US3769184A - Acid zinc electroplating - Google Patents
Acid zinc electroplating Download PDFInfo
- Publication number
- US3769184A US3769184A US00256179A US3769184DA US3769184A US 3769184 A US3769184 A US 3769184A US 00256179 A US00256179 A US 00256179A US 3769184D A US3769184D A US 3769184DA US 3769184 A US3769184 A US 3769184A
- Authority
- US
- United States
- Prior art keywords
- range
- pyridinium
- bath
- carboxamido
- zinc
- 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
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011701 zinc Substances 0.000 title claims abstract description 36
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 36
- 238000009713 electroplating Methods 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 27
- -1 halide ion Chemical group 0.000 claims abstract description 46
- 239000007859 condensation product Substances 0.000 claims abstract description 34
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims abstract description 21
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 28
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000011592 zinc chloride Substances 0.000 claims description 14
- 235000005074 zinc chloride Nutrition 0.000 claims description 14
- 239000011260 aqueous acid Substances 0.000 claims description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 150000001805 chlorine compounds Chemical group 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 13
- 125000000217 alkyl group Chemical group 0.000 abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 235000019256 formaldehyde Nutrition 0.000 abstract 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000003222 pyridines Chemical class 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- ZHQRIQJPXINGOY-UHFFFAOYSA-N pyridin-1-ium-3-carbonitrile;bromide Chemical compound [Br-].N#CC1=CC=C[NH+]=C1 ZHQRIQJPXINGOY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide 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
Definitions
- R is CONH,, -CN, CHO or COOR;
- This invention relates to acid zinc electroplating baths and processes, and additives useful therein, and, more particularly, to such baths and processes for depositing bright zinc plates.
- Quaternary pyridine compound additives useful in alkaline cyanide zinc plating are described in U.S. Pat. No. 3,318,787 issued to Gustav Rindt and Donald H. Becking on May 9, 1967, and certain pyridinium compounds useful in alkaline zinc plating are described in U.S. Pat. No. 3,411,996, issued to John D. Rushmere on Nov. 19, 1968.
- an aqueous acid zinc electroplating bath comprising an aqueous solution of zinc ions, said solution maintained at a pH in the range of about 3.5 and 7.5 and having dissolved therein in an amount effective to give a bright zinc deposit, (a) a pyridinium compound of the general formula:
- a is -coNH,, -CN, CHO or COOR";
- a water-soluble condensation product of a benzene or naphthalene sulfonic acid, or salt thereof, with formaldehyde said condensation product containing at least 2 benzene or naphthalene sulfonic acid groups connected with each other by methylene bridges.
- an aqueous addition agent for a zinc electroplating bath consisting essentially of an aqueous solution with about 1 to 25 percent by weight of the above-described pyridinium compound and about 1 to 50 percent by weight of the above-described condensation product.
- This invention pertains to the electrodeposition of zinc from acid zinc plating baths known to those skilled in the art. These baths may be formed by the dissolution of zinc oxide in common industrial acids such as hydrochloric, sulfuric, sulfamic and fluoboric. More commonly, however, the baths are formed by the dissolution of commercial zinc and ammonium salts such as the sulfates, chlorides, acetates, fluoborates or sulfamates in water with subsequent adjustment of pH to the normal or desired range by means of aqueous ammonia, ammonium hydroxide or other bases, or an acid as required.
- bath pH will generally be at a slightly acidic pH between 3.5 and 6
- a higher pH bath such as to pH 7.5
- a base such as ammonium hydroxide
- ammonium chloride is added to improve electrical conductivity.
- the bath will have a chloride ion to zinc ion weight ratio in the range from 4/1 to 16/ l preferably from 6/1 to 12/ 1.
- Zinc metal content in the zinc chloride bath, as well as the other acid 'zinc baths, will range from about 6 to 45 grams per liter, preferably about 6 to 20 grams per liter.
- Bath formulations may contain mixtures of zinc salts such as the use of both zinc chloride and zinc sulfate. However, there appears to be little practical advantage for doing this. Bath formulations may also contain other metal salts such as a conductivity increasing salt, like sodium sulfamate or potassium sulfate.
- Zinc deposits of acceptable commercial quality can be obtained from a bath operated at a temperature 'in the range of about 10 to 45C. Normally, the bath is operated at about 20 to 30C.
- Zinc deposits obtained from such acid baths are typically coarse and dull gray in appearance and have little commercial value, especially in decorative plating of screws, chains and other items of hardware. It has now been found that when an additive combination comprising a mixture of certain quaternized pyridine compounds and water-soluble condensation products of an aryl sulfonic acid with formaldehyde is added to the acid z'inc bath, bright, shiny zinc of high decorative quality can be obtained from both barrel plating and rack plating operations.
- the pyridinium compounds useful in the present invention have the general formula:
- R" is an alkyl group of one to four carbon atoms
- R is CONH -CN, Cl-l or COOR
- X is a halogen selected from fluorine, chlorine and bromine.
- the pyridinium compound is used at a concentration level of about 0.02 to 20 grams per liter, preferably about 0.05 to grams per liter.
- Preferred pyridinium compounds are l-allyl, 3- carbox-amido pyridinium halide where the halide is chloride, bromide or iodide.
- Other compounds that have been found useful include:
- the second component of the additive is a watersoluble condensation product of a benzene or naphthalene sulfonic acid, or salt thereof (usually alkali metal), with formaldehyde containing at least two benzene or naphthalene sulfonic acid groups which are connected with each other by means of methylene bridges.
- a naphthalene sulfonic acid is preferred. Preparation of these products is known and one such method is mentioned in US. Pat. No. 3,537,959.
- the condensation product is added in an amount to give a bath concentration of about 0.5 to 50 grams per liter, preferably about t to 20 grams per liter. The particular concentration used and found effective will depend upon the type and amount of pyridinium compound used and whether rack or barrel plating is being used.
- the brightener combination of the present invention is preferably and effectively used as an aqueous solution addition agent containing about 1 to 25 percent by weight, preferably about -1 to percent, of the pyridinium compound and about i to 50 percent by weight, preferably about 1 to 20 percent, of the condensation product.
- a particularly effective addition agent uses l-allyl, 3-carboxamido pyridinium chloride as the pyridinium compound and the sodium salt of a naphthalene sulfonic acid-formaldehyde condensation product.
- the addition agent is normally used by adding about 5 to 20 ml. of solution per liter of bath although larger amounts (such as up to 50 ml./l. can be used with effectiveness).
- EXAMPLE 1 A steel Hull Cell panel was plated at 2 amps for 5 minutes in the basic bath containing 2.0 g./l. of a waters'oluble condensation product between naphthalene sulfonic acid and formaldehyde (Darvan No. 1) and 0.8 g./l. l-methyl, 3-carboxamido pyridinium bromide. Bright plate was obtained over the current density range 8-80 amps/ft. Some pitting of the deposit occurred.
- EXAMPLE 2 A steel Hull Cell panel was plated at 2 amps for 5 minutes in the basic bath containing 2.0 g./l. Darvan No. l and 2.0 g./l. l-propargyl, 3-carboxamido pyridinium bromide. Very bright plate free of pits was obtained over the current density range 2-60 amps/ft.
- EXAMPLE 3 EXAMPLE 4 30 g. No. 6 X 7% inch steel wood screws were barrel plated in a minibarrel at 2 amps for 20 minutes in the basic bath containing 2.0 g./l. Darvan No. l and 0.4 g./l. l-allyl, 3-car boxamido pyridinium bromide. A very bright lustrous zinc deposit was obtained. The deposit took both a nitric acid bright dip and a chromate con version dip without difficulty.
- EXAMPLE 5 A 30 g. load of No. 6 X 12 inch steel wood screws was barrel plated at 2 amps for 20 minutes in the basic bath containing 1.0 g./l. of a water-soluble condensation product between benzene sulfonic acid and formalde- EXAMPLES 6-1 1 Minibarrel plating tests were conducted on 30 g. loads of screws, plated at 2 amps for 20 minutes, using the basic zinc chloride bath to which had been added 2.0 g./l. Daxad No. ll. In addition, quaternized pyridines were added in the amounts stated and with the results shown in Table l.
- EXAMPLE 14 A 4-liter basic basic zinc chloride bath was operated for 610 ampere hours of barrel plating electrolysis using a 10 percent by weight aqueous brightener containing parts of a water-soluble condensation product between naphthalene sulfonic acid and formaldehyde and 1 part of l-allyl, 3-carboxamido pyridinium chloride. Average temperature of operation was 20-25C. and the bath was producing fully bright zinc deposits. Temperature of the bath was raised successively to C., C., C. and C. As the temperature was raised, some brightness was lost from the deposit, more particularly the liquid luster. However, work of acceptable commercial quality was obtained, after bright dipping, even at 45C.
- An aqueous acid zinc electroplating bath comprising an aqueous solution of zinc ions, said solution maintained at a pH in the range of about 3.5 to 7.5, and having dissolved therein in an amount effective to give a bright zinc'deposit, (a) a pyridinium compound of the general formula:
- R" is an alkyl group of one to four carbon atoms
- X is a halogen selected from iodine, chlorine and bromine; and b. a water-soluble condensation product of a benzene or naphthalene sulfonic acid, or salt thereof, with formaldehyde, said condensation product containing at least 2 benzene or naphthalene sulfonic acid groups connected with each other by methylene bridges.
- the pyridinium compound is selected from the group consisting of l-allyl, 3-carboxamido pyridinium halide; 1- methyl, 3-carboxamido pyridinium halide; l-propargyl, 3-carboxamido pyridinium halide; l-(4-chlorobutene- 2), 3-carboxamido pyridinium halide; 2-butene 1,4 bis (3-carboxami'clo pyridinium halide); l-carbomethoxymethyl, 3-carboxamido pyridinium halide; lpropargyl, Zi-carbomethoxy pyridinium halide; l-allyl, 3-cyano pyridinium halide and l-allyl, 3-formyl pyridinium halide.
- the acid electroplating bath of claim 4 wherein the pyridinium compound is present in an amount in the range of about 0.05 to 5 grams per liter and the condensation product is present in an amount in the range of about 1 to 20 grams per liter.
- The'acid electroplating bath of claim 5 wherein the pyridinium compound is l-allyl 3-carboxamido pyridinium halide and the sulfonic acid used in the condensationproduct is naphthalene sulfonic acid.
- the acid electroplating bath of claim 4 wherein the bath is an aqueous acid zinc chloride bath having zinc ions at a concentration in the range of about 6 to 45 4 0 grams per liter and having a chloride ion to zinc ion carboxamido pyridinium halide wherein the halide is chloride, bromide or iodide, and (b) about 1 to 20 grams per liter of a water-soluble condensation product of a naphthalene sulfonic acid with formaldehyde, said condensation product containing at least two naphthalene sulfonic acid groups connected with each other by methylene bridges.
- the bath is an aqueous acid zinc chloride bath having zinc ions at a concentration in the range of about 6 to 45 4 0 grams per liter and having a chloride ion to zinc ion carboxamido pyridinium halide wherein the halide is chloride, bromide or iodide, and
- R is an alkyl group of one to four carbon atoms, 1
- R" is an alkyl group of one to four carbon atoms;
- R is CONH -CN, CHO or COOR";
- X is a halogen selected from iodine, chlorine and brorange of about 0.02 to 20 grams per liter and the condensation product is added to give a bath concentration in the range of about 0.5 to 50 grams per liter.
- the pyridinium compound is selected from the group consisting of lallyl, 3-carboxamido pyridinium halide; l-methyl, 3- carboxamido pyridinium halide; l-propargyl, 3- carboxamido pyridinium'halide; l-(4-chlorobutene-2), 3-carboxamido pyridinium halide; 2-butene 1,4 bis (3- carboxamido pyridinium halide); l-carbomethoxymethyl, 3-carboxamido pyridinium halide; lpropargyl, 3-carbomethoxy pyridinium halide; l-allyl, S-cyano pyridinium halide and l-allyl, 3-formyl pyridinium halide.
- bath is an aqueous acid zinc chloride bath having zinc ions at a concentration in the range of about 6 to 45 grams per liter and having a chloride ion to zinc ion weight ratio in the range of about 4/ 1 to 16/1.
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 |
|---|---|---|---|
| US25617972A | 1972-05-23 | 1972-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3769184A true US3769184A (en) | 1973-10-30 |
Family
ID=22971343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00256179A Expired - Lifetime US3769184A (en) | 1972-05-23 | 1972-05-23 | Acid zinc electroplating |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3769184A (enrdf_load_stackoverflow) |
| JP (1) | JPS4942531A (enrdf_load_stackoverflow) |
| BE (1) | BE799734A (enrdf_load_stackoverflow) |
| DE (1) | DE2326300A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2185692B1 (enrdf_load_stackoverflow) |
| IT (1) | IT987816B (enrdf_load_stackoverflow) |
| NL (1) | NL7307195A (enrdf_load_stackoverflow) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3920528A (en) * | 1973-10-25 | 1975-11-18 | Schering Ag | Bright acid zinc plating method and electrolyte |
| US4207150A (en) * | 1978-01-25 | 1980-06-10 | Oxy Metal Industries Corporation | Electroplating bath and process |
| EP0987349A1 (de) * | 1998-09-15 | 2000-03-22 | LPW-Chemie GmbH | Verfahren zur galvanischen Abscheidung von Zinkniederschlägen und/oder Zinklegierungsniederschlägen |
| US6238542B1 (en) | 1998-09-15 | 2001-05-29 | Thomas Helden | Water soluble brighteners for zinc and zinc alloy electrolytes |
| US6468411B1 (en) * | 2001-07-11 | 2002-10-22 | Taskem Inc. | Brightener for zinc-nickel plating bath and method of electroplating |
| US9976227B2 (en) | 2014-05-15 | 2018-05-22 | Baker Hughes, A Ge Company, Llc | Electrochemical machining method for rotors or stators for moineau pumps |
| CN116463693A (zh) * | 2023-04-15 | 2023-07-21 | 崇辉半导体(江门)有限公司 | 一种提升半导体引线框架镀层稳定性的处理方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2422736A1 (fr) * | 1978-01-25 | 1979-11-09 | Oxy Metal Industries Corp | Procede de revetement electrolytique de zinc et bains sans cyanure utilises dans ce but |
| US4162947A (en) * | 1978-05-22 | 1979-07-31 | R. O. Hull & Company, Inc. | Acid zinc plating baths and methods for electrodepositing bright zinc deposits |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3318787A (en) * | 1964-02-07 | 1967-05-09 | Udylite Corp | Electrodeposition of zinc |
| US3411996A (en) * | 1965-12-02 | 1968-11-19 | Du Pont | Process for brightening zinc and cadmium electroplate using an inner salt of a quaternized pyridine carboxylic acid and compositions containing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2041397C3 (de) * | 1970-08-15 | 1980-11-06 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Saures, Glanzbildner jedoch keine organischen Komplexbildner enthaltendes Zinkbad |
-
1972
- 1972-05-23 US US00256179A patent/US3769184A/en not_active Expired - Lifetime
-
1973
- 1973-05-18 BE BE131277A patent/BE799734A/xx unknown
- 1973-05-22 IT IT24423/73A patent/IT987816B/it active
- 1973-05-22 FR FR7318522A patent/FR2185692B1/fr not_active Expired
- 1973-05-23 DE DE2326300A patent/DE2326300A1/de active Pending
- 1973-05-23 JP JP48057659A patent/JPS4942531A/ja active Pending
- 1973-05-23 NL NL7307195A patent/NL7307195A/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3318787A (en) * | 1964-02-07 | 1967-05-09 | Udylite Corp | Electrodeposition of zinc |
| US3411996A (en) * | 1965-12-02 | 1968-11-19 | Du Pont | Process for brightening zinc and cadmium electroplate using an inner salt of a quaternized pyridine carboxylic acid and compositions containing the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3920528A (en) * | 1973-10-25 | 1975-11-18 | Schering Ag | Bright acid zinc plating method and electrolyte |
| US4207150A (en) * | 1978-01-25 | 1980-06-10 | Oxy Metal Industries Corporation | Electroplating bath and process |
| EP0987349A1 (de) * | 1998-09-15 | 2000-03-22 | LPW-Chemie GmbH | Verfahren zur galvanischen Abscheidung von Zinkniederschlägen und/oder Zinklegierungsniederschlägen |
| US6238542B1 (en) | 1998-09-15 | 2001-05-29 | Thomas Helden | Water soluble brighteners for zinc and zinc alloy electrolytes |
| US6468411B1 (en) * | 2001-07-11 | 2002-10-22 | Taskem Inc. | Brightener for zinc-nickel plating bath and method of electroplating |
| US9976227B2 (en) | 2014-05-15 | 2018-05-22 | Baker Hughes, A Ge Company, Llc | Electrochemical machining method for rotors or stators for moineau pumps |
| CN116463693A (zh) * | 2023-04-15 | 2023-07-21 | 崇辉半导体(江门)有限公司 | 一种提升半导体引线框架镀层稳定性的处理方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| IT987816B (it) | 1975-03-20 |
| FR2185692B1 (enrdf_load_stackoverflow) | 1977-02-11 |
| BE799734A (fr) | 1973-09-17 |
| JPS4942531A (enrdf_load_stackoverflow) | 1974-04-22 |
| FR2185692A1 (enrdf_load_stackoverflow) | 1974-01-04 |
| DE2326300A1 (de) | 1973-12-06 |
| NL7307195A (enrdf_load_stackoverflow) | 1973-11-27 |
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