CN104561960B - 一种高稳定性镍锡磷化学镀液 - Google Patents
一种高稳定性镍锡磷化学镀液 Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 53
- 239000000126 substance Substances 0.000 title abstract description 7
- XLLNQZKHYSHONN-UHFFFAOYSA-N [Sn].[P].[Ni] Chemical compound [Sn].[P].[Ni] XLLNQZKHYSHONN-UHFFFAOYSA-N 0.000 title abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 28
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 239000002738 chelating agent Substances 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 18
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 16
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 13
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 13
- YLIMHFXLIKETBC-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCC[Na] YLIMHFXLIKETBC-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004471 Glycine Substances 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 2
- 229910009256 Sn(CH3SO3)2 Inorganic materials 0.000 abstract description 7
- 239000008139 complexing agent Substances 0.000 abstract description 5
- 239000003094 microcapsule Substances 0.000 abstract description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract description 2
- 235000017281 sodium acetate Nutrition 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 abstract 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 abstract 1
- 239000001632 sodium acetate Substances 0.000 abstract 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 239000007921 spray Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 229910001096 P alloy Inorganic materials 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 2
- 229960003019 loprazolam Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical class O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000013632 homeostatic process Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- -1 thio sulfur Chemical compound 0.000 description 1
Classifications
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
本发明公开了一种高稳定性镍锡磷化学镀液，包括每升镀液含六水合二氯化镍20~45g，次亚磷酸钠15~25g，甲烷磺酸锡微胶囊（Sn(CH3SO3)2@SiO2），醋酸钠5~35g，醋酸6~35ml，络合剂3~10g，稳定剂4~15g，表面活性剂2~6g，余量为水，所述溶液的PH为4.0~5.0；本发明的有益效果是：高稳定性、镀速平缓可控。
Description
技术领域
本发明涉及一种高稳定性镍锡磷化学镀液，属于化学试剂领域。
背景技术
目前国内外对二元镍系尤其是Ni-P合金的研究已相当普遍，Ni-P合金镀层有着明亮光着的表面和突出的机械性能，与基体附着良好，耐磨性和耐腐蚀性与其他合金镀相比优势比较明显，在化工、机械、电子、航天、能源、交通等工业领域都已大量的应用，然而随着现代化的发展，人们的要求不断提高，二元镍系合金已经不能满足科学生产的某些要求，随后又有学者开展了镍系三元复合镀的研究，目前三元化学镀层采用的自催化镍-锡-磷合金镀液及其镀层，但其不足之处是在实际操作中锡的添加量难以控制，镀液不稳定易形成絮凝性偏锡酸盐从镀液中析出，降低锡离子利用率，同时也会堆积在反应表面影响镀层性能，镀液沉积速率过快，镀层致密性不足，机械硬度和耐腐蚀性能均难以达到理想效果；为了解决上述困难，需要开发一款高稳定性、镀速平缓可控的镍锡磷合金镀液。
发明内容
本发明的目的是提供一种高稳定性镍锡磷化学镀液。
本发明要解决的问题是目前镍锡磷化学镀液不稳定，锡盐利用率低和添加量难以控制，易形成沉淀的问题。
为实现本发明的目的，本发明采用的技术方案是：
一种高稳定性镍锡磷化学镀液，包括每升镀液含六水合二氯化镍20~45g，次亚磷酸钠15~25g，甲烷磺酸锡微胶囊（Sn(CH3SO3)2@SiO2），醋酸钠5~35g，醋酸6~35ml，络合剂3~10g，稳定剂4~15g，表面活性剂 2~6g，余量为水，溶液的PH为4.0~5.0。
所述NiCl2·6H2O为25g，NaH2PO2·H2O为20g，Sn(CH3SO3)2@SiO2为15g，CH3COONa为8g，CH3COOH为10ml，络合剂为3.5g，稳定剂为4g，表面活性剂为2g，溶液的PH为4.7，络合剂按重量百分比由下述组分组成：甘氨酸35%，柠檬酸20%，乳酸45%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸（ENSA）45%，硫脲35%，硫代硫酸钠20%，表面活性剂为正辛基硫酸钠。
所述NiCl2·6H2O为25g，NaH2PO2·H2O为20g，Sn(CH3SO3)2@SiO2为6.5g，CH3COONa为7g，CH3COOH为10ml，络合剂为4g，稳定剂为4g，表面活性剂为2.5g，溶液的PH为4.0，络合剂按重量百分比由下述组分组成：甘氨酸60%，己二酸40%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸（ENSA）占45%，硫脲占35%，硫代硫酸钠占20%，表面活性剂为正辛基硫酸钠。
所述NiCl2·6H2O为35g，NaH2PO2·H2O为25g，Sn(CH3SO3)2@SiO2为20g，CH3COONa为15g，CH3COOH为20ml，络合剂为5g，稳定剂为8g，表面活性剂为3.5g，溶液的PH为4.8，络合剂按重量百分比由下述组分组成：柠檬酸30%、丙酸40%、己二酸30%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸（ENSA）占40%，硫脲占30%，硫代硫酸钠占30%，表面活性剂为正辛基硫酸钠。
所述NiCl2·6H2O为40g，NaH2PO2·H2O为20g，Sn(CH3SO3)2@SiO2为10g，CH3COONa为9g，CH3COOH为15ml，络合剂为8g，稳定剂为10g，表面活性剂为5g，溶液的PH为5.0，络合剂按重量百分比由下述组分组成：甘氨酸10%，丙酸20%、柠檬酸20%，乳酸50%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸（ENSA）占70%，硫脲占20%，硫代硫酸钠占10%，表面活性剂为正辛基硫酸钠。
本发明的优点是：
1、添加甲烷磺酸锡微胶囊（Sn(CH3SO3)2@SiO2）作为锡盐，利用其特殊核壳结构能够在相对高温下保持高分散性和热稳定性，微胶囊中的SnCl4能够在特定条件下缓慢渗透进入镀液参与氧化还原反应，边渗透、边反应的动态平衡过程使镀液中锡离子浓度维持恒定，避免了锡盐加入量过多时锡离子生成沉淀析出，提高了锡盐的利用率进而增加镀层中锡的含量，也使锡盐的添加量更容易控制；选用乙氧基-a-萘酚磺酸(ENSA)、硫脲和硫代硫酸钠的复合组合作为稳定剂，因ENSA具有强还原性和配位性，使溶液更加稳定的同时能与还原剂次亚磷酸钠形成协同作用，还可作为光亮剂提高镀层光亮度；
2、本发明实施简单，锡盐添加量没有严格限制，镀液具有较高的稳定性，得到的镀层相比常规的镍锡磷三元镀层耐腐蚀性能和致密性均有明显提高，能够满足特殊用途需求，延长使用寿命降低成本，具有较好的推广应用价值。
附图说明
图1 为本发明一种高稳定性镍锡磷化学镀液化学镀层的微观形貌图；
图2 为本发明一种高稳定性镍锡磷化学镀液制得的化学镀层的电化学交流阻抗曲线；
图3 为本发明一种高稳定性镍锡磷化学镀液制得的化学镀层的电化学极化曲线。
具体实施方式
下面结合附图及实施例对本发明作进一步的说明。
实施例1：
按照如下配方配制一种高稳定性镍锡磷化学镀液，每升溶液中含有：
NiCl2·6H2O 25g
NaH2PO2·H2O 20g
Sn(CH3SO3)2@SiO2 15g
CH3COONa 8g
CH3COOH 10ml
络合剂 3.5g
稳定剂 4g
表面活性剂 2g
余量为水；
其中络合剂为按照如下比例配制的：甘氨酸35%，柠檬酸20%，乳酸45%，稳定剂为乙氧基-a-萘酚磺酸（ENSA）、硫脲、硫代硫酸钠混合，其中乙氧基-a-萘酚磺酸（ENSA）占45%，硫脲占35%，硫代硫酸钠占20%，表面活性剂为正辛基硫酸钠，依次配制完溶液后，用稀硫酸和碳酸氢钾溶液调节PH为4.7，施镀温度为85℃；
得到的镍磷合金镀层性能指标：
腐蚀电位 -645mV（vs SCE）
中性盐雾试验（32μm） 2000~2500h
沉积速率 25μm/h
显微硬度 1122HV
孔隙率 无
其中显微硬度采用 HXR-1000TM数字式显微硬度计，中性盐雾采用上海JK-FH90复合盐雾试验箱。
实施例2：
按照如下配方配制一种高稳定性镍锡磷化学镀液，每升溶液中含有：
NiCl2·6H2O 25g
NaH2PO2·H2O 20g
Sn(CH3SO3)2@SiO2 6.5g
CH3COONa 7g
CH3COOH 10ml
络合剂 4g
稳定剂 4g
表面活性剂 2.5g
余量为水；
其中络合剂为按照如下比例配制的：甘氨酸60%，己二酸40%，稳定剂为乙氧基-a-萘酚磺酸（ENSA）、硫脲、硫代硫酸钠混合，其中乙氧基-a-萘酚磺酸（ENSA）占45%，硫脲占35%，硫代硫酸钠占20%，表面活性剂为正辛基硫酸钠，依次配制完溶液后，用稀硫酸和碳酸氢钾溶液调节PH为4.0，施镀温度为90℃；
得到的镍磷合金镀层性能指标：
腐蚀电位 -575mV（vs SCE）
中性盐雾试验（25μm） 1900~2200h
沉积速率 20μm/h
显微硬度 1300HV
孔隙率 无
其中显微硬度采用 HXR-1000TM数字式显微硬度计，中性盐雾采用上海JK-FH90复合盐雾试验箱。
实施例3：
按照如下配方配制一种高稳定性镍锡磷化学镀液，每升溶液中含有：
NiCl2·6H2O 35g
NaH2PO2·H2O 25g
Sn(CH3SO3)2@SiO2 20g
CH3COONa 15g
CH3COOH 20ml
络合剂 5g
稳定剂 8g
表面活性剂 3.5g
余量为水；
其中络合剂为按照如下比例配制的：柠檬酸30%、丙酸40%、己二酸30%，稳定剂为乙氧基-a-萘酚磺酸（ENSA）、硫脲、硫代硫酸钠混合，其中乙氧基-a-萘酚磺酸（ENSA）占40%，硫脲占30%，硫代硫酸钠占30%，表面活性剂为正辛基硫酸钠，依次配制完溶液后，用稀硫酸和碳酸氢钾溶液调节PH为4.8，施镀温度为93℃；
得到的镍磷合金镀层性能指标：
腐蚀电位 -580mV（vs SCE）
中性盐雾试验（35μm） 1900~2400h
沉积速率 30μm /h
显微硬度 1380HV
孔隙率 无
其中显微硬度采用 HXR-1000TM数字式显微硬度计，中性盐雾采用上海JK-FH90复合盐雾试验箱。
实施例4：
按照如下配方配制一种高稳定性镍锡磷化学镀液，每升溶液中含有：
NiCl2·6H2O 40g
NaH2PO2·H2O 20g
Sn(CH3SO3)2@SiO2 10g
CH3COONa 9g
CH3COOH 15ml
络合剂 8g
稳定剂 10g
表面活性剂 5g
余量为水。
其中络合剂为按照如下比例配制的：甘氨酸10%，丙酸20%、柠檬酸20%，乳酸50%，稳定剂为乙氧基-a-萘酚磺酸（ENSA）、硫脲、硫代硫酸钠混合，其中乙氧基-a-萘酚磺酸（ENSA）占70%，硫脲占20%，硫代硫酸钠占10%，表面活性剂为正辛基硫酸钠，依次配制完溶液后，用稀硫酸和碳酸氢钾溶液调节PH为5.0，施镀温度为85℃；
得到的镍磷合金镀层性能指标：
腐蚀电位 -525mV（vs SCE）
中性盐雾试验（45μm） 2100~2500h
沉积速率 20μm /h
显微硬度 920HV
孔隙率 无
其中显微硬度采用 HXR-1000TM数字式显微硬度计，中性盐雾采用上海JK-FH90复合盐雾试验箱。
上述各实例表明：本发明的一种高稳定性镀液层实际操作中相比传统镍锡磷自催化镀液中锡盐含量更容易控制：传统镀液中SnCl4·3H2O 10~15g/L，可操作的浓度范围较小，本发明镀液中锡盐添加浓度为 5~20g/L时均能得到良好施镀效果，且施镀过程中不会出现因锡含量过多或PH变化等情况而出现絮凝沉淀等现象；本发明的镀液施镀过程相比传统施镀配方镀速更加快速可控：传统镀液的镀速为5~9μm /h，本发明的镀速可根据镀层性能需要通过调节稳定剂浓度实现控制镀层为5~35μm /h。
此外本发明的一种高稳定性镀液得到的镀层各项性能均比传统镍锡磷镀层有明显提高：本发明得到的镀层致密性和非晶程度比传统镀层明显提高，镀层电化学自腐蚀电位比传统镀层正移0.050~0.100V左右，腐蚀电流密度减小0.5~1数量级，显微硬度为900HV~1300HV之间，远高于传统镀层的硬度500~700HV，因此本发明得到的镀层电化学耐蚀性能和机械性能比传统镀层有大幅度提高。
Claims (5)
1.一种高稳定性镍锡磷化学镀液，其特征是：包括每升镀液含NiCl2·6H2O为20~45g，NaH2PO2·H2O为15~25g， Sn(CH3SO3)2@SiO2为 5~20g，CH3COONa为5~35g，CH3COOH为6~35mL，络合剂3~10g，稳定剂4~15g，表面活性剂 2~6g，余量为水，所述溶液的pH为4.0~5.0。
2.根据权利要求1所述的一种高稳定性镍锡磷化学镀液，其特征是：所述NiCl2·6H2O为25g，NaH2PO2·H2O为20g，Sn(CH3SO3)2@SiO2为15g，CH3COONa为8g，CH3COOH为10mL，络合剂为3.5g，稳定剂为4g，表面活性剂为2g，溶液的pH为4.7，络合剂按重量百分比由下述组分组成：甘氨酸35%，柠檬酸20%，乳酸45%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸45%，硫脲35%，硫代硫酸钠20%；表面活性剂为正辛基硫酸钠。
3.根据权利要求1所述的一种高稳定性镍锡磷化学镀液，其特征是：所述NiCl2·6H2O为25g，NaH2PO2·H2O为20g，Sn(CH3SO3)2@SiO2为6.5g，CH3COONa为7g，CH3COOH为10mL，络合剂为4g，稳定剂为4g，表面活性剂为2.5g，溶液的pH为4.0，络合剂按重量百分比由下述组分组成：甘氨酸60%，己二酸40%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸占45%，硫脲占35%，硫代硫酸钠占20%；表面活性剂为正辛基硫酸钠。
4.根据权利要求1所述的一种高稳定性镍锡磷化学镀液，其特征是：所述NiCl2·6H2O为35g，NaH2PO2·H2O为25g，Sn(CH3SO3)2@SiO2为20g，CH3COONa为15g，CH3COOH为20mL，络合剂为5g，稳定剂为8g，表面活性剂为3.5g，溶液的pH为4.8，络合剂按重量百分比由下述组分组成：柠檬酸30%、丙酸40%、己二酸30%，稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸占40%，硫脲占30%，硫代硫酸钠占30%，表面活性剂为正辛基硫酸钠。
5.根据权利要求1所述的一种高稳定性镍锡磷化学镀液，其特征是：所述NiCl2·6H2O为40g，NaH2PO2·H2O为20g，Sn(CH3SO3)2@SiO2为10g，CH3COONa为9g，CH3COOH为15mL，络合剂为8g，稳定剂为10g，表面活性剂为5g，溶液的pH为5.0，络合剂按重量百分比由下述组分组成：甘氨酸10%，丙酸20%、柠檬酸20%，乳酸50%；稳定剂按重量百分比由下述组分组成：乙氧基-a-萘酚磺酸占70%，硫脲占20%，硫代硫酸钠占10%，表面活性剂为正辛基硫酸钠。
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