GB2086940A - Composition and Process for High Speed Electrodeposition of Silver - Google Patents
Composition and Process for High Speed Electrodeposition of Silver Download PDFInfo
- Publication number
- GB2086940A GB2086940A GB8133721A GB8133721A GB2086940A GB 2086940 A GB2086940 A GB 2086940A GB 8133721 A GB8133721 A GB 8133721A GB 8133721 A GB8133721 A GB 8133721A GB 2086940 A GB2086940 A GB 2086940A
- Authority
- GB
- United Kingdom
- Prior art keywords
- electroplating bath
- silver
- alkali metal
- acid
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 4
- 238000004070 electrodeposition Methods 0.000 title description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 amine silver cyanide Chemical class 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940000207 selenious acid Drugs 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 229940098221 silver cyanide Drugs 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000009713 electroplating Methods 0.000 claims description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 20
- 239000011669 selenium Substances 0.000 claims description 18
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 8
- 229940065287 selenium compound Drugs 0.000 claims description 7
- 239000002659 electrodeposit Substances 0.000 claims description 6
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 claims description 6
- 239000001508 potassium citrate Substances 0.000 claims description 6
- 229960002635 potassium citrate Drugs 0.000 claims description 6
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 6
- 235000011082 potassium citrates Nutrition 0.000 claims description 6
- 150000003343 selenium compounds Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical group [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 4
- 229960003975 potassium Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims description 2
- 229940082569 selenite Drugs 0.000 claims description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 4
- IBGIKQMUVKJVCW-UHFFFAOYSA-N diazanium;selenite Chemical compound [NH4+].[NH4+].[O-][Se]([O-])=O IBGIKQMUVKJVCW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 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 abstract 1
- 229940095064 tartrate Drugs 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910003597 H2SeO3 Inorganic materials 0.000 description 1
- 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 1
- IONPIQWTAGULLK-UHFFFAOYSA-N N#C[Ag].N Chemical compound N#C[Ag].N IONPIQWTAGULLK-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GOEMFERYUOQIHS-UHFFFAOYSA-N [NH4+].[SeH-] Chemical compound [NH4+].[SeH-] GOEMFERYUOQIHS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- RNGFNLJMTFPHBS-UHFFFAOYSA-L dipotassium;selenite Chemical compound [K+].[K+].[O-][Se]([O-])=O RNGFNLJMTFPHBS-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- VNPSWPSRITWUFD-UHFFFAOYSA-J potassium antimony(3+) 2,3-dihydroxypropanoate Chemical compound C(C(O)CO)(=O)[O-].[K+].[Sb+3].C(C(O)CO)(=O)[O-].C(C(O)CO)(=O)[O-].C(C(O)CO)(=O)[O-] VNPSWPSRITWUFD-UHFFFAOYSA-J 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
-
- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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)
- Cosmetics (AREA)
Abstract
An electrolytic bath for the production of mirror bright silver deposits comprises an alkali metal, ammonium or amine silver cyanide; boric acid, citric acid, an alkali metal or ammonium salt of such acid, or mixture thereof; a soluble Se<-3> compound e.g. selenious acid or alkali metal or ammonium selenite; and, in certain preferred baths, antimony in the form of an alkali metal carboxylic acid salt e.g. KSb tartrate. The bath is designed to be operated at current densities of from 20 to 550 ASD.
Description
SPECIFICATION
Composition and Process for High Speed
Electrodeposition of Silver
The present invention relates to the electrodeposition of silver.
Although the electrodeposition of silver from a variety of plating baths has been disclosed in the art, there is still a need for baths capable of functioning effectively for high speed bright silver plating.
The present invention relates to new and improved electroplating baths, utilizing an alkali metal silver cyanide as the source of the silver, for high speed silver plating. More particularly, the invention pertains to particular electroplating baths wherein mirror bright silver plating is achieved at current densities up to 5000 ASF (540 ASD).
As is well known in the art, silver cyanide plating baths have been employed for many years.
Many efforts also have been made to develop non-cyanide or low-cyanide silver plating baths.
See, for example, U.S. Patents 4,1 55,817 (Fletcher) and 4,024,031 (Lerner); where the latter patent is directed to an electroplating bath with a low silver content, which is essentially at a neutral pH and operates substantially without free cyanides.
The patent to Fletcher (No. 4,155,817) also contains a detailed description of silver plating; and when this is considered along with disclosures in the prior art cited in this patent as well as in the Lerner patent, one obtains an excellent background to the historical silver plating art as well as the numerous endeavours to develop improved electroplating baths for a variety of commercial advantages such as high speed deposition and high quality, bright silver deposits.
The patent to Fletcher discloses, inter alia, the use of a divalent (-2) selenium complex together with an electrolyte bath having a free cyanide content of less than 1.5 g/l. The use of alkali metal selenium compounds as brighteners is also disclosed in U.S. Patent No. 2,613,179 (Wolfson) and U.S. Patent No.4,121,982 (Fletcher).
Wolfson discloses, inter alia, that the use of a selenite of an alkali metal together with alkali metal cyanides and nitrates results in the formation of a high speed bright silver deposit because of the presence of nitrate (100-150 g/l) and potassium selenite up to 1.0 g/l. Wolfson states that the presence of the nitrates permits him to plate at up to 100 ASF (10 ASD) and that without the nitrates this current density could not be achieved.
Another relevant patent for the present purposes is U.S. Patent No. 2,735,808 (Greenspan) which teaches that the use of a glycerol complex and potassium cyanide are necessary to obtain bright silver deposits from an electroplating bath, which is tartrate-free.
Greenspan states that his baths must be tartratefree when using the glycerol complex of antimony.
Furthermore, in U.S. Patent No.2,777,810 (Ostrow) there is a disclosure that divalent (-2) selenium compounds in the presence of antimony
compounds and free cyanide gives bright deposits
at up to 100 ASF (10.8 ASD).
It should further be noted that when divalent or tetravalent selenium compounds are used, either by themselves or in combination with antimony, they do not give bright deposits over a wide current density range, i.e. over the range 200 to 5000 ASF (21.6 to 540 ASD).
The present invention relates to a particular electroplating bath for producing mirror bright silver deposits. More particularly selenium, or combinations of selenium and antimony, are added as additives. The selenium component may be any bath soluble selenium compound in which the selenium is trivalent, i.e. is in a valency state of 3, and in which the anions and/or cations associated with the trivalent selenium do not have an adverse effect on either the electroplating bath or the silver electrodeposit produced.
Generally, the selenium (iii) is added as either selenious acid or as an alkali metal or ammonium selenite. Similarly, the antimony component may be any bath soluble compound or complex of antimony in which the anions end/or cations associated with the antimony do not have an adverse effect on either the electroplating bath or the silver electrodeposit produced. Desirably, the antimony component is employed in the form of its complex with an alkali metal carboxylic acid salt With selenium or both antimony and selenium present a mirror bright silver deposit results.
The source of silver may be an alkali metal or ammonium or amine silver cyanide. Other essential components are boric acid or citric acid or mixtures thereof, or the alkali metal or ammonium salts of such acids. Preferably, for operations at current densities above about 500
ASF (54 ASD), both boric acid and citric acid are employed; and most preferably the acids are utilized in the form of their alkali metal salts.
In general, the electroplating bath will be substantially free of free cyanide. It is preferably formulated to have a pH within the range of about 7.0 to about 9.0; and it is preferably operated within a temperature range of about 200 to about 800C and at a high current density of up to about 5000 ASF (540 ASD).
The silver will be present in the bath in an amount which is at least sufficient to produce a smooth electrodeposit of silver on the substrate.
The citrate and borate will be present in amounts which are at least sufficient, either alone or in combination, to effect buffering of the bath to maintain it within the desired operable pH range.
The selenium or selenium and antimony will be present in amounts which are at least sufficient to produce a bright electrodeposit of silver.
As previously set forth, the goal of the present invention is to provide an electroplating bath, which can be operated at high speed up to 5000
ASF (540 ASD) to produce a mirror bright silver deposit on various substrates or workpieces such as copper alloys or nickel alloys.
The source of the silver in the bath is desirably an alkali metal or ammonium silver cyanide.
Although ammonium, potassium, sodium, and lithium silver cyanides may be employed, the most preferred material is potassium silver cyanide. It will be further understood that for most purposes of the present invention wherever the use of an alkali metal is prescribed, potassium is especially preferred unless otherwise indicated.
The amount of silver, derived from the potassium silver cyanide, is preferably in the range from about 20 to 120 g/l, more preferably from 30 to 100 g/l.
The citric acid or its alkali metal or ammonium salt, preferably potassium citrate, is preferably employed in amounts ranging from about 50 to 200 g/l, more preferably 75 to 140 g/l.
The boric acid or its alkali metal or ammonium salt, which for operations at current densities above about 500 ASF (54 ASD), will be employed not in place of the citric acid or its alkali metal salt but rather in conjunction with the citric acid, is preferably utilized in amounts ranging from about 10 to 50 girl, preferably 20 to 40 girl. Again, the preferred boric acid component will be its potassium metal salt, namely potassium borate.
The selenium component is desirably selenious acid (H2SeO3) or an alkali metal or ammonium selenium salt wherein the valence is 3 (i.e.
trivalent) rather than divalent as prescribed in the prior art teaching described above. The selenium component is preferably utilized in tha bath in amounts ranging from about 2.0 to 5 g/l, and preferably 2.5 to 5 g/l. In forming the alkali metal salt, the selenious acid need merely be neutralized with an alkali metal material such as the hydroxide. Thus, for example, potassium hydroxide may be readily employed to neutralize the selenoous acid. Based on selenium metal alone, the bath will preferably contain 1 to 3 g/l, and more preferably 1.5 to 3 g/l.
For certain purposes of this invention an antimony component is also employed in the bath to ensure the deposition of mirror bright silver deposits. Preferably the antimony is used in the form of an alkali metal carboxylic acid complex, and most preferably as potassium antimony tartrate. Other complexes that could be employed in the present invention include antimony potassium glycerate, or antimony oxide dissolved in other carboxylic acids. The amount of antimony metal used in the bath will preferably range from about 0.5 to 2.5 g/l, more preferably 1.0 to 1.5 g/l.
It is an important feature of the present invention that the resulting electroplating bath be substantially free of free cyanide, which is another distinction between the present invention and the known baths of the prior art. By substantially free of free cyanide one means a cyanide ion content of less than 1.5 g/l, and preferably less than 0.25 g/l. Furthermore, the electroplating bath is preferably also free of nitrate ions.
One of the preferred class of bath compositions in accordance with the present invention is set forth below: Concentration
Component gfl Silver as potassium silver
cyanide 30-100 Potassium Citrate 75-140 Potassium Borate 20-40 H2SeO3 (neutralized
with KOH) 2-5
Antimony (as potassium
antimony tartrate) 1-1.5 The pH of the bath may range from about 7.0 to 9.0 and preferably is 7.5 to 8.5; while the temperature is maintained with the range of 20 to 800C, preferably about 40 to 700C. As described above the current density may be relatively high, i.e. up to 5000 ASF (540 ASD).Although the current density employed may be as low as 100
ASF (10.8 ASD), in order to ensure the production of mirror bright silver deposits the densities will preferably range from about 200 to 5000 ASF, i.e. about 20 to 540 A/dm2 (ASD).
The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying
Examples.
Example 1
An electrolytic bath was prepared having the following composition:- Silver as potassium silver cyanide 60 g/l
Potassium citrate 100 g/l
Boric Acid 30 g/l
Selenium as Selenious acid 2.0 g/l
This electrolyte at 700C deposited mirror bright plates when selectively plated at current densities between 1000 and 4000 ASF (108 to 423 ASD) on copper alloys. The pH of the bath was 8.
Example 2
Example 1 was repeated but at 500C, and plated selectively mirror bright deposits at current densities between 400 and 1 500 ASF (43.2 and
162 ASD).
Example 3
Example 1 was repeated at 300 C, and plated selectively mirror bright deposits between 200 and 400 ASF (2t.6 and 43.2 ASD).
Example 4
Example 3 was repeated except that the potassium citrate was omitted from the bath and similar results were obtained.
Example 5
Example 3 was repeated except that the boric acid was omitted from the bath and similar results were obtained.
Example 6
An electrolytic bath was prepared having the following composition: Silver as potassium silver cyanide 80 g/l
Potassium citrate 75 g/l
Boric acid 20 g/l
Selenium as selenious acid 2.0 g/l
Antimony as potassium
antimony tartrate 1.5 g/l
This electrolyte when operated at 60CC selectively plated mirror bright silver deposits at current densities from 1000 to 5000 ASF (108 to 540 ASD).
The above Examples demonstrate that the electrolytic baths of the present invention give outstanding silver deposits.
Examples 7 and 8
By way of comparison, it was found that when the selenious acid or salt of the illustrative embodiment was substituted with a selenide (where the selenium is divalent) (Example 7) or selenate (where the selenium is tetravalent) (Example 8) the thus formed electrolytes did not give mirror bright or bright silver deposits when plated selectively at current densities in excess of 500 ASF (54 ASD).
Claims (15)
1. An aqueous, stable electroplating bath comprising
a) an alkali metal, ammonium or amine silver cyanide;
b) citric acid, boric acid, an alkali metal salt of citric acid or of boric acid, or an ammonium salt of citric acid or boric acid, or mixtures thereof; and
c) a bath soluble selenium compound in which the selenium has a valence of 3.
2. An electroplating bath as claimed in Claim 1 substantially free of free cyanide.
3. An electroplating bath as claimed in Claim 1 or Claim 2 which also contains a bath soluble compound or complex of antimony.
4. An electroplating bath as claimed in Claim 3 in which the antimony is present in the form of an alkali metal carboxylic acid complex.
5. An electroplating bath as claimed in any one of Claims 1 to 4 which contains potassium silver cyanide.
6. An electroplating bath as claimed in any one of Claims 1 to 5 which contains both alkali metal citrate and borate.
7. An electroplating bath as claimed in Claim 6 which contains potassium citrate and potassium borate.
8. An electroplating bath as claimed in any one of Claims 1 to 7 in which the selenium compound comprises selenious acid, or an alkali metal or ammonium salt of selenious acid.
9. An electroplating bath as claimed in any one of Claims 1 to 7 in which the selenium compound is selenious acid.
10. An electroplating bath as claimed in Claim 8 in which the selenium component is an alkali metal selenite.
11. An electroplating bath as claimed in any one of Claims 3 to 10 in which the antimony is present in the form of a potassium carboxylic acid salt complex.
12. An electroplating bath as claimed in Claim 11 in which the antimony complex is potassium antimony tartrate.
1 3. An electroplating bath as claimed in any one of Claims 1 to 12 having a pH of from about 7.0 to 9.0.
14. An electroplating bath as claimed in Claim 1 substantially as specifically described herein with reference to any one of Examples 1 to 6.
1 5. A method of electrodepositing bright silver on a substrate which comprises passing an electric current between a cathode and an anode through an electroplating bath as claimed in any one of Claims 1 to 14 at a current density of from about 200 to about 5000 ASF (20 to 550 ASD) for a period of time sufficient to deposit the desired thickness of silver.
1 6. A substrate carrying an electrodeposit of silver containing selenium (III) values.
1 7. A substrate carrying an electrodeposit of silver whenever made by a method as claimed in
Claim
15.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20580380A | 1980-11-10 | 1980-11-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2086940A true GB2086940A (en) | 1982-05-19 |
| GB2086940B GB2086940B (en) | 1984-06-13 |
Family
ID=22763700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8133721A Expired GB2086940B (en) | 1980-11-10 | 1981-11-09 | Composition and process for high speed electrodeposition of silver |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS57110688A (en) |
| BE (1) | BE891078A (en) |
| BR (1) | BR8107252A (en) |
| CA (1) | CA1181715A (en) |
| DE (1) | DE3143225C2 (en) |
| FR (1) | FR2493881B1 (en) |
| GB (1) | GB2086940B (en) |
| HK (1) | HK67086A (en) |
| IT (1) | IT1171647B (en) |
| NL (1) | NL8104883A (en) |
| PT (1) | PT73880B (en) |
| SE (1) | SE8106495L (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014808A1 (en) * | 1990-03-28 | 1991-10-03 | Siemens Aktiengesellschaft | Process for depositing silver/graphite dispersion-hardened coatings |
| EP1801266A1 (en) * | 2005-12-21 | 2007-06-27 | F.Lli Calegaro di Luigi di Francesco Calegaro S.P.A. | Method for the surface finishing of silver and its alloys |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5983788A (en) * | 1982-11-04 | 1984-05-15 | Shinko Electric Ind Co Ltd | High-speed silver plating method |
| JPS61195986A (en) * | 1985-02-25 | 1986-08-30 | Nippon Engeruharudo Kk | Lusterless high-velocity silver plating liquid |
| CN110392751B (en) * | 2017-03-31 | 2022-05-17 | 日本电镀工程股份有限公司 | Electrolytic silver plating solution |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2777810A (en) * | 1956-10-03 | 1957-01-15 | Elechem Corp | Bath for electroplating silver |
| GB1234793A (en) * | 1967-06-26 | 1971-06-09 | Tesla Np | Brightening and hardening additive for electrolytic silvering baths |
| JPS5814519B2 (en) * | 1976-08-11 | 1983-03-19 | 三菱電機株式会社 | Low cyanide high speed electrolytic silver plating solution |
| SU620515A1 (en) * | 1976-10-19 | 1978-08-25 | Всесоюзный Научно-Исследовательский Проектно-Конструкторский Институт Ювелирной Промышленности (Внииювелирпром) | Silver plating electrolyte |
| US4155817A (en) * | 1978-08-11 | 1979-05-22 | American Chemical And Refining Company, Inc. | Low free cyanide high purity silver electroplating bath and method |
-
1981
- 1981-10-16 CA CA000388152A patent/CA1181715A/en not_active Expired
- 1981-10-26 PT PT73880A patent/PT73880B/en unknown
- 1981-10-27 JP JP56171969A patent/JPS57110688A/en active Granted
- 1981-10-28 NL NL8104883A patent/NL8104883A/en not_active Application Discontinuation
- 1981-10-31 DE DE3143225A patent/DE3143225C2/en not_active Expired
- 1981-11-03 SE SE8106495A patent/SE8106495L/en not_active Application Discontinuation
- 1981-11-09 FR FR8120954A patent/FR2493881B1/en not_active Expired
- 1981-11-09 GB GB8133721A patent/GB2086940B/en not_active Expired
- 1981-11-09 IT IT49659/81A patent/IT1171647B/en active
- 1981-11-09 BR BR8107252A patent/BR8107252A/en not_active IP Right Cessation
- 1981-11-10 BE BE0/206513A patent/BE891078A/en not_active IP Right Cessation
-
1986
- 1986-09-11 HK HK670/86A patent/HK67086A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014808A1 (en) * | 1990-03-28 | 1991-10-03 | Siemens Aktiengesellschaft | Process for depositing silver/graphite dispersion-hardened coatings |
| US5290422A (en) * | 1990-03-28 | 1994-03-01 | Siemens Aktiengesellschaft | Process for applying silver-graphite dispersion electrodeposits |
| EP1801266A1 (en) * | 2005-12-21 | 2007-06-27 | F.Lli Calegaro di Luigi di Francesco Calegaro S.P.A. | Method for the surface finishing of silver and its alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3143225C2 (en) | 1983-12-29 |
| GB2086940B (en) | 1984-06-13 |
| HK67086A (en) | 1986-09-18 |
| NL8104883A (en) | 1982-06-01 |
| JPH0124230B2 (en) | 1989-05-10 |
| BR8107252A (en) | 1982-07-27 |
| IT8149659A0 (en) | 1981-11-09 |
| FR2493881A1 (en) | 1982-05-14 |
| PT73880A (en) | 1981-11-01 |
| SE8106495L (en) | 1982-05-11 |
| FR2493881B1 (en) | 1986-04-18 |
| IT1171647B (en) | 1987-06-10 |
| DE3143225A1 (en) | 1982-06-16 |
| CA1181715A (en) | 1985-01-29 |
| BE891078A (en) | 1982-05-10 |
| JPS57110688A (en) | 1982-07-09 |
| PT73880B (en) | 1983-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951109 |