US3276979A - Baths and processes for the production of metal electroplates - Google Patents
Baths and processes for the production of metal electroplates Download PDFInfo
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- US3276979A US3276979A US218841A US21884162A US3276979A US 3276979 A US3276979 A US 3276979A US 218841 A US218841 A US 218841A US 21884162 A US21884162 A US 21884162A US 3276979 A US3276979 A US 3276979A
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- 229910052751 metal Inorganic materials 0.000 title claims description 46
- 239000002184 metal Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title description 16
- 238000009713 electroplating Methods 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 30
- 150000002739 metals Chemical class 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 24
- 239000002659 electrodeposit Substances 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 36
- 229910052802 copper Inorganic materials 0.000 description 36
- 239000010949 copper Substances 0.000 description 36
- -1 sulfothio Chemical group 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 13
- 238000005282 brightening Methods 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- SIDURXWHELGWNV-UHFFFAOYSA-N benzene;prop-1-ene;sodium Chemical compound [Na].CC=C.CC=C.CC=C.CC=C.C1=CC=CC=C1 SIDURXWHELGWNV-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 2
- 229950004394 ditiocarb Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical class OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000933336 Ziziphus rignonii Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-N carbonotrithioic acid Chemical compound SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
Definitions
- a further object of this invention is to provide an electroplating process and bath operable at higher tem peratures.
- Another object is to provide additives for electroplating baths which give both a brightening and a leveling etfect.
- R represents an aliphatic radical
- the substituents R and K" may also form a ring system together with the nitrogen atom, which may contain a further heteroatom.
- R represents an aliphatic, cycloaliphatic or aromatic hydrocarbon radical
- R is a bivalent hydrocarbon radical, which contains an -aryl group
- G is a cation of an inorganic or organic base or also su-lfonic acids which contain alkyl radicals and which may be used as bright electroplating additives in accordance with the present invention:
- the electroplating additives according to the present invention may be employed in all types of electroplating processes, especially for copper plating, nickel plating, silver plating, zinc plating, as well as for the preparation of cadmium, bronze or brass electroplates. These agents may also be employed in conjunction with other known brightening agents as Well as with leveling agents, porosity prevention agents, hardness binding agents, inhibitors, wetting agents, conductive salts, etc.
- the amounts in which the agents according to the present invention, are added to the baths lie between about 0.01 to 20 g./l. of bath fluid.
- the baths are operated at current densities between 0.5 and 12 amperes per dm. and in special cases at temperatures up to 70 C.
- the bath containing the agents according to the present invention may be operated within a temperature range of 15 to 50 C., and under these conditions the bath produces complete mirror brightening elfects and the leveling efiect of the baths as a rule completely satisfies the practical requirements.
- the base metal to be electroplated may be any type of metal previously employed for this purpose, such as iron, steel, zinc, and other non-precious metals or metal alloys. If necessary, in conjunction with the copper electroplating of non-precious metals, the base metal is as usual provided with .a' thin preliminary copper plate in a cyanide bath. However, the baths according to the present invention may also be employed with success in the direct acid copper plating process, that is, by subjecting the objects to be copperplated to a preliminary 3 treatment in an acid pickling bath with pickiling agents or wetting agents having a high inhibitor eifect and subsequently directly and without intermediate rinsing, transferring the objects into the acid copper electroplating bath.
- the brightening agents according to the present invention produce metal electroplates which exhibit an excellent mirror brightening effect vwhicihmakes it unnecessary to subject the electroplated object to a subsequent polishing treatment.
- Example I 0.2 to 1.5 g./l. of N,N-diethyl-dithio-carbamic acid- S-benzylester-o-sodium sulfonate of the formula C H I are dissolved in an acid copper electroplating bath which contains 200 g./l. of crystallized copper sulfate, 60 g./l. of sulfuric acid, and 1 g./l of the addition product of 20 mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture.
- Example 11 When a bath of the same composition as that in Example I is modified with 0.2 to 1.5 g./l. of N,N-diethy1dithiocarbamic acid-S-benzylester-p-sodium sulfonate of the formula CgH5 S CgH5 as the brightening agent, equally good results as those in Example I are achieved.
- Example III 0.1 to 1 g./1, of N,N-diethyl-dithiocarbamic acid-S- benzylester-o-sodium sulfon-ate are added to an acid zinc electroplating bath which contains 300 g./l, of zinc sulfate, g./l. of aluminum sulfate, and 20 g./l. of boric acid.
- the bath is operated in a pH range between 3 and 5 and produces bright, ductile, very fine grained zinc electrodeposits which adhere well to the iron surface in a current density range of 0.5 to 4 amperes per rim. with a temperature tolerance of to 45 C.
- Example IV 0.5 to 1 g./l. of N,N-diethyl-dithiooarbamic acid-S- benzylester-p-sodium-sulfonate aredissolved in a nickel electroplating bath which contains 60 g./l. of nickel chloride, 220 g./l. of crystallized nickel sulfate, and 35 g./l. of boric acid. When operated at 60? C. and in current density ranges of 4 to 8 amperes per drn. this nickel electroplating bath produces bright electrodeposits.
- Example V When an acid copper electroplating bath, which con tains 200 g./l. of copper sulfate and 60 g./l. of sulfuric acid, is modified with 10 mg./l. of N,N-l,5-pentamethyl 4 ene-dithio oarbamic acid-S- (m-methyl benzylester-sodiumsulfonate bright copper electroplates are obtained at room temperature in a current density range of 0.5 to 5 amperes per dmF.
- Example VI When an acid copper electroplating bath, which contains 260 g./'l. of copper sulfate and 40 g./l. of sulfonic acid, is modified with 5 mg./1. of 3-oxa-l,5-pentamethylenerdithi ocarbamic acid-S-(p-methyl)-2-phenyl-ethylestersodium sulfonate bright electroplates are obtained in a current density range of l to 2.5 amperes pe-r dm. Above 2.5 amperes per dm. a certain increase in the fineness of the grain can also be observed.
- the brightening range can be broadened to 0.25 to 6 amperes per dm.
- the best brightening-effects are obtained ina temperature range of 23 to 29 C.
- Example VII 30 mg./l. of 'S-phenyl-trithiocarbonic acid-S-(3,5-dimethyl) -benzyle ster-methyl-sodium-sulfonate S CH SO Na E I S--S-CH 1 to 5 mg./l. of n-butyl-xanthogenic acid-S-naphthylmethylester-sodium-sulfonate SO Na are added to an acid copper electroplating bath consist-v ing of 260 g./l. of copper sulfate and 40 g./l. of sulfuric acid. Operation of this bath produces bright copper electrodeposits in a current density range of 1 to 7 amperes per dmfi. The addition of a wetting agent for increasing the brightness or for broadeningthe current density range is not necessary.
- Example IX 15 g./l. of the reaction product of sodium diethyldithiocarbamate and tetrapropylene benzene sodium sulfonate which is halogenated in the carbon chain C2H5 S Ni JsCH --so,Na C2415 are added to an acid copper electroplating bath containing 220 g./l. of copper sulfate and 60 g./l. of sulfuric acid.
- the bright copper electroplates obtained with the aid of this bath extend at room temperature from about 0.5 to 8 amperes per dm. The addition of a wetting agent is not required.
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an acid aqueous solution of the metal to be electrodeposited and an additive compound of the formula wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals, X is selected irom the group consisting of O-, S- and NR"-, R" is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicals and R and R" taken together with the nitrogen atom may form a heterocyclic radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G group is attached and G is selected from the group consisting of hydrogen and alkali metal; said additive being added in sufficient amount to obtain said bright and level electrodeposit.
- R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals
- X is selected irom the group consisting of O-, S- and
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to g./l. of an additive compound of the formula wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals, X is selected from the group consisting of O, and NR, R is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicalls and Rand R taken together with the nitrogen atom may form a 'heterocycli'c radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G group is attached and G is selected from the group consisting of hydrogen and alkali metal.
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising electrodepositing the said metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of an additive compound of the formula wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals, X is selected from the group consisting of O-, -S and -NR", R is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicals and R and R" taken together with the nitrogen atom may form a heterocyclic radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G group is attached and G is selected from the group consisting of hydrogen and alkali metal.
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and Zinc comprising electrodepositing the said metals from a bath comprising an I acid aqueous solution of the metal to be electrodeposited 6 in the presence of from 0.01 to 20 g./l.
- R is selected from the group consisting of allphatic, cycloaliphatic and aromatic radicals
- X is selected from the group consisting of O, S- and -NR"-
- R" is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicals and R and R taken together with the nitrogen atom may form a heterocyclic radical
- R is a bivalent hydrocarbon radical having an aryl group to which the SO G groups is attached and G is selected from the groupconsisting of hydrogen and alkali metal.
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and Zinc comprising an acid aqueous solution of the metal to .be electrodeposited and from 0.01 to 20 g./l. of an additive compoundhaving a structural formula as follows:
- An electroplating bath for'producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and Zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising an acid aqueous solution of the metal to be electrodeposited CH3 SO NB r 7 and from 0.01 to g./l. of an additive compound having a structural formula as follows:
- An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- A11 electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper. nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./l. of an additive com pound having a structural formula as follows:
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metalsfrom a bath comprising an acid in the presence from 0.01 to 20 g./l. of ,an additive com: pound having a structural formula as follows:
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./-l. of an additive compound having a structural formula as follows:
- An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodepos-ited in the presence of from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
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- 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)
Description
United States Patent 18 Claims. (c1. 204-49 This invention relates to improved brightening additives for electroplating baths and to the electroplating process using these brighteners. It more particularly relates to the use of organic sulfonic acid derivatives in electroplating baths whereby the electroplating process may be operated at higher temperatures.
It is known from German Patent No. 888,493 that electrolyte soluble derivatives of esters of sulfothio or trithiocarbonic acid or of dithiocarbamic acid, which contain the grouping I! cs at least once in the molecule, can be added to copper electroplating baths of customary compositions in order to achieve an improved brightening effect on the objects to be copper electroplated. The solubilizing group, a carboxyl or sulfonic acid group, in these derivatives is attached to the sulfur atom of the s ll C S grouping through a short chain bivalent aliphatic radical. At bath temperatures up to about 30 C., these additives exhibit an excellent brightening effect, but their leveling effect is not always completely satisfactory.
It is an object of this invention to provide an electroplating bath and process for obtaining bright and level electrodeposits of metals.
A further object of this invention is to provide an electroplating process and bath operable at higher tem peratures.
Another object is to provide additives for electroplating baths which give both a brightening and a leveling etfect.
These and other objects of my invention will become apparent as the description thereof proceeds.
hydrogen. In the event that R represents an aliphatic radical, the substituents R and K" may also form a ring system together with the nitrogen atom, which may contain a further heteroatom.
Compounds of this type are obtained in known fashion, -for example, by reaction of dithiocarbamates with tolyls-ultone (inner ester of O-oxymethyl sulfon-ic acid), correspondingly substituted tolyl sultones or halogen-alkylaryl sulfonates. The latter are accessible through halogenation of alkylaryl sult'onates, for instances, in suspension in a high-boiling point inert solvent which is inert toward halogen or by treatment of the halogen al-kyl aromates with chlorosulfonic acids at C. or with thionyl chloride; in the last case a hydrolysis of the sulfochloride to form sulfonic acid must be excluded. The
. following are a few examples of salts of such aromatic We have now found that it is possible to obtain full grouping through a bivalent hydrocarbon radical which contains an aryl group. Compounds of the type contemplated in accordance with the invention are characterized by the following general formula:
In this formula R represents an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, X is a heteroatom such as oxygen, NR (-R='I-I or R) or S, R is a bivalent hydrocarbon radical, which contains an -aryl group, and G is a cation of an inorganic or organic base or also su-lfonic acids which contain alkyl radicals and which may be used as bright electroplating additives in accordance with the present invention:
N,N-diethyl-dithiocarbamic acid S benzylester-o-sodium sulfonate,
N-butyl-dithiocarbatnic acid-S-benzylester-psodium sulfonate,
S-phenyl-trithiocarbonate acid S-benylester-o-sodium sulfonate,
N,N-l,S-pentamethylene-dithiocarbamic acid-S- benzylester-o-sodium sulfionate,
N,N-1,S-pentamethylene-dithiocarbamic acid-S-(mmethyl)benzylester-sodium sulfonate,
3-oxa-N,N-1,5pentamethylene-dithiocarbamic acid-S- (p-methyl)2-phenylethylester-sodium sulfonate,
S-phenyl-trit-hiocarb-onic acid-S-(3,5-dimcthyl) benzylester sodium sulfonate,
n-Butyl-xanthogenic acid-S-naphthyl-methyl ester sodium sulfonate,
the reaction product of diethyl dithio carbamate and tetrapropylene benzene sodium sulf-onate which is halogenated in the carbon chain, and the like.
The electroplating additives according to the present invention may be employed in all types of electroplating processes, especially for copper plating, nickel plating, silver plating, zinc plating, as well as for the preparation of cadmium, bronze or brass electroplates. These agents may also be employed in conjunction with other known brightening agents as Well as with leveling agents, porosity prevention agents, hardness binding agents, inhibitors, wetting agents, conductive salts, etc.
The amounts in which the agents according to the present invention, are added to the baths lie between about 0.01 to 20 g./l. of bath fluid. In general, the baths are operated at current densities between 0.5 and 12 amperes per dm. and in special cases at temperatures up to 70 C. It should be particularly emphasized that in the case of an acid copper electroplating bath, the bath containing the agents according to the present invention may be operated within a temperature range of 15 to 50 C., and under these conditions the bath produces complete mirror brightening elfects and the leveling efiect of the baths as a rule completely satisfies the practical requirements.
The base metal to be electroplated may be any type of metal previously employed for this purpose, such as iron, steel, zinc, and other non-precious metals or metal alloys. If necessary, in conjunction with the copper electroplating of non-precious metals, the base metal is as usual provided with .a' thin preliminary copper plate in a cyanide bath. However, the baths according to the present invention may also be employed with success in the direct acid copper plating process, that is, by subjecting the objects to be copperplated to a preliminary 3 treatment in an acid pickling bath with pickiling agents or wetting agents having a high inhibitor eifect and subsequently directly and without intermediate rinsing, transferring the objects into the acid copper electroplating bath.
The brightening agents according to the present inventionproduce metal electroplates which exhibit an excellent mirror brightening effect vwhicihmakes it unnecessary to subject the electroplated object to a subsequent polishing treatment.
The following examples are set forth to further illustrate the invention and to enable persons skilled in the art to better understand and practice they invention, and not intended to be limitative.
Example I 0.2 to 1.5 g./l. of N,N-diethyl-dithio-carbamic acid- S-benzylester-o-sodium sulfonate of the formula C H I are dissolved in an acid copper electroplating bath which contains 200 g./l. of crystallized copper sulfate, 60 g./l. of sulfuric acid, and 1 g./l of the addition product of 20 mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture. When brass or iron sheets are copper plated in this bath in a current density range of 0.5 to 8 amperes per dmf, ductile, pore-free, uniformly bright copper electroplates are obtained in a temperature range of 15 to 50 C. which completely level a 280 grain scratch with a copper deposit of 20 mu thick.
Example 11 When a bath of the same composition as that in Example I is modified with 0.2 to 1.5 g./l. of N,N-diethy1dithiocarbamic acid-S-benzylester-p-sodium sulfonate of the formula CgH5 S CgH5 as the brightening agent, equally good results as those in Example I are achieved.
Example III 0.1 to 1 g./1, of N,N-diethyl-dithiocarbamic acid-S- benzylester-o-sodium sulfon-ate are added to an acid zinc electroplating bath which contains 300 g./l, of zinc sulfate, g./l. of aluminum sulfate, and 20 g./l. of boric acid. The bath is operated in a pH range between 3 and 5 and produces bright, ductile, very fine grained zinc electrodeposits which adhere well to the iron surface in a current density range of 0.5 to 4 amperes per rim. with a temperature tolerance of to 45 C.
Example IV 0.5 to 1 g./l. of N,N-diethyl-dithiooarbamic acid-S- benzylester-p-sodium-sulfonate aredissolved in a nickel electroplating bath which contains 60 g./l. of nickel chloride, 220 g./l. of crystallized nickel sulfate, and 35 g./l. of boric acid. When operated at 60? C. and in current density ranges of 4 to 8 amperes per drn. this nickel electroplating bath produces bright electrodeposits.
Example V When an acid copper electroplating bath, which con tains 200 g./l. of copper sulfate and 60 g./l. of sulfuric acid, is modified with 10 mg./l. of N,N-l,5-pentamethyl 4 ene-dithio oarbamic acid-S- (m-methyl benzylester-sodiumsulfonate bright copper electroplates are obtained at room temperature in a current density range of 0.5 to 5 amperes per dmF.
Example VI When an acid copper electroplating bath, which contains 260 g./'l. of copper sulfate and 40 g./l. of sulfonic acid, is modified with 5 mg./1. of 3-oxa-l,5-pentamethylenerdithi ocarbamic acid-S-(p-methyl)-2-phenyl-ethylestersodium sulfonate bright electroplates are obtained in a current density range of l to 2.5 amperes pe-r dm. Above 2.5 amperes per dm. a certain increase in the fineness of the grain can also be observed. By addition of the reaction product of 1 mol of dooecyl alcohol and 6 mols of ethylene oxide in an amount of 2 g./l., which acts as a wetting agent, the brightening range can be broadened to 0.25 to 6 amperes per dm. The best brightening-effects are obtained ina temperature range of 23 to 29 C.
Example VII 30 mg./l. of 'S-phenyl-trithiocarbonic acid-S-(3,5-dimethyl) -benzyle ster-methyl-sodium-sulfonate S CH SO Na E I S--S-CH 1 to 5 mg./l. of n-butyl-xanthogenic acid-S-naphthylmethylester-sodium-sulfonate SO Na are added to an acid copper electroplating bath consist-v ing of 260 g./l. of copper sulfate and 40 g./l. of sulfuric acid. Operation of this bath produces bright copper electrodeposits in a current density range of 1 to 7 amperes per dmfi. The addition of a wetting agent for increasing the brightness or for broadeningthe current density range is not necessary.
Example IX 15 g./l. of the reaction product of sodium diethyldithiocarbamate and tetrapropylene benzene sodium sulfonate which is halogenated in the carbon chain C2H5 S Ni JsCH --so,Na C2415 are added to an acid copper electroplating bath containing 220 g./l. of copper sulfate and 60 g./l. of sulfuric acid. The bright copper electroplates obtained with the aid of this bath extend at room temperature from about 0.5 to 8 amperes per dm. The addition of a wetting agent is not required.
While we have set forth certain specific embodiments and preferred modes of practice of our invention, it will be understood that the invention is not limited thereby, and that various changes and modifications may be made Without departing from the spirit of the disclosure or the scope of the appended claims.
We claim:
1. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an acid aqueous solution of the metal to be electrodeposited and an additive compound of the formula wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals, X is selected irom the group consisting of O-, S- and NR"-, R" is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicals and R and R" taken together with the nitrogen atom may form a heterocyclic radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G group is attached and G is selected from the group consisting of hydrogen and alkali metal; said additive being added in sufficient amount to obtain said bright and level electrodeposit.
2. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to g./l. of an additive compound of the formula wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals, X is selected from the group consisting of O, and NR, R is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicalls and Rand R taken together with the nitrogen atom may form a 'heterocycli'c radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G group is attached and G is selected from the group consisting of hydrogen and alkali metal.
3. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising electrodepositing the said metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of an additive compound of the formula wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals, X is selected from the group consisting of O-, -S and -NR", R is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicals and R and R" taken together with the nitrogen atom may form a heterocyclic radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G group is attached and G is selected from the group consisting of hydrogen and alkali metal.
4. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and Zinc, comprising electrodepositing the said metals from a bath comprising an I acid aqueous solution of the metal to be electrodeposited 6 in the presence of from 0.01 to 20 g./l. of an additive compound of the formula wherein R is selected from the group consisting of allphatic, cycloaliphatic and aromatic radicals, X is selected from the group consisting of O, S- and -NR"-, R" is selected from the group consisting of hydrogen and aliphatic, cycloaliphatic and aromatic radicals and R and R taken together with the nitrogen atom may form a heterocyclic radical, R is a bivalent hydrocarbon radical having an aryl group to which the SO G groups is attached and G is selected from the groupconsisting of hydrogen and alkali metal.
5. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
C H5 S N-ll CgHs SO Na 6. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and Zinc comprising an acid aqueous solution of the metal to .be electrodeposited and from 0.01 to 20 g./l. of an additive compoundhaving a structural formula as follows:
8. An electroplating bath"for'producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
C z-CH2 S ll O\ N SCH2CH2 CH3 CHPCHI soaNa 9. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and Zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
10. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising an acid aqueous solution of the metal to be electrodeposited CH3 SO NB r 7 and from 0.01 to g./l. of an additive compound having a structural formula as follows:
11. An electroplating bath for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
12. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited and from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
13. A11 electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper. nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
14. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
15. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./l. of an additive com pound having a structural formula as follows:
16. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metalsfrom a bath comprising an acid in the presence from 0.01 to 20 g./l. of ,an additive com: pound having a structural formula as follows:
CH SOQNB S V I 17. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodeposited in the presence of from 0.01 to 20 g./-l. of an additive compound having a structural formula as follows:
18. An electroplating process for producing bright and level electrodeposits of metals selected from the group consisting of copper, nickel, and zinc comprising electrodepositing the metals from a bath comprising an acid aqueous solution of the metal to be electrodepos-ited in the presence of from 0.01 to 20 g./l. of an additive compound having a structural formula as follows:
ca s S References Cited by the Examiner UNITED STATES PATENTS JOHN H. MACK, Primary Examiner.-
G. KAPLAN, Assistant Examiner.
Claims (1)
1. AN ELECTROPLATING BATH FOR PRODUCING BRIGHT AND LEVEL ELECTRODEPOSITS OF METALS SELECTED FROM THE GROUP CONSISTING OF COPPER, NICKEL AND ZINC COMPRISING AN ACID AQUEOUS SOLUTION OF THE METAL TO BE ELECTRODEPOSITED AND AN ADDITIVE COMPOUND OF THE FORMULA
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED36927A DE1184172B (en) | 1961-08-31 | 1961-08-31 | Process for the galvanic deposition of firmly adhering and high-gloss copper coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3276979A true US3276979A (en) | 1966-10-04 |
Family
ID=7043356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US218841A Expired - Lifetime US3276979A (en) | 1961-08-31 | 1962-08-23 | Baths and processes for the production of metal electroplates |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3276979A (en) |
| DE (1) | DE1184172B (en) |
| GB (1) | GB1000669A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3400059A (en) * | 1964-03-07 | 1968-09-03 | Dehydag Gmbh | Acidic copper electroplating baths and method |
| US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
| US3518171A (en) * | 1969-07-24 | 1970-06-30 | Metalux Corp The | Purification of nickel electroplating solutions |
| US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
| US3878067A (en) * | 1972-07-03 | 1975-04-15 | Oxy Metal Finishing Corp | Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits |
| US3945894A (en) * | 1975-04-11 | 1976-03-23 | Oxy Metal Industries Corporation | Bath composition and method of electrodepositing utilizing the same |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US6709568B2 (en) | 2002-06-13 | 2004-03-23 | Advanced Technology Materials, Inc. | Method for determining concentrations of additives in acid copper electrochemical deposition baths |
| US20050067304A1 (en) * | 2003-09-26 | 2005-03-31 | King Mackenzie E. | Electrode assembly for analysis of metal electroplating solution, comprising self-cleaning mechanism, plating optimization mechanism, and/or voltage limiting mechanism |
| US20050109624A1 (en) * | 2003-11-25 | 2005-05-26 | Mackenzie King | On-wafer electrochemical deposition plating metrology process and apparatus |
| US20050224370A1 (en) * | 2004-04-07 | 2005-10-13 | Jun Liu | Electrochemical deposition analysis system including high-stability electrode |
| US20050247576A1 (en) * | 2004-05-04 | 2005-11-10 | Tom Glenn M | Electrochemical drive circuitry and method |
| US20060102475A1 (en) * | 2004-04-27 | 2006-05-18 | Jianwen Han | Methods and apparatus for determining organic component concentrations in an electrolytic solution |
| US20070261963A1 (en) * | 2006-02-02 | 2007-11-15 | Advanced Technology Materials, Inc. | Simultaneous inorganic, organic and byproduct analysis in electrochemical deposition solutions |
| US7435320B2 (en) | 2004-04-30 | 2008-10-14 | Advanced Technology Materials, Inc. | Methods and apparatuses for monitoring organic additives in electrochemical deposition solutions |
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| BE572016A (en) * | 1957-11-30 | |||
| BE572186A (en) * | 1957-12-17 | |||
| DE888493C (en) * | 1951-11-03 | 1953-09-03 | Hydrierwerke A G Deutsche | Process for the production of firmly adhering and shiny galvanic copper coatings |
| US2830014A (en) * | 1954-03-22 | 1958-04-08 | Dehydag Gmbh | Electroplating process |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| GB873753A (en) * | 1957-03-16 | 1961-07-26 | Arthur Riedel | Improvements in or relating to acid baths for producing brilliant electrolytic copper levelling coatings |
-
1961
- 1961-08-31 DE DED36927A patent/DE1184172B/en active Pending
-
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- 1962-08-23 US US218841A patent/US3276979A/en not_active Expired - Lifetime
- 1962-08-28 GB GB32909/62A patent/GB1000669A/en not_active Expired
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE888493C (en) * | 1951-11-03 | 1953-09-03 | Hydrierwerke A G Deutsche | Process for the production of firmly adhering and shiny galvanic copper coatings |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2830014A (en) * | 1954-03-22 | 1958-04-08 | Dehydag Gmbh | Electroplating process |
| GB873753A (en) * | 1957-03-16 | 1961-07-26 | Arthur Riedel | Improvements in or relating to acid baths for producing brilliant electrolytic copper levelling coatings |
| BE572016A (en) * | 1957-11-30 | |||
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3400059A (en) * | 1964-03-07 | 1968-09-03 | Dehydag Gmbh | Acidic copper electroplating baths and method |
| US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
| US3518171A (en) * | 1969-07-24 | 1970-06-30 | Metalux Corp The | Purification of nickel electroplating solutions |
| US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
| US3878067A (en) * | 1972-07-03 | 1975-04-15 | Oxy Metal Finishing Corp | Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits |
| US3945894A (en) * | 1975-04-11 | 1976-03-23 | Oxy Metal Industries Corporation | Bath composition and method of electrodepositing utilizing the same |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US6709568B2 (en) | 2002-06-13 | 2004-03-23 | Advanced Technology Materials, Inc. | Method for determining concentrations of additives in acid copper electrochemical deposition baths |
| US20050067304A1 (en) * | 2003-09-26 | 2005-03-31 | King Mackenzie E. | Electrode assembly for analysis of metal electroplating solution, comprising self-cleaning mechanism, plating optimization mechanism, and/or voltage limiting mechanism |
| US20050109624A1 (en) * | 2003-11-25 | 2005-05-26 | Mackenzie King | On-wafer electrochemical deposition plating metrology process and apparatus |
| US20050224370A1 (en) * | 2004-04-07 | 2005-10-13 | Jun Liu | Electrochemical deposition analysis system including high-stability electrode |
| US20060102475A1 (en) * | 2004-04-27 | 2006-05-18 | Jianwen Han | Methods and apparatus for determining organic component concentrations in an electrolytic solution |
| US7427344B2 (en) | 2004-04-27 | 2008-09-23 | Advanced Technology Materials, Inc. | Methods for determining organic component concentrations in an electrolytic solution |
| US7435320B2 (en) | 2004-04-30 | 2008-10-14 | Advanced Technology Materials, Inc. | Methods and apparatuses for monitoring organic additives in electrochemical deposition solutions |
| US20050247576A1 (en) * | 2004-05-04 | 2005-11-10 | Tom Glenn M | Electrochemical drive circuitry and method |
| US7427346B2 (en) | 2004-05-04 | 2008-09-23 | Advanced Technology Materials, Inc. | Electrochemical drive circuitry and method |
| US20070261963A1 (en) * | 2006-02-02 | 2007-11-15 | Advanced Technology Materials, Inc. | Simultaneous inorganic, organic and byproduct analysis in electrochemical deposition solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1000669A (en) | 1965-08-11 |
| DE1184172B (en) | 1964-12-23 |
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