US2782153A - Nickel electrodeposition - Google Patents
Nickel electrodeposition Download PDFInfo
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- US2782153A US2782153A US410713A US41071354A US2782153A US 2782153 A US2782153 A US 2782153A US 410713 A US410713 A US 410713A US 41071354 A US41071354 A US 41071354A US 2782153 A US2782153 A US 2782153A
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- Prior art keywords
- nickel
- per liter
- coumarin
- pyridinium
- bis
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004070 electrodeposition Methods 0.000 title claims description 4
- 229910052759 nickel Inorganic materials 0.000 title description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 229960000956 coumarin Drugs 0.000 description 10
- 235000001671 coumarin Nutrition 0.000 description 10
- -1 aromatic sulfonamides Chemical class 0.000 description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 description 8
- 150000002830 nitrogen compounds Chemical group 0.000 description 8
- 238000009499 grossing Methods 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- 239000010953 base metal Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000004775 coumarins Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 150000003456 sulfonamides Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002659 electrodeposit Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- 229940081974 saccharin Drugs 0.000 description 3
- 235000019204 saccharin Nutrition 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- GJJPLKJBULCRQI-UHFFFAOYSA-N 2-pyridin-1-ium-1-ylacetate Chemical class [O-]C(=O)C[N+]1=CC=CC=C1 GJJPLKJBULCRQI-UHFFFAOYSA-N 0.000 description 2
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 2
- PPVDWGGTPALFNU-UHFFFAOYSA-N COS([O-])(=O)=O.Cc1ccc2ccccc2[nH+]1 Chemical compound COS([O-])(=O)=O.Cc1ccc2ccccc2[nH+]1 PPVDWGGTPALFNU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- OPADBMMEJWLYBL-UHFFFAOYSA-L 1-(pyridin-1-ium-1-ylmethyl)pyridin-1-ium;dichloride Chemical compound [Cl-].[Cl-].C=1C=CC=C[N+]=1C[N+]1=CC=CC=C1 OPADBMMEJWLYBL-UHFFFAOYSA-L 0.000 description 1
- YUJRQSUIQASWHJ-UHFFFAOYSA-N 2-oxochromene-3-sulfonic acid Chemical class C1=CC=C2OC(=O)C(S(=O)(=O)O)=CC2=C1 YUJRQSUIQASWHJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WSUYMOPGQMYJBT-UHFFFAOYSA-N CC(C)C(C([O-])=O)[N+]1=CC=CC=C1 Chemical class CC(C)C(C([O-])=O)[N+]1=CC=CC=C1 WSUYMOPGQMYJBT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000861718 Chloris <Aves> Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical class C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
Definitions
- This invention relates to electrodeposition of nickel and more specifically to a process for producing electrodeposits of greatly increased brightness and smoothness, as taken from the plating solution, without buifing or polishing of any sort.
- This invention is primarily concerned with the fact that although electrodeposits taken from acid nickel plating solutions containing coumarin exhibit extraordinary smoothness they are only semi-bright, and attempts to increase their brightness by the use of addition agents of the type of saccharin or naphthalene sulfonic acids result in improved brightness with loss of smoothness when the surface being coated is quite smooth, and can result in decrease in both smoothness and brightness when the surface to be coated is quite rough.
- Quaternary nitrogen compounds containing'the grouping and at least one aliphatic carbon atom attached to the nitrogen of said group This group maybe substituted to form a double ring structure :of the form 0:0 I '(quinolinium) and one or more hydrogen atoms may be replaced by methyl or ethyl or other substituents.
- the compound may be of the bis-pyridinium or bis-lsoquinolinium type joined by a carbon or carbon and oxygen chain such as (CHzM-or (CH2)1LO(CH2)1L .
- CHzM-or (CH2)1LO(CH2)1L a carbon or carbon and oxygen chain
- d N,N-(oxydimethylene)-bis-pyridinium salts
- p-Xylylene-pyridinium salts g) N-( 2-ehloroa1lyl) pyridinium salts
- the preferredacid nickel solution in connection with which the invention may be realized is an aqueous solution containing nickel sulfate equivalent to from 100 to 400 grams per liter of nickel sulfate heptahydrate, nickel chloride equivalent to from 10 to grams per liter of nickel chloride hexa-hydrate, and from 10 to 50 grams .per liter, :preferably 15 to 40 grams per liter, of boric acid or other buffer such as formic acid or citric acid.
- one or more aromatic sulfonamides to a concentration from /2 gram per liter to saturation, one or more coumarin compounds to a concentration from 0.01 to 0.5 gram per liter, and one or more leveling agents of the above indicated class in concentrations less than half a gram .per liter, for example, from 0.0005 to 0.3 gram per liter.
- concentrations of these compounds required for best results will be within the ranges indicated in the respective tables opposite each of said compounds, and very desirably will be approximately the specific concentration set forth opposite each compound in the tables.
- the compounds listed in Table I are examples of sulfur compounds which when used in connection with coumarin and certain coumarin derivatives produce an increase in brightness with some loss in smoothness. Numerous other similar compounds produce the same effect in varying degree. They are aromatic sulfonamides and 'sulfimides.
- the compounds of Table II are examples of coumarin compounds which can be used. Alkyl and acyl .derivativesof coumarin having 1 to 4 carbon atoms, and the chlorine and carboxy derivatives thereof are suitable.
- Thev compounds listed in Table III are examples of .organiccompounds effective to increase smoothing power (and brightness) of coumarin 3 type smoothing agents lost by the addition of sulfur compounds of the type of those listed in Table I. Coumarin sulfonic acids are not equivalent to the above indicated coumarin compounds.
- the solutions are operated in pH range from 2.5 to 4.5, the temperature is maintained within the range from 110 F. to 160 F., and the cathode current density is maintained within the range from 5 to 100 a. s. f.
- Formaldehyde may be used in the above described solutions at a concentration of from 0.05 to 0.5 gram per liter for the purpose of retarding or minimizing the effect of breakdown products of coumarin or derivatives such as listed in Table II.
- nickel ions for electrodeposition may be employed.
- the nickel ion concentration should in any case be within the range which would result from the presence of from 100 to 400 grams per liter of NiSO4.7H2O.
- N-(2'ohloroallyl) pyridinium chloride 0.05 to 0.12 0.08 N-mcthallyl pyridinium chloride--. 0. 05 to 0. 12 0.08 (9) N,N methylene bis pyridinium chloride 0.05 to 0. 15 0.08 (10) N-(carboxy lsobutyl) pyridinium chloride 0 03 to 0 1 0.05
- a process for producing bright, smooth electrodeposits of nickel comprising electrolyzing between an anode and a cathode a solution containing nickel sulfate equivalent to from to 400 grams per liter of nickel sulfate heptahydrate, nickel chloride equivalent to from 10 to 75 grams per liter of nickel chloride hexahydrate and a group of three cooperating addition agents, one of said addition agents being an organic sulfur compound containing the group one thereof being selected from the class consisting of coumarin and its alkyl, acyl, chlorine and carboxy derivatives and a third thereof being a quaternary nitrogen compound containing the grouping addition agent being present in concentration from 0.01
- said quaternary nitrogen compound is an N,N'-(oxydiethylene)-bis pyridinium compound and said organic sulfur compound is bidibenzene sulfonamide.
- said quaternary nitrogen compound is an N,N-(oxydiethy1- ene)-bis isoquinolinium compound and said organic sulfur compound is bidibenzene sulfonamide.
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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 C) No Drawing. Application February 16, 1954, Serial No. 410,713
9 Claims. (Cl. 204-49) This invention relates to electrodeposition of nickel and more specifically to a process for producing electrodeposits of greatly increased brightness and smoothness, as taken from the plating solution, without buifing or polishing of any sort.
This application is a continuation-in-part of our copending application, serial No. 278,957, filed March 27, 1952, and our copending application, serial No. 338,560, filed February 24, 1953, .which was a continuation-in-part of application serial No. 278,958, filed March 27, 1952, all now abandoned.
This invention is primarily concerned with the fact that although electrodeposits taken from acid nickel plating solutions containing coumarin exhibit extraordinary smoothness they are only semi-bright, and attempts to increase their brightness by the use of addition agents of the type of saccharin or naphthalene sulfonic acids result in improved brightness with loss of smoothness when the surface being coated is quite smooth, and can result in decrease in both smoothness and brightness when the surface to be coated is quite rough. I-t'was found, for-example, that when a aqueous, acid solution containing 240 grams per liter of nickel sulfate heptahydr'ate, 40 grams per liter of nickel chloride hexahydrate and 40 grams per liter of boric acid was utilized and coumarin was used in concentration of 0.25 gram per liter as the'sole addition agent, a semi-bright deposit was obtained having a smoothness increase over the base metal of approximately 4 microinches where the base metal had a smoothness in the order of 6 *to 10 microinches, measurements having been made with the Brush surface analyzer. Such an increase in smoothness is remarkable, and :this property of coumarin has formed the basis of a commercial semi-bright solution now being widely used. When the attempt was made to increase the brightness by the addition of agents such as saccharin of naphthalene sulfonic "acids, it was found that increased brightness was secured, but at the cost of a part of the smoothing action of the coumarin. For example, it was found that when the above described solution was varied by adding 3.5 grams per liter of naphthalene disulfonic acid an increase in brightness was secured, but the gain in smoothness over the base metal was only about 2.2 microinches, the same ltype of base metal being used. If, instead of using naphthalenesulfonic acids, saccharin was used to improve the brightness, improved brightness was obtained and the gain in smoothness was about the same. Many other sulfonic acids and sulfonamides show similar results. When the surface to be coated is not so smooth, e. g. 20 to 29 R. M. S. as shown by the Brush surface analyzer the loss of the smoothing action may be so great as to overshadow the tendency toward increased brightness and actually appear to decrease the lusterof the deposit.
In accordance with the present invention it has now beendiscovered that a largevportion of the lost smoothing action :just described can berestoredsif there is added, in addition to the coumarin, not only an aromatic sul- 2 fonamide, but also one or more of certain organic, levelmg addition agents of the' following class:
Quaternary nitrogen compounds containing'the grouping and at least one aliphatic carbon atom attached to the nitrogen of said group. This group maybe substituted to form a double ring structure :of the form 0:0 I '(quinolinium) and one or more hydrogen atoms may be replaced by methyl or ethyl or other substituents. Preferably the compound may be of the bis-pyridinium or bis-lsoquinolinium type joined by a carbon or carbon and oxygen chain such as (CHzM-or (CH2)1LO(CH2)1L .As examples may be mentioned, (a) .N,N-(oxydiethylene) -bis isoquinolinium salts (b) N,N-(oxydiethylene) -bis pyridinium salts '(c) N-carboxymethyl pyridinium salts (d) N,N-(oxydimethylene)-bis-pyridinium salts e) Quinaldine methyl sulfate (f) p-Xylylene-pyridinium salts (g) N-( 2-ehloroa1lyl) pyridinium salts (h) N-methallyl pyridinium salts '(i) N,N-methylene-bis-pyridinium salts (j) N-(carboxy isobutyl) pyridinium salts.
While these leveling agents do not completely restore the full smoothing action of coumarin, they do, in someinstances restore a large portion of it.
The preferredacid nickel solution in connection with which the invention may be realized is an aqueous solution containing nickel sulfate equivalent to from 100 to 400 grams per liter of nickel sulfate heptahydrate, nickel chloride equivalent to from 10 to grams per liter of nickel chloride hexa-hydrate, and from 10 to 50 grams .per liter, :preferably 15 to 40 grams per liter, of boric acid or other buffer such as formic acid or citric acid. To this fundamental solution there may be added in accordance withthe present invention one or more aromatic sulfonamides to a concentration from /2 gram per liter to saturation, one or more coumarin compounds to a concentration from 0.01 to 0.5 gram per liter, and one or more leveling agents of the above indicated class in concentrations less than half a gram .per liter, for example, from 0.0005 to 0.3 gram per liter. The concentrations of these compounds required for best results will be within the ranges indicated in the respective tables opposite each of said compounds, and very desirably will be approximately the specific concentration set forth opposite each compound in the tables.
The compounds listed in Table I are examples of sulfur compounds which when used in connection with coumarin and certain coumarin derivatives produce an increase in brightness with some loss in smoothness. Numerous other similar compounds produce the same effect in varying degree. They are aromatic sulfonamides and 'sulfimides. The compounds of Table II are examples of coumarin compounds which can be used. Alkyl and acyl .derivativesof coumarin having 1 to 4 carbon atoms, and the chlorine and carboxy derivatives thereof are suitable. Thev compounds listed in Table III are examples of .organiccompounds effective to increase smoothing power (and brightness) of coumarin 3 type smoothing agents lost by the addition of sulfur compounds of the type of those listed in Table I. Coumarin sulfonic acids are not equivalent to the above indicated coumarin compounds.
Preferably, the solutions are operated in pH range from 2.5 to 4.5, the temperature is maintained within the range from 110 F. to 160 F., and the cathode current density is maintained within the range from 5 to 100 a. s. f.
Formaldehyde may be used in the above described solutions at a concentration of from 0.05 to 0.5 gram per liter for the purpose of retarding or minimizing the effect of breakdown products of coumarin or derivatives such as listed in Table II.
Specific examples which have yielded excellent results are indicated in Table IV.
Other basic solutions capable of yielding nickel ions for electrodeposition may be employed. Preferably there should be present in the solution at least one nickel salt of the class consisting of nickel sulfate, nickel chloride, nickel fiuoborate and nickel sulfamate. The nickel ion concentration should in any case be within the range which would result from the presence of from 100 to 400 grams per liter of NiSO4.7H2O.
Table 1 Optimum Preferred Range, Concentrag./l. tion, g./l.
(1) Benzene sulfonamide (PhSOZNH2) 0. 5 to 3.0 1. (2) p-Toluene sultonarnide (CH3CQH4SO2' NHr) 0.5130 3.0 1.0 (3) Sacchariu (o-benzosulfirnld) 0. to 3.0 1, 0 (4) Dtbenzene sulfonamide (PhSOzNHSOz- Ph) and its mono-and-dichlor0 derivatives" 0. 5 to 5.0 1. 0 (5) p-Benzene-bls (N-sylphonylbenzenesul- Ph 0.511000 1.0 26) N-ethane sulionyl benzene sulfonnmide- 0. 5 to 5.0 1.0
7) Monoand di-chlorobenzene su]fonan1ldes 0. 5 to 5. 0 1.0 (8) Monoand di-chloro derivatives of (2) and (5) above 0. 5 to 5.0 .0 (9) Bi-dibenzenesulfonamide (PhSOzNHSOfi' otniotrnsomnsogrm O. 5 to 5. 0 1.0 (10) Monoand di-chloro derivatives 01 (9) above 0. 5 to 5.0 1.0 (11) Dlbenzene sulfouamide ether (PhSOz NHS01CBE4OC5H4S02NHSO2P11) 0. 5 to 5.0 1.0
Table II Preferred Range, g./1. Concentration g./l.
Cournarln 0.05 to 0.25 0.1 3-Chloro couniarin 0. 05 to 0.25 0.1 6-Chloro eoumarin 0.05 to 0.25 0.1 4-methyl eoumnrln 0.05 to 0.25 0. 1 fi-carboxy cournarim; 0.05 to 0.25 0.1
Table III Preferred Range, g./l. Concentration, g./l.
(1) N,N-(oxydiethylene)-bis-isoquin0- linium chloride 0.003 to 0. 01 0. 005 (2) N,N-(qxydiethylene)-bis pyridinium ch r1 0 0.003 to 0. 01 0.007 (3) N-eerboxymethyl pyridinium chloride 0. 25 to 0.6 0. 4 (4) N,N-(oxydimethy1ene)-bis-pyridinrid 0.05 to 0.1 0. 08
0.05 to 0. 1 0. 08 (6) p-Xylylene pyridinium chlori e.. 0.0025 to 0.015 0.005 (7) N-(2'ohloroallyl) pyridinium chloride 0.05 to 0.12 0.08 (8) N-mcthallyl pyridinium chloride--. 0. 05 to 0. 12 0.08 (9) N,N methylene bis pyridinium chloride 0.05 to 0. 15 0.08 (10) N-(carboxy lsobutyl) pyridinium chloride 0 03 to 0 1 0.05
4 Table IV Grams per Liter NiSOtJH O giclzfiHzoflq- Dibenzene sultonamide. Bi-dibenzene sultonamide N,N-(oxydiethylene)-bispyridinium bromide N-cgrboxymethyl pyridinium chlorl e (at O l C=C one thereof being selected from the class consisting of coumarin and its alkyl, acyl, chlorine and carboxy derivatives and a third thereof being a quaternary nitrogen compound containing the grouping 6:5 -C N+ o-o l and having at least one aliphatic carbon atom attached to the nitrogen atom of said group, said first mentioned addition agent being present in concentration from onehalf gram per liter to saturation, said second mentioned addition agent being present in concentration from 0.01 to 0.5 gram per liter and said third mentioned addition agent being present in concentration from 0.0005 to 0.3 gram per liter.
2. A process for producing bright, smooth electrodeposits of nickel comprising electrolyzing between an anode and a cathode a solution containing nickel sulfate equivalent to from to 400 grams per liter of nickel sulfate heptahydrate, nickel chloride equivalent to from 10 to 75 grams per liter of nickel chloride hexahydrate and a group of three cooperating addition agents, one of said addition agents being an organic sulfur compound containing the group one thereof being selected from the class consisting of coumarin and its alkyl, acyl, chlorine and carboxy derivatives and a third thereof being a quaternary nitrogen compound containing the grouping addition agent being present in concentration from 0.01
to 0.5 gram per liter and said third mentioned addition agent being present in concentration from 0.0005 to 0.3 gram per liter.
3. A process according to claim 2 wherein said solution contains from 10 to 50 grams per liter of boric acid.
4. The invention as defined in claim 2 wherein said quaternary nitrogen compound is a bis-pyridinium compound.
5. The invention defined in claim 2 wherein said organic sulfur compound is bidibenzene sulfonamide.
6. The invention as defined in claim 2 wherein said quaternary nitrogen compound is an N,N'-(oxydiethylene) -bis pyridinium compound.
7. The invention as defined in claim 2 wherein said quaternary nitrogen compound is an N,N'-(oxydiethylenc) -bis isoquinolinium compound.
8. The invention as defined in claim 2 wherein said quaternary nitrogen compound is an N,N'-(oxydiethylene)-bis pyridinium compound and said organic sulfur compound is bidibenzene sulfonamide.
9. The invention as defined in claim 2 wherein said quaternary nitrogen compound is an N,N-(oxydiethy1- ene)-bis isoquinolinium compound and said organic sulfur compound is bidibenzene sulfonamide.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. A SOLUTION FOR ELECTRODEPOSITION OF NICKEL IN THE FORM OF BRIGHT AND SMOOTH DEPOSITS, SAID SOLUTION CONTAINING A NICKEL ION YIELDING COMPOUND OF THE CLASS CONSISTING OF NICKEL SULFATE, NICKEL CHLORIDE, NICKEL SULFAMATE AND NICKEL FLUOBORATE TOGETHER WITH COOPERATING ADDITION AGENTS, ONE OF SAID ADDITION AGENTS BEING AN ORGANIC SULFUR COMPOUND CONTAINING THE GROUP
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US410713A US2782153A (en) | 1954-02-16 | 1954-02-16 | Nickel electrodeposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US410713A US2782153A (en) | 1954-02-16 | 1954-02-16 | Nickel electrodeposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2782153A true US2782153A (en) | 1957-02-19 |
Family
ID=23625919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US410713A Expired - Lifetime US2782153A (en) | 1954-02-16 | 1954-02-16 | Nickel electrodeposition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2782153A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245887A (en) * | 1963-01-31 | 1966-04-12 | M & T Chemicals Inc | Electrodeposition of nickel |
| DE1225015B (en) * | 1960-10-10 | 1966-09-15 | Riedel & Co | Galvanic nickel bath |
| US3314868A (en) * | 1963-05-15 | 1967-04-18 | Dehydag Gmbh | Acid nickel electroplating baths and processes |
| DE1259169B (en) * | 1960-03-29 | 1968-01-18 | Riedel & Co | Bath for galvanic deposition of mirror-glossy, leveled and homogeneous nickel coatings |
| US3414491A (en) * | 1965-10-22 | 1968-12-03 | Kewanee Oil Co | Electrodeposition of nickel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635076A (en) * | 1947-01-29 | 1953-04-14 | Harshaw Chem Corp | Bright nickel plating |
| US2647866A (en) * | 1950-07-17 | 1953-08-04 | Udylite Corp | Electroplating of nickel |
-
1954
- 1954-02-16 US US410713A patent/US2782153A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635076A (en) * | 1947-01-29 | 1953-04-14 | Harshaw Chem Corp | Bright nickel plating |
| US2647866A (en) * | 1950-07-17 | 1953-08-04 | Udylite Corp | Electroplating of nickel |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1259169B (en) * | 1960-03-29 | 1968-01-18 | Riedel & Co | Bath for galvanic deposition of mirror-glossy, leveled and homogeneous nickel coatings |
| DE1225015B (en) * | 1960-10-10 | 1966-09-15 | Riedel & Co | Galvanic nickel bath |
| US3245887A (en) * | 1963-01-31 | 1966-04-12 | M & T Chemicals Inc | Electrodeposition of nickel |
| US3314868A (en) * | 1963-05-15 | 1967-04-18 | Dehydag Gmbh | Acid nickel electroplating baths and processes |
| US3414491A (en) * | 1965-10-22 | 1968-12-03 | Kewanee Oil Co | Electrodeposition of nickel |
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