CN1287187A - 一种铜及铜合金表面抗腐蚀改性处理剂 - Google Patents
一种铜及铜合金表面抗腐蚀改性处理剂 Download PDFInfo
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- 239000003607 modifier Substances 0.000 title claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052802 copper Inorganic materials 0.000 title claims description 34
- 239000010949 copper Substances 0.000 title claims description 34
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims abstract description 24
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012964 benzotriazole Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 150000003852 triazoles Chemical class 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 22
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 2
- 239000003791 organic solvent mixture Substances 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000011877 solvent mixture Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 46
- 230000005764 inhibitory process Effects 0.000 description 24
- 238000007654 immersion Methods 0.000 description 23
- 239000011780 sodium chloride Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 238000005238 degreasing Methods 0.000 description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- -1 nitrogen heterocyclic organic compound Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IPIVUPVIFPKFTG-UHFFFAOYSA-N 4-butyl-2h-benzotriazole Chemical compound CCCCC1=CC=CC2=C1N=NN2 IPIVUPVIFPKFTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
一种铜及铜合金表面抗腐蚀改性处理剂,其特征在于:该处理剂为缓蚀剂、电解质、溶剂所构成的溶液体系;缓蚀剂选自苯并三氮唑(BTA)、三氮唑(BTA)衍生物、2-巯基苯并恶唑(MBO)、2-巯基苯并恶唑(MBO)衍生物之一种;电解质为不具备氧化或钝化性并在电离时所产生的阳离子是第一主旋、第二主族元素阳离子或铵离子的化合物;溶剂是水、极性有机溶剂、水与能和水互溶的有机溶剂所组成的混合溶剂或者是彼此间互溶的不同极性有机溶剂组成的混合溶剂。本方法具有处理时间短、操作简便、造价低廉、基本不改变原金属色泽的优点。
Description
本发明涉及金属材料的腐蚀防护,特别提供了一种对铜及其合金腐蚀防护的处理剂。
缓蚀剂是指少量添加于腐蚀介质中即可使材料的腐蚀速度显著降低的物质。因而,缓蚀剂在使用过程中的通常特征是腐蚀介质或环境中要维持其一定的浓度。铜及其合金是用缓蚀剂进行腐蚀防护最早和最成功的材料之一。一些氮杂环有机化合物,如本并三氮唑(BTA)等对铜的腐蚀有很好的防护作用,已被工业规模应用了多年。但是,铜的缓蚀剂也作为防腐蚀表面改性(预置抗腐蚀膜)物质使用,主要是:1)通过用缓蚀剂的水溶液或者其它溶剂的溶液对铜样品在加热或不加热的条件下进行浸泡处理(Walker R,″Benzotriazole asa Corrosion Inhibitor for Immersed Copper″,Corrosion,1973,29(7):290-296;Brunoro G,Parmigiani F,Perboni G,RocchiniG,Trabanelli G,″Corrosion Inhibition of OFHC Copper byPrefilming with Organic Compounds″,British Corrosion Journal,1992,27(1):75-79;祝鸿范,“BTA缓蚀剂在文物保护中的应用”,腐蚀科学与防护技术,1999,11(4):255-256);2)通过用缓蚀剂+氧化或钝化物质的溶液对铜或铜合金在常温或加热的条件下进行浸泡处理(祝鸿范,“BTA缓蚀剂在文物保护中的应用”,腐蚀科学与防护技术,1999,11(4):255-256;王朝铭,“铜及铜合金零件的BTA.H钝化”,材料保护,1993,26(1):40-41)。实验和研究结果均表明,若要达到较好的防护效果仅仅用缓蚀剂水溶液的作处理剂需要长的处理时间,而用添加氧化性物质的缓蚀剂溶液作处理剂,则由于改变了缓蚀膜的形成机制,所获得的缓蚀膜的保护性能并不理想。
本发明的目的在干提供一种铜及铜合金表面防腐蚀改性处理剂,其处理时间短、操作简便、造价低廉、基本不改变原金属色泽。
本发明提供了一种铜及铜合金表面抗腐蚀改性处理剂,其特征在于:该处理剂为缓蚀剂、电解质、溶剂所构成的溶液体系;缓蚀剂选自苯并三氮唑(BTA)、三氮唑(BTA)衍生物、2-巯基苯并恶唑(MBO)、2-巯基苯并恶唑(MBO)衍生物之一种;电解质为不具备氧化或钝化性并在电离时所产生的阳离子是第一主族、第二主族元素阳离子或铵离子的化合物;溶剂可以是水、极性有机溶剂,也可以是水与能和水互溶的有机溶剂所组成的混合溶剂或者是彼此间互溶的不同极性有机溶剂组成的混合溶剂;缓蚀剂的浓度范围在10-2mmol/L-103mmol/L之间;电解质的浓度范围在0.001%-50%之间。
一般地说,铜的氮杂环缓蚀剂的缓蚀机制和实质是:缓蚀剂在样品/溶液腐蚀介质界面处与腐蚀产生的一价铜离子发生化学反应生成一价铜的不溶复合物(complex),在样品表面构成致密的缓蚀膜层,从而对腐蚀过程的传质和电荷转移产生阻碍,起到对腐蚀过程的控制作用。例如,铜在含有氮杂环缓蚀剂的氯化物溶液介质中的铜/溶液界面处,有如下变化发生:
在不存在络合性离子的条件下,如KNO3或Na2SO4等溶液中有:
本发明中电解质所起的作用仅仅是通过电离作用使介质的导电性增加,即保证了铜或铜合金的电化学腐蚀过程得以顺利进行,也即保证反应(1)、(2)、(3)或者反应(4)、(5)的进行。用本发明处理剂对铜或铜合金样品进行处理后,使样品在液相腐蚀介质中或大气环境中的耐腐蚀能力获得提高。
本发明有如下优点:
1.不需要在样品使役或存放环境或介质中保持缓蚀剂;
2.处理时间短;
3.成本低廉;
4.操作简便;
5.基本不改变原金属色泽。
实施例1
以1mmol/L BTA+40%NaCl水溶液为处理剂,于室温下,对除油除锈的铜样作浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为90%。
实施例2
以1mmol/L BTA+20%高氯酸四乙基铵盐的三氯甲烷溶液为处理剂,于室温下,对除油除锈的铜样作浸泡处理1小时。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为83%。
实施例3
以0.5mol/L BTA+5%K3[Fe(SCN)6]的水溶液为处理剂,于室温下,对除油除锈的铜样作浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为88%。
实施例4
以5mmol/L BTA+1%Na2SO4溶液(溶剂为10∶90的乙醇/水的混合)为处理剂,于50℃下,对除油除锈的铜样作浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为92%。
实施例5
以50mmol/L BTA+1%LiBr+3%Na2SO4的溶液为处理剂,于60℃下,对除油除锈的铜样作浸泡处理0.5小时,后以水清洗样品。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为96%。
实施例6
以50mmol/L 5-甲基苯并三氮唑+5%KSCN的溶液为处理剂,于50℃下,对除油除锈的铜样作浸泡处理0.5小时,后以水清洗样品。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为84%。
实施例7
以1mmol/L 4-丁基苯并三氮唑+3%NaCl水溶液为处理剂,于室温下,对除油除锈的铜样作浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为70%。
实施例8
以1mmol/L MBO(2-巯基苯并恶唑,英文名称:2-mercaptobenzoxazole)+10%CaCl2的溶液为处理剂,于室温下,将除油除锈抛光铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为92%。
实施例9
以5mmol/L 4-甲基-5-乙基-2-巯基苯并恶唑+15%NH4Ac的溶液(溶剂为10∶90的乙醇/水的混合)为处理剂,于室温下,将铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为93%。
实施例10
以5mmol/L 4-甲基-5-乙基-2-巯基苯并恶唑+15%HAc的溶液(溶剂为10∶90的乙醇/水的混合)为处理剂,于室温下,将铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为90%。
实施例11
以0.5mmol/L MBO+0.01%MgSO4的溶液为处理剂,于50℃下,将除油除锈抛光黄铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为82%。
实施例12
以1mmol/L MBO+3%Na2SO4的溶液为处理剂,于35℃下,将除油除锈青铜样在其中浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为91%。
实施例13
以1mmol/L MBO+5%NaOH的溶液为处理剂,于35℃下,将除油除锈青铜样在其中浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为87%。
实施例14
以0.3mmol/L MBO+3%氢氧化四甲基铵的乙醇溶液为处理剂,于35℃下,将除油除锈青铜样在其中浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为71%。
实施例15
以0.1mmol/L MBO+45%Na2SO4的溶液为处理剂,于35℃下,将除油除锈青铜样在其中浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为68%。
实施例16
以1mmol/L MBO+5%H2SO4的溶液为处理剂,于40℃下,将除油除锈青铜样在其中浸泡处理1小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为71%。
实施例17
以1mmol/L MBO+0.1%Cs2SO4的乙醇/甲醇溶液为处理剂,于室温下,将除油除锈铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为93%。
实施例18
以0.5mmol/L MBO+3%NaNO3的乙醇溶液为处理剂,于室温下,将除油除锈抛光铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为72%。
实施例19
以0.5mol/L MBO+0.1mol/L HCl的溶液(溶剂为15∶85的甲醇/水的混合)为处理剂,于室温下,将除油除锈铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为86%。
实施例20
以10mmol/L MBO+0.5mol/L HCl的溶液(溶剂为15∶85的丙酮/水的混合)为处理剂,于室温下,将除油除锈抛光铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为83%。
实施例21
以10 mmol/L MBO+0.5 mol/L HCl的乙醇溶液为处理剂,于室温下,将除油除锈抛光铜样在其中浸泡处理0.5小时,后以水清洗。被处理样品在3.5%氯化钠介质中浸泡一周后,测得的缓蚀效率为87%。
Claims (1)
1.一种铜及铜合金表面抗腐蚀改性处理剂,其特征在于:该处理剂为缓蚀剂、电解质、溶剂所构成的溶液体系;缓蚀剂选自苯并三氮唑(BTA)、三氮唑(BTA)衍生物、2-巯基苯并恶唑(MBO)、2-巯基苯并恶唑(MBO)衍生物之一种;电解质为不具备氧化或钝化性并在电离时所产生的阳离子是第一主族、第二主族元素阳离子或铵离子的化合物;溶剂是水、极性有机溶剂、水与能和水互溶的有机溶剂所组成的混合溶剂或者是彼此间互溶的不同极性有机溶剂组成的混合溶剂;缓蚀剂的浓度范围在10-2mmol/L-103mmol/L之间;电解质的浓度范围在0.001%-50%之间。
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Cited By (5)
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CN100400709C (zh) * | 2004-03-25 | 2008-07-09 | 中国印钞造币总公司 | 铜合金硬币坯饼抗变色工艺及其抗变色制剂 |
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CN104310603A (zh) * | 2014-11-10 | 2015-01-28 | 乌鲁木齐市科发展精细化工有限公司 | 高度浓缩的铜缓蚀剂及其制备方法 |
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CN101812690B (zh) * | 2010-04-13 | 2011-09-21 | 范伟京 | 一种硬膜防锈剂及其制备方法 |
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Cited By (5)
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CN100400709C (zh) * | 2004-03-25 | 2008-07-09 | 中国印钞造币总公司 | 铜合金硬币坯饼抗变色工艺及其抗变色制剂 |
CN101445923B (zh) * | 2008-12-30 | 2012-07-04 | 森鹤乐器股份有限公司 | 一种黄铜防变色的钝化方法 |
CN101935839A (zh) * | 2010-09-01 | 2011-01-05 | 六安市晖润粉末新材料有限公司 | 一种预防铜粉氧化保护液及其制备方法和使用方法 |
CN104310603A (zh) * | 2014-11-10 | 2015-01-28 | 乌鲁木齐市科发展精细化工有限公司 | 高度浓缩的铜缓蚀剂及其制备方法 |
CN113976529A (zh) * | 2021-10-25 | 2022-01-28 | 宁波江丰电子材料股份有限公司 | 一种铜靶材的清洗方法 |
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