US3558448A - Method of electroplating zinc and electrolyte therefor - Google Patents
Method of electroplating zinc and electrolyte therefor Download PDFInfo
- Publication number
- US3558448A US3558448A US764337A US3558448DA US3558448A US 3558448 A US3558448 A US 3558448A US 764337 A US764337 A US 764337A US 3558448D A US3558448D A US 3558448DA US 3558448 A US3558448 A US 3558448A
- Authority
- US
- United States
- Prior art keywords
- zinc
- thio
- aldehyde
- group
- compound
- 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
- 239000011701 zinc Substances 0.000 title abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910052725 zinc Inorganic materials 0.000 title abstract description 18
- 238000009713 electroplating Methods 0.000 title description 9
- 238000000034 method Methods 0.000 title description 6
- 239000003792 electrolyte Substances 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 21
- 238000005282 brightening Methods 0.000 abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 15
- -1 THIO-SEMICARBAZONE COMPOUND Chemical class 0.000 abstract description 12
- 239000008151 electrolyte solution Substances 0.000 abstract description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229960001763 zinc sulfate Drugs 0.000 abstract 1
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical group O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- 235000009529 zinc sulphate Nutrition 0.000 description 8
- 239000011686 zinc sulphate Substances 0.000 description 8
- 239000001166 ammonium sulphate Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229940081310 piperonal Drugs 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229940012017 ethylenediamine Drugs 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- IXWOUPGDGMCKGT-UHFFFAOYSA-N 2,3-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1O IXWOUPGDGMCKGT-UHFFFAOYSA-N 0.000 description 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000005265 Lupinus mutabilis Species 0.000 description 1
- 235000008755 Lupinus mutabilis Nutrition 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000019095 Sechium edule Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical group NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000003583 thiosemicarbazides Chemical class 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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 zinc plating art, and is concerned with the provision of an improved electrolytic solution for zinc plating.
- electrolytic deposits of zinc are generally made from a cyanided bath, the latter having a good penetrating power,
- zinc baths with a pyrophosphate basis have the disadvantage of being expensive and must be employed at high temperature, and baths with a zincate basis present difiicu-lties due to anodic polarisation and formation of mud on the anodes.
- the present invention has the object of remedying the greater part of these various disadvantages.
- the invention there is introduced, into acidic aqueous electrolytes containing zinc salts, an organic additive which promotes the production of bright and level zinc coatings.
- the utilization of these acid baths thus eliminates the special treatment of residual waters and enables treatment at ambient temperature.
- the invention also has the object of introducing, in conjunction with the brightening agent, agents increasing the levelling power of the baths.
- a zinc salt such as zinc sulphate
- alkali metal or ammonium salt such as ammonium sulphate
- a thio-semicarbazone compound forming the brightening agent A thio-semicarbazone compound forming the brightening agent.
- R is an aryl group containing at least one hydroxy, alkyloxy or alkyleneoxy (--O--CH O) group
- x is equal either to 0 or 1
- y being 1 or 2
- R is hydrogen or
- the brightening agent can be prepared by condensing (a) an aldehyde of the RCHO form, in which R is an aryl group containing at least one hydroxy, alkyloxy or alkyleneoxy group, with (b) the thio-semicarbazide followed by a condensation of this product with the thiourea for producing a brightening agent of the formula:
- the thiourea can firstly be condensed with aromatic aldehyde followed by a condensation of the reaction product with the thiosemicarbazide to give a compound of the formula:
- the thiosemicarbazide can be replaced by dithiocarbamic acid to give compounds according to the Formulas l or 2 above, according to the order of adding the thiourea and the dithiocarbamic acid.
- the RCHO aromatic aldeyhde can have hydroxy substituents, for instance, mono-hydroxybenzaldehyde or dihydroxybenzaldehyde with the hydroxy group in ortho, meta or para position in relation to the aldehyde group.
- the aromatic ring can have other substituents in the form of alkyloxy groups, such as anisaldehyde or alkylene oxide rings such as piperonal, Alternatively, both hydroxy and alkyloxy groups can be present as in vanillaldehyde.
- the brightening agent thus obtained can be used directly or after purifying.
- the final condensation product in hydro-alcoholic solution is precipitated by adding a volume of water five or six times the initial volume. After filtering and washing on a filter with a small quantity of alcohol, the precipitate is re-dissolved in a solvent which can be an acetone alcohol mixture.
- the electrolytic solution can also contain additional products enabling the brightness area to be increased, i.e., the possibility of utilizing current densities in a relatively wide scope, for instance, between 0.2 and a./dm. Moreover, these additives also improve the polish effect of the deposit. These additives can be utilized in association with the thiosemicarbazone compound mentioned above. Among these products, we can use alone, or in association with non-ionic tensioactive agents, for example, fatty alcohol derivatives and ethylene oxide or fatty acid and ethylene oxide or phenol alcohol and ethylene oxide derivatives especially nonyl-phenol on which to 13 ethylene oxide molecules are condensed. One can also use aliphatic diamines such as diamino ethylene, diamino propylene, diamino diethylene as Well as hexamethylenetetramine.
- non-ionic tensioactive agents for example, fatty alcohol derivatives and ethylene oxide or fatty acid and ethylene oxide or phenol alcohol and ethylene oxide
- Anionic surface-active products such, for instance, as sulphated alcohols of C8 to C12 chain length, or their salts, can also be used in the composition of the electrolytic solution in place of the non-ionic surface-active products described above or in association with them.
- compositions also consists of using compounds of the imidazole group, and in particular that obtained by the action of an amine on glyoxal, for example, by action molecule by molecule of CHO--CHO glyoxal on the diethylenetriamine, the reaction taking place at a moderate temperature (40 to 80) in an aqueous medium, the diethylenetriamine being able to be replaced by ethylenediamine or diethylenediamine.
- EXAMPLE I For depositing zinc on screws in bulk in a drum revolving appreciably at 10 r.p.m., and with a capacity of 50 kg. of parts, 1,000 litres of an aqueous electrolytic solution was used, containing:
- the content of the brightening agent may be from 0.2 to 0.6 grams per liter and the content of the dispersing agent may be from 2 to 6 grams per liter.
- the results were not appreciably altered by varying the quantity of zinc sulphate in a bracket of 100 to 250 g./l. and the ammonium sulphate or the ammonium chloride in a bracket of 50 to 200 g./l., taking the quantities into account indicated for the other products.
- An electroplating bath for producing bright deposits of zinc comprising,
- R is an arylic radical comprising at least one member of the group consisting of OH, O.CH and -OCH O; x is selected from the group consisting of O and 1 and y is selected from the group consisting of 1 and 2, the sum of x+y being 2; R is hydrogen, and
- a complementary additive a significant amount of surface-active dispersing agent selected from the group consisting of non-ionic and anionic wetting agents.
- the surface-active dispersing agent is a non-ionic wetting agent consisting of the condensation product of a fatty acid having 18 carbon atoms per molecule with 30 moles of ethylene oxide.
- R is the radical of aldehyde methylene pyrocatechic (piperonal) 5.
- Method of electroplating a bright deposit of zinc on a metal object which comprises passing electric current through said object as cathode immersed in a bath, said bath comprising an aqueous acidic solution of a zinc salt, an inorganic salt of an alkali metal of the group consisting of ammonium sulphate, ammonium chloride and ammonium citrate,
- R is an arylic radical comprising at least one member selected from the group consisting of OH, O--CH and OCH O; x is 0 or 1 and y is 1 or 2, the sum of x and y being 2; and R is hydrogen, and
- R is the radical of the aldehyde methylene pyrocatechic (piperonal).
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)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR124825A FR1547678A (fr) | 1967-10-18 | 1967-10-18 | Bain électrolytique acide permettant l'obtention de dépôts de zinc possédant desqualités de brillance et de nivellement |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3558448A true US3558448A (en) | 1971-01-26 |
Family
ID=8640244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US764337A Expired - Lifetime US3558448A (en) | 1967-10-18 | 1968-10-01 | Method of electroplating zinc and electrolyte therefor |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3558448A (en:Method) |
| BE (1) | BE717833A (en:Method) |
| DE (1) | DE1803357A1 (en:Method) |
| FR (1) | FR1547678A (en:Method) |
| GB (1) | GB1204807A (en:Method) |
| NL (1) | NL6814927A (en:Method) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US4176017A (en) * | 1979-01-31 | 1979-11-27 | Oxy Metal Industries Corporation | Brightening composition for acid zinc electroplating bath and process |
-
1967
- 1967-10-18 FR FR124825A patent/FR1547678A/fr not_active Expired
-
1968
- 1968-07-09 BE BE717833D patent/BE717833A/xx unknown
- 1968-10-01 US US764337A patent/US3558448A/en not_active Expired - Lifetime
- 1968-10-09 GB GB47786/68A patent/GB1204807A/en not_active Expired
- 1968-10-16 DE DE19681803357 patent/DE1803357A1/de active Pending
- 1968-10-18 NL NL6814927A patent/NL6814927A/xx unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US4176017A (en) * | 1979-01-31 | 1979-11-27 | Oxy Metal Industries Corporation | Brightening composition for acid zinc electroplating bath and process |
Also Published As
| Publication number | Publication date |
|---|---|
| BE717833A (en:Method) | 1969-01-09 |
| NL6814927A (en:Method) | 1969-04-22 |
| GB1204807A (en) | 1970-09-09 |
| FR1547678A (fr) | 1968-11-29 |
| DE1803357A1 (de) | 1969-05-22 |
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