US3594291A - Bright zinc plating from an acid electrolyte - Google Patents
Bright zinc plating from an acid electrolyte Download PDFInfo
- Publication number
- US3594291A US3594291A US844644A US3594291DA US3594291A US 3594291 A US3594291 A US 3594291A US 844644 A US844644 A US 844644A US 3594291D A US3594291D A US 3594291DA US 3594291 A US3594291 A US 3594291A
- Authority
- US
- United States
- Prior art keywords
- zinc
- polyvinylpyrrolidone
- electrolyte
- alkylene
- zinc plating
- 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.)
- Expired - Lifetime
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052725 zinc Inorganic materials 0.000 title abstract description 20
- 239000011701 zinc Substances 0.000 title abstract description 20
- 238000007747 plating Methods 0.000 title abstract description 13
- 239000002253 acid Substances 0.000 title abstract description 9
- 239000003792 electrolyte Substances 0.000 title description 23
- -1 DIHYDROXYPHENYL Chemical class 0.000 abstract description 12
- 239000002659 electrodeposit Substances 0.000 abstract description 5
- 150000002576 ketones Chemical class 0.000 abstract description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 24
- 238000013019 agitation Methods 0.000 description 15
- 229960001040 ammonium chloride Drugs 0.000 description 12
- 235000019270 ammonium chloride Nutrition 0.000 description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 12
- 229960001763 zinc sulfate Drugs 0.000 description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229960002668 sodium chloride Drugs 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 3
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 2
- GBKGJMYPQZODMI-UHFFFAOYSA-N 4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)C=CC1=CC=CO1 GBKGJMYPQZODMI-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 125000006519 CCH3 Chemical group 0.000 description 2
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- OIKUPYQBJLSNAS-VOTSOKGWSA-N (e)-4-(2-hydroxyphenyl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CC=C1O OIKUPYQBJLSNAS-VOTSOKGWSA-N 0.000 description 1
- XUYBNDHXZMIALN-SNAWJCMRSA-N (e)-4-(3,4-dimethoxyphenyl)but-3-en-2-one Chemical compound COC1=CC=C(\C=C\C(C)=O)C=C1OC XUYBNDHXZMIALN-SNAWJCMRSA-N 0.000 description 1
- WEGYGNROSJDEIW-UHFFFAOYSA-N 3-Acetylpyridine Chemical compound CC(=O)C1=CC=CN=C1 WEGYGNROSJDEIW-UHFFFAOYSA-N 0.000 description 1
- CSPIFKKOBWYOEX-UHFFFAOYSA-N 3-acetylcoumarin Chemical compound C1=CC=C2OC(=O)C(C(=O)C)=CC2=C1 CSPIFKKOBWYOEX-UHFFFAOYSA-N 0.000 description 1
- WPSNJCPNIUVDHW-UHFFFAOYSA-N 4-(2-methylphenyl)but-3-en-2-one Chemical compound CC(=O)C=CC1=CC=CC=C1C WPSNJCPNIUVDHW-UHFFFAOYSA-N 0.000 description 1
- NGEZPLCPKXKLQQ-UHFFFAOYSA-N 4-(3-methoxyphenyl)but-3-en-2-one Chemical compound COC1=CC=CC(C=CC(C)=O)=C1 NGEZPLCPKXKLQQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003751 zinc Chemical class 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
Definitions
- This invention relates to the electrodeposition of bright zinc, and particularly to bright zinc plating from acid electrolytes.
- a wide variety of bright zinc plating solutions of the cyanide type is available.
- the cyanide baths are relatively unstable because of the decomposition of cyanide to carbonate, and the cyanide drag-out into rinsing baths presents a serious disposal problem.
- the deposits formed from known acid zinc plating baths free from organic complexing agents are at best smooth, but not bright, and complex forming organic components in acid zinc plating solutions, such as EDTA present a disposal and pollution problem as difiicult to solve as that caused by cyanide.
- Zinc and other heavy metals cannot be precipitated from the rinse water and other wastes bearing EDTA by means of alkaline reagents.
- Bright coatings can be produced from baths containing EDTA (ethylenediaminetetra-acetic acid) only if other heavy metals, particularly iron, copper, and nickel, are carefully and initially removed.
- EDTA ethylenediaminetetra-acetic acid
- the object of the invention is the provision of a brightener system for acid zinc plating solutions which permits the zinc dragged out into rinsing baths to be precipitated by an alkaline reagent because of the absence of complex forming compounds, is insensitive to substantial amounts of other heavy metal, provides bright and ductile deposits over a wide range of cathode current densities, and is stable under the operating conditions usual for the electrodeposition of dull coatings from acid electrolytes including agitation by means of compressed air.
- Such a brightener system has been found in the combination of N-polyvinylpyrrolidone-( 2) with a secondary brightener of the formula wherein R is R is lower alkyl, lower alkenyl, lower-alkyl-carbonyllower-alkylene, cyano-lower-alkylene, lower-alkoxycarbonyl-lower-alkylene, or ---(CH CH) C H 3,594,291 Patented July 20, 1971
- R R and R each are hydrogen, hydroxy, lower alkyl, or lower alkoxy, and R and R together represent the methylenedioxy group, and
- n 1 or 0.
- the concentration of polyvinylpyrrolidone-(Z) in the electrolytes of the invention may be between 0.5 to g./l., and that of the secondary brightener between 0.01 and 0.5 g./l., with best results usually being obtained at respective concentrations of 2-l0 g./l. and 0.050.3 g./l.
- the two brighteners synergistically cooperate, the brightness of the electrodeposit obtained by their simultaneous presence being far superior to the sum of their individual effects. Neither of them alone can produce the mirror brightness available from the combination.
- the brighteners of the invention are known compounds, and may be prepared from readily available starting ma terials by known methods.
- the solution polymerization of vinyl pyrrolidone in the presence of azoisobutyronitrile has been described in German Pat. No. 922,378.
- the degree of polymerization of the polyvinylpyrrolidone is not critical, acceptable results being obtained with products whose degree of polymerization is between 5 and 1000. Most consistently satisfactory results are achieved with a polymer having an average molecular weight of about 10,000 to 30,000, and a corresponding intrinsic viscosity of about 17 to 25.
- Representative secondary brighteners of the invention II o Acetophenone ll Ethinylphenylketone Propiophenone II o Benzalacetone 25 OH 2-Hydroxybenzalacetone II 0 CH 3-Methoxybenzalacetone @Cli CH-C-CH;
- aqueous electrolyte which may be improved by the use of the brighteners may typically contain zinc sulfate and ammonium chloride, and optionally boric acid within the following ranges:
- the zinc sulfate may be replaced as a source of zinc ions partly or entirely by other Zinc salts such as the chloride, acetate, fiuoborate, and sulfamate.
- Ammonium chloride has the primary function of improving the conductivity of the electrolyte, and may therefore be replaced by other conductive salts such as sodium chloride, sodium sulfate, sodium acetate, aluminum sulfate, and many others, as is well known in itself according to the art.
- the electrolytes of the invention may be operated over a wide range of plating conditions, particularly a pH value of 3 to 6, a temperature of 10 to 45 0, most conveniently at 20-30 C., and at cathode current densities from 0.1 to 10.0 amps. per dm
- cathode rod agitation or aeration is necessary.
- Still baths produce coatings which are not truly mirror bright, particularly at relatively high current densities.
- the electrolytes of the invention are particularly useful for barrel plating, both in oblique barrels containing the electrolyte and in horizontal barrels immersed in a tank. Racked objects have been handled successfully on conveyors, with highest brightness being achieved with air agitation. Such zinc plates of the invention are completely free from haze.
- the brighteners of the invention undergo neither chemical nor electrolytic decomposition in the acid zinc plating solutions and can be used for a long time without additions other than those needed to make up for drag-out losses. They are relatively insensitive to contamination with heavy metals other than zinc, particularly to iron contamination.
- the electrolytes of the invention are not impaired if steel parts are accidentally immersed in the bath without current as may occur if a rack drops into the electrolyte from a conveyor.
- Ammonium chloride 25 g./l.
- Ammonium chloride 53 g./l. Boric acid: g./l. Polyvinylpyrrolidone-(Z): 3 g./l. 1-(2-Furyl)-1-buten-3-one: 0.1 g./l. Nonylphenol-ethylenoxide 0.4 g./l. pH: 4.2 Temperature: C. Current density: 0.1-5 amps/dm. Cathode rod agitation EXAMPLE 5 Zinc sulfate (ZnSO -7H O): 290 g./l. Ammonium chloride: 25 g./l. -Polyvinylpyrrolidone-(2): 5 g./l. S-Acetylpyridine: 3 g./l.
- Fatty alcohol polyglycolether 0.2 g./l. pH: 4.8
- Ammonium chloride 53 g./l.
- Polyvinylpyrrolidone-(Z) 2.5 g./l.
- 1-(2-Furyl)-1-buten-3-one 0.2 g./1.
- Polyvinylpyrrolidone-(2) 2.5 g./l.
- Z-thienylideneaceton 0.2 g./1.
- an aqueous acid plating electrolyte for the deposition of zinc electrodeposits in the absence of organic compounds forming complex ions with heavy metals, the electrolyte containing a source of zinc ions, the improvement which comprises having present in said electrolyte:
- a secondary brightener dispersed in said electrolyte, said secondary brightener being a compound of the formula R is lower alkyl, lower alkenyl, lower alkyl-carbonyllower-alkylene, cyano-lower alkylene, lower-alkoxycarbonyl-lower-alkylene, or
- R R and R each are hydrogen, hydroxy, lower alkyl, or lower alkoxy, and R and R together represent the methylenedioxy group
- n 1 or 0.
- the concentration of said N-polyvinylpyrrolidone-(2) being between 2 and 10 grams per liter, and the concentration of said secondary brighteners between 0.05 and 0.3 gram per liter.
- R being methyl or ethyl.
- R being ethenyl
- R being CH -CO-CH 6.
- R being 7.
- the pH being 3 to 6.
- a method of forming bright zinc electrodeposits which comprises making an object the cathode in the electrolyte as set forth in claim 1.
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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681771983 DE1771983C3 (de) | 1968-08-10 | Saures galvanisches Zinkbad zur Herstellung glänzender Zinküberzüge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3594291A true US3594291A (en) | 1971-07-20 |
Family
ID=5701063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US844644A Expired - Lifetime US3594291A (en) | 1968-08-10 | 1969-07-24 | Bright zinc plating from an acid electrolyte |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3594291A (enrdf_load_stackoverflow) |
| BE (1) | BE737280A (enrdf_load_stackoverflow) |
| CH (1) | CH516646A (enrdf_load_stackoverflow) |
| ES (1) | ES369249A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2015422A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1283095A (enrdf_load_stackoverflow) |
| NL (1) | NL163571C (enrdf_load_stackoverflow) |
| SE (1) | SE350772B (enrdf_load_stackoverflow) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
| US3787296A (en) * | 1970-04-24 | 1974-01-22 | H Hayashida | Non-poisonous zinc plating baths |
| US3855085A (en) * | 1973-06-14 | 1974-12-17 | Du Pont | Acid zinc electroplating electrolyte, process and additive |
| US3891520A (en) * | 1970-04-09 | 1975-06-24 | Schering Ag | Acid, galvanic zinc bath |
| US3909373A (en) * | 1972-06-16 | 1975-09-30 | Oxy Metal Industries Corp | Non-cyanide zinc plating |
| US3960677A (en) * | 1974-09-27 | 1976-06-01 | The Harshaw Chemical Company | Acid zinc electroplating |
| US4119502A (en) * | 1977-08-17 | 1978-10-10 | M&T Chemicals Inc. | Acid zinc electroplating process and composition |
| US4138294A (en) * | 1977-12-06 | 1979-02-06 | M&T Chemicals Inc. | Acid zinc electroplating process and composition |
| EP0545089A3 (en) * | 1991-11-05 | 1993-09-22 | Mcgean-Rohco, Inc. | Additive composition, acid zinc and zinc-alloy plating baths and methods for electrodepositing zinc and zinc alloys |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2111602C2 (de) * | 1970-03-18 | 1982-07-01 | The Udylite Corp., Detroit, Mich. | Cyanidfreies wäßriges galvanisches Glanzzinkbad und Verfahren zur galvanischen Abscheidung von Glanzzink unter Verwendung dieses Bades |
-
1969
- 1969-07-07 ES ES369249A patent/ES369249A1/es not_active Expired
- 1969-07-24 US US844644A patent/US3594291A/en not_active Expired - Lifetime
- 1969-07-29 CH CH1156569A patent/CH516646A/de not_active IP Right Cessation
- 1969-08-04 SE SE10888/69A patent/SE350772B/xx unknown
- 1969-08-05 NL NL6911951.A patent/NL163571C/xx not_active IP Right Cessation
- 1969-08-08 BE BE737280D patent/BE737280A/xx not_active IP Right Cessation
- 1969-08-08 FR FR6927340A patent/FR2015422A1/fr not_active Withdrawn
- 1969-08-11 GB GB39984/69A patent/GB1283095A/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3891520A (en) * | 1970-04-09 | 1975-06-24 | Schering Ag | Acid, galvanic zinc bath |
| US3787296A (en) * | 1970-04-24 | 1974-01-22 | H Hayashida | Non-poisonous zinc plating baths |
| US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
| US3909373A (en) * | 1972-06-16 | 1975-09-30 | Oxy Metal Industries Corp | Non-cyanide zinc plating |
| US3855085A (en) * | 1973-06-14 | 1974-12-17 | Du Pont | Acid zinc electroplating electrolyte, process and additive |
| US3960677A (en) * | 1974-09-27 | 1976-06-01 | The Harshaw Chemical Company | Acid zinc electroplating |
| US4119502A (en) * | 1977-08-17 | 1978-10-10 | M&T Chemicals Inc. | Acid zinc electroplating process and composition |
| US4138294A (en) * | 1977-12-06 | 1979-02-06 | M&T Chemicals Inc. | Acid zinc electroplating process and composition |
| EP0545089A3 (en) * | 1991-11-05 | 1993-09-22 | Mcgean-Rohco, Inc. | Additive composition, acid zinc and zinc-alloy plating baths and methods for electrodepositing zinc and zinc alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| BE737280A (enrdf_load_stackoverflow) | 1970-02-09 |
| DE1771983B2 (de) | 1976-09-16 |
| SE350772B (enrdf_load_stackoverflow) | 1972-11-06 |
| DE1771983A1 (de) | 1972-02-03 |
| FR2015422A1 (enrdf_load_stackoverflow) | 1970-04-24 |
| ES369249A1 (es) | 1971-05-16 |
| GB1283095A (en) | 1972-07-26 |
| NL6911951A (enrdf_load_stackoverflow) | 1970-02-12 |
| NL163571C (nl) | 1980-09-15 |
| CH516646A (de) | 1971-12-15 |
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