US2402801A - Electrodeposition of nickel - Google Patents
Electrodeposition of nickel Download PDFInfo
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- US2402801A US2402801A US456362A US45636242A US2402801A US 2402801 A US2402801 A US 2402801A US 456362 A US456362 A US 456362A US 45636242 A US45636242 A US 45636242A US 2402801 A US2402801 A US 2402801A
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- Prior art keywords
- nickel
- thallium
- bath
- sulfate
- plate
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 56
- 229910052759 nickel Inorganic materials 0.000 title description 28
- 238000004070 electrodeposition Methods 0.000 title description 3
- 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
- 239000000203 mixture Substances 0.000 description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 17
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 14
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 13
- 229910052716 thallium Inorganic materials 0.000 description 13
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 13
- 229940119523 thallium sulfate Drugs 0.000 description 13
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 13
- -1 thallium sulfate Chemical compound 0.000 description 10
- 238000007747 plating Methods 0.000 description 8
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000011260 aqueous acid Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 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
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- RPRMTKNGBKVEAN-UHFFFAOYSA-N 1,4-diphenylcyclohexa-2,4-diene-1-sulfonic acid Chemical compound C1(=CC=CC=C1)C1(CC=C(C=C1)C1=CC=CC=C1)S(=O)(=O)O RPRMTKNGBKVEAN-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LTASFWDWBYFZQQ-UHFFFAOYSA-N 2-amino-5-nitrobenzenesulfonic acid Chemical compound NC1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O LTASFWDWBYFZQQ-UHFFFAOYSA-N 0.000 description 1
- PXACTUVBBMDKRW-UHFFFAOYSA-N 4-bromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 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 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910021515 thallium hydroxide Inorganic materials 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 1
- CULOEOTWMUCRSJ-UHFFFAOYSA-M thallium(i) fluoride Chemical compound [Tl]F CULOEOTWMUCRSJ-UHFFFAOYSA-M 0.000 description 1
- QGYXCSSUHCHXHB-UHFFFAOYSA-M thallium(i) hydroxide Chemical compound [OH-].[Tl+] QGYXCSSUHCHXHB-UHFFFAOYSA-M 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
Definitions
- This invention relates to the electrodeposition of nickel from an aqueous acid bath.
- the object of this invention is the electrodeposition, of brilliant, highly lustrous ductile nickel plate having good bond to the basis metal.
- This object can be achieved by using a salt of the metal thallium, such as thallium sulfate, in an aqueous acid nickel bath together with an organic compound containing the linkage,
- the combination of these brightening addition agents can best be used in the acid nickel baths of the Watts type and its modifications, using formates, citrates, etc., as well as boric acid as buifers.
- the most suitable nickel plating baths and their temperatures and preferred hydrogen ion concentration are given in Table 11. Small concentrations of citric acid especially, and also of formic, can often be used with the boric with benefit. At the higher temperatures, it is better to use the lower pH values.
- Nickel sulfamate can be used in concentrations up to saturation toreplace the nickel sulfate.
- any thallous (11+) salt soluble in the bath can be used, as for example, thallium sulfate, thallium chloride, thallium fluoride, thallium carbonate 6 Claims. (01. 204-43) and thallium hydroxide; the important thing is that in introducing the thallous ion into the bath, it is not desirable to introduce any harmful anion such as the nitrate ion into the nickel plating bath.
- the thallium is usually added to the bath in the form of thallium sulfate (T12SO4), as this is about the most readily available salt.
- c-s0- I type of compound such as saccharin or p-toluene sulfonamide, or 1,5-naphthalene disulfonic acid, is also added to the warm acid nickel bath containing the thallium sulfate, a brilliant, very ductile plate, having good bond to the basis metal, is obtained. That is, not only is the plate made brighter and over a wider current density range, but also the bond and ductility of the plate are improved. These organic compounds, thus, not only increase the tolerance of the bath to the thallium ion but also greatly enhance the brightness obtained.
- Too high concentration of thallium like that of zinc and cadmium, causes the plate to be exceedingly brilliant but too hard and brittle and also makes the recesses dark; however, at optimum concentrations, the plate is both ductile and bright with a very good rate of brightening.
- a plate of .0005"-.001" of such nickel will have a brilliant luster even when plated over steel ilnished with a final grease emery. The best used with small amounts brightene'r.
- pH values are from 2.5 to 4.5 at a temperature of about 50 C., with the widest bright plating range at the lower pH values.
- the presence of ammonium salts are not desirable, especially in warm baths, as they decreasethe ductility of the plate. In cold baths, a greater concentration of ammonium salts can be tolerated and less thallium must be used.
- Sodium, and es cially magnesium salts are not nearly as cri lcal but in general, it is preferred not to have much of such salts present. I
- the concentrations of thallium sulfate to be used with the compounds (Table I) is from 0.3 gram per liter to even 2 grams per liter depending on such conditions as the pH of the bath, temperature and the exact compounds used, etc.
- the concentrations of thallium must always be less than with the compounds present, or else the plate will be of poor color and bond (unless, of course, the purpose is to obtain dark plate).
- the cold double ammonium salt bath can be of thallium alone as
- the *o compounds listed in Table I are not the only compounds that show the beneficial eflects with the thallium ion but others also do, though they are not as effective, for example, benzene sulfonic acid (in large concentration), p-brom benzene sulfonic acid, diphenyl sulfonic acid, p-diphenyl benzene sulfonic acid and the naphthalene sulfonic acids.
- aryl sulflnic acids containing the 4 group
- benzene or toluene sulflnates are even more eflective than the aryl suli'onamides and aryl sulionates (containing the v 3SOr compounds.
- a very useful application or the sulfinic acids would be if by accident too much T1+ is added to a bath, the addition of even a small amount (.1 g./l. or less) of the sulflnate will counteract the harmful eifects immediately.
- the hydroxy groups decrease the brightness but do not affect the ductility.
- the nitro groups on the ring tendto.
- the process involving the reduction and hydrogenolysis or the sulfur of the positive valent compounds to a negative valence produces. in part at least, an inhibitor or poison of the nickel (as catalyst in perhaps many cases) in the reduction of (or addition of electrons to) Tl+ (and other active ions or active unsaturated organic materials).
- the plating bath is made more tolerant to larger concentrations of these active substances (see United 'States Patent 2,191,813). That is, the plating bath is made more tolerant to these substances because they are less easily reduced in the presence. of the hill)- compounds.
- T1 active inorganic and organic materials
- a bath for electrodepositing ductile bright nickel plate comprising an aqueous acid nickel solution comprising essentially amaterial selected from the group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfate and nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within a range of from .1 gram per liter to 2 grams per liter and an aryl organic compound containing the group where the sulfur is positive valent and attached to at least one oxygen radical.
- the said bath having a pH falling within a range of from 2.5 to 4.5.
- the said bath having a pH falling within a range of from 2.5 to 4.5 at a temperature of about 50 C.
- the method of electrodepositing nickel comprising electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulfate. nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfate and nickel chloride, said solution having thallium sulfate dissolved therein in an amount falling within a range of from .1 gram per liter to 2 grams per liter, the
- said bath having a pH falling within a range of from 2.5 to 4.5
- the method of electrodepositlng nickel comprising electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from th group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfateand nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within a range of from .1 gram per liter to 2 grams per liter and an aryl organic compound containing the group where the sulfur is positive valent and attached to at least one oxysen radical, the said bath havterial selected from the group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and
- nickel plate comprising an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamaie and nickel chloride, a mixture of nickel sulfamate, nickel chloride andnickelsulfataandamixtureot a mixture of nickel sulfate and nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within arange of from .lgrampe'rlitertoilgramsperliterand anaryl organic compound containing the group n un consisting 0!
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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
Patented June 1946 Henry Brown, Detroit, Mich, mini); to The Udylite Corporation, Detroit, Mich" a corporation of Delaware No Drawing. Application August 27, 1942,
, Serial No. 456,362
This invention relates to the electrodeposition of nickel from an aqueous acid bath.
The object of this invention is the electrodeposition, of brilliant, highly lustrous ductile nickel plate having good bond to the basis metal. This object can be achieved by using a salt of the metal thallium, such as thallium sulfate, in an aqueous acid nickel bath together with an organic compound containing the linkage,
(an unsaturated carbon atom connected to a positive valent'sulfur atom), as illustrated by the aryl sulfonamidcs, aryl sulfonates, aryl sulflnates, etc. (see Table I) Tut: I
The most eflective type 0] compounds Optimum cone. in bath, g./l. o-Benzoic sulfimide '1-3' Benzene disulfonamide 0.25-1.0. Benzene sulfonamide 1-3 o-Toluene sulfonamide a- 1-2 p-Toluene sulfonamide 1-2.5 Diphenyl sulfone sulfonic acid 3 Naphthalene 1,5-disulfonic acid 3 Benzene m-disulfonic acid Benzene sulfinic acid .l-1.0 p-Toluene'sulilnic acid; .1-1.0
The combination of these brightening addition agents can best be used in the acid nickel baths of the Watts type and its modifications, using formates, citrates, etc., as well as boric acid as buifers. The most suitable nickel plating baths and their temperatures and preferred hydrogen ion concentration are given in Table 11. Small concentrations of citric acid especially, and also of formic, can often be used with the boric with benefit. At the higher temperatures, it is better to use the lower pH values. Nickel sulfamate can be used in concentrations up to saturation toreplace the nickel sulfate.
Any thallous (11+) salt soluble in the bath can be used, as for example, thallium sulfate, thallium chloride, thallium fluoride, thallium carbonate 6 Claims. (01. 204-43) and thallium hydroxide; the important thing is that in introducing the thallous ion into the bath, it is not desirable to introduce any harmful anion such as the nitrate ion into the nickel plating bath. The thallium is usually added to the bath in the form of thallium sulfate (T12SO4), as this is about the most readily available salt. In a warm Watts type of nickel bath, thallium sulfate alone in concentration of about 1 gram per liter and less brightens, in the high current density areas, e. g. 30 amps. per sq. ft. and higher, but the lower current densities are darkish. By increasing the concentration, the dark plate forming at the low current density areas, e. g. 5 amps. per sq. ft., extends to the higher current density areas. Lowering the pH tends to decrease this eflect, the thallium ion acting like the zinc ion and somewhat (though to a slighter extent) like the copper ion in the nickel bath in this respect. When, however, a
=c-s0- I type of compound (see Table I) such as saccharin or p-toluene sulfonamide, or 1,5-naphthalene disulfonic acid, is also added to the warm acid nickel bath containing the thallium sulfate, a brilliant, very ductile plate, having good bond to the basis metal, is obtained. That is, not only is the plate made brighter and over a wider current density range, but also the bond and ductility of the plate are improved. These organic compounds, thus, not only increase the tolerance of the bath to the thallium ion but also greatly enhance the brightness obtained.
Thus, on the addition of 1 gram per liter or less of thallium sulfate and 1.5 grams per liter of o-benzoyl suliimide and l'gram per liter of p-toluene sulfonamide to an acid nickel bath such as those listed in Table II. a brilliant, ductile plate is obtained over the entire plate except the lowest current density areas (e. g. 3 amps. per sq. ft. or less) which are white rather than brilliant. If the pH is too high, this white area extends to the higher current density areas. The thallium now acts very much like zinc and cadmium in the nickel bath (and not like copper). Too high concentration of thallium, like that of zinc and cadmium, causes the plate to be exceedingly brilliant but too hard and brittle and also makes the recesses dark; however, at optimum concentrations, the plate is both ductile and bright with a very good rate of brightening. A plate of .0005"-.001" of such nickel will have a brilliant luster even when plated over steel ilnished with a final grease emery. The best used with small amounts brightene'r.
pH values are from 2.5 to 4.5 at a temperature of about 50 C., with the widest bright plating range at the lower pH values. The presence of ammonium salts are not desirable, especially in warm baths, as they decreasethe ductility of the plate. In cold baths, a greater concentration of ammonium salts can be tolerated and less thallium must be used. Sodium, and es cially magnesium salts, are not nearly as cri lcal but in general, it is preferred not to have much of such salts present. I
The optimum concentration range for the thallium ion is from .24 g./l. to 1.6 g./l. depending on such conditions as pH of the bath, temperature, and the particular V =c-socompounds used. Thus, where the thallium ion is obtained from dissolving T12804- in the bath, the concentrations of thallium sulfate to be used with the compounds (Table I) is from 0.3 gram per liter to even 2 grams per liter depending on such conditions as the pH of the bath, temperature and the exact compounds used, etc. Also, if another brightener such as an unsaturated organic compound is also used in conjunction with the thallium and the I ;io compounds, the concentrations of thallium must always be less than with the compounds present, or else the plate will be of poor color and bond (unless, of course, the purpose is to obtain dark plate). In barrel plating even the cold double ammonium salt bath can be of thallium alone as The *o compounds listed in Table I are not the only compounds that show the beneficial eflects with the thallium ion but others also do, though they are not as effective, for example, benzene sulfonic acid (in large concentration), p-brom benzene sulfonic acid, diphenyl sulfonic acid, p-diphenyl benzene sulfonic acid and the naphthalene sulfonic acids.
The aryl sulflnic acids (containing the 4 group) e. g. benzene or toluene sulflnates are even more eflective than the aryl suli'onamides and aryl sulionates (containing the v 3SOr compounds. A very useful application or the sulfinic acids would be if by accident too much T1+ is added to a bath, the addition of even a small amount (.1 g./l. or less) of the sulflnate will counteract the harmful eifects immediately.
If certain substituting groups are present on the aryl ring, the beneficial effects produced by the I =o-so compounds will be minimized or even completely overshadowed; for example, hydroxy groups on the ring, nitro groups, amine groups and too many alkyl groups on the ring which introduces insolubility and colloidality. The hydroxy groups decrease the brightness but do not affect the ductility. The nitro groups on the ring tendto.
make the plate less ductile. An amine group on the ring in the case of a sulfonamide as with p-amino benzene sulfonamide completely nullifies its beneficial properties in that the plate produced by this compound is dark, fine-grained and brittle which the addition of o-benzoyl sulilmide does not remedy. On the other hand, theharmful effect 01' an amine group on the ring of an aryl sulfonic acid is greatly decreased through.
inner salt formation. However, where the amine groups exceed the sulfonic, then brittle grey plate is obtained as with 2,5-diamino benzene suli'onic acid. Also, p-nitro aniline o-sulfonic acid gives grey brittle plate.
The uniqueness of the group to negative valent sulfur, and the mechanism oi. its deposition. That the mechanism of the reduction is not necessarily of the simplest form is indicated by the fact that with s-naphthalene sulfonamide as the only organic compound in the bath, not only is the odor of naphthalene apparent at the cathode during the plating, but the analysis of the plate shows the presence of carbon as well as sulfur.
It seems that the process involving the reduction and hydrogenolysis or the sulfur of the positive valent compounds to a negative valence produces. in part at least, an inhibitor or poison of the nickel (as catalyst in perhaps many cases) in the reduction of (or addition of electrons to) Tl+ (and other active ions or active unsaturated organic materials). Hence, the plating bath is made more tolerant to larger concentrations of these active substances (see United 'States Patent 2,191,813). That is, the plating bath is made more tolerant to these substances because they are less easily reduced in the presence. of the hill)- compounds. The
=t io compounds thus regulate to varying extents the reduction or such active substance as T1 (and other active inorganic and organic materials) in the nickel bath. The difference in degree of eifectiveness of the various =i o compounds would seemto depend on the exact inhibitor formed and its amount and on its own particular eflect on the nickel plate.
The aryl sulflnic acids are evidently more easily reduced than the aryl sulfonamides and sul-- The use of a wetting agent to prevent pitting,
without materially affecting the brightness is desirable in baths using Tl+ and =i io compounds. Also, it is important to use the proper type of rubber in any rubber-lined tanks or other equipment used in contact with this type of plating solution or at least to check an unknown type for its eifect on the plate.
I claim:
1. A bath for electrodepositing ductile bright nickel plate comprising an aqueous acid nickel solution comprising essentially amaterial selected from the group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfate and nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within a range of from .1 gram per liter to 2 grams per liter and an aryl organic compound containing the group where the sulfur is positive valent and attached to at least one oxygen radical. the said bath having a pH falling within a range of from 2.5 to 4.5.
2. A bath for electrodepositing ductile bright 6 nickel sulfate and nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within a range of from .1 gram per liter to 2 grams per liter and an aryl organic compound containing the group where the sulfur is positive valent and attached to at least one oxygen radical. the said bath having a pH falling within a range of from 2.5 to 4.5 at a temperature of about 50 C.
3. The method of electrodepositing nickel comprising electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulfate. nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfate and nickel chloride, said solution having thallium sulfate dissolved therein in an amount falling within a range of from .1 gram per liter to 2 grams per liter, the
said bath having a pH falling within a range of from 2.5 to 4.5
4. The method of electrodepositlng nickel comprising electrodepositing nickel from an aqueous acid nickel solution comprising essentially a material selected from th group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfateand nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within a range of from .1 gram per liter to 2 grams per liter and an aryl organic compound containing the group where the sulfur is positive valent and attached to at least one oxysen radical, the said bath havterial selected from the group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and
nickel platecomprising an aqueous acid nickel solution comprising essentially a material selected from the group consisting of nickel sulfate, nickel chloride, a mixture of nickel sulfamaie and nickel chloride, a mixture of nickel sulfamate, nickel chloride andnickelsulfataandamixtureot a mixture of nickel sulfate and nickel chloride, said solution having dissolved therein thallium sulfate in an amount falling within arange of from .lgrampe'rlitertoilgramsperliterand anaryl organic compound containing the group n un consisting 0! nickel sulfate, nickel chloride, nickel sulfamate, a mixture of nickel sulfamate and nickel chloride, a mixture of nickel sulfamate, nickel chloride and nickel sulfate, and a mixture of nickel sulfate and nickel chloride, said solution having thallium sulfate unsolved therein in an amountfallingwithinarangeoffromaboutd gramperliterto2gramsperliter.
. mar
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US456362A US2402801A (en) | 1942-08-27 | 1942-08-27 | Electrodeposition of nickel |
GB8408/43A GB564232A (en) | 1942-08-27 | 1943-05-26 | Improvement in electrodeposition of nickel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US456362A US2402801A (en) | 1942-08-27 | 1942-08-27 | Electrodeposition of nickel |
Publications (1)
Publication Number | Publication Date |
---|---|
US2402801A true US2402801A (en) | 1946-06-25 |
Family
ID=23812460
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US456362A Expired - Lifetime US2402801A (en) | 1942-08-27 | 1942-08-27 | Electrodeposition of nickel |
Country Status (2)
Country | Link |
---|---|
US (1) | US2402801A (en) |
GB (1) | GB564232A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2513280A (en) * | 1945-10-31 | 1950-07-04 | Udylite Corp | Electrodeposition of nickel from an acid bath |
US6045682A (en) * | 1998-03-24 | 2000-04-04 | Enthone-Omi, Inc. | Ductility agents for nickel-tungsten alloys |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE931623C (en) * | 1950-09-27 | 1955-09-22 | W Kampschulte & Cie Dr | Process for the electrolytic production of high-gloss nickel coatings |
-
1942
- 1942-08-27 US US456362A patent/US2402801A/en not_active Expired - Lifetime
-
1943
- 1943-05-26 GB GB8408/43A patent/GB564232A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2513280A (en) * | 1945-10-31 | 1950-07-04 | Udylite Corp | Electrodeposition of nickel from an acid bath |
US6045682A (en) * | 1998-03-24 | 2000-04-04 | Enthone-Omi, Inc. | Ductility agents for nickel-tungsten alloys |
Also Published As
Publication number | Publication date |
---|---|
GB564232A (en) | 1944-09-19 |
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