CN1061806A - 钢件镀保护层的方法 - Google Patents
钢件镀保护层的方法 Download PDFInfo
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- 239000011737 fluorine Substances 0.000 claims abstract description 20
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Abstract
一种钢件镀保护层的方法,先在热态下在含氟或
氟化物气体的气氛中保持工件,以便除去工件表面层
上的SiOx和MnOx之类的氧化皮,并在工件上形成
氟化层以防止产生新的氧化皮。通过在镀槽中加入
助熔剂或者在浸入镀槽前在含氢的气氛中加热氟化
了的工件使工件表面活化。活化的钢表面与镀槽中
液态金属有较好的相容性,因此可得到优质的镀层。
Description
本发明涉及钢件镀保护层的方法。
由于热镀锌和热镀铝的方法所得到的镀层有很好的防锈性能,并且这些方法的成本很低,因此这些热镀方法得到很广泛的应用。像热镀锌和热镀铝之类的镀层工艺是这样进行的:首先用酸洗等方法对钢工件进行预清洗,然后在还原气氛中用退火工艺把它们加热到650°到800℃,再把它们冷却到接近镀槽的温度,然后把它们浸在镀槽内以形成镀层。在这种镀覆方法中,为了得到优质的镀层,不仅要求对钢工件进行充分的预清洗,并且最好在还原气氛下在用退火工艺对钢工件处理时,在钢工件的表面不产生像SiOn,MnOx之类的氧化皮。现时,由于使用连续铸造生产的材料和要求钢有高强度,所以在钢工件中硅含量较高。而在还原气氛中对工件进行退火处理时,钢工件中含有的硅容易转变成氧化皮。这对形成镀层是一个障碍,会造成不均匀的镀覆和外观很差等问题。
为了防止产生氧化皮,必须在还原气氛下进行退火处理时使Si之类的元素不转变为氧化皮。但是,一般在普通的连续处理方法中,还原气氛用N2和H2的混合气体构成,而上述的钢材就在这一气氛下加热和冷却。由于生成硅或铝的氧化物只需要较低的能量,因此,很容易形成氧化皮。因此,即使增加还原气氛的还原性以及降低加热温度,也不可能完全限制上述氧化物生成。例如,在热镀锌时,含硅量不低于0.5%的钢材的镀层质量很差,因为由于生成了上述氧化物而妨碍了镀锌槽液的润湿性。在热镀铝时,含硅量不低于2%的情况下也会发生上述问题。
因此,本发明的目的是提供一种容易得到优质镀层的钢件镀保护层的方法。
为了实现本发明的上述目的,本发明的镀层方法包括把钢工件或制品保持在含氟或氟化物的气体的气氛中,然后在氟化的工件上形成镀层。
在本发明中,在钢工件或制品上进行镀层前,先把钢工件在热态保持在含氟气或氟化物气体的气氛中,从而除去钢工件表面上的SiOx和MiOx之类的氧化皮,并生成氟化层,使得钢工件的表面包着一层氟化层。这一氟化层一般包括厚度为几十至几千埃( )的薄膜,在300℃到600℃范围内是稳定的,可防止生成新的氧化皮。由于与在同样温度下生成的氧化层相比,氟化层更疏松,而且氟化层有较强的升华作用,因此在下一工序的镀槽中用像氯化物和/或铝之类的助熔剂的作用,可方便地除去该氟化层。为了除去氟化层,在浸入上述的镀槽中前,把在表面带有氟化层的钢工件放入含氢的惰气气体中或含水份的气氛中并加热以除去该氟化层。由于清除掉氟化层后的钢表面是活性的,因此改善了钢工件与镀槽中金属液等的相容性,因而可形成优质的镀层。
下面对本发明进行详细说明。
在本发明中,钢工件是装入加热和冷却炉中,并在热态下保持在含氟或含氟化物的气氛中,然后再在工件上形成镀层。
要进行镀覆的是钢工件。钢工件包括碳钢、或不锈钢等各种钢材。钢工件的形状等没有特别的限制。钢工件可以是板、片、卷材和加工成的螺钉等形状。本发明适用的材料不仅包括单一的材料,也包括以铁为主要成分并加有其它金属材料的合金。
用来制造含氟气或氟化物气体的气氛的含氟或含氟化物气体是指在N2之类的惰性气体中含有从NF3、BF3、CF4、HF、SF6、F2、C2F6、WF6、CHF3、SiF4等之中的一种或它们的混合物的氟源成分的气体。除了上述气体外,用热裂装置对BF3、CF4、HF、SF6、C2F6、WF6、CHF3、SiF4等含氟化合物进行分解而产生的F2可用作含氟或氟化物的气体。当对BF3之类化合物进行分解时,在加热冷却炉前或附近设置了一个裂化器来对化合物进行热裂。然后把热裂产生的F2和N2混和,再把该混合物通入炉中。在本发明中使用的含氟或氟化物的气体包括如上所述热裂产生的F2。
在上述的氟源成分中,NF3最适合实际使用,因为它在安全性、反应性、可控制性和易于操作等方面具有优点。一种混合的气体,例如由1%NF3气体+5%F2+94%N2(重量百分比)组成的混合气体也是实际使用的。从效率的角度出发,在如此含氟和氟化物的气体中,像NF3之类的含氟成分的浓度应调整到1到15%,最好为2到7%(重量百分比,下面同)。把如此的气体或混合物充入预定的空间中而形成含氟或氟化物气体的气氛。
按照本发明,钢材按照例如下述方法镀保护层。也就是在普通的整个镀层方法的冷却步骤中加进一点变化。更详细地说,将加热到650℃到750℃的钢材送入冷却步骤,然后进入含氟或氟化物气体的气氛中在300℃到600℃下保温1-8分钟,最好为2-3分钟。通过把钢材保持在该气氛下,钢材表面的SiOx和MnOx之类的氧化物被清除掉,在上面形成一层氟化物层。然后带着在表面上形成的氟化物膜的钢材浸入如镀锌槽或铝槽等槽液中以形成镀层。在这种情况下,氟化的钢工件并不直接浸入镀槽液中,而是先与由氢和氮气组成的混合气体(H2:90到10%+N2:余量)接触以除去氟化层,然后再浸入到镀槽中。在一系列工艺中,得到优质镀层的NF3量约为每吨钢材50克到700克。
下面通过附图及实例进一步说明本发明,附图中:
图1示出了本发明使用的处理炉的一个实例的横截面图;
图2示出了图1所示的处理炉在圈A中的部分的局部放大图;
图3,图4和图5是用二次离子质谱分析(SIMS)得到的钢件沿深度方向元素分析曲线。
实例1
本例使用了图1所示的试验性热处炉。在图中,标号20是带有绝热炉壁的炉体,21是沿炉体周边埋置的加热器,而22是设置在炉体20的底部上的滑动门,该门22可沿图1所示的左右方向滑动。在炉体20的顶壁上连着一根把气体通入炉体20的导管23。而标号24表示要处理的钢制件。在炉体20下面设置了装锌液的罐炉25,该罐炉被滑动门22隔开。在装锌液的罐炉25中设置了感应圈26,它埋设在周围的壁中,如图2所示,在罐炉25中装了温度为480℃的锌液。
在上述的处理炉中,把一些钢工件(冷轧钢材、1%Si,0.2%Mn)的试样在氮气氛下加热到750℃,然后冷却到350℃,然后向样品吹入含氟气体(N2+5%NF3)1分钟,并在此状态下保持2到5分钟。然后,往炉中吹入N2,在N2气氛下把炉温升高到500℃,然后从炉中取出一个试样作元素分析。然后打开滑动门22,把其余的试样送入锌液罐炉25中,并浸入镀锌槽中镀锌。在镀锌后,把试样从罐炉25中取出,同时向其吹N2。然后冷却与干燥,这样得到了镀锌的试样。另外,在向炉中通入由N2+5%NF3组成的含氟气体并保持2-5分钟后,再通往由N2+25%H2组成的混合气体,试样在此气氛下加热到500℃,并保持10分钟。然后把试样送入锌液罐炉25中镀锌。也得到了如上述的镀锌试样。
实例2
在N2气氛下把钢试件加热到750℃,然后冷却到500℃。在该温度下,在有如实例1所示的同样成分的含氟或含氟化物气体的气氛中保持试样。除上述外,镀锌试样按实例1制备。
实例3
除了使用1%NF3+5%F2-94%HN2组成的混合气体作为含氟或氟化物气体外,其余都按实例1来制备镀锌试样。
比较实例
使用与实例1相同的试样,将它们在N2+50%H2气氛下加热到750℃,然后冷却到500℃,如实例1一样把试样浸入到镀锌槽中,但是没有经过氟化。除上述这点外,都按实例1制备镀锌试样。
用二次离子质谱分析仪(SIMS)对实例1,2,3和比较实例中取得的未镀锌试样(在镀锌前一步得到)的大部分表面层部分沿深度方向进行了元素分析。其结果示于图3、4、5。在这些图中,曲线A表示铁,曲线B表示硅,而曲线C表示锰含量。图3相应于实例1,图4相应于实例2,而图5相应于比较实例。也就是,如图3和4明显可见,在实例1和2的大部分外表面层部分没有见到Si和/或Mn的“富集”(即Si和/或Mn的浓度较高)的情况。而相反的,在图5所示的比较实例中,大部分表面层发生氧化,在表面层形成了SiOx和MnOx之类的氧化物。因此可见在表面层Si和Mn的浓度比较高,我们称这一状态为“富集”。
用弯曲零件试验来检查在实例1、2和比较实例中形成的每个试样的镀层的附着性。结果,在实例1和2的弯曲零件未见到镀层起皮。而在比较实例的弯曲零件大部分引起镀层的起皮,也就是镀层的附着性较差。实例3得到的试样显示出与实例1的试样有同样的结构和同样的镀层性能。
从上述结果明显可见,按照本发明可以进行优质的镀保护层,譬如高硅含量的钢材,用普通方法难以镀保护层的,可用本发明进行热镀锌之类的镀保护层,而得到优质的镀层。这样也可用本发明制造具有高强度的钢板或薄钢板。另外,由于它可大大减少或取消在普通退火工艺中用作为还原气体的H2,而得到经济性的优点。在实例中使用一试验炉装置用来镀金属层,但是使用现有的生产设备,只要部分改进冷却阶段的设备,就可用于实际的热镀锌连续生产线。
如上所述,在本发明的钢件镀保护层的方法中,由于在热态把钢材保持在含氟或氟化物气体的气氛中以后再在钢材表面上形成镀层,钢表面的氧化层被除去,在表面上形成了一层氟化物层覆盖以保护该表面层。在表面上形成氟化物的钢材可以直接浸入镀槽中,或先在含氢的惰气气氛下加热经分解和除去该氟化物层,然后再浸入镀槽中。在直接浸入镀槽中的情况下,可通过在镀槽中加入氯化物和Al之类的助熔剂的作用来分解和除去该氟化物层。而在先把钢件放在含氢的惰性气体气氛中然后浸入镀槽中的情况下,由于在浸入镀槽前已除去氟化物层,镀层处理可迅速地进行。用此方法处理时,钢工件上的氟化物层被除掉,并露出活化的钢表面。因此,镀层的附着性很好并在活化的钢表面上形成而得到质量高的镀层。
Claims (2)
1、一种在钢工件或制品上形成镀层的镀保护层的方法,包括在含氟或氟化物气体的气氛中保持钢工件或制品,然后在氟化的钢工件或制品上形成镀层的步骤。
2、按照权利要求1所述的镀保护层的方法,其特征在于所述的含氟或氟化物气体是在一种惰性气体中含有从NF3、BF3、CF4、HF、SF6、F2、CH2F2、CH3F、C2H6、WF6、CHF3、Si5F4中选择的至少一种含氟组分。
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EP (1) | EP0488497B1 (zh) |
JP (1) | JP2842712B2 (zh) |
KR (1) | KR100200945B1 (zh) |
CN (1) | CN1032373C (zh) |
AT (1) | ATE129752T1 (zh) |
DE (1) | DE69114249T2 (zh) |
DK (1) | DK0488497T3 (zh) |
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Cited By (3)
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CN106637267A (zh) * | 2015-10-28 | 2017-05-10 | 通用电气公司 | 用于从金属基材去除氧化物的方法和装置 |
CN106637266A (zh) * | 2015-10-28 | 2017-05-10 | 通用电气公司 | 用于从金属基材去除氧化物的方法和装置 |
US9677166B2 (en) | 2003-03-31 | 2017-06-13 | Mahle International Gmbh | Method for producing pieces having a modified surface |
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JP3379041B2 (ja) | 1997-03-27 | 2003-02-17 | 大洋製鋼株式会社 | メッキ浴中機材及び製造法 |
US7451143B2 (en) | 2002-08-28 | 2008-11-11 | Cisco Technology, Inc. | Programmable rule processing apparatus for conducting high speed contextual searches and characterizations of patterns in data |
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DE152947C (zh) * | 1903-09-10 | 1904-06-30 | ||
US2121412A (en) * | 1936-11-28 | 1938-06-21 | Burgess Lab Inc C F | Method for treating zinc and product formed thereby |
US3129124A (en) * | 1959-12-30 | 1964-04-14 | Gen Electric | Process for producing interlaminar insulation for electrical apparatus |
US3765929A (en) * | 1972-03-31 | 1973-10-16 | Ibm | In situ fluorination of graphite in iron alloy |
JPS60215756A (ja) * | 1984-01-27 | 1985-10-29 | プロセダイン コ−ポレイシヨン | ステンレス鋼の硬化方法 |
EP0352061B1 (en) * | 1988-07-20 | 1994-09-21 | Hashimoto Chemical Industries Co., Ltd. | Metal material with film passivated by fluorination and apparatus composed of the metal material |
DE69009603T2 (de) * | 1989-07-10 | 1995-01-12 | Daido Oxygen | Verfahren zur Vorbehandlung von metallischen Werkstücken und zur Nitrierhärtung von Stahl. |
JP2501925B2 (ja) * | 1989-12-22 | 1996-05-29 | 大同ほくさん株式会社 | 金属材の前処理方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US9677166B2 (en) | 2003-03-31 | 2017-06-13 | Mahle International Gmbh | Method for producing pieces having a modified surface |
CN106637267A (zh) * | 2015-10-28 | 2017-05-10 | 通用电气公司 | 用于从金属基材去除氧化物的方法和装置 |
CN106637266A (zh) * | 2015-10-28 | 2017-05-10 | 通用电气公司 | 用于从金属基材去除氧化物的方法和装置 |
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DE69114249D1 (de) | 1995-12-07 |
US5399211A (en) | 1995-03-21 |
DE69114249T2 (de) | 1996-06-05 |
ATE129752T1 (de) | 1995-11-15 |
JP2842712B2 (ja) | 1999-01-06 |
TW208722B (zh) | 1993-07-01 |
JPH055168A (ja) | 1993-01-14 |
DK0488497T3 (da) | 1996-03-04 |
EP0488497B1 (en) | 1995-11-02 |
KR920010013A (ko) | 1992-06-26 |
CN1032373C (zh) | 1996-07-24 |
KR100200945B1 (ko) | 1999-06-15 |
EP0488497A2 (en) | 1992-06-03 |
ES2080902T3 (es) | 1996-02-16 |
EP0488497A3 (en) | 1993-01-20 |
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