TWI385275B - 將鎳電解地溶入無電鎳電鍍溶液中之方法 - Google Patents
將鎳電解地溶入無電鎳電鍍溶液中之方法 Download PDFInfo
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- TWI385275B TWI385275B TW098107649A TW98107649A TWI385275B TW I385275 B TWI385275 B TW I385275B TW 098107649 A TW098107649 A TW 098107649A TW 98107649 A TW98107649 A TW 98107649A TW I385275 B TWI385275 B TW I385275B
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- nickel
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 165
- 229910052759 nickel Inorganic materials 0.000 title claims description 77
- 238000007747 plating Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 11
- 229910001453 nickel ion Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003014 ion exchange membrane Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 230000008021 deposition Effects 0.000 description 9
- -1 i.e. Substances 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910001096 P alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 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
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1676—Heating of the solution
-
- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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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)
- Chemically Coating (AREA)
Description
本發明係關於一種補充無電鎳電鍍槽之鎳濃度以避免導入不要的陰離子之改良方法。
無電電鍍係表示水溶液中之金屬離子自催化地或化學地還原成沉積於基材上之金屬。一般無電電鍍槽包括，例如但不限於，無電鎳及無電銅。無電電鍍槽之組份包括金屬離子的水溶液、還原劑、錯合劑、槽穩定劑、和在特定金屬離子濃度與在系統之特定溫度及pH範圍中作用的催化劑。基材，取決於所欲電鍍之金屬，通常在中性具催化性。故，較佳之製備係提供一具有催化性表面之基材，而一旦將該基材導入無電溶液，即開始均勻的沉積。沉積於基材上之微少量之金屬，即，鎳，進一步催化此反應。在原本的表面覆蓋金屬之後，沉積係自催化。只要補充金屬離子及還原劑及維持適當之槽的pH，無電沉積會持續下去。
無電鎳電鍍通常將鎳合金沉積於基材上，該基材係能夠從含有鎳離子、及之適當的化學還原劑(其係能夠將溶液中之鎳離子還原成金屬鎳)之加工溶液，催化此合金之沉積。此等還原劑一般包括硼氫化物及次磷酸離子。一般說來，無電鎳電鍍係使用次磷酸離子作為還原劑而加以實施。在次磷酸於催化表面還原鎳時，一些磷係與鎳共沉積而產生了含有約1至13%磷的鎳/磷合金。此合金在抗腐蝕性及(熱處理後)硬度及抗磨損性上具有獨特的性質。無電鎳電鍍之通常應用包括，例如但不限於，電子、電腦、閥、飛行器部件、與影印機及打字機部件。除了鎳磷合金之獨特性質以外，使用化學而非電化學方法來沉積此等合金具有沉積厚度分布上的優點，其相對於藉由電化學方法所產生的塗層，可得到非常均勻的塗層。
在無電電鍍，金屬離子藉由化學還原劑之作用還原成金屬。該還原劑係在製程中氧化。催化劑可為基材或基材上的金屬表面，其可使還原-氧化反應在基材上發生具有最多的金屬沉積。
金屬離子與還原劑濃度必須被監控，且密切的控制以維持適當的比例，並維持在電鍍槽中整體的化學平衡。無電電鍍沉積速率係藉由選擇適當溫度、pH及金屬離子/還原劑濃度而控制。錯合劑可用作為催化抑制劑以降低無電槽之自發性分解的可能性。
最常用於無電槽之化學還原劑為結果產生鎳磷合金之次磷酸鈉。其他包括氫硼化鈉、二甲胺硼、及N-二乙胺硼，其提供鎳硼合金及肼與氫，其提供純鎳合金。無電鎳電鍍槽通常有四種形式：(1)鹼性鎳磷；(2)酸性鎳磷；(3)鹼性鎳硼；(4)酸性鎳硼。次磷酸鹽、硼烷及肼具有許多可能的及實際的配方。然而，在所有情況中鎳離子係被還原成鎳金屬，還原劑大多被氧化，但有少量程度亦可能成為鎳沉積的一部分。
儘管由工程上的觀點上來看，無電鎳電鍍具有許多優點，但無電鎳之沉積產生顯著的廢棄物。隨著溶液老化，其亦變的更有黏性且因此電鍍速度及沉積物之亮度會被降低。大多數用來還原鎳的次磷酸鹽變成氧化為亞磷酸鹽，其殘留在加工溶液中並累積濃度直到槽被更換。
鎳係藉由添加可溶性鎳鹽維持於溶液中，其一般為硫酸鎳、氯化鎳、醋酸鎳、次磷酸鎳或前述之一或二種的組合。陰離子及自還原劑氧化之產物(通常為正磷酸鹽)累積並限制了溶液的壽命。在傳統的系統中，這表示在鹽的濃度到達溶解度的極限之前，僅有約60g/L之鎳可被沉積。在大多數的工業製程中，鎳源為硫酸鎳，故加工溶液亦累積硫酸離子。在槽的操作期間，由於產生氫原子pH傾向下降，其必須藉由添加鹼，例如氨水、氫氧化鈉或碳酸鉀，來加以中和。又，此等離子在槽操作期間在濃度上累積。最終，槽到達飽和(或在此之前，金屬的沉積速率對於工業操作來說變的太慢)而必須被更換。
延長槽壽命之一種方式為以次磷酸鎳而非硫酸鎳添加鎳至槽中。其可藉由將碳酸鎳溶入次磷酸而製造。然而，次磷酸鎳為相當昂貴的原料，且具有有限的溶解度其會對槽的維持性帶來問題。
在任何無電槽中，產生得到氧化產物及金屬鎳之氧化-還原反應。pH隨著移去金屬陽離子留下鎳鹽的陰離子或錯合劑及還原劑之氧化產物(即，次磷酸鹽氧化成正磷酸鹽)而減少。鎳離子及還原劑濃度隨著沉積而減少。在鎳沉積時，在槽中之錯合劑、槽穩定劑及其他添加劑保持可接受之濃度為非常重要的，如此預防槽的自發性分解，及將必須監控並控制之化學品的數量減至最少。
故可看見現今使用之無電鎳槽具有有限的壽命。槽的pH必須不斷的以酸(通常為硫酸)或鹼(通常為氫氧化氨)調節。次磷酸鹽氧化產生正磷酸鹽與鎳離子還原成金屬鎳的組合，通常結果產生過度的酸性，而需要添加氫氧化銨以得到所需的pH。
本發明之發明人己發現，藉由浸漬鎳陽極，無論是直接或間接的使用選擇性離子交換膜於無電鎳槽，並使電流流經該槽，較佳使用具有全氟化陽離子交換膜以區隔陽離子電解質及陰離子電解質之分隔的電解槽配置，電鍍槽之鎳含量可被維持而不須導入不期望之陰離子。此使得所使用的槽相較於傳統的維持槽有更多的金屬轉換率(metal turnover)，其將所產生之廢棄物減至最少，並改善電鍍速率的一貫性。
使用本發明之製程來維持無電鎳槽之鎳含量的另一個未預料到的好處為槽的pH更為穩定。傳統的維持無電鎳電鍍槽，槽的pH在操作期間下降，而需要添加氨水或碳酸鉀或氫氧化物，其有時會產生局部的槽的不穩定。在本發明中，槽的維持係藉由鎳的電解溶解及pH保持在相對的穩定，因為溶液的離子平衡係藉由將氫離子經由陽離子交換膜輸送至陰極電解質(以取代在陰極以氫氣形式排放之氫離子)維持。此亦促成增加槽壽命及穩定度。
本發明之一目的為提供改善的鎳電鍍槽溶液。
本發明之另一目的為藉由避免添加不要的陰離子於製程，以延長無電鎳電鍍槽之壽命。
本發明之又另一目的為改善槽的pH穩定性，並將pH調節添加劑的添加減至最少。
為此，本發明係大致上關於使用電解槽將鎳溶入無電鎳電鍍槽。本發明亦大致上關於對陰極及陽極使用以膜區隔開的電解槽(以預防鎳經過陰極，讓鎳不會電鍍析出(plated out))，使其它槽的組成成分不會在鎳溶解期間氧化。
於一實施例中，本發明係關於藉由自浸漬於槽中的鎳陽極電解溶解鎳，以維持作業中之無電鎳槽之鎳離子濃度之方法，所供應至陽極之電流經過相對電極，其由下列所組成：鉛、電鍍鈦、或銥/鉭氧化物塗布之陰極，該陰極係與作業槽使用(全氟)離子交換膜區隔開來，並使用由下列所組成之陰極電解質：硫酸、磷酸、亞磷酸或次磷酸或鹽。
本發明係關於藉由在電鍍槽電解溶解鎳來補充無電鎳電鍍槽之鎳含量的方法。
為了最大化無電鎳電鍍槽的效率，必須將不要的陰離子之添加減至最少。
於一實施例中，本發明係關於補充無電鎳電鍍槽之鎳含量的方法，包括下列步驟：
a)自無電鎳電鍍槽將無電鎳沉積於基材上；
b)將鎳陽極浸漬於電鍍槽；
c)藉由使用與鎳電極槽以離子交換膜加以區隔開之陰極、以及使用包括酸或其鹽之陰極電解質，來完成電路；及
d)使電流流過該槽，
藉此鎳係溶入無電鎳電鍍槽以維持槽的鎳濃度，及氫係自陰極排出於一實施例中，鎳電鍍槽包括鎳離子源及次磷酸離子源。鎳離子源可為任何適當的鎳離子源，包括例如次磷酸鎳，但較佳為硫酸鎳。
陰極電解質一般包括選自於下列所組成之群組之酸：硫酸、磷酸、亞磷酸、次磷酸及可溶性鹽。
鎳陽極一般選自於下列所組成的群組：鎳金屬、及含有選自於下列所組成之群組之額外元素的鎳金屬：硫、磷及碳。於較佳實施例中，鎳陽極包括在鈦籃中之S-鎳餅(Nickel S-rounds)，及陽極電流密度較佳為約30-40Amps/sq.ft。
離子交換膜為陽離子交換膜。於較佳實施例中，為全氟陽離子交換膜，例如離子交換膜(可得自DuPont de Nemours)或IONAC MC 3470(Sybron Chemicals,Inc. Birmingham,NJ,USA製造)。
陰極一般選自於由下列所組成的群組：電鍍鈦、塗布了銥/鉭的鈦與鉛。其它適當的陰極亦可於本發明之製程中使用。
無電電鍍槽一般於範圍在約75及約95℃之間的範圍操作。此外，陰極電流密度一般維持在約20-30Amps/sq.ft。
本發明的好處之一為鎳係藉由傳統的鎳陰極補充，其可在陽極電流開啟時直接用於槽，或者以膜與溶液隔開。電解地補充鎳可提供許多優點，包括(1)降低對使用者的成本；(2)由於沒有陰離子隨著鎳導入，槽的壽命提高2-3倍；及(3)由於鎳係電解地溶解，槽中的pH增加，其減少pH調整的需求及減少了導入隱性的傷害性的鹼的需求。
電解槽可以所有一般使用的槽改造使用，包括例如不鏽鋼、聚丙烯及鈦。此外，沉積物中的磷可在約1-13重量%間變動，及/或沉積物中的硼可在約0.1-5重量%間變動。
此外，所產生之沉積物取決於顧客之需求可為亮色至暗色的。
儘管關於本發明具體實施例係如上所述，但很清楚的可以完成許多種變化、變更、以及變體，而不會超除揭示於此的進步的構思。因此，其係意欲囊括所有落於所添附之申請專利範圍之精神及大致範圍內的這些變化、變更、以及變體。所有本文中所引用的專利申請案、專利案、及其他出版品係以引用方式將全文併入本文。
Claims (11)
- 一種補充無電鎳電鍍槽中鎳濃度之方法，該方法包括下列步驟：a)自無電鎳電鍍槽將無電鎳沉積於基材上；b)將包括鎳之陽極浸漬於電鍍槽；c)藉由使用與鎳電極槽以離子交換膜加以區隔開之陰極、以及使用包括酸或其鹽之陰極電解質，來完成電路；及d)使電流流過該槽，藉此鎳係溶入無電鎳電鍍槽。
- 如申請專利範圍第1項之方法，其中無電鎳電鍍槽包括鎳離子源及次磷酸離子源。
- 申請專利範圍第1項之方法，其中陰極電解質包括選自於下列所組成之群組之酸：硫酸、磷酸、亞磷酸、次磷酸及可溶性鹽。
- 如申請專利範圍第2項之方法，其中鎳離子源為硫酸鎳。
- 如申請專利範圍第1項之方法，其中鎳陽極係選自於下列所組成之群組：鎳金屬、及含有選自於下列所組成之群組之額外元素的鎳金屬：硫、磷及碳。
- 如申請專利範圍第5項之方法，其中鎳陽極包括：S-鎳餅(Nickel S-rounds)。
- 如申請專利範圍第1項之方法，其中離子交換膜包括全氟化之陽離子交換膜。
- 如申請專利範圍第1項之方法，其中陰極係選自電鍍鈦、經銥/鉭塗布之鈦、及鉛所組成之群組。
- 如申請專利範圍第1項之方法，其中無電電鍍浴係在約75及約95℃之間的溫度操作。
- 如申請專利範圍第1項之方法，其中陰極電流密度細維持在約20-30 Amps/sq.ft。
- 如申請專利範圍第1項之方法，其中陽極係藉由第二離子交換膜與無電鎳電鍍浴加以區隔開。
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| JP6344269B2 (ja) * | 2015-03-06 | 2018-06-20 | 豊田合成株式会社 | めっき方法 |
| CN106048638B (zh) * | 2016-06-23 | 2018-05-04 | 广东佳纳能源科技有限公司 | 一种小阴极周期反向电流电溶金属镍造液的方法 |
| CN107675199A (zh) * | 2017-11-20 | 2018-02-09 | 中国科学院兰州化学物理研究所 | 一种电解法制备硫酸镍的工艺 |
| JP6984540B2 (ja) * | 2018-05-23 | 2021-12-22 | トヨタ自動車株式会社 | 金属皮膜の成膜方法 |
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| US5944879A (en) * | 1997-02-19 | 1999-08-31 | Elf Atochem North America, Inc. | Nickel hypophosphite solutions containing increased nickel concentration |
| US6406611B1 (en) * | 1999-12-08 | 2002-06-18 | University Of Alabama In Huntsville | Nickel cobalt phosphorous low stress electroplating |
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| WO2009114217A1 (en) | 2009-09-17 |
| ES2661519T3 (es) | 2018-04-02 |
| US8177956B2 (en) | 2012-05-15 |
| US20090232999A1 (en) | 2009-09-17 |
| WO2009114217A8 (en) | 2009-11-19 |
| EP2242871B1 (en) | 2017-12-27 |
| TW201002860A (en) | 2010-01-16 |
| CN101960046A (zh) | 2011-01-26 |
| EP2242871A1 (en) | 2010-10-27 |
| EP2242871A4 (en) | 2016-11-16 |
| PL2242871T3 (pl) | 2018-06-29 |
| JP2011514936A (ja) | 2011-05-12 |
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