CN114763613A - 一种退除金属镀镉层的退镀液及其退镀方法 - Google Patents
一种退除金属镀镉层的退镀液及其退镀方法 Download PDFInfo
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/40—Alkaline compositions for etching other metallic material
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明涉及化学退镀技术领域,IPC分类号为C23G,具体涉及一种退除金属镀镉层的退镀液及其退镀方法。所述一种退除金属镀镉层的退镀液,其制备原料,按重量百分比计,包括:硅氧烷类化合物2%‑4%、胺类化合物3%‑5%、盐类化合物7%‑10%、水补足余量至100%。本发明通过将硅氧烷类化合物、胺类化合物、盐类化合物加入水中搅拌,混合后制备得到一种退除金属镀镉层的退镀液,将具有镀镉层的金属镀件浸入退镀液中,翻动镀件,使工件没入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件,本发明提供的一种退除金属镀镉层的退镀液可很好的去除铝、铁、铜基材的金属镀镉层,适用于多种基材,退镉效果好,且金属基材表面没有被腐蚀,不伤金属基材。
Description
技术领域
本发明涉及化学退镀技术领域,IPC分类号为C23G,具体涉及一种退除金属镀镉层的退镀液及其退镀方法。
背景技术
退镀液是通过浸泡、超声波、电解等方式去除工件表面的特殊金属镀层,是一种不会对工件本身造成溶解、腐蚀的化学液体。工业生产的零件不合格或等于工件进行重复利用时,需要对工件进行退镀重新加工,如果对工件上的镀层处理不彻底,会导致镀液污染。
金属镀层的去除方法主要分为两类:化学法和电化学法,一般基于镀层和基体的化学性质来选择,镀层的主要金属成份要比基体主要金属成份化学性质更活泼,选择添加配位剂或螯合剂,降低被去除镀层的主要金属成份的离子活性,或添加适量的促进剂或催化剂,促使退镀在预期时间节点内完成。
专利CN111020587A公开了一种用于铜表面去除镍层的退镀液及其退镀工艺,其制备原料包括:溴化钠、氧化剂、酒石酸、尿素、苯并三氮唑、乙酸钴以及水,氧化剂等,具有对镍层退镀效率高、同时不会对铜基体造成腐蚀等优异性能,但其制备原料中含有乙酸钴对皮肤具有刺激性,存在一定生理毒性。
专利CN111690933A公开了一种不合格镀镉层的退镀液及退镀方法,其制备原料包括硫、2,4-二硝基苯磺酸水合物、六次甲基四胺,其退镀液成分中不含高毒性的六价铬,避免了使用铬酸退镀液的高污染问题,但其只适用于钢铁基材的退镀,使用范围受限。
发明内容
为了解决上述问题,本发明的第一方面提供了一种退除金属镀镉层的退镀液的制备原料,按重量百分比计,包括:硅氧烷类化合物2%-4%、胺类化合物3%-5%、盐类化合物7%-10%、水补足余量至100%。
优选的,所述硅氧烷类化合物为聚二甲基硅氧烷、硅氧烷酮、甲基硅氧烷、甲基三氟丙基硅氧烷、环甲基硅氧烷、二甲基硅氧烷中的一种或几种的组合;
进一步优选的,所述硅氧烷类化合物为硅氧烷酮、聚二甲基硅氧烷的复配,硅氧烷酮、聚二甲基硅氧烷的质量比为1.3-1.6:0.4-0.8;
所述胺类化合物为氨水、氯化铵、季铵盐、碳酸氢铵、碳酸铵、丙基胺、乙基胺、二甲基亚璜酰亚胺、双-(4-甲氧基苄基)-胺、8-(2-羟基苯甲酰胺基)辛酸钠、2,4-二甲氧基苄胺、3-氨基苯磺酸、聚丙烯酰胺、聚酰胺、2-呋喃甲胺中的一种或几种的组合;
进一步优选的,所述胺类化合物为氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的复配,氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的质量比为0.8-1.3:0.1-0.3:1.2-1.5;
所述盐类化合物为硫酸亚铁、碳酸钠、磷酸钠、硫酸亚铁铵、硫酸铁、硫化钠中的一种或几种的组合;
进一步优选的,所述盐类化合物为碳酸钠、硫化钠的复配,碳酸钠、硫化钠的质量比为1.3-1.6:0.3-0.7;
本发明的第二方面提供了一种退除金属镀镉层的退镀液的退镀方法,包括以下步骤:
(1)按重量份,将硅氧烷类化合物、胺类化合物、盐类化合物加入水中搅拌,混合后制备得到一种退除金属镀镉层的退镀液;
(2)温度为25℃-80℃条件下,将步骤(1)所得退镀液置入耐腐蚀塑料容器中,根据退镀产品数量、班次不断添加原液,将具有镀镉层的金属镀件浸入退镀液中,翻动镀件,使工件没入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件即可。
有益效果
(1)本发明通过将硅氧烷类化合物、胺类化合物、盐类化合物加入水中,混合后制备得到一种退除金属镀镉层的退镀液,将其置入耐腐蚀塑料容器中,根据退镀产品数量、班次不断添加原液,并将具有镀镉层的金属镀件浸入退镀液中,使工件没入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件,本发明提供的一种退除金属镀镉层的退镀液可很好的去除铝、铁、铜基材的金属镀镉层,适用于多种基材,退镉效果好,且金属基材表面没有被腐蚀,不伤金属基材。
(2)本发明通过加入硅氧烷类化合物可提高所制得一种退除金属镀镉层的退镀液的对基材的缓释效果,使金属基材表面不被腐蚀,不伤金属基材,尤其是硅氧烷类化合物为硅氧烷酮、聚二甲基硅氧烷的复配,硅氧烷酮、聚二甲基硅氧烷的质量比为1.3-1.6:0.4-0.8时,所制得一种退除金属镀镉层的退镀液对金属基材的缓释效果优异,原因可能是硅氧烷酮、聚二甲基硅氧烷为链状结构,含有较多的Si-O键,与铝原子间具有极强的相互作用,Si-O键对铝原子起瞄定作用,硅氧烷酮中的磺酸基吸附在铝合金表面,形成极强的吸附膜,且聚二甲基硅氧烷的长链结构通过Si-O键,紧密缠结在铝合金表面,进一步在铝合金表面形成致密保护膜,本申请人发现当胺类化合物为氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的复配,氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的质量比为0.8-1.3:0.1-0.3:1.2-1.5时,在盐类化合物为碳酸钠、硫化钠的复配,碳酸钠、硫化钠的质量比为1.3-1.6:0.3-0.7的共同作用下,可进一步有效除去金属表面的镀镉层,并且不伤金属基材,氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺中的极性活性基团中的氮原子及氧原子与金属间具有较强的螯合作用,紧密吸附在金属表面形成螯合薄膜,对铝、铁、铜基材具有较好的缓蚀作用,且胺类化合物可促进盐类化合物对镉离子的有效沉积,减少金属表面镀镉层的去除时间,本发明提供的一种退除金属镀镉层的退镀液可有效去除铝、铁、铜基材的金属镀镉层,适用于多种基材,退镉效果好,且不伤基材。
(3)本发明通过将硅氧烷类化合物、胺类化合物、盐类化合物加入水中搅拌,混合后制备得到一种退除金属镀镉层的退镀液,将其置入耐腐蚀塑料容器中,根据退镀产品数量、班次不断添加原液,并将具有镀镉层的金属镀件浸入退镀液中,翻动镀件,使工件没入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件,本发明提供的一种退除金属镀镉层的退镀液可很好的去除铝、铁、铜基材的金属镀镉层,适用于多种基材,退镉效果好,且金属基材表面没有被腐蚀,不伤金属基材。
具体实施方式
实施例1
实施例1提供了一种退除金属镀镉层的退镀液的制备原料,按重量百分比计,包括:硅氧烷类化合物3%、胺类化合物4%、盐类化合物8%、水补足余量至100%。
所述硅氧烷类化合物为硅氧烷酮、聚二甲基硅氧烷的复配,硅氧烷酮、聚二甲基硅氧烷的质量比为1.4:0.6,硅氧烷酮CAS号为63148-62-9,购自杭州拜斯化工科技有限公司,聚二甲基硅氧烷CAS号为9016-00-6,购自西格玛奥德里奇(上海)贸易有限公司;
所述胺类化合物为氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的复配,氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的质量比为1.0:0.2:1.4,氨水CAS号为1336-21-6,购自上海阿拉丁生化科技股份有限公司,聚丙烯酰胺CAS号为9003-05-8,购自上海阿拉丁生化科技股份有限公司,双-(4-甲氧基苄基)-胺CAS号为17061-62-0,购自上海麦克林生化科技有限公司;
所述盐类化合物为碳酸钠、硫化钠的复配,碳酸钠、硫化钠的质量比为1.5:0.5,碳酸钠CAS号为497-19-8,购自阿法埃莎(中国)化学有限公司,硫化钠CAS号为1313-82-2,购自西格玛奥德里奇(上海)贸易有限公司。
本发明的第二方面提供了一种退除金属镀镉层的退镀液的退镀方法,包括以下步骤:
(1)按重量份,将硅氧烷类化合物、胺类化合物、盐类化合物加入水中搅拌,混合后制备得到一种退除金属镀镉层的退镀液;
(2)温度为60℃条件下,将步骤(1)所制得一种退除金属镀镉层的退镀液置入耐腐蚀塑料容器中,根据退镀产品数量、班次不断添加原液,将具有镀镉层的金属镀件浸入退镀液中,翻动镀件,使工件没入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件即可。
实施例2
实施例2提供了一种退除金属镀镉层的退镀液的制备原料,按重量百分比计,包括:硅氧烷类化合物4%、胺类化合物5%、盐类化合物10%、水补足余量至100%。
所述硅氧烷类化合物为硅氧烷酮、聚二甲基硅氧烷的复配,硅氧烷酮、聚二甲基硅氧烷的质量比为1.4:0.6,硅氧烷酮CAS号为63148-62-9,购自杭州拜斯化工科技有限公司,聚二甲基硅氧烷CAS号为9016-00-6,购自西格玛奥德里奇(上海)贸易有限公司;
所述胺类化合物为氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的复配,氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的质量比为1.0:0.2:1.4,氨水CAS号为1336-21-6,购自上海阿拉丁生化科技股份有限公司,聚丙烯酰胺CAS号为9003-05-8,购自上海阿拉丁生化科技股份有限公司,双-(4-甲氧基苄基)-胺CAS号为17061-62-0,购自上海麦克林生化科技有限公司;
所述盐类化合物为碳酸钠、硫化钠的复配,碳酸钠、硫化钠的质量比为1.5:0.5,碳酸钠CAS号为497-19-8,购自阿法埃莎(中国)化学有限公司,硫化钠CAS号为1313-82-2,购自西格玛奥德里奇(上海)贸易有限公司。
本发明的第二方面提供了一种退除金属镀镉层的退镀液的退镀方法,包括以下步骤:
(1)按重量份,将硅氧烷类化合物、胺类化合物、盐类化合物加入水中搅拌,混合后制备得到一种退除金属镀镉层的退镀液;
(2)温度为60℃条件下,将步骤(1)所制得一种退除金属镀镉层的退镀液置入耐腐蚀塑料容器中,根据退镀产品数量、班次不断添加原液,将具有镀镉层的金属镀件浸入退镀液中,翻动镀件,使工件没入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件即可。
对比例1
具体实施方式同实施例1,不同之处在于,所述硅氧烷类化合物为硅氧烷酮、聚二甲基硅氧烷的复配,硅氧烷酮、聚二甲基硅氧烷的质量比为0.3:0.4,硅氧烷酮CAS号为63148-62-9,购自杭州拜斯化工科技有限公司,聚二甲基硅氧烷CAS号为9016-00-6,购自西格玛奥德里奇(上海)贸易有限公司。
对比例2
具体实施方式同实施例1,不同之处在于,所述胺类化合物为聚丙烯酰胺、双-(4-甲氧基苄基)-胺的复配,胺类化合物为聚丙烯酰胺、双-(4-甲氧基苄基)-胺的质量比为0.3:0.5:0.4,聚丙烯酰胺CAS号为9003-05-8,购自上海阿拉丁生化科技股份有限公司,双-(4-甲氧基苄基)-胺CAS号为17061-62-0,购自上海麦克林生化科技有限公司。
对比例3
具体实施方式同实施例1,不同之处在于,所述盐类化合物为碳酸钠,碳酸钠CAS号为497-19-8,购自阿法埃莎(中国)化学有限公司。
性能测试:良率测试、退镀时间、基材腐蚀情况
良率测试与基材腐蚀情况:取表面具有镀镉层的铝、铁、铜的镀件各500片,共1500片,均分为5组,依据实施例1-2,对比例1-3的良率进行测试(每组具有镀镉层的铝、铁、铜的镀件均为100片)提供的一种退除金属镀镉层的退镀液的退镀方法对各组具有镀镉层的铝、铁、铜的镀件进行退镀工艺处理,记录处理后的具有镀镉层的铝、铁、铜的镀件表面镀镉层的去除情况,计算实施例1-2,对比例1-3各组具有镀镉层的铝、铁、铜的镀件表面镀镉层的去除良率,并观察金属基材的腐蚀情况计算金属基材被腐蚀比例,结果见表1。
退镀时间:取表面具有镀镉层的具有镀镉层的铝镀件5片,分为五组,依据实施例1-2,对比例1-3提供的一种退除金属镀镉层的退镀液的退镀方法对各组具有镀镉层的铝镀件进行退镀工艺处理,退镀过程使具有镀镉层的铝镀件浸没于退镀液中,并不断搅拌具有镀镉层的铝镀件,目测至镀镉层被完全退镀后取出工件,记录各组具有镀镉层的铝镀件的退镉层时间,结果见表2。
表1:具有镀镉层的铝、铁、铜的镀件表面镀镉层的去除良率及金属基材被腐蚀比例。
表2:具有镀镉层的铝镀件表面镀镉层的退镀时间。
退镀时间(s) | |
实施例1 | 20 |
实施例2 | 22 |
对比例1 | 25 |
对比例2 | 27 |
对比例3 | 26 |
Claims (10)
1.一种退除金属镀镉层的退镀液,其特征在于,按重量百分比计,制备原料包括:硅氧烷类化合物2%-4%、胺类化合物3%-5%、盐类化合物7%-10%、水补足余量至100%。
2.根据权利要求1所述的一种退除金属镀镉层的退镀液,其特征在于,所述硅氧烷类化合物为聚二甲基硅氧烷、硅氧烷酮、甲基硅氧烷、甲基三氟丙基硅氧烷、环甲基硅氧烷、二甲基硅氧烷中的一种或几种的组合。
3.根据权利要求2所述的一种退除金属镀镉层的退镀液,其特征在于,所述硅氧烷类化合物为硅氧烷酮、聚二甲基硅氧烷的复配,硅氧烷酮、聚二甲基硅氧烷的质量比为1.3-1.6:0.4-0.8。
4.根据权利要求1所述的一种退除金属镀镉层的退镀液,其特征在于,所述胺类化合物为氨水、氯化铵、季铵盐、碳酸氢铵、碳酸铵、丙基胺、乙基胺、二甲基亚璜酰亚胺、双-(4-甲氧基苄基)-胺、8-(2-羟基苯甲酰胺基)辛酸钠、2,4-二甲氧基苄胺、3-氨基苯磺酸、聚丙烯酰胺、聚酰胺、2-呋喃甲胺中的一种或几种的组合。
5.根据权利要求1、2、3或4所述的一种退除金属镀镉层的退镀液,其特征在于,所述胺类化合物为氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的复配,氨水、聚丙烯酰胺、双-(4-甲氧基苄基)-胺的质量比为0.8-1.3:0.1-0.3:1.2-1.5。
6.根据权利要求1所述的一种退除金属镀镉层的退镀液,其特征在于,所述盐类化合物为硫酸亚铁、碳酸钠、磷酸钠、硫酸亚铁铵、硫酸铁、硫化钠中的一种或几种的组合。
7.根据权利要求6所述的一种退除金属镀镉层的退镀液,其特征在于,所述盐类化合物为碳酸钠、硫化钠的复配,碳酸钠、硫化钠的质量比为1.3-1.6:0.3-0.7。
8.根据权利要求1所述的一种退除金属镀镉层的退镀液,按重量百分比计,制备原料包括:硅氧烷类化合物3%、胺类化合物4%、盐类化合物8%、水补足余量至100%。
9.根据权利要求1所述的一种退除金属镀镉层的退镀液,按重量百分比计,制备原料包括:硅氧烷类化合物4%、胺类化合物5%、盐类化合物10%、水补足余量至100%。
10.一种根据权利要求1-9任一项所述的一种退除金属镀镉层的退镀液的退镀方法,其特征在于,包括以下步骤:
(1)按重量份,将硅氧烷类化合物、胺类化合物、盐类化合物加入水中搅拌,混合后制备得到一种退除金属镀镉层的退镀液;
(2)温度为25℃-80℃条件下,将步骤(1)所得退镀液置入耐腐蚀塑料容器中,根据退镀产品数量、班次不断添加原液,将具有镀镉层的金属镀件浸入退镀液中,翻动镀件,使工件默入退镀液中,至镀层退尽,用水清洗具有镀镉层的金属镀件即可。
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