用与实施例1相同的方法制备相当于热冲压制品的镀锌钢板。在镀锌钢板的表面上实施磷酸盐化学转化处理,并在其上形成涂膜,由此制备试样。使用试样的涂膜进行剥离试验。比较例2与实施例1的区别在于:不是利用激光而是利用干冰喷丸处理来除去氧化膜。具体地,在0.6MPa的气压、10mm/sec的处理速度、1kg/min的干冰丸粒消耗速率和3mm的丸粒尺寸的条件下除去氧化膜。采用与实施例1相同的方法,在涂装之前测定磷酸盐化学转化膜的涂层重量,并在涂装之后测定其剥离面积。结果示于表2。
(比较例3)
采用与实施例1相同的方法制备相当于热冲压制品的镀锌钢板。在镀锌钢板的表面上实施磷酸盐化学转化处理,并在其上形成涂膜,由此制备试样。使用试样的涂膜进行剥离试验。比较例3与实施例1的区别在于:不是利用激光而是利用强化碱来除去氧化膜。具体地,将镀锌钢板浸入具有2%的浓度及50℃的温度的NaOH水溶液中持续30分钟以除去氧化膜。采用与实施例1相同的方法,在涂装之前测定磷酸盐化学转化膜的涂层重量,并在涂装之后测定其剥离面积。结果示于表2。
(比较例4)
采用与实施例1相同的方法制备相当于热冲压制品的镀锌钢板。在镀锌钢板的表面上实施磷酸盐化学转化处理,并在其上形成涂膜,由此制备试样。使用试样的涂膜进行剥离试验。比较例4与实施例1的区别在于:不是利用激光而是利用磨料来除去氧化膜。具体地,通过使用Scotch Bright#300(由3M制造)作为磨料在5秒的抛光时间的条件下除去氧化膜。采用与实施例1相同的方法,在涂装之前测定磷酸盐化学转化膜的涂层重量,并在涂装之后测定其剥离面积。结果示于表2。
(参考例)
在未经加热的镀锌钢板的表面上实施磷酸盐化学转化处理,并在其上形成涂膜,由此制备试样。使用试样的涂膜进行剥离试验。即,在参考例中,由于未经加热镀锌钢板,因此在镀锌层的表面上没有形成氧化膜。采用与实施例1相同的方法,在涂装之前测定磷酸盐化学转化膜的涂层重量,并在涂装之后测定其剥离面积。结果示于表2。
[结果和讨论]
如表2所示,当如实施例1至3那样利用激光除去氧化膜时,磷酸盐化学转化膜的涂层重量与没有进行热处理的参考例的涂层重量同样。另外,根据实施例1至3的镀锌钢板的剥离面积率低于根据比较例1至4的镀锌钢板的剥离面积率。因此可认为,根据实施例1至3的镀锌钢板的涂膜的粘合性高于根据比较例1至4的镀锌钢板的涂膜的粘合性。
当如比较例1那样没有除去氧化膜时,磷酸盐化学转化膜的涂层重量小于实施例1至3。其原因可认为在于:磷酸盐化学转化膜的形成因氧化膜而受到抑制。进一步,在比较例1(图8A)中,由于在镀锌层和氧化膜之间形成了空隙,因此盐水侵入到这些空隙中,且腐蚀发展。可认为出于上述原因,剥离面积率高于实施例1至3的剥离面积率。
另外,在根据比较例2的镀锌钢板中,利用干冰丸粒除去了氧化膜,并且由此磷酸盐化学转化膜的涂层重量增加。但是,氧化膜被压破,且部分氧化膜和空隙残留在镀锌钢板中(参考图8B)。因此可认为,出于以上所述的原因,剥离面积率高于实施例1至3的剥离面积率。
另外,在根据比较例3的镀锌钢板(图8C)中,利用强化碱(reinforced alkali)除去氧化膜。但是,当使用强化碱来均匀除去氧化膜的整个表面时,担心镀锌层也可能被除去。因此可认为,部分氧化膜和空隙残留在镀锌钢板中,并且由此剥离面积率高于实施例1至3的剥离面积率。
另外,在根据比较例4的镀锌钢板中,通过物理抛光除去氧化膜。在该情况下,部分氧化膜以被压破的状态残留在镀锌钢板中。因此可认为,部分氧化膜和空隙残留在镀锌钢板中,并且由此剥离面积率高于实施例1至3的剥离面积率。
以上已描述了本发明的实施方案。但是,本发明不限于上述实施方案,并且可进行各种的设计改变。
Claims (2)
1.热冲压制品的制造方法,其特征在于,包括:
成形工序,对其上形成有镀锌层的镀锌钢板进行加热并通过热冲压将经加热的镀锌钢板成形;
除去工序,在所述成形工序后对形成于所述镀锌层的表面上的氧化膜照射激光以除去所述氧化膜和空隙,该空隙通过热冲压形成于所述镀锌层和所述氧化膜之间;和
涂装工序,在所述除去工序后在通过热冲压成形的镀锌钢板上进行涂装处理。
2.根据权利要求1所述的方法,其特征在于,
在所述涂装工序中,在除去了所述氧化膜的镀锌层的表面上进行磷酸盐化学转化处理,并在进行了磷酸盐化学转化处理的表面上形成涂膜。
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