US3254007A - Electrodeposition of nickel - Google Patents
Electrodeposition of nickel Download PDFInfo
- Publication number
- US3254007A US3254007A US256228A US25622863A US3254007A US 3254007 A US3254007 A US 3254007A US 256228 A US256228 A US 256228A US 25622863 A US25622863 A US 25622863A US 3254007 A US3254007 A US 3254007A
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- nickel
- per liter
- cyanosulfonamide
- substituted
- group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/60—Unsaturated compounds containing ether groups, groups, groups, or groups the non-carboxylic part of the ether being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
Definitions
- the invention is based on the discovery that N-cyanosulfonamides which contain the structural configuration when incorporated in a nickel electroplating bath, either as the sole brightener or in conjunction with various Class I carrier brightness or Class II leveling brightening addition agents (or both), are remarkably effective for promoting the formation of nickel deposits which are bright over a very wide current density range and which also possess satisfactory mechanical properties, particularly low internal stress and fair ductility.
- N-cyanosulfonamide which contains the structural configuration may be selected for inclusion in the plating bath.
- Many of these N-cyanosulfonamides produce fully bright nickel deposits over the entire, or almost the entire,- current density range of the Hull Cell panel, yielding bright nickel deposits with low internal stress.
- these N-cyanosulfonamide brighteners impart to the plating solution high tolerances to contamination with zinc and copper, which usually occurs upon plating zinc-base die castings.
- a preferred process according to this invention for producing low-stress, ductile nickel deposits comprises electrodepositing nickel from an aqueous solution of at least one nickel salt in which there is dissolved from about 0.01 to about 25 millimoles per liter of a watersoluble N-cyanosulfonamide having a structure represented by the formula in which R is a radical selected from the group consisting of (i) alkyl and substituted-alkyl radicals, (ii) mononuclear and binuclear aromatic and alkyl-, sulfo-, halo-, sulfoalkyl-, haloalkyl-, acetamido-substituted aromatic radicals, and (iii) heterocyclic radicals, M is a cation substituent of the group consisting of hydrogen, the alkali metals, magnesium, cobalt, and nickel, and n is an integer from 1 to 3.
- N-cyanosulfonamides as benzene-N-cyanosulfonamide, p-bromobenzene-N-cyanosulfonamide, 3,4-dichlorobenzene N-cyanosulfonamide, p-toluene-N cyanosulfonamide, benzyl-N cyanosulfonamide, p-acetamidobenzene-N-cyanosulfonamide, m-ben zenedi-(N-cyanosulfonamide), diphenylsulfone 3,3'-di- (N-cyanosulfonamide), or their alkali metal, magnesium, cobalt, or nickel salts.
- N-cyanosulfonamides as benzene-N-cyanosulfonamide, p-bromobenzene-N-cyanosulfonamide, 3,4-dichlorobenzene N-cyanosulfonamide
- the N-cyanosulfonamides are much more effective brighteners than the related sulfonarnides which do not contain the N-cyano group, such as benzene sulfonamide, p-toluenesulfonamide, N-chloro p-toluenesulfonamide, m-benzenedisulfonarnide.
- benzene sulfonamide p-toluenesulfonamide
- N-chloro p-toluenesulfonamide m-benzenedisulfonarnide.
- o-sulfobenzoic imide sach-arin
- benzene-N-cyanosulfonamide o-sulfobenzoic imide produces low-current discoloration in presence of 0.15 'gram per liter of zinc, While the bcnzene-N-cyanosulfonamide does not.
- Preparation of the N-cyanosulfonamides may be accomplished by reacting a sulfonyl halide, generally the chloride, with a stoichiometric amount of hydrogen cyanamide, and twice the stoichiometric amount of aqueous alkali metal hydroxide.
- a sulfonyl halide generally the chloride
- N-cyanosulfonamides In contrast to sulfur free 'cyano compounds, such as ethylenecyanohydrin or hydrogen cyanamide, many N-cyanosulfonamides yield bright nickel deposits with low internal stress when used as the sole addition agents to a nickel bath, but do not exert any appreciable leveling effect. -If in addition to brightness, leveling is desired, the N-cyanosulfonamides may be used in the plating bath in conjunction with leveling agents, e.g.
- water-soluble acetylenic compounds such as propargyl alcohol,- 2- butyne 1,4-diol or 1,4-di-(5-hydroxyethoxy) -2-butyne; olefinic glycols, such as 2-butene-l,4-diol; nitriles such as ethylenecyanohydrin; hydrogen cyanamide; coumarin; and quinolinimum compounds.
- any water-soluble acetylenic brightening compound may be employed in a nickel plating bath conjointly with an N-cyanosulfonamide, particularly satisfactory results have been obtained using (it-substituted acetylenic compounds having a structure represented by the formula in which each of R and R are substituents of the group consisting of hydrogen, alkyl, alkenyl, alkynyl, and hydroxy-substituted and alkoxy-substituted alkyl, alkenyl, and alkynyl groups, and each of R, and R, are substituents of the group consisting of hydroxy, alkoxy, carboxy-sub stituted alkoxy, formoxy, alkanoxy, halogen, and polyoxy groups, Where R is a substituted-alkyl group having the above-illustrated structuralconfiguration, then the acetylenic compound is termed an a,u'- disubstituted -acetylenic compound, since both carbon atom
- the compounds listed'in Table I are examples of various 'a-substituted acetylenic compounds which may be used successfully in plating baths containing an N-cyanosulfonamide bright- 2-b-utyne-1,4-diol reacts with ethylene oxide in the presence of a base to form a 1,4-di-(hydroxypolyethoxy)- ener.
- These acetylenic-compounds are preferably used in concentrations from about 0.1 to about 25 millimoles 10 and with epichlorohydnn to form a 1,4-d1-[hydroxypolyper liter.
- H -H C E CCH: O H O H 1-butyn-3-ol -0H, H H OH 1,2-di- (fl-hydroxyethoxy)-3- CH;O CH:CH
- Table II sets forth examples of a,a'-disubstituted acetylenic compounds which, when used in the plating bath in conjunction with an N-cyanosulfonamide brightener, yield bright nickel electroplates which possess good ductility, have low internal stress and have excellent leveling.
- the usual Class I carrier sulfooxygen brightening "additives may also be employed in the bath together with the N-cyanosulfonamides.
- These sulfo-oxygen carrier brighteners which are generally used in concentrations in the range fromabout to about '80 grams per liter (and preferably in the range from about 1 to about 20 grams per liter), are unsaturated aliphatic sulfonic acids, mononuclear and binuclear aromatic sulfonic acids, heterocyclic sulfonic acids, mononuclear aromatic sulfinic acids, the alkali metal, mag- Grams/liter Nickel sulfate, NiSO -6H O 300 Nickel chloride, NiCl -6H O 60 Boric acid, H 30 42 Plating operations in each example were carried out in Example I Nickel was electrodeposited from the basic Watts bath to which had been added 0.8 gramper liter '(ca)
- Patents 3,002,902 and 3,002,903) (iv) 0.06 gram per liter of 1,4-(diethylamino)-2 bu-tyne (ii-hydrochloride, (v) 1 to 1.6 gram-s per liter of Q-butene-lA-diol, (vi) 0.04 to 0.06 gram per liter of hydrogen cyanamide, (vii) 0.08 gram per liter of acetylcyanamide, or (viii) 0.08 gram per liter of N-ethylquinolinium iodide were added to the bath containing sodium benzene-N-cyanosulfonamide, the resultant nickel deposits were bright over the entire current density range .of the Hull Cell and were appreciably smoother than the basis metal to which the particular deposit was applied.
- Example 11 When nickel was electrodeposited from the standard Watts solution described above, to which had been added 9 grams per liter of sodium benzenesulfonate, and 0.27 gram per liter of 2-butyne-l,4-diol, the resultant deposit was marred by a haze in the low current density areas. Upon the addition of 0.2 gram per liter of sodium benzene N-cyanosulfonamide to this bath, this haze was completely eliminated. Addition of 0.15 gram per liter of zinc (as zinc sulfate) to the bath did not result in any deleterious effect to the appearance of the electroplate.
- Example III When 0.8 gram per liter (ca. 2.4 millimoles per liter) of disodium un-benzenedi-(N-cyanosulfonimide) was added to thebasic Watts solution, the resultantnickel deposit was bright over the entire current density range of the Hull Cell panel. Cooperation with 0.1 gram per liter of 2-butyne-1,4-diol, or with the acetylenic diol and 4 grams per liter of sodium benzenesul-fonate, was excellent, with addition of 0.2 gram per liter of zinc (as the sulfate) having no harmful eifect on the appearance of the electroplate.
- Example IV The addition otf 0.8 gram per liter of sodium p-bromobenzene-N-cyanosulfonarnide to the basic Watts bath produced a fully bright nickel electrodeposit over the entire current density range of the Hull Cell panel. Cooperation with the leveling agent, 2-butyne-l,4-diol (0.16 gram per liter), was satisfactory.
- Example V The addition of 0.8 gram per liter of sodium 3,4-dichlorobenzene-N-cyanosulfonamide to -a Watts nickel bath produced a bright nickel deposit over the whole current density range of the Hull Cell with the exception of the very low current density areas (below 10 amp/ sq. ft), Where the deposit was somewhat dark. At a pH of 3.2 this low current density darkness disappeared. Further addition of 0.24 gram per liter of 2-butyne-1,4-diol produced fully bright and strongly leveled deposits.
- Example VI The addition of 0.8 gram per liter of sodium p-to luene- N-cyanosulfonamide to a Watts nickel bath gave a bright nickel deposit over almost the whole current density range of the Hull Cell panel at 60 C., and a pH of 3.8. Even better results were obtained at a pH of 3.2.
- Example VIII To a mixture of 0.1 mole (23.37 g.) N-acetylsulfanilyl chloride, 0.1 mole cyanamide (50% aqueous solution) and 8 ml. of Water, was slowly added dropwise a solution of 0.2 mole (8 g.) of sodium hydroxide in 16 ml. of water. The temperature was maintained at 45 C. Since the reaction product did not separate out easily, it was diluted with Water to 200 ml. and treated with 2 g. of activated carbon. Addition of 16 milliliters per liter of this prodnot, equivalent to 8 millimoles per liter, produced a fully brig-ht deposit over almost the whole current density range of the Hull Cell panel.
- Example X Addition of only 0.8 millimole per liter of N-acetylsulfanilylcyanamide removed the residual hazes from the nickel deposit obtained from a Watts nickel bath (pH :38) containing 4.5 grams per liter of sodium benzenesulfonate and 0.24 gram per liter of 2-butyne-1,4-diol.
- the non-acetylated sulfanilylcyanam-ide had a much stronger embrittling effect and a much weaker brightening effect than the N-acety-lated derivative.
- Example XI nickel bath containing 4 grams per liter sodium benzenesulfonate and 0.16 gram per liter of 2-butyne-l,4-diol was very effective in brightening local haze areas on the Hull Cell panel and thus promoting the production of a leveling nickel deposit which was fully bright over the whole current density range of the Hull Cell.
- Example XII To 0.5 mole hydrogen cyanamide (50% aqueous solution) and 1.0 mole sodium hydroxide (25% aqueous solution), 0.25 mole of sulfuryl chloride, SO Cl were added dropwise and with stirring and cooling, the temperature being maintained at 45 C. The reaction mixture was then diluted to 400 ml. Addition of 1.6 milliliters per liter of this reaction product (equivalent to 1 millimole per liter of'SO C1 to a' Watts nickel bath containing 4.5 grams per liter of sodium benzenesulfonate gave bright nickel deposits over almost the entire current density range of the Hull Cell, instead of the essentially semibright deposit obtained with benzenesulfonate by itself.
- Example XIII To a mixture of 0.1 mole (21.8 grams) of trichloromethanesulfonyl chloride, 0.1 mole hydrogen cyanamide (50% aqueous solution) and 8 ml. of Water was added 0.2 mole of sodium hydroxide (8 grams in 24 ml. of
- Example XV 0.1 mole of m-benzenedisulfonyl chloride and 0.1 mole of hydrogen cyanamide were allowed to react in pres- 'ence of 0.4 mole of aqueous sodium hydroxide.
- leveling agents such' as 2-butyne-1,4-diol (0.16 gram per liter) or hydrogen cyanamide (0.06 gram per liter) produced bright and leveled nickel deposits.
- the' N- cyanosulfonamides were successfully employed alone and in combination with various lacetylenic and Class I carrier brighteners in the standard Watts nickel electroplating bath, which is prepared by dissolving nickel sulfate, nickel chloride, and boric acid in water. Similar advantages are also attained when the N-cyanosulfonamide is used in other types of aqueous acidic nickelelectroplating baths. For example, these N-cyan-osulfonamides are beneficial when used in high chloride. nickel baths, and in various other nickel plating baths based on using nickel sulfamate or nickel fluoborate as the principal nickel salt which is dissolved in an aqueous acidic solvent.
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved from about 0.01 to about 25 millimoles per liter of a water-soluble N-cyanosulfonamide which contains the structural configuration 2.
- the process for producing bright nickel deposits which compriseselectrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved from about 0.01 to about 10 millimoles per liter of a water-soluble N-cyanosulfonamide having a structure represented by the formula 3.
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved from about 0.01 to about 10 millimoles per liter of an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, M-benzenedi (N-cyanosulfonamide), toluene-N-cyanosulfonamide, the halo-substituted derivatives of said N-cyanosulfonamides and the alkali metal, magnesium, cobalt, and nickel salts thereof.
- an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, M-benzenedi (N-cyanosulfonamide), toluene-N-cyanosulfonamide, the halo-substituted derivatives of said N-cyanosulfonamides and the alkali metal, magnesium
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from about 0.01 to about 10 millimoles per liter of an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, mbenZene-di-(N-cyanosulfonamide) toluene N cyanosulfonamide, the halo-substituted derivatives of said N-cyanosulfonamides, and the alkali metal, magnesium, cobalt, and nickel salts thereof; and (b) from about 0.1 to about 25 millimoles per liter of a water-soluble leveling agent.
- an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, mbenZene-di-(N-cyanosulfonamide) toluene
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from about 0.01 to about 10 millimoles per liter of an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, mbenzene di (N cyanosulfonamide), toluene-N-cyano sulfonamide, the halo-substituted derivatives of said N- cyanosulfonarnides and the alkali metal, magnesium, cobalt, and nickel salts thereof; (b) from about A to about 80 grams per liter of a water-soluble sulfooxygen compound of the group consisting of unsaturated aliphatic sulfonic acids, mononuclear and binuclear aromatic sulfonic acids, heterocyclic sulfonic acids, mononuclear aromatic sulfinic acids, the alkali
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from about 0.01 to about 25 millimoles per liter of a water-soluble N-cyanosulfonamide having a structure represented by the formula ii 1 R IS NC EN in which R is a radical selected from the group consisting of (i) alkyl and substituted-alkyl radicals, (ii) mononuclear and binuclear aromatic and alkyl-, sulfo-, halo, sulfoalkyl, haloalkyl-, acetamido-substituted aromatic radicals, and (iii) heterocyclic radicals, M is a cation substituent of the group consisting of hydrogen, the alkali metals, magnesium, cobalt, and nickel, and n is an integer from 1 to 3; and (b) from about A to about 80 grams per liter of a water-soluble N
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved from about 0.01 to about 25 millimoles per liter of a water-soluble N-cyanosulfonamide having a structure represented by the formula in which R is a radical selected from the group consisting of (i) alkyl and substituted-alkyl radicals, (ii) mononuclear and binuclear aromatic and alkyl-, sulfo-, halo-, sulfoalkyl-, haloalkyl-, acetamido-substituted aromatic radicals, and (iii) heterocyclic radicals, M is a cation substituent of the group consisting of hydrogen, the alkali metals, magnesium, cobalt, and nickel, and n is an integer from 1 to 3; and (b) from about 0.1 to about 25 millimoles per liter of a leveling agent selected from the group consisting
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved from about 0.01 to about 25 millimoles per liter of a water-soluble N-cyanosulfonamide having a structure represented by the formula in which R is a radical selected from the group consisting of (i) alkyl and substituted-alkyl radicals (ii) mononuclear and binuclear aromatic and alkyl-, sulfo-, halo-, sulfoalkyl-, haloalkyl-, acetamido-substituted aromatic radicals, and (iii) heterocyclic radicals, M is a cation substituent of the group consisting of hydrogen, the
- R and R are substituents of the group consisting of hydrogen, alkyl, alkenyl, alkynyl, and hydroXy-substituted and alkoxy-substituted alkyl, alkenyl, and alkynyl groups
- R is a substituent of the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxy-substituted and alkoXy-substituted alkenyl and alkynyl groups, and substituted-alkyl groups having the structural configuration in which each of R and R are substituents of the group consisting of hydrogen, alkyl, alkenyl, alkynyl, and hydroxy-substituted and alkoxy-substituted alkyl, alkenyl, and alkynyl'groups, and each of R, and R, are substituents of the group consisting of hydroxy, alkoxy, carboxysubstituted alkoxy
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from about 0.01 to about 25 millimoles per liter of a Water-soluble N-cyanosulfonamide having a structure represented by the formula /i l RA' fiN-CEN in which R is a radical selected from the group consisting of (i) alkyl and substituted-alkyl radicals, (ii) mononuclear and binuclear aromatic and alkyl-, sulfo-, halo-, sulfoalkyl-, haloalkyl-, acetamido-substituted aromatic radicals, and (iii) heterocyclic radicals, M is a cation in which each of R R R and R are substituents of (b) from about A to about grams per liter of a Water-soluble sulfo-oxygen compound of the group consisting of unsaturated
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from -about 0.01 to about 25 millimoles per liter of a watersoluble N-cyanosulfonamide having a structure represented by the formula in which R is a radical selected from the group consisting of (i) alkyl and substituted-alkyl radicals, (ii) mononuclear and binuclear aromatic and alkyl-, sulfo-, halo-, sulfoalkyl-, haloalkyl-, acetamido-substituted aromatic radicals, and (iii) heterocyclic radicals, M is a cation substituent of the group consisting of hydrogen, the alkali metals, magnesium, cobalt, and nickel, and n is an integer form 1 to 3; (b) from about A to about 80 grams per liter of a water-soluble sulfo-oxy
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from about 0.01 to about'10 millimoles per liter of an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, m-benzenedi-(N-cyanosulfonamide), toluene-N-cyanosulfonamide, the halo-substituted derivatives of said N-cyanosulfonamides and the alkali metal, magnesium, cobalt, and nickel salts thereof; and (b) from about 0.1 to about millimoles per liter of a water-soluble acetylenic brightening compound.
- an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, m-benzenedi-(N-cyanosulfonamide), toluene-
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (at) from about 0.01 to about 10 millimoles per liter of an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, m-benzene-di- (N-cyanosulfonamide), toluene-N-cyanosulfonamide, the halo-substituted derivatives of said N-cyanosulfonamides and the alkali metal, magnesium, cobalt, and nickel salts thereof; (b) from about A to about grams per liter of a Water-soluble sulfo-oxygen compound of the group consisting of unsaturated aliphatic sulfonic acids, mononuclear and binuclear aromatic sulfonic acids, heterocyclic sulfonic acids, mononuclear aromatic sulfinic acids, the al
- the process for producing bright nickel deposits which comprises electrodepositing nickel from an aqueous acidic solution of at least one nickel salt in which there is dissolved (a) from about 0.01 to about 10 millimoles per liter of an N-cyanosulfonamide selected from the group consisting of benzene-N-cyanosulfonamide, m-benzene di-(N-cyanosulfonamide), toluene-N-cyanosulfonamide, the halo-substituted derivatives of said N-cyanosulfona-mides and the alkali metal, magnesium, cobalt, and nickel salts thereof; and (b) from about 0.01 to about 10 millimoles per liter of a water-soluble, u,a-di(polyoxy)- 2-butyne having a structure represented by the formula in which x and y are integers from 1 to 8.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US256228A US3254007A (en) | 1963-02-05 | 1963-02-05 | Electrodeposition of nickel |
DE19641496817 DE1496817B1 (de) | 1963-02-05 | 1964-02-01 | Galvanisches Nickelbad |
CH123664A CH432172A (fr) | 1963-02-05 | 1964-02-03 | Procédé de préparation d'un dépôt brillant de nickel |
BE643298D BE643298A (de) | 1963-02-05 | 1964-02-03 | |
NL646400893A NL139093B (nl) | 1963-02-05 | 1964-02-04 | Werkwijze voor de vorming van een glanzende nikkelafzetting en voorwerpen, voorzien van een zodanige afzetting. |
FR962634A FR1386668A (fr) | 1963-02-05 | 1964-02-04 | Procédé de dépôt électrolytique de nickel à partir d'un bain acide aqueux galvanoplastique de nickel |
ES296050A ES296050A1 (es) | 1963-02-05 | 1964-02-04 | Un procedimiento para producir depósitos de níquel brillantes |
AT92464A AT250120B (de) | 1963-02-05 | 1964-02-05 | Bad zur Herstellung glänzender Nickelüberzüge |
GB4922/64A GB1058841A (en) | 1963-02-05 | 1964-02-05 | Electrodeposition of nickel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US256228A US3254007A (en) | 1963-02-05 | 1963-02-05 | Electrodeposition of nickel |
Publications (1)
Publication Number | Publication Date |
---|---|
US3254007A true US3254007A (en) | 1966-05-31 |
Family
ID=22971483
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US256228A Expired - Lifetime US3254007A (en) | 1963-02-05 | 1963-02-05 | Electrodeposition of nickel |
Country Status (8)
Country | Link |
---|---|
US (1) | US3254007A (de) |
AT (1) | AT250120B (de) |
BE (1) | BE643298A (de) |
CH (1) | CH432172A (de) |
DE (1) | DE1496817B1 (de) |
ES (1) | ES296050A1 (de) |
GB (1) | GB1058841A (de) |
NL (1) | NL139093B (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049711A (en) * | 1974-02-04 | 1977-09-20 | Ciba-Geigy Corporation | N-cyanosulfonamides |
US4416741A (en) * | 1981-03-06 | 1983-11-22 | Langbein-Pfanhauser Werke Ag | Method and bath for the electrodeposition of palladium/nickel alloys |
WO2008154722A1 (en) * | 2007-06-18 | 2008-12-24 | Vale Inco Limited | Method for improving nickel cathode morphology |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2782155A (en) * | 1954-02-16 | 1957-02-19 | Harshaw Chem Corp | Electroplating of nickel |
US2994648A (en) * | 1960-04-22 | 1961-08-01 | Harshaw Chem Corp | Nickel plating additives |
US3002904A (en) * | 1958-09-26 | 1961-10-03 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
US3116225A (en) * | 1960-07-30 | 1963-12-31 | Dehydag Gmbh | Nickel electroplating baths |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3002903A (en) * | 1958-09-26 | 1961-10-03 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
-
1963
- 1963-02-05 US US256228A patent/US3254007A/en not_active Expired - Lifetime
-
1964
- 1964-02-01 DE DE19641496817 patent/DE1496817B1/de not_active Withdrawn
- 1964-02-03 BE BE643298D patent/BE643298A/xx unknown
- 1964-02-03 CH CH123664A patent/CH432172A/fr unknown
- 1964-02-04 NL NL646400893A patent/NL139093B/xx unknown
- 1964-02-04 ES ES296050A patent/ES296050A1/es not_active Expired
- 1964-02-05 AT AT92464A patent/AT250120B/de active
- 1964-02-05 GB GB4922/64A patent/GB1058841A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2782155A (en) * | 1954-02-16 | 1957-02-19 | Harshaw Chem Corp | Electroplating of nickel |
US3002904A (en) * | 1958-09-26 | 1961-10-03 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
US2994648A (en) * | 1960-04-22 | 1961-08-01 | Harshaw Chem Corp | Nickel plating additives |
US3116225A (en) * | 1960-07-30 | 1963-12-31 | Dehydag Gmbh | Nickel electroplating baths |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049711A (en) * | 1974-02-04 | 1977-09-20 | Ciba-Geigy Corporation | N-cyanosulfonamides |
US4416741A (en) * | 1981-03-06 | 1983-11-22 | Langbein-Pfanhauser Werke Ag | Method and bath for the electrodeposition of palladium/nickel alloys |
WO2008154722A1 (en) * | 2007-06-18 | 2008-12-24 | Vale Inco Limited | Method for improving nickel cathode morphology |
JP2010525170A (ja) * | 2007-06-18 | 2010-07-22 | ヴァーレ、インコ、リミテッド | カソード構造を改良する方法 |
Also Published As
Publication number | Publication date |
---|---|
ES296050A1 (es) | 1964-08-16 |
NL139093B (nl) | 1973-06-15 |
NL6400893A (de) | 1964-08-06 |
DE1496817B1 (de) | 1970-01-15 |
AT250120B (de) | 1966-10-25 |
GB1058841A (en) | 1967-02-15 |
BE643298A (de) | 1964-05-29 |
CH432172A (fr) | 1967-03-15 |
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