TWI507571B - 藉由電鑄法但不使用有毒金屬或類金屬而獲致黃金合金沉積的方法 - Google Patents
藉由電鑄法但不使用有毒金屬或類金屬而獲致黃金合金沉積的方法 Download PDFInfo
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- TWI507571B TWI507571B TW103113847A TW103113847A TWI507571B TW I507571 B TWI507571 B TW I507571B TW 103113847 A TW103113847 A TW 103113847A TW 103113847 A TW103113847 A TW 103113847A TW I507571 B TWI507571 B TW I507571B
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- metal
- electroplating bath
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 8
- 239000000956 alloy Substances 0.000 title claims abstract description 8
- 239000010930 yellow gold Substances 0.000 title abstract description 3
- 229910001097 yellow gold Inorganic materials 0.000 title abstract description 3
- 238000000034 method Methods 0.000 title description 7
- 230000008021 deposition Effects 0.000 title description 4
- 229910052752 metalloid Inorganic materials 0.000 title description 3
- 150000002738 metalloids Chemical class 0.000 title description 3
- 231100000331 toxic Toxicity 0.000 title description 3
- 230000002588 toxic effect Effects 0.000 title description 3
- 150000002739 metals Chemical class 0.000 title description 2
- 239000010949 copper Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- 239000000080 wetting agent Substances 0.000 claims abstract description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008139 complexing agent Substances 0.000 claims abstract description 3
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 229910001020 Au alloy Inorganic materials 0.000 claims description 7
- 239000003353 gold alloy Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- -1 propane sulfonate Methyldodecyl ammonium Chemical compound 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 15
- 238000002360 preparation method Methods 0.000 claims 14
- 238000009713 electroplating Methods 0.000 claims 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 2
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 238000007747 plating Methods 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- YUXIYMHONWTAID-UHFFFAOYSA-N 1-(2H-pyridin-1-yl)propane-1-sulfonic acid Chemical compound CCC(N1CC=CC=C1)S(=O)(=O)O YUXIYMHONWTAID-UHFFFAOYSA-N 0.000 description 1
- JEFWGOBOQPHWRG-UHFFFAOYSA-N 1-sulfanylideneimidazol-1-ium Chemical compound S=[N+]1C=CN=C1 JEFWGOBOQPHWRG-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical class NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- NYUQKKWCYPVQGE-UHFFFAOYSA-N dodecyl(dimethyl)azanium;propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O.CCCCCCCCCCCC[NH+](C)C NYUQKKWCYPVQGE-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Physical Vapour Deposition (AREA)
Description
本發明係關於厚層金合金形式之電解沉積物及其製造方法。
在裝飾電鍍領域中，製造金電解沉積物之方法已眾所周知，該金電解沉積物為黃色具有純度大於或等於9克拉，10微米厚度時易延展，並有高程度的耐蝕性。這些沉積物係在含有金及銅之外還含有0.1至3公克/公升鎘的鹼性電鍍槽中經由電解而獲得。然而，經由這些已知方法所獲得的沉積物具有介於1至10%之間的鎘量。鎘可促進厚膜層之沉積，例如在1與800微米之間，並可藉由減少內含於合金之銅數量而提供黃色合金，然而，鎘非常毒且在某些國家中是被禁止。
其他已知之黃色沉積物是含有金及銀的合金。
含有銅和鋅且不含鎘之18克拉金合金也已知悉。然
而，這些沉積物太過粉紅色(成色上富含太多銅)。最後，這些沉積物有很差的耐腐蝕性，此舉表示彼等會快速地變暗。
本發明之目標係藉由提供一可沉積厚層金合金層之方法而克服所有或部份上述之缺點，該金合金層為黃色且不含鋅也不含鎘作為主要成份。
因此，本發明係關於金合金形式之電解沉積物，該合金之厚度在1與800微米之間且含有銅，其特徵在於，該沉積物包含以銦作為第三個主要成份。
根據本發明之其他有利特徵：- 該沉積物實質上不含有毒金屬或類金屬；- 該沉積物含有電場1N至3N內所包含的顏色(根據ISO標準8654)；- 該沉積物很閃亮且具高度耐腐蝕性。
本發明也關於一種使金合金電鑄沉積在浸於鍍浴中之電極的方法，該鍍浴含有鹼性氰化金(aurocyanide alkaline)形式之金金屬、有機金屬成分、潤濕劑、錯合劑及游離氰化物，其特徵在於，該合金金屬為氰化銅II形式之銅和鉀，及以胺基羧酸或胺基磷酸形式錯合之銦，以沉積一閃亮反射的黃色類型之金合金。
根據本發明之其他有利特徵：- 該鍍浴含有1至10g.l-1
之鹼性氰化金(alkaline aurocyanide)形式的金金屬；- 該鍍浴含有30至80g.l-1
之鹼性氰化銅II；- 該鍍浴含有10mg.l-1
至5g.l-1
之錯合形式之銦金屬；- 該鍍浴含有15至35g.l-1
之游離氰化物；- 該鍍浴中之潤濕劑含有介於0.05至10ml.l-1
之間的濃度；- 該潤濕劑係選自：聚氧化烯、醚磷酸鹽、硫酸月桂酯、二甲基十二烷基胺-N-氧化物、丙烷磺酸二甲基十二烷基銨形式或能在鹼性氰化物介質中潤濕之任何其他者；- 胺基羧酸系錯合劑含有介於0.1至20g.l-1
之間的濃度；- 該鍍浴含有介於0.01至5ml.l-1
之間濃度的胺；- 該鍍浴含有介於0.1mg.l-1
至20mg.l-1
之間濃度的去極化劑；- 該鍍浴含有下列類型之導電鹽：磷酸鹽、碳酸鹽、檸檬酸鹽、硫酸鹽、酒石酸鹽、葡萄糖酸鹽及/或膦酸鹽；- 該鍍浴之溫度係維持在50與80℃之間；- 該鍍浴之pH係維持在8與12之間；- 該方法係以介於0.2至1.5A.dm-2
的電流密度進
行。
為了獲得最佳沉積品質，電解之後較佳地係進行熱處理，該熱處理在至少攝氏450度下進行至少30分鐘。
該鍍浴也可含有亮光劑。此亮光劑較佳地為丁炔二醇衍生物、N-吡啶基-丙烷磺酸酯或此二者之混合物、錫鹽、磺化蓖麻油、甲基咪唑、二硫羧酸如硫脲、硫巴比妥酸、咪唑啶硫酮或硫蘋果酸。
在實施例之沉積物中，有金合金，不含有毒金屬或類金屬(特別地不含鎘)，具有2N黃色，厚度200微米，極好之亮度及高度耐磨損性和晦暗抗力。
此沉積物係在下列類型之電解槽中經由電解而獲得：
- Au：3g.l-1
- Cu：45g.l-1
- In：0.1g.l-1
- KCN：22g.l-1
- pH：10.5
- 溫度：65℃
- 電流密度：0.5A.dm-2
- 潤濕劑：0.05ml.l-1
之NN-二甲基十二烷基N氧化物
- 亞胺基二乙酸：20g.l-1
- 乙二胺：0.5ml.l-1
- 硒氰酸鉀：1mg.l-1
- Au：6g.l-1
- Cu：60g.l-1
- In：2g.l-1
- KCN：30g.l-1
- NTA：4g.l-1
- Ag：10mg.l-1
- 二伸乙基三胺：0.2ml.l-1
- 鎵、硒或碲：5mg.l-1
- 次磷酸鈉：0.1g.l-1
- 硫蘋果酸：50mg.l-1
- 電流密度：0.5A.dm-2
- 溫度：70℃
- pH：10.5
- 潤濕劑：2ml.l-1
之醚磷酸酯
在這些實施例中，電解槽內含於具有絕熱性之聚丙烯或PVC槽支持物內。該鍍浴利用石英、PTFE、瓷器或穩定之不銹鋼杵熱活塞(thermo-plunger)棒加熱。適當之陰極攪動及電解質流動必須被維持。陽極由鍍鉑之鈦、不銹鋼、釕、銥或彼等之合金製成。
在此類條件下可獲得62mg.A.min-1
之陰極效率，在實施例1中沉積速度為3分鐘內1微米，而在實施例2中
30分鐘內會有10微米的閃亮沉積物。
當然，本發明並不受限於解說之實施例，但可有各種熟諳此藝者知悉的變數及變更。特定言之，該鍍浴可含有可以忽略數量的下列金屬：Ag、Cd、Zr、Se、Te、Sb、Sn、Ga、As、Sr、Be、Bi。
此外，潤濕劑可為任何能在鹼性氰化物介質中潤濕者。
Claims (15)
- 一種用於電鍍浴之前製液(make-up solution)，該前製液包含有機金屬成分、潤濕劑、錯合劑及游離氰化物，特徵在於該前製液另外包含氰化銅II形式之銅和鉀、以及錯合銦，以使在添加鹼性氰化金(alkaline aurocyanide)添加之後電鍍沈積金合金。
- 如申請專利範圍第1項之前製液，其中該錯合銦為胺基羧酸或胺基膦酸形式。
- 如申請專利範圍第2項之前製液，其中該胺基羧酸錯合劑的濃度介於在0.1mg.l-1 至20g.l-1 之間。
- 如申請專利範圍第1項之前製液，其中該前製液含有30至80g.l-1 之鹼性氰化物形式的銅II金屬。
- 如申請專利範圍第1項之前製液，其中該前製液含有10mg.l-1 至5g.l-1 之錯合銦金屬。
- 如申請專利範圍第1項之前製液，其中該前製液含有15至35g.l-1 之游離氰化物。
- 如申請專利範圍第1項之前製液，其中該潤濕劑的濃度介於0.05至10ml.l-1 之間。
- 如申請專利範圍第7項之前製液，其中該潤濕劑係選自下列類型：聚氧化烯、醚磷酸鹽、硫酸月桂酯、二甲基十二烷基胺N氧化物、丙烷磺酸二甲基十二烷基銨。
- 如申請專利範圍第1項之前製液，其中該前製液含有介於0.01至5ml.l-1 之間的胺濃度。
- 如申請專利範圍第1項之前製液，其中該前製液 含有濃度介於0.1mg.l-1 至20mg.l-1 之間的去極化劑。
- 如申請專利範圍第1項之前製液，其中該前製液含有下列類型之導電鹽：磷酸鹽、碳酸鹽、檸檬酸鹽、硫酸鹽、酒石酸鹽、葡萄糖酸鹽及/或膦酸鹽。
- 一種電鍍浴，特徵在於其包含如申請專利範圍第1至11項中任一項之前製液和鹼性氰化金形式之金金屬，以電鍍沉積閃亮反射的黃色類型之金合金。
- 如申請專利範圍第12項之電鍍浴，其中該電鍍浴包含1至10g.l-1 之鹼性氰化金形式的金金屬。
- 如申請專利範圍第12項之電鍍浴，其中該電鍍浴包含選自由下列所組成之群組中之金屬：Ag、Cd、Zr、Se、Te、Sb、Sn、Ga、As、Sr、Be和Bi，作為電鍍浴中之第4種較少重量濃度的金屬。
- 如申請專利範圍第14項之電鍍浴，其中該所選取之金屬為銀，且銀金屬在電鍍浴中的濃度為10mg.l-1 。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01494/07A CH710184B1 (fr) | 2007-09-21 | 2007-09-21 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201428143A TW201428143A (zh) | 2014-07-16 |
| TWI507571B true TWI507571B (zh) | 2015-11-11 |
Family
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW097135667A TWI441959B (zh) | 2007-09-21 | 2008-09-17 | 藉由電鑄法但不使用有毒金屬或類金屬而獲致黃金合金沉積的方法 |
| TW103113847A TWI507571B (zh) | 2007-09-21 | 2008-09-17 | 藉由電鑄法但不使用有毒金屬或類金屬而獲致黃金合金沉積的方法 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW097135667A TWI441959B (zh) | 2007-09-21 | 2008-09-17 | 藉由電鑄法但不使用有毒金屬或類金屬而獲致黃金合金沉積的方法 |
Country Status (11)
| Country | Link |
|---|---|
| US (3) | US10233555B2 (zh) |
| EP (1) | EP2205778B1 (zh) |
| JP (2) | JP5563462B2 (zh) |
| KR (1) | KR101280675B1 (zh) |
| CN (1) | CN101815814B (zh) |
| AT (1) | ATE499461T1 (zh) |
| CH (1) | CH710184B1 (zh) |
| DE (1) | DE602008005184D1 (zh) |
| IN (1) | IN2014CN02464A (zh) |
| TW (2) | TWI441959B (zh) |
| WO (1) | WO2009037180A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
| CH710184B1 (fr) | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
| EP2312021B1 (fr) * | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
| EP2505691B1 (fr) * | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
| ITFI20120103A1 (it) * | 2012-06-01 | 2013-12-02 | Bluclad Srl | Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni. |
| WO2016020812A1 (en) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Electrolytic bath, electrolytic deposition method and item obtained with said method |
| CN109504991B (zh) * | 2019-01-21 | 2020-08-07 | 南京市产品质量监督检验院 | 一种无氰18k金电铸液、其制备方法及其应用 |
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-
2007
- 2007-09-21 CH CH01494/07A patent/CH710184B1/fr unknown
-
2008
- 2008-09-11 IN IN2464CHN2014 patent/IN2014CN02464A/en unknown
- 2008-09-11 KR KR1020107008598A patent/KR101280675B1/ko active Active
- 2008-09-11 EP EP08804009A patent/EP2205778B1/fr active Active
- 2008-09-11 DE DE602008005184T patent/DE602008005184D1/de active Active
- 2008-09-11 WO PCT/EP2008/062042 patent/WO2009037180A1/fr not_active Ceased
- 2008-09-11 JP JP2010525308A patent/JP5563462B2/ja active Active
- 2008-09-11 CN CN200880107881XA patent/CN101815814B/zh active Active
- 2008-09-11 US US12/678,984 patent/US10233555B2/en active Active
- 2008-09-11 AT AT08804009T patent/ATE499461T1/de not_active IP Right Cessation
- 2008-09-17 TW TW097135667A patent/TWI441959B/zh active
- 2008-09-17 TW TW103113847A patent/TWI507571B/zh active
-
2014
- 2014-04-03 US US14/244,071 patent/US9683303B2/en active Active
- 2014-06-12 JP JP2014121169A patent/JP5887381B2/ja active Active
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2019
- 2019-01-28 US US16/259,444 patent/US10619260B2/en active Active
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| US5256275A (en) * | 1992-04-15 | 1993-10-26 | Learonal, Inc. | Electroplated gold-copper-silver alloys |
| CN1896334A (zh) * | 2005-06-02 | 2007-01-17 | 罗门哈斯电子材料有限公司 | 改进的金合金电解液 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190153608A1 (en) | 2019-05-23 |
| DE602008005184D1 (de) | 2011-04-07 |
| KR101280675B1 (ko) | 2013-07-01 |
| TW201428143A (zh) | 2014-07-16 |
| JP5887381B2 (ja) | 2016-03-16 |
| TW200930844A (en) | 2009-07-16 |
| EP2205778B1 (fr) | 2011-02-23 |
| JP2010539335A (ja) | 2010-12-16 |
| US10233555B2 (en) | 2019-03-19 |
| EP2205778A1 (fr) | 2010-07-14 |
| JP5563462B2 (ja) | 2014-07-30 |
| CN101815814A (zh) | 2010-08-25 |
| IN2014CN02464A (zh) | 2015-08-07 |
| CN101815814B (zh) | 2012-05-16 |
| US20100206739A1 (en) | 2010-08-19 |
| ATE499461T1 (de) | 2011-03-15 |
| CH710184B1 (fr) | 2016-03-31 |
| US9683303B2 (en) | 2017-06-20 |
| TWI441959B (zh) | 2014-06-21 |
| HK1147782A1 (zh) | 2011-08-19 |
| JP2014194087A (ja) | 2014-10-09 |
| US10619260B2 (en) | 2020-04-14 |
| US20140299481A1 (en) | 2014-10-09 |
| WO2009037180A1 (fr) | 2009-03-26 |
| KR20100075935A (ko) | 2010-07-05 |
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