US2321182A - Electrodeposition of nickel from an acid bath - Google Patents
Electrodeposition of nickel from an acid bath Download PDFInfo
- Publication number
- US2321182A US2321182A US287057A US28705739A US2321182A US 2321182 A US2321182 A US 2321182A US 287057 A US287057 A US 287057A US 28705739 A US28705739 A US 28705739A US 2321182 A US2321182 A US 2321182A
- Authority
- US
- United States
- Prior art keywords
- nickel
- solution
- group
- aldehyde
- electrodepositing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 89
- 229910052759 nickel Inorganic materials 0.000 title description 44
- 239000002253 acid Substances 0.000 title description 4
- 238000004070 electrodeposition Methods 0.000 title description 2
- 150000001299 aldehydes Chemical class 0.000 description 32
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 24
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 24
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 24
- 239000011260 aqueous acid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 125000003172 aldehyde group Chemical group 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- NJHVMXFNIZTTBV-UHFFFAOYSA-N 2,2,2-tribromoethane-1,1-diol Chemical compound OC(O)C(Br)(Br)Br NJHVMXFNIZTTBV-UHFFFAOYSA-N 0.000 description 6
- -1 fl clilor Chemical compound 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 4
- 229960002327 chloral hydrate Drugs 0.000 description 4
- QVYLNOUOIXTUGA-UHFFFAOYSA-N 2,2,3-trichlorobutane-1,1-diol Chemical compound CC(Cl)C(Cl)(Cl)C(O)O QVYLNOUOIXTUGA-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- SQBGBQRDPZHDOG-UHFFFAOYSA-N 1,1,1-tribromohexan-2-one Chemical compound C(CCC)C(=O)C(Br)(Br)Br SQBGBQRDPZHDOG-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- BUYMVQAILCEWRR-UHFFFAOYSA-N naled Chemical compound COP(=O)(OC)OC(Br)C(Cl)(Cl)Br BUYMVQAILCEWRR-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Description
Patented June 8, 1943 ELECTRODEPOSITION OF NICKEL FROM AN (ID BATH Henry Brown, Detroit, Mich, assignor to The Udylite Corporation, Detroit, Mich, a corporation of Delaware No Drawing. Application July 28, 1939, Serial No. 287,057
13 Claims.
This invention relates to the electro-deposltion of nickel from an acid bath.
It is an object of this invention to produce a fine-grained, lustrous, ductile nickel deposit.
Another object of the invention is to decrease the tendency of the formation of pits in the plate, such pitting being detrimental from the standpoint of both appearance and corrosion-resistance afforded by the plate.
These objects are accomplished by the addition to a standard nickel sulphate plating bath (commonly called the Watts type nickel plating bath) of certain organic compounds, to wit; halogenated aldehydes. The term halogenated aldehydes as used herein includes not only the halogenated aldehydes but also their hydrates and their acetals, the latter which in water solution regenerate the halogenated aldehydes or bydrates.
This application is a continuation in part of my prior application Serial No. 162,697, filed September '7, 1937.
These halogenated aldehydes, particularly the alpha halogenated aldehydes, have certain definite advantages over the ordinary aldehydes. Several of the ordinary aldehydes are very powerful brighteners, for example, furfural, croton aldehyde, and acrolein. These powerful aldehydes, however, tend to resinify in the plating bath and form products which adversely affect both bond and brightness. The alpha halogenated aldehydes are equally or more powerful brighteners and do not resinify in the warm acid bath. Consequently, the baths are more stable and require less attention. The baths can be left idle for long periods without the need of purification from resinous materials. Since no harmful products are formed, one does not need constant drag-out to keep the amount of such products within necessary limits.
In general, therefore the substitution of halogens in the alpha position relative to the aldehyde group improves the effectiveness of the compound in the nickel bath. The bright plate range is widened and the ability of smoothing out polishing lines and other imperfections with the plating is greatly increased. The bromine atom is more effective than the chlorine atom except where it decreases the solubility unduly as in tribrom obutyraldehyde hydrate.
The use of air agitation in the baths further increases the efficacy of the halogenated aldehydes more so than with ordinary aldehydes.
A number of compounds containing the desired group are listed in Table 1 in the order of their decreasing effectiveness and with their optimum concentrations in baths at 50 C. prepared from nickel sulphate, nickel chloride and boric acid and containing 60'75 grams per liter Ni, 15 grams per liter Cl, 30-375 grams per liter H3130; and pH=2-6 and at a current density of 1 to 5 amp/sq. dm. The temperature of the plating solution can range from 15 C. to the boiling point of the solution. The optimum temperature of the solution when plating, is between 15 C. and 55 C. The preferred temperature of the solution is about 50 C. The solution has better throwing power at lower temperatures and higher pH values than at higher temperatures and lower pH values. The optimum pH- falls between 4 and 5.3 electrometric.
Table 1 Opt. come. all
a Brom, fl clilor, crotonaldehyde hydrate,
ClI3.CC1=CBr-CHO.H20 0.1-0.2
a Chlor, B chlor, crotonaldehyde hydrate,
CH;.CC1=CC1.CHO.HO 0.1-0.2
aa, Dibrom, B mono chlor butyraldehyde hydrate,
drate), CH3.CHC|.CC]2.CHO.H:O 0. 2-1. 25 aafl, Tribromobutyraldehyde hydrate (butyl bromal hy- (irate), CHJ.CI]BT.CBT2.0HO.H2O 0.1- .4 Bromal hydrate, CBmCHOIhO l- .7
p-Proprionchloral hydrate brom benzenesulphonic acid,
llOrS-OOHCLCCl1.Cll0.Ilz0 ;34.0
p-l'roprionchloi'al hydrate benzene sulphonic acid,
1l aS-C 'CHCLC(Jl .ClI ).liz() .:i--'4.o
p-Butyl chloral hydrate benzene sulphonic acid,
ll (MS-O C1l2.Cl1 (11.(1 C]I-C}IO.]]20. .34. U
" Chloral hydrate, (7 (311.011 0.11:0 0. 5-1. 5
Chloral social, 0 Ch.C=(0 C2115): 0. -2. 0
Mixtures of two or more aldehydes widens the plating range. Desirable mixtures include: .3 g./l. bromal hydrate and 1 g./l. butyl chloral hydrate; .5 g./l. chloral hydrate and .4 g./l. dibrommonochlorbutyraldehyde hydrate; 1 g./l. butyl chloral hydrate and 2 ml./l. formaldehyde (40% solution). 4
The concentration of the halogenated aldehydes should not be allowed to increase above the upper limit of the optimum concentration. as larger quantities tend to hurt the adhesion of the nickel coating and the covering power in recesses (now current density areas) I claim: g
l. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of eleetrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickelchloride, and a mixture of nickel chloride and nickel sulphate in the presence of an aliphatic polyhalogenated aldehyde soluble in the solution and having at least one halogen the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
2. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate and having a pH falling within a range from about 2 to about 6 electrometric in the presence of an aliphatic polyhalogenated aldehyde soluble in the solution and having at least one halogen atom in alpha position to the aldehyde group,
A the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
3. 'A method for electrodepositing nickel to obtain a fine-grained deposit comprising the stepof electrodepositing nickel from an aqueous acid? nickel solution comprising essentially a material selected from the group consisting of {nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate and having a pH falling within a range from about 2 to about 6"-,el ectrometric in the presence of an aliphatic polyhalogenated aldehyde soluble in the solution and having a concentration in the solution of at, least .1 gram per liter and having at least one halogen atom in alpha position to the aldehyde group, the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
4. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution containing boric acid, nickel sulphate and nickel chloride in the presence or an aliphatic polyhalogenated aldehyde soluble in the solution and having at least one halogen atom in alpha position to the aldehyde group, the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
5. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution containing boric acid, nickel sulphate and nickel chloride having a pH falling within a range from about 2 to about 6 electrometric in the presence of an aliphatic polyhalogenated aldehyde soluble in the solution and having at least one halogen atom in alpha position to the aldehyde group, the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
6. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution containing boric acid, nickel suiphate and nickel chloride having a pH falling within a range from about 2 to about 6 electrometric in the presence of an aliphatic polyhalogenated aldehyde soluble in the solution and having a concentration in the solution of at least .1 gram per liter and having at least one halogen atom in alpha position to the aidehyde group, the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
7. A bath for electrodepositing nickel to obatom in alpha position to the aldehyde group,
tain a fine-grained deposit comprising an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate containing an aliphatic polyhalogenated aldehyde soluble in the solution and having at least one halogen atom in alpha position to the aldehyde group, the halogen substituents oi the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
8. A bath for electrodepositing nickel to obtain a fine-grained deposit comprising an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate and having a pH falling within a range from about 2 to about 6 electrometric containing an aliphatic polyhalogenated aldehyde soluble in the solution andhaving at least one halogen atom in alpha position to the aldehyde group, the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
9. A bath for electrodepositing nickel to obtain a fine-grained deposit comprising an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate and having a pH falling within a range from about 2 to about 6 electrometric containing an aliphatic polyhalogenated aldehyde soluble in the solution and having a concentration in the solution of at least .1 gram per liter and having at least one halogen atom in alpha position to the aldehyde group, the halogen substituents of the polyhalogenated aldehyde being selected from the group consisting of chlorine and bromine.
10. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate in the presence of chloral hydrate.
11. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate in the presence of bromal hydrate.
12. A method for electrodepositing nickel to obtain a fine-grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate in the presence of butyl chloral hydrate.
13. A method for electrodepositing nickel to obtain a fine grained deposit comprising the step of electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulphate, nickel chloride, and a mixture of nickel chloride and nickel sulphate and containing chloral hydrate in an amount not greater than 1.5 grams per liter of solution.
HENRY BROWN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US287057A US2321182A (en) | 1939-07-28 | 1939-07-28 | Electrodeposition of nickel from an acid bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US287057A US2321182A (en) | 1939-07-28 | 1939-07-28 | Electrodeposition of nickel from an acid bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2321182A true US2321182A (en) | 1943-06-08 |
Family
ID=23101277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US287057A Expired - Lifetime US2321182A (en) | 1939-07-28 | 1939-07-28 | Electrodeposition of nickel from an acid bath |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2321182A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2534911A (en) * | 1948-04-03 | 1950-12-19 | Houdaille Hershey Corp | Process of removing hydrogen embrittlement of bright nickel electrodeposits |
| US2900707A (en) * | 1954-08-06 | 1959-08-25 | Udylite Corp | Metallic protective coating |
-
1939
- 1939-07-28 US US287057A patent/US2321182A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2534911A (en) * | 1948-04-03 | 1950-12-19 | Houdaille Hershey Corp | Process of removing hydrogen embrittlement of bright nickel electrodeposits |
| US2900707A (en) * | 1954-08-06 | 1959-08-25 | Udylite Corp | Metallic protective coating |
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