CA1040132A - Electroplating brightener compositions and process - Google Patents
Electroplating brightener compositions and processInfo
- Publication number
- CA1040132A CA1040132A CA223,306A CA223306A CA1040132A CA 1040132 A CA1040132 A CA 1040132A CA 223306 A CA223306 A CA 223306A CA 1040132 A CA1040132 A CA 1040132A
- Authority
- CA
- Canada
- Prior art keywords
- molar equivalent
- equivalent amount
- veratraldehyde
- vanillin
- parts
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000009713 electroplating Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 11
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims abstract description 70
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000012141 vanillin Nutrition 0.000 claims abstract description 27
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 22
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 20
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000007747 plating Methods 0.000 claims description 37
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 230000006872 improvement Effects 0.000 claims 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 abstract description 12
- 240000008042 Zea mays Species 0.000 abstract description 11
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 11
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 11
- 235000005822 corn Nutrition 0.000 abstract description 11
- 235000020357 syrup Nutrition 0.000 abstract description 11
- 239000006188 syrup Substances 0.000 abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 9
- 239000008103 glucose Substances 0.000 abstract description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 2
- 235000001727 glucose Nutrition 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 235000008504 concentrate Nutrition 0.000 description 13
- 239000012141 concentrate Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 5
- 238000005282 brightening Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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
- -1 alkali metal salts Chemical class 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 108010070551 Meat Proteins Proteins 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229940016373 potassium polysulfide Drugs 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
- C25D3/24—Electroplating: Baths therefor from solutions of zinc from cyanide baths
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (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)
Abstract
A B S T R A C T
Zinc or cadmium electroplating brightener compositions for addition to alkaline cyanide electroplating baths comprising an aqueous solu-tion of corn syrup or glucose, vanillin, veratraldehyde, sodium lignin sul-fonate and sodium bisulfite.
Zinc or cadmium electroplating brightener compositions for addition to alkaline cyanide electroplating baths comprising an aqueous solu-tion of corn syrup or glucose, vanillin, veratraldehyde, sodium lignin sul-fonate and sodium bisulfite.
Description
This invention relates to compositions and processes useful in the art of electroplating. More specifically, it relates -to compositions useful as brightener additives to alkaline cyanide zinc or cadmium electro-plating baths and to processes of bright electroplating using said compositions.It is known in the ar~ to use as brighteners in electroplating baths such materials as waste sulfite liquors ~U.S. Patent 1,544,726); various sulfonic acid derivatives (including the alkali metal salts thereof) such as alkyl-substituted-aromatic sulfonic acids (U.S. Patent 2,312,097), sulfonic acid deriva~ives of phenols (U.S. Patent 1,607,870); lignin sulfonic acid and metal salts thereof including the sodium salt (U.S. Patents 2,740,754;
2,872,3g2 and 3,146,178); certain aromatic aldehydes such as anisic aldehyde (U.S. Patent 2,740,754); and various proteins, such as peptone (U.S. Patent 2,799,635) or hydrolyzed meat protein (~.S. Patent 3,751,348).
It has now been surprisingly found that a combination in an aqueous medium of corn syrup or glucose, vanillin, veratraldehyde and sodium ~ lignin sulfonate (together with a molar equivalent amount of sodium bisulfite ; equal to the molar equivalent amount of vanillin and veratraldehyde which is used to solubilize the vanillin and veratraldehyde through the bisulfite addition compound), when used as an additive to alkaline cyanide zinc or cadmium plating baths, provides advantages over the use of the separate brightener ingredients when used alone.
Thus, although sodium lignin sulfonate does provide a brighten-ing effect, the degree of brilliance obtained over a range of low to high current densities is not uniform when the material is used alone. On the other hand, when combined with the other ingredients of the present invention, consistently brilliant deposits are obtained at both high and low current densities, and furthermore the inclusion of the sodium lignin sulfonate with the other ingredients tends to extend the lifetime of the bath over its normal limit. Glucose or corn syrup, when used alone, provide only a small degree of brightening, and like sodium lignin sulfonate, give inconsistent resùlts over ~
broad ranges of current densities. Vanillin used alone also provides a brightening effect, but consistent results are only obtained at high current densities, and darkening of the deposit is caused at low current densities.
Veratraldehyde alone causes pitting of the deposit at low current densities, and furthermore the tolerance of the bath to impurities is diminished relative to results obtained with the instant compositions. As indicated hereinbelow ammonium heptamolybdate, a known electroplating brightener, can also be used in con~unction with the compositions of the present invention. However, this material used alone causes blistering of the deposit at high current densities and fails to deposit at low densities and thus is useful alone only at inter-mediate current densities. On the other hand the novel combination of ingred-ients used in the practice of the present invention provides consistently good results, in terms of brightening effect, tolerance to impurities, extended bath life and adherence, over a broad range of current densities.
Moreover, the bath additive compositions useful in the practice of the present invention can, if desired, be used in conjunction with other agents known to provide added brilliance to the electrodeposit such as moly-bdate salts, for example ammonium heptamolybdate, or with polysulfides in the case of cyanide zinc baths, for example ammonium, sodium or potassium poly-sulfide, which are used to combine with metallic impurities in the electro-plating bath and thereby serve to prevent impurities from interfering with deposition of the pure metal.
The invention relates to an electroplating brighten composition for addition to zinc or cadmium alkaline cyanide electroplating baths comprising an aqueous solution containing, in parts by weight:
Sodium lignin sulfonate 1.1 - 4.8 Veratraldehyde 1.0 Vanillin 0.1 - 2.5 Corn syrup or glucose 1.7 - 5.0 and a molar equi~alent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
The invention also relates to, in a process for bright plating of ~ - 2 -q, ~ r .
.
zinc or cadium from aq~eous alkaline cyanide electroplating baths, the im-provement which comprises adding to said baths an aqueous composition con-taining, in parts by weight:
Sodium lignin sulfonate 1.1 - 4.8 Veratraldehyde 1.0 Vanillin 0.1 - 2.5 ; Corn syrup or glucose 1.7 - 5.0 and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and vera~raldehyde.
The bath additive compositions provided by ~he present invention are preferably prepared in concentrated form, and in use are further diluted with water for addition to new or ~old working electroplating solutions in amounts to be described hereinafter. The concentrated form contains from 1.0 to 4.3 pounds/gallon of sodium lignin sulfonate, about 0.9 pound/gallon of veratraldehyde, from 0.1 to 2.2 pounds/gallon of vanillin, from 1.5 to 4.5 ~ pounds/gallon of corn syrup or glucose, and a molar equivalent amount of sodium bisulfite corresponding to the total weight of the vanillin and - 2a -
It has now been surprisingly found that a combination in an aqueous medium of corn syrup or glucose, vanillin, veratraldehyde and sodium ~ lignin sulfonate (together with a molar equivalent amount of sodium bisulfite ; equal to the molar equivalent amount of vanillin and veratraldehyde which is used to solubilize the vanillin and veratraldehyde through the bisulfite addition compound), when used as an additive to alkaline cyanide zinc or cadmium plating baths, provides advantages over the use of the separate brightener ingredients when used alone.
Thus, although sodium lignin sulfonate does provide a brighten-ing effect, the degree of brilliance obtained over a range of low to high current densities is not uniform when the material is used alone. On the other hand, when combined with the other ingredients of the present invention, consistently brilliant deposits are obtained at both high and low current densities, and furthermore the inclusion of the sodium lignin sulfonate with the other ingredients tends to extend the lifetime of the bath over its normal limit. Glucose or corn syrup, when used alone, provide only a small degree of brightening, and like sodium lignin sulfonate, give inconsistent resùlts over ~
broad ranges of current densities. Vanillin used alone also provides a brightening effect, but consistent results are only obtained at high current densities, and darkening of the deposit is caused at low current densities.
Veratraldehyde alone causes pitting of the deposit at low current densities, and furthermore the tolerance of the bath to impurities is diminished relative to results obtained with the instant compositions. As indicated hereinbelow ammonium heptamolybdate, a known electroplating brightener, can also be used in con~unction with the compositions of the present invention. However, this material used alone causes blistering of the deposit at high current densities and fails to deposit at low densities and thus is useful alone only at inter-mediate current densities. On the other hand the novel combination of ingred-ients used in the practice of the present invention provides consistently good results, in terms of brightening effect, tolerance to impurities, extended bath life and adherence, over a broad range of current densities.
Moreover, the bath additive compositions useful in the practice of the present invention can, if desired, be used in conjunction with other agents known to provide added brilliance to the electrodeposit such as moly-bdate salts, for example ammonium heptamolybdate, or with polysulfides in the case of cyanide zinc baths, for example ammonium, sodium or potassium poly-sulfide, which are used to combine with metallic impurities in the electro-plating bath and thereby serve to prevent impurities from interfering with deposition of the pure metal.
The invention relates to an electroplating brighten composition for addition to zinc or cadmium alkaline cyanide electroplating baths comprising an aqueous solution containing, in parts by weight:
Sodium lignin sulfonate 1.1 - 4.8 Veratraldehyde 1.0 Vanillin 0.1 - 2.5 Corn syrup or glucose 1.7 - 5.0 and a molar equi~alent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
The invention also relates to, in a process for bright plating of ~ - 2 -q, ~ r .
.
zinc or cadium from aq~eous alkaline cyanide electroplating baths, the im-provement which comprises adding to said baths an aqueous composition con-taining, in parts by weight:
Sodium lignin sulfonate 1.1 - 4.8 Veratraldehyde 1.0 Vanillin 0.1 - 2.5 ; Corn syrup or glucose 1.7 - 5.0 and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and vera~raldehyde.
The bath additive compositions provided by ~he present invention are preferably prepared in concentrated form, and in use are further diluted with water for addition to new or ~old working electroplating solutions in amounts to be described hereinafter. The concentrated form contains from 1.0 to 4.3 pounds/gallon of sodium lignin sulfonate, about 0.9 pound/gallon of veratraldehyde, from 0.1 to 2.2 pounds/gallon of vanillin, from 1.5 to 4.5 ~ pounds/gallon of corn syrup or glucose, and a molar equivalent amount of sodium bisulfite corresponding to the total weight of the vanillin and - 2a -
3;~
vertraldehyde. Since, as will be described hereinafter, the additive compo-sitions can be made up in varying concentrations ranging from dilute solutions that can be added directly to the plating bath to more concentrated solutions that require further dilution before addition to the plating bath, the composi-tions can also be described in terms of the relative amounts of the separate - ingredients. Thus, relative to the veratraldehyde present, the operative amounts of the separate ingredients, expressed in parts by weight, are:
Sodium lignin sulfonate 1.1 - 4.8 Veratraldehyde 1.0 Vanillin 0.1 - 2.5 Corn syrup or glucose 1.7 - 5.0 and a molar equivalent amount of sodium bisulfite corresponding to the total molar equivalent amount of the vanillin and veratraldehyde.
The compositions can be used in either barrel or still plating procedures, and when employed in barrel or still plating of cadmium, they may optionally contain, in addition to the ingredients described above, from 0.018 to 0.4 pound/gallon of ammonium heptamolybdate ~or from 0.02 to 0.4 part by weight relative to veratraldehyde) to improve the brilliance of the deposit.
When employed in barrel or still plating of zinc, they may optionally contain, respectively, from 0.018 to 0.4 pound/gallon (0.02 to 0.4 part by weight rela-tive to veratraldehyde) or from 0.015 to 0.18 pound/gallon ~0.017 to 0.2 part by weight relative to veratraldehyde) of ammonium heptamolybdate.
A preferred composition contains from 1.35 to 3.2 pounds/gallon of sodium lignin sulfonate, 0.9 pound/gallon of veratraldehyde, from 0.18 to 1.35 pounds/gallon of vanillin, from 2.0 to 4.0 pounds/gallon of corn syrup or glucose, and a molar equivalent amount of sodium bisulfite equal to the total amount of vanillin and veratraldehyde. When ammonium heptamolybdate is used to enhance the brilliance of the deposit in cadmium barrel or still plating, it is preferred to use from 0.045 to 0.27 pound/gallon of the hepta-molybdate, and when the heptamolybdate is used in barrel or still plating of zinc, it is preferred to use, respectively, from 0.045 to 0.27 pound/gallon 3~
or from 0.018 to 0.18 pound/gallon of the heptamolybdate. Expressed in parts by weigh~ relative to veratraldehyde, the preferred composition contains:
Sodium lignin sulfonate 1.5 - 3.5 Veratraldehyde 1.0 Vanillin 0.2 - 1.5 Corn syrup or glucose 2.2 - 4.5 and a molar equivalent amount of sodium bisulfite equal to the total amount of vanillin and veratraldehyde. When ammonium heptamolybdate is used in barrel or still plating of cadmium or in barrel plating of zinc, a preferred amount is from 0.05 to 0.3 part by weight relative to the veratraldehyde, and when it is used in still plating of zinc, a preferred amount is from 0.02 to 0.2 part by weigh~ relative to veratraldehyde.
In use, the concentrates described above are diluted with three parts of water and added to the electroplating bath. In the case of new baths, an amount of the so-diluted solution to provide 1-2% by volume of the final plating solution is used, whereas in the case of old working baths, it is sufficient to add 1/2% by volume of the diluted concentrate.
The compositions of the invention, when used in barrel plating of cadmium, give best results at 9-12 volts E.M.F., while in barrel plating of 7inc, best results are obtained at 10-15 volts E.M.F. In still plating of cadmium, a current density of 5-80 amperes/ft2 can be used with advantage, a current density of 10-40 amperes/ft being preferred. In still plating of zinc, good results are obtained at current densities of 10-80 amperes/ft2, a preferred range being 20-50 amperes/ft~. In all cases, plating is advantage-ously carried out at temperatures from 70-90F.
Having described the general manner of making and using the inven-tion, the best mode of carrying out the invention is described by the follow-ing specific examples.
Example 1 Basic Concentrate A concentrate containing the following ingredients:
Sodium lignin sulfonate 1.49 pounds/gal.
~eratraldehyde 0.9 pound/gal.
Vanillin 0.6 pound/gal.
Corn syrup 2.08 pounds/gal.
Sodium bisulfite 0.84 pound/gal.
is prepared as ~ollows:
A container of adequate size is charged with ~bout 40% of the necessary quantity of water at 140-150F., and the sodium lignin sulfonate is added with stirring, followed by the corn syrup which is previously warmed to ; 10 about 120F. The vanillin and veratraldehyde are liquified by warming together on a hot water bath, and the liquid melt is added to the main mixture with stirring. The sodium bisulfite is then added slowly with stirring, and stir-ring is continued until all material is dissolved. Sufficient wa~er is added to give the desired final volume, the solution is cooled to below 100F., and then packed with stirring in polyethylene containers.
A. Zinc Barrel or Still Plating Composition The concentrate so-prepared is diluted with three parts of water, and 10 to 20 gallons of the diluted solution are added to 1,000 gallons of a standard zinc cyanide bath containing:
Zinc cyanide 8.0 oz./gal.
Sodium cyanide 5.6 oz./gal.
Sodium hydroxide 8 - 10 oz./gal.
Sodium polysulfide 0.12 oz./gal.
The so-prepared bath when used in barrel plating at 10-15 volts E.M.F. at 70-90F
for 20-25 minutes gives an even, bright deposit of about 0.0002" thickness.
The same bath when used in still plating at a current density of 20-50 amperes/ft2 at 70-90F for 6-10 minutes gives an even, bright deposit of 0.0002" thickness.
B. Cadmium Barrel Pl ting Composition The concentrate described in Example 1 above is diluted with three parts of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of a cadmium barrel plating solution containing:
~41~3~
Cadmium oxide 3.0 oz./gal.
Sodium cyanide 10.4 - 13.4 oz./gal.
Sodium hydroxide 1.0 oz./gal.
The bath so-prepared, when used in the barrel plating of cadmium a$ 9-12 volts E.M.F. at 70-90F. for 10-15 minutes gives an even, bright deposit of about 0.0002" thickness.
C. Cadmium Still Plating Composi~ion The concentrate described in Example 1 above is diluted with ; three parts of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of a cadmium still plating solution containing:
Cadmium oxide 3.0 oz./gal.
Sodium cyanide 10.4 - 18.4 oz./gal.
The bath so-prepared, when used in the still plating of cadmium at 10-40 amperes/ft2 at 70-90F. for 5 minutes gives an even, bright deposit of about 0.0002" thickness.
Example 2 To the basic concentrate described in Example 1 above is added i 0.06 pound/gallon (about 4 grams/liter) of ammonium heptamolybdate. The concentrate so-obtained is diluted with three parts of water, and 10-20 gallons of the diluted solution are added, respectively, to 1,000 gallons of the solutions described in Examples lB and lC above. The baths so-obtained in each case when used, respectively, in barrel plating and still plating of cadmium under the conditions described in Examples lB and lC, respectively, give deposits similar to those described in Examples lB and lC, respectively, but having improved brilliance thereover.
Example 3 To the basic concentrate described in Example 1 above is added 0.03 pound/gallon (about 2 grams/liter) of ammonium heptamolybdate. The con-centrate so-obtained is diluted with three parts of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of the solution described in Example lA above. The bath so-obtained when used in still plating of zinc under the conditions described in Example lA gives a deposit similar to that described in Example lA but having improved brilliance thereover.
Example 4 To the basic concentrate described in Example l is added 0.06 pound/gallon ~about 4 grams/liter) of ammonium heptamolybdate. The concen trate so-obtained is diluted with three par~s of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of the solution described in Example lA above. The bath so-obtained when used in barrel plating of zinc under the conditions described in Example lA gives a deposit similar to that obtained in Example lA but having improved brilliance thereover.
vertraldehyde. Since, as will be described hereinafter, the additive compo-sitions can be made up in varying concentrations ranging from dilute solutions that can be added directly to the plating bath to more concentrated solutions that require further dilution before addition to the plating bath, the composi-tions can also be described in terms of the relative amounts of the separate - ingredients. Thus, relative to the veratraldehyde present, the operative amounts of the separate ingredients, expressed in parts by weight, are:
Sodium lignin sulfonate 1.1 - 4.8 Veratraldehyde 1.0 Vanillin 0.1 - 2.5 Corn syrup or glucose 1.7 - 5.0 and a molar equivalent amount of sodium bisulfite corresponding to the total molar equivalent amount of the vanillin and veratraldehyde.
The compositions can be used in either barrel or still plating procedures, and when employed in barrel or still plating of cadmium, they may optionally contain, in addition to the ingredients described above, from 0.018 to 0.4 pound/gallon of ammonium heptamolybdate ~or from 0.02 to 0.4 part by weight relative to veratraldehyde) to improve the brilliance of the deposit.
When employed in barrel or still plating of zinc, they may optionally contain, respectively, from 0.018 to 0.4 pound/gallon (0.02 to 0.4 part by weight rela-tive to veratraldehyde) or from 0.015 to 0.18 pound/gallon ~0.017 to 0.2 part by weight relative to veratraldehyde) of ammonium heptamolybdate.
A preferred composition contains from 1.35 to 3.2 pounds/gallon of sodium lignin sulfonate, 0.9 pound/gallon of veratraldehyde, from 0.18 to 1.35 pounds/gallon of vanillin, from 2.0 to 4.0 pounds/gallon of corn syrup or glucose, and a molar equivalent amount of sodium bisulfite equal to the total amount of vanillin and veratraldehyde. When ammonium heptamolybdate is used to enhance the brilliance of the deposit in cadmium barrel or still plating, it is preferred to use from 0.045 to 0.27 pound/gallon of the hepta-molybdate, and when the heptamolybdate is used in barrel or still plating of zinc, it is preferred to use, respectively, from 0.045 to 0.27 pound/gallon 3~
or from 0.018 to 0.18 pound/gallon of the heptamolybdate. Expressed in parts by weigh~ relative to veratraldehyde, the preferred composition contains:
Sodium lignin sulfonate 1.5 - 3.5 Veratraldehyde 1.0 Vanillin 0.2 - 1.5 Corn syrup or glucose 2.2 - 4.5 and a molar equivalent amount of sodium bisulfite equal to the total amount of vanillin and veratraldehyde. When ammonium heptamolybdate is used in barrel or still plating of cadmium or in barrel plating of zinc, a preferred amount is from 0.05 to 0.3 part by weight relative to the veratraldehyde, and when it is used in still plating of zinc, a preferred amount is from 0.02 to 0.2 part by weigh~ relative to veratraldehyde.
In use, the concentrates described above are diluted with three parts of water and added to the electroplating bath. In the case of new baths, an amount of the so-diluted solution to provide 1-2% by volume of the final plating solution is used, whereas in the case of old working baths, it is sufficient to add 1/2% by volume of the diluted concentrate.
The compositions of the invention, when used in barrel plating of cadmium, give best results at 9-12 volts E.M.F., while in barrel plating of 7inc, best results are obtained at 10-15 volts E.M.F. In still plating of cadmium, a current density of 5-80 amperes/ft2 can be used with advantage, a current density of 10-40 amperes/ft being preferred. In still plating of zinc, good results are obtained at current densities of 10-80 amperes/ft2, a preferred range being 20-50 amperes/ft~. In all cases, plating is advantage-ously carried out at temperatures from 70-90F.
Having described the general manner of making and using the inven-tion, the best mode of carrying out the invention is described by the follow-ing specific examples.
Example 1 Basic Concentrate A concentrate containing the following ingredients:
Sodium lignin sulfonate 1.49 pounds/gal.
~eratraldehyde 0.9 pound/gal.
Vanillin 0.6 pound/gal.
Corn syrup 2.08 pounds/gal.
Sodium bisulfite 0.84 pound/gal.
is prepared as ~ollows:
A container of adequate size is charged with ~bout 40% of the necessary quantity of water at 140-150F., and the sodium lignin sulfonate is added with stirring, followed by the corn syrup which is previously warmed to ; 10 about 120F. The vanillin and veratraldehyde are liquified by warming together on a hot water bath, and the liquid melt is added to the main mixture with stirring. The sodium bisulfite is then added slowly with stirring, and stir-ring is continued until all material is dissolved. Sufficient wa~er is added to give the desired final volume, the solution is cooled to below 100F., and then packed with stirring in polyethylene containers.
A. Zinc Barrel or Still Plating Composition The concentrate so-prepared is diluted with three parts of water, and 10 to 20 gallons of the diluted solution are added to 1,000 gallons of a standard zinc cyanide bath containing:
Zinc cyanide 8.0 oz./gal.
Sodium cyanide 5.6 oz./gal.
Sodium hydroxide 8 - 10 oz./gal.
Sodium polysulfide 0.12 oz./gal.
The so-prepared bath when used in barrel plating at 10-15 volts E.M.F. at 70-90F
for 20-25 minutes gives an even, bright deposit of about 0.0002" thickness.
The same bath when used in still plating at a current density of 20-50 amperes/ft2 at 70-90F for 6-10 minutes gives an even, bright deposit of 0.0002" thickness.
B. Cadmium Barrel Pl ting Composition The concentrate described in Example 1 above is diluted with three parts of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of a cadmium barrel plating solution containing:
~41~3~
Cadmium oxide 3.0 oz./gal.
Sodium cyanide 10.4 - 13.4 oz./gal.
Sodium hydroxide 1.0 oz./gal.
The bath so-prepared, when used in the barrel plating of cadmium a$ 9-12 volts E.M.F. at 70-90F. for 10-15 minutes gives an even, bright deposit of about 0.0002" thickness.
C. Cadmium Still Plating Composi~ion The concentrate described in Example 1 above is diluted with ; three parts of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of a cadmium still plating solution containing:
Cadmium oxide 3.0 oz./gal.
Sodium cyanide 10.4 - 18.4 oz./gal.
The bath so-prepared, when used in the still plating of cadmium at 10-40 amperes/ft2 at 70-90F. for 5 minutes gives an even, bright deposit of about 0.0002" thickness.
Example 2 To the basic concentrate described in Example 1 above is added i 0.06 pound/gallon (about 4 grams/liter) of ammonium heptamolybdate. The concentrate so-obtained is diluted with three parts of water, and 10-20 gallons of the diluted solution are added, respectively, to 1,000 gallons of the solutions described in Examples lB and lC above. The baths so-obtained in each case when used, respectively, in barrel plating and still plating of cadmium under the conditions described in Examples lB and lC, respectively, give deposits similar to those described in Examples lB and lC, respectively, but having improved brilliance thereover.
Example 3 To the basic concentrate described in Example 1 above is added 0.03 pound/gallon (about 2 grams/liter) of ammonium heptamolybdate. The con-centrate so-obtained is diluted with three parts of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of the solution described in Example lA above. The bath so-obtained when used in still plating of zinc under the conditions described in Example lA gives a deposit similar to that described in Example lA but having improved brilliance thereover.
Example 4 To the basic concentrate described in Example l is added 0.06 pound/gallon ~about 4 grams/liter) of ammonium heptamolybdate. The concen trate so-obtained is diluted with three par~s of water, and 10-20 gallons of the diluted solution are added to 1,000 gallons of the solution described in Example lA above. The bath so-obtained when used in barrel plating of zinc under the conditions described in Example lA gives a deposit similar to that obtained in Example lA but having improved brilliance thereover.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for bright plating of zinc or cadmium from aqueous alkaline cyanide electroplating baths, the improvement which comprises adding to said baths an aqueous composition containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
2. An improved process according to claim 1 for barrel or still bright plating of cadmium or barrel plating of zinc from aqueous alkaline cyanide electroplating baths, in which the improvement comprises adding to said baths an aqueous composition containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
3. An improved process according to claim 1 for still bright plating of zinc from aqueous alkaline cyanide electroplating baths, in which the improve-ment comprises adding to said baths an aqueous composition containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
4. A process according to claim 1 wherein the bath additive composi-tion contains, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
5. A process according to claim 2 wherein the bath additive composi-tion contains, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
6. A process according to claim 3 wherein the bath additive composi-tion contains, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
7. An electroplating brightener composition for addition to zinc or cadmium alkaline cyanide electroplating baths comprising an aqueous solution containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
8. An electroplating brightener composition according to claim 7 for addition to cadmium barrel or still plating or zinc barrel plating alkaline cyanide electroplating baths comprising an aqueous solution containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
9. An electroplating brightener composition according to claim 7 for addition to zinc still plating alkaline cyanide electroplating baths com-prising an aqueous solution containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
10. A composition according to claim 7 containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
11. A composition according to claim 8 containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
12. A composition according to claim 9 containing, in parts by weight:
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
and a molar equivalent amount of sodium bisulfite equal to the total molar equivalent amount of the vanillin and veratraldehyde.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00455526A US3850766A (en) | 1974-03-28 | 1974-03-28 | Electroplating brightener compositions and process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040132A true CA1040132A (en) | 1978-10-10 |
Family
ID=23809169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA223,306A Expired CA1040132A (en) | 1974-03-28 | 1975-03-27 | Electroplating brightener compositions and process |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3850766A (en) |
| CA (1) | CA1040132A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969219A (en) * | 1975-08-06 | 1976-07-13 | Sterling Drug Inc. | Zinc or cadmium electroplating brightener compositions and process |
| DE3335009A1 (en) * | 1983-09-28 | 1985-04-18 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR ELECTROLYTIC GALVANIZING STEEL |
| US20080028976A1 (en) * | 2003-12-09 | 2008-02-07 | Kansai Paint Co., Ltd. | Electroplated Coating of Zinc Alloy with Excellent Corrosion Resistance and Plated Metal Material Having Same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL52721C (en) * | 1936-08-29 | |||
| US2196588A (en) * | 1937-05-26 | 1940-04-09 | Du Pont | Electroplating |
| US3088884A (en) * | 1960-11-07 | 1963-05-07 | Metal & Thermit Corp | Electrodeposition |
| GB1051624A (en) * | 1963-05-21 |
-
1974
- 1974-03-28 US US00455526A patent/US3850766A/en not_active Expired - Lifetime
-
1975
- 1975-03-27 CA CA223,306A patent/CA1040132A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US3850766A (en) | 1974-11-26 |
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