CN114921741B - 一种热镀锌工艺 - Google Patents
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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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- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C—CHEMISTRY; METALLURGY
- 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
- C23C2/04—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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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
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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
- 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
- C23C22/06—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 acidic solutions with pH less than 6
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- C23C22/50—Treatment of iron or alloys based thereon
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明提出了一种热镀锌工艺,包括如下步骤:酸洗、助镀、热浸镀锌、冷却和钝化,其中酸洗过程中所用除铁剂包括无机酸7%‑10%、有机酸8%‑15%、表面活性剂3%‑5%、纤维素交联聚合物1%‑3%,余量为去离子水,其中纤维素交联聚合物一方面与去除下来的氧化铁螯合,使其沉淀,另一方面还能将氧化铁从溶液中脱离出来,从而有效去除酸洗后的氧化铁残渣。发明的除铁剂可以有效的渗透工件,去除工件表面的铁锈,无残留,提高酸洗效率。
Description
技术领域
本发明涉及镀锌技术领域,尤其涉及一种热镀锌工艺。
背景技术
热镀锌将除锈后的钢件浸入500℃左右熔化的锌液中,使钢构件表面附着锌层,从而起到防腐的目的,是钢铁材料防腐最基本、最经济有效的方法。其防腐的机理是由于锌的标准电极电位负于铁,因此在水和潮湿的空气中镀锌层具有牺牲阳极保护钢基的作用,从而可以大大的延长钢材的使用寿命。热浸镀锌工艺一般包括以下步骤:酸洗、清洗、助镀、热浸镀锌、冷却和钝化。其中清洗是对酸洗后残留与工件表明的铁盐等物质进行去除,需耗费大量的清水,而且清洗效果较差,导致镀锌层附着性较差,后期容易出现剥离和脱落等问题。
发明内容
有鉴于此,本发明提出了一种可以有效清除酸洗产生的铁盐,提高镀锌层附着力的热镀锌工艺。
本发明的技术方案是这样实现的:本发明提供了一种热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗5-10min,酸洗温度为30-50℃,酸洗结束后用水冲洗3-5min;以重量百分比为100%计算,所述除铁剂包括无机酸7%-10%、有机酸8%-15%、表面活性剂3%-5%、纤维素交联聚合物1%-3%,余量为去离子水;
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在40-60℃条件下浸渍1-2min;
S3,热浸镀锌,将助镀后的工件于100-240℃条件下烘干,烘干后浸入锌液中,锌液温度控制为400-500℃,时间控制为5-7min;
S4,冷却、钝化,将镀锌后的工件冷却至20-30℃后,浸入钝化液中,浸渍1-2min,然后漂洗3-5次即可。
在以上技术方案的基础上,优选的,所述纤维素交联聚合物为纤维素与聚羧酸类化合物在100-150℃条件下交联得到,所述纤维素:聚羧酸类化合物的质量比为(5-8):(3-5)。
在以上技术方案的基础上,优选的,所述纤维素为羟甲基纤维素和羧甲基纤维素,所述聚羧酸类化合物为聚甲基丙烯酸、聚羟基丙烯酸和水解聚马来酸酐中的一种或多种。
在以上技术方案的基础上,优选的,所述无机酸为硫酸、磷酸和硝酸中的一种或多种组合。
在以上技术方案的基础上,优选的,所述有机酸为氨基三亚甲基膦酸、乙二胺四亚甲基膦酸、羟基次乙基二膦酸、二乙烯三胺五甲叉膦酸和羟基乙叉二膦酸中的一种或多种组合。
在以上技术方案的基础上,优选的,所述表面活性剂为聚氧乙烯脂肪酸酯、月桂醇聚氧乙烯醚、失水山梨醇脂肪酸酯和脂肪醇聚氧乙烯醚中的一种或多种组合。
在以上技术方案的基础上,优选的,所述除铁剂还包括重量百分比为1-2%的乙二胺四乙酸二钠。
在以上技术方案的基础上,优选的,所述助镀剂由氯化锌、氯化铵和柠檬酸盐组成。
在以上技术方案的基础上,优选的,所述钝化液由钛酸盐、纳米SiO2、聚氨酯、紫外线吸收剂、有机酸和异丙醇组成。
在以上技术方案的基础上,优选的,所述紫外线吸收剂为2-羟基-4-正辛氧基二苯甲酮、对异丙基水杨酸苯酯和2-(2'-羟基-5'-叔辛基苯基)苯并三唑中的一种或多种组合。
本发明的一种热镀锌工艺相对于现有技术具有以下有益效果:
(1)本发明的酸洗剂包括无机酸、有机酸、表面活性剂、纤维素交联聚合物可以有效的渗透工件,去除工件表面的铁锈,无残留,从而提高镀锌层的附着性和均一性,避免后期容易出现剥离和脱落等问题
(2)纤维素交联聚合物一方面与去除下来的氧化铁螯合,使其沉淀,另一方面还能将氧化铁从溶液中脱离出来,从而有效去除酸洗后的氧化铁残渣。
(3)本发明酸洗液可以将工件表面的氧化铁一次性清洗,酸洗后仅需水洗2-3min,即可去除工件表面的酸洗液和铁锈。
(4)本发明酸洗液中的乙二胺四乙酸二钠具有缩短酸洗时间的作用,酸洗时间仅需5-6min即可,而且无需二次水洗。
具体实施方式
下面将结合本发明实施方式,对本发明实施方式中的技术方案进行清楚、完整地描述,显然,所描述的实施方式仅仅是本发明一部分实施方式,而不是全部的实施方式。基于本发明中的实施方式,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式,都属于本发明保护的范围。
实施例一
本实施例的热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗10min,酸洗温度为30℃,酸洗结束后用水冲洗2min;以重量百分比为100%计算,除铁剂包括硫酸7%、氨基三亚甲基膦酸8%、聚氧乙烯脂肪酸酯3%、纤维素交联聚合物1%,余量为去离子水。
纤维素交联聚合物为羟甲基纤维素与聚甲基丙烯酸100℃条件下交联得到,羟甲基纤维素:聚甲基丙烯酸的质量比为5:3。
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在40℃条件下浸渍1min;助镀剂由氯化锌、氯化铵和柠檬酸盐组成,其中,氯化锌:氯化铵:柠檬酸盐的质量比为6:4:1。
S3,热浸镀锌,将助镀后的工件于100℃条件下烘干,烘干后浸入锌液中,锌液温度控制为400℃,时间控制为5min。
S4,冷却、钝化,将镀锌后的工件冷却至20℃后,浸入钝化液。浸渍1min,然后漂洗3次即可。钝化液由钛酸盐、纳米SiO2、聚氨酯、2-羟基-4-正辛氧基二苯甲酮、柠檬酸和异丙醇组成,紫外线吸收剂为2-羟基-4-正辛氧基二苯甲酮;其中,钛酸盐:纳米SiO2:聚氨酯:2-羟基-4-正辛氧基二苯甲酮:柠檬酸:异丙醇的质量比为7:5:3:2:1:10。
实施例二
本实施例的热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗8min,酸洗温度为40℃,酸洗结束后用水冲洗2.5min;以重量百分比为100%计算,除铁剂包括无机酸磷酸8%、乙二胺四亚甲基膦酸9%、月桂醇聚氧乙烯醚3.5%、纤维素交联聚合物1.5%,乙二胺四乙酸二钠1%,余量为去离子水。
纤维素交联聚合物为羧甲基纤维素与聚羟基丙烯酸在120℃条件下交联得到,羧甲基纤维素:聚羟基丙烯酸的质量比为6:5。
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在50℃条件下浸渍1.5min;助镀剂由氯化锌、氯化铵和柠檬酸盐组成;其中,氯化锌:氯化铵:柠檬酸盐的质量比为6:4:1。
S3,热浸镀锌,将助镀后的工件于150℃条件下烘干,烘干后浸入锌液中,锌液温度控制为450℃,时间控制为6min。
S4,冷却、钝化,将镀锌后的工件冷却至25℃后,浸入钝化液浸渍1.5min,然后漂洗4次即可。钝化液由钛酸盐、纳米SiO2、聚氨酯、对异丙基水杨酸苯酯、乳酸和异丙醇组成;其中,钛酸盐:纳米SiO2:聚氨酯:对异丙基水杨酸苯酯:乳酸:异丙醇的质量比为7:5:3:2:1:10。
实施例三
本实施例的热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗6min,酸洗温度为50℃,酸洗结束后用水冲洗3min;以重量百分比为100%计算,除铁剂包括硝酸)9%、羟基次乙基二膦酸10%、失水山梨醇脂肪酸酯5%、纤维素交联聚合物2.5%,乙二胺四乙酸二钠1.5%,余量为去离子水。
纤维素交联聚合物为羟甲基纤维素与水解聚马来酸酐在130℃条件下交联得到,羟甲基纤维素:水解聚马来酸酐的质量比为7:4。
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在55℃条件下浸渍2min;助镀剂由氯化锌、氯化铵和柠檬酸盐组成;其中,氯化锌:氯化铵:柠檬酸盐的质量比为6:4:1。
S3,热浸镀锌,将助镀后的工件于200℃条件下烘干,烘干后浸入锌液中,锌液温度控制为480℃,时间控制为6min。
S4,冷却、钝化,将镀锌后的工件冷却至30℃后,浸入钝化液。浸渍2min,然后漂洗5次即可。钝化液由钛酸盐、纳米SiO2、聚氨酯、2-(2'-羟基-5'-叔辛基苯基)苯并三唑、草酸和异丙醇组成;其中,钛酸盐:纳米SiO2:聚氨酯:2-(2'-羟基-5'-叔辛基苯基)苯并三唑:草酸:异丙醇的质量比为7:5:3:2:1:10。
实施例四
本实施例的热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗5min,酸洗温度为50℃,酸洗结束后用水冲洗3min;以重量百分比为100%计算,除铁剂包括硫酸、10%、二乙烯三胺五甲叉膦酸15%、脂肪醇聚氧乙烯醚5%、纤维素交联聚合物3%,乙二胺四乙酸二钠2%,余量为去离子水。
纤维素交联聚合物为羧甲基纤维素与水解聚马来酸酐在150℃条件下交联得到,羧甲基纤维素:水解聚马来酸酐的质量比为8:5。
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在60℃条件下浸渍2min;助镀剂由氯化锌、氯化铵和柠檬酸盐组成;其中,氯化锌:氯化铵:柠檬酸盐的质量比为6:4:1。
S3,热浸镀锌,将助镀后的工件于240℃条件下烘干,烘干后浸入锌液中,锌液温度控制为500℃,时间控制为7min。
S4,冷却、钝化,将镀锌后的工件冷却至30℃后,浸入钝化液浸渍2min,然后漂洗5次即可。钝化液由钛酸盐、纳米SiO2、聚氨酯、2-羟基-4-正辛氧基二苯甲酮、柠檬酸和异丙醇组成;其中,钛酸盐:纳米SiO2:聚氨酯:2-羟基-4-正辛氧基二苯甲酮:柠檬酸:异丙醇的质量比为7:5:3:2:1:10。
对比例一
对比例一的热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗,酸洗温度为30℃,酸洗结束后用水冲洗2min;除铁剂为体积分数为20%的硫酸。
S2,助镀,将水洗后的工件浸入助镀剂中浸渍,在40℃条件下浸渍1min;助镀剂由氯化锌、氯化铵和柠檬酸盐组成;其中,氯化锌:氯化铵:柠檬酸盐的质量比为6:4:1。
S3,热浸镀锌,将助镀后的工件于100℃条件下烘干,烘干后浸入锌液中,锌液温度控制为400℃,时间控制为5min。
S4,冷却、钝化,将镀锌后的工件冷却至20℃后,浸入钝化液。浸渍1min,然后漂洗3次即可。钝化液由钛酸盐、纳米SiO2、聚氨酯、2-羟基-4-正辛氧基二苯甲酮、柠檬酸和异丙醇组成,其中,钛酸盐:纳米SiO2:聚氨酯:2-羟基-4-正辛氧基二苯甲酮:柠檬酸:异丙醇的质量比为7:5:3:2:1:10。
对比例二
对比例二的热镀锌工艺,包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗10min,酸洗温度为30℃,酸洗结束后用水冲洗2min;以重量百分比为100%计算,除铁剂包括硫酸7%、氨基三亚甲基膦酸8%、聚氧乙烯脂肪酸酯3%,余量为去离子水。
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在40℃条件下浸渍1min;助镀剂由氯化锌、氯化铵和柠檬酸盐组成;其中,氯化锌:氯化铵:柠檬酸盐的质量比为6:4:1。
S3,热浸镀锌,将助镀后的工件于100℃条件下烘干,烘干后浸入锌液中,锌液温度控制为400℃,时间控制为5min。
S4,冷却、钝化,将镀锌后的工件冷却至20℃后,浸入钝化液。浸渍1min,然后漂洗3次即可。钝化液由钛酸盐、纳米SiO2、聚氨酯、2-羟基-4-正辛氧基二苯甲酮、柠檬酸和异丙醇组成,其中,钛酸盐:纳米SiO2:聚氨酯:2-羟基-4-正辛氧基二苯甲酮:柠檬酸:异丙醇的质量比为7:5:3:2:1:10。
镀锌层的附着性检测参考GB/T 9286-1998《色漆和清漆漆膜的划格试验》对实施例和对比例的镀锌工件进行镀层抗划测试,结果见表1。
表1实施例和对比例对比结果
表1所示,本发明镀锌工艺酸洗液可以有效去除铁锈残留,而且除锈时间仅需5-8min,酸洗后,镀层与工件附着性好,镀层外观平整没有鼓包,不易脱落,抗划等级为1级,而且酸洗后不需要第二次水洗,减少了废液排放;有效解决了铁锈去除效果差,镀锌层附着性差,易出现剥离和脱落的技术问题。酸洗液中加入乙二胺四乙酸二钠可以有效缩短除锈时间,使得除锈时间缩短为5-6min。
以上所述仅为本发明的较佳实施方式而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种热镀锌工艺,其特征在于:包括如下步骤:
S1,酸洗,将除油后的工件置入除铁剂中酸洗5-10min,酸洗温度为30-50℃,酸洗结束后用水冲洗2-3min;以重量百分比为100%计算,所述除铁剂包括无机酸7%-10%、有机酸8%-15%、表面活性剂3%-5%、纤维素交联聚合物1%-3%,余量为去离子水;
所述无机酸为硫酸、磷酸和硝酸中的一种或多种组合;
所述有机酸为氨基三亚甲基膦酸、乙二胺四亚甲基膦酸、羟基次乙基二膦酸、二乙烯三胺五甲叉膦酸和羟基乙叉二膦酸中的一种或多种组合;
所述纤维素交联聚合物为纤维素与聚羧酸类化合物在100-150℃条件下交联得到,所述纤维素:聚羧酸类化合物的质量比为(5-8):(3-5);
所述纤维素为羟甲基纤维素和羧甲基纤维素,所述聚羧酸类化合物为聚甲基丙烯酸、聚羟基丙烯酸和水解聚马来酸酐中的一种或多种;
所述除铁剂还包括重量百分比为1-2%的乙二胺四乙酸二钠;
S2,助镀,将酸洗后的工件浸入助镀剂中浸渍,在40-60℃条件下浸渍1-2min;
S3,热浸镀锌,将助镀后的工件于100-240℃条件下烘干,烘干后浸入锌液中,锌液温度控制为400-500℃,时间控制为5-7min;
S4,冷却、钝化,将镀锌后的工件冷却至20-30℃后,浸入钝化液中,浸渍1-2min,然后漂洗3-5次即可。
2.如权利要求1所述的一种热镀锌工艺,其特征在于:所述表面活性剂为聚氧乙烯脂肪酸酯、月桂醇聚氧乙烯醚、失水山梨醇脂肪酸酯和脂肪醇聚氧乙烯醚中的一种或多种组合。
3.如权利要求1所述的一种热镀锌工艺,其特征在于:所述助镀剂由氯化锌、氯化铵和柠檬酸盐组成。
4.如权利要求1所述的一种热镀锌工艺,其特征在于:所述钝化液由钛酸盐、纳米SiO2、聚氨酯、紫外线吸收剂、有机酸和异丙醇组成。
5.如权利要求4所述的一种热镀锌工艺,其特征在于:所述紫外线吸收剂为2-羟基-4-正辛氧基二苯甲酮、对异丙基水杨酸苯酯和2-(2'-羟基-5'-叔辛基苯基)苯并三唑中的一种或多种组合。
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