CN107723694B - 一种碳钢常温磷化方法 - Google Patents

一种碳钢常温磷化方法 Download PDF

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CN107723694B
CN107723694B CN201710862556.5A CN201710862556A CN107723694B CN 107723694 B CN107723694 B CN 107723694B CN 201710862556 A CN201710862556 A CN 201710862556A CN 107723694 B CN107723694 B CN 107723694B
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李丽波
谢明
宋移辑
刘波
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Harbin University of Science and Technology
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    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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 containing fluorides or complex fluorides
    • C23C22/36Chemical 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 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364Chemical 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 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
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    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • C23G1/081Iron or steel solutions containing H2SO4

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Abstract

一种碳钢常温磷化方法,它涉及一种适用于钢铁表面防腐的常温磷化液的制备方法。本发明要解决传统常温磷化挂灰、泛黄、成膜不匀和耐蚀性能差的问题。本发明的方法如下:一、除油液的配制;二、酸洗液的配制;三、磷化液的配制;四、磷化膜制备工艺流程:低碳钢片→除油→水洗→打磨→水洗→酸洗→水洗→磷化→水洗→吹干。本发明制备的锌锰系环保型常温磷化液不仅能够缩短工艺流程,而且能够降低能耗,节能减排。

Description

一种碳钢常温磷化方法
技术领域
本发明涉及钢铁表面处理试剂及工艺,尤其涉及一种碳钢常温磷化方法。
背景技术
磷化是一种使钢铁等金属在相关的磷化液中发生特定的化学浸蚀反应在其金属表面上形成一种致密的、稳定的、具有不溶性的无机磷化保护膜,该反应所生成的薄膜称之为磷化膜。工程上主要应用于钢铁件表面磷化,但也可应用于其它有色金属件(如铝、锌等)或合金。磷化工艺技术经过多年的发展与进步,早已成为金属表面处理及加工、金属表面防腐蚀、润滑、减少摩擦、表面装饰及上漆前的保护打底等过程中不可忽视的处理技术。
目前,国内外的诸多领域(如金属加工业、汽车、自行车、高低压开关柜、防盗门、铁路等制造业)普遍采用的是中、高温磷化。但中、高温磷化能耗大,造成能源和资源的巨大浪费,成本过高;磷化过程中调整过于频繁,磷化液的稳定性较难控制,操作不便;除此之外还存在成膜速度慢、环境污染、对操作工身体有害等问题。常温磷化具有低成本、快速、能耗低等优点,能够有效地解决以上问题,此外,常温磷化还可以与发黑工艺相结合,提高材料的耐蚀性能,因而常温磷化已成为国际磷化行业的必然和研究课题。本文对常温磷化液进行研制,并对磷化膜的耐蚀性能和表面形貌进行表征,旨在开发一种耐蚀性优异、成本低廉、可常温磷化的磷化液。
发明内容
本发明的目的是为了在保证磷化液耐蚀性能的条件下,旨在开发一种耐蚀性优异、成本低廉、可常温磷化的磷化液。
本发明的一种碳钢常温磷化方法,是按照以下步骤进行的:
一、除油液的配制,取适量无水碳酸钠、磷酸三钠、OP-10乳化剂、蒸馏水进行配置;
二、酸洗液的配制,取适量浓硫酸、浓盐酸、硫脲以及蒸馏水进行配置;
三、磷化液的配制,取适量磷酸二氢锌、硝酸锌、亚硝酸钠、氟化钠、柠檬酸、硝酸锰以及蒸馏水进行配置;
四、将低碳钢片进行打磨,水洗,然后放入除油液中除油,取出后水洗,之后进行酸洗,取出后水洗,最后进行磷化,取出后水洗,最后吹干。
本发明包含以下有益效果:
与现有技术相比,本发明磷化液的优点在于,具有耐磨性能优良、膜附着力强、耐蚀性好、操作简单、成本低等优点,该配制的磷化液磷化膜表面均匀,呈现针柱状,利于油漆高分子的嵌入,能够使漆膜涂层具有很好的附着力,本文开发出的常温磷化工艺,能够节约能源,达到经济性的要求。
附图说明
图1是磷化膜的原子力显微镜(AFM)图。
图2是磷化膜的扫描电子显微镜(SEM)图(500×)。
图3是磷化膜的扫描电子显微镜(SEM)图(2000×)。
具体实施方式
下面结合最佳的实施例对本发明做进一步说明,但本发明的保护范围并不仅限有以下实施例。
具体实施方式一:本实施方式的一种碳钢常温磷化方法是按照以下步骤进行的:
一、除油液的配制,取适量无水碳酸钠、磷酸三钠、OP-10乳化剂、蒸馏水进行配置;
二、酸洗液的配制,取适量浓硫酸、浓盐酸、硫脲以及蒸馏水进行配置;
三、磷化液的配制,取适量磷酸二氢锌、硝酸锌、亚硝酸钠、氟化钠、柠檬酸、硝酸锰以及蒸馏水进行配置;
四、将低碳钢片进行打磨,水洗,然后放入除油液中除油,取出后水洗,之后进行酸洗,取出后水洗,最后进行磷化,取出后水洗,最后吹干。
具体实施方式二:本实施方式与具体实施方式一不同点在于:步骤一所述的除油流程为用碱性液脱脂法对低碳钢片表面除油处理,所用除油的配方为无水碳酸钠30g/L、磷酸三钠12g/L、OP-10乳化剂8g/L以及蒸馏水,除油时将除油液加热至50℃,并在整个除油过程中保持溶液温度在50±5℃范围内,时间为3~6min,取出,水洗。其它与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式一或二不同点在于:步骤二所述的酸洗除锈配方及工艺为:200ml/L的98%浓硫酸、20ml/L浓盐酸、3g/L硫脲以及蒸馏水,时间为5min,温度为室温。其它与具体实施方式一或二相同。
具体实施方式四:本实施方式与具体实施方式一至三之一不同点在于:步骤三所述的磷化液各组分质量浓度如下:磷酸二氢锌70-110g/L,硝酸锌45-85g/L,亚硝酸钠0.8-2.4g/L,氟化钠2-4g/L,柠檬酸2.5-4.5g/L,硝酸锰35-55g/L,其余为水。其它与具体实施方式一至三之一相同。
本发明内容不仅限于上述各实施方式的内容,其中一个或几个具体实施方式的组合同样也可以实现发明的目的。
通过以下实施例验证本发明的有益效果。
具体实施例
本实施例方式的一种碳钢常温磷化方法,是按照以下步骤进行的:
一、除油液的配制,取适量无水碳酸钠、磷酸三钠、OP-10乳化剂、蒸馏水进行配置;
二、酸洗液的配制,取适量浓硫酸、浓盐酸、硫脲以及蒸馏水进行配置;
三、磷化液的配制,取适量磷酸二氢锌、硝酸锌、亚硝酸钠、氟化钠、柠檬酸、硝酸锰以及蒸馏水进行配置;
四、将低碳钢片进行打磨,水洗,然后放入除油液中除油,取出后水洗,之后进行酸洗,取出后水洗,最后进行磷化,取出后水洗,最后吹干。
本实施例中所述的除油流程为用碱性液脱脂法对低碳钢片表面除油处理,所用除油的配方为无水碳酸钠30g/L、磷酸三钠12g/L、OP-10乳化剂8g/L以及蒸馏水,除油时将除油液加热至50℃,并在整个除油过程中保持溶液温度在50±5℃范围内,时间为3~6min,取出,水洗。
本实施例中所述的酸洗除锈配方及工艺为:200ml/L的98%浓硫酸、20ml/L浓盐酸、3g/L硫脲以及蒸馏水,时间为5min,温度为室温。
本实施例中所述的磷化液各组分质量浓度如下:磷酸二氢锌70-110g/L,硝酸锌45-85g/L,亚硝酸钠0.8-2.4g/L,氟化钠2-4g/L,柠檬酸2.5-4.5g/L,硝酸锰35-55g/L,其余为水。
本实施例制得的最佳比例锌锰系磷化膜的原子力显微镜(AFM)和扫描电子显微镜(SEM)如图1、图2和图3所示,最优配方所处理钢件得到的磷化膜表面均匀致密,呈现针柱状,利于油漆高分子的嵌入,能够使漆膜涂层具有很好的附着力。
本实施例制得的最佳比例锌锰系磷化膜的腐蚀性能检测结果为用质量分数为3%NaCl溶液对磷化膜进行抗腐蚀性能检测,平均达到4小时不出现锈点。
本实施例制得的最佳比例锌锰系磷化膜的耐磨性能检测结果为磷化膜能够经受对其进行300次以上的擦拭均而不发生脱落或损伤,耐磨性能优良。
本实施例制得的最佳比例锌锰系磷化膜的热震实验测试结果表明经受10次以上的反复热震而没有出现脱落或起皮的现象,附着力优良。

Claims (2)

1.一种碳钢常温磷化方法,其特征在于一种适用于钢铁表面的常温磷化是按照以下步骤进行的:
一、除油液的配制,取30g/L无水碳酸钠、12g/L磷酸三钠、8g/L OP-10乳化剂、蒸馏水进行配置,除油时将除油液加热至50℃,并在整个除油过程中保持溶液温度在50±5℃范围内,时间约为3~6min,取出,水洗;
二、酸洗液的配制,取适量浓硫酸、浓盐酸、硫脲以及蒸馏水进行配置;
三、磷化液的配制,取100.0g/L磷酸二氢锌、55.0g/L硝酸锌、2.0g/L亚硝酸钠、3.0g/L氟化钠、2.5g/L柠檬酸、50g/L硝酸锰以及蒸馏水进行配置;
四、将低碳钢片进行打磨,水洗,然后放入除油液中除油,取出后水洗,之后进行酸洗,取出后水洗,最后进行磷化,取出后水洗,最后吹干。
2.根据权利要求1所述的一种碳钢常温磷化方法,其特征在于所述的酸洗除锈配方及工艺为:200ml/L的98%浓硫酸、20ml/L浓盐酸、3g/L硫脲以及蒸馏水,时间为5min,温度为室温。
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