US2057476A - Electrodeposition of rhodium - Google Patents
Electrodeposition of rhodium Download PDFInfo
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- US2057476A US2057476A US2057476DA US2057476A US 2057476 A US2057476 A US 2057476A US 2057476D A US2057476D A US 2057476DA US 2057476 A US2057476 A US 2057476A
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- Prior art keywords
- rhodium
- plating
- metal
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- ammonium
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- 239000010948 rhodium Substances 0.000 title description 32
- 229910052703 rhodium Inorganic materials 0.000 title description 32
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title description 32
- 238000004070 electrodeposition Methods 0.000 title description 3
- 238000007747 plating Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- -1 rhodium ammonium Oxalate Chemical compound 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 230000001464 adherent effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 150000001559 benzoic acids Chemical class 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- DMCMMSCDJUQSIK-UHFFFAOYSA-N N.[Rh+3] Chemical compound N.[Rh+3] DMCMMSCDJUQSIK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DLBDQPTYDPUKHZ-UHFFFAOYSA-K [Rh+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [Rh+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O DLBDQPTYDPUKHZ-UHFFFAOYSA-K 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229940001447 lactate Drugs 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000725101 Clea Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000344110 Erysimum rhodium Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 229940050390 benzoate Drugs 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229940001468 citrate Drugs 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- QNEIVTNMGMUAEX-UHFFFAOYSA-H oxalate rhodium(3+) Chemical compound [Rh+3].[Rh+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O QNEIVTNMGMUAEX-UHFFFAOYSA-H 0.000 description 1
- 239000010957 pewter Substances 0.000 description 1
- 229910000498 pewter Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
-
- 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
Definitions
- This which forms a salt with the above metal may form of bath in order to be at all effective conbe employ d in connection with said metal for tains a high concentration of free sulfuric acid furnishing e e c on to he ec y e. 10 with the result, that during electrolysis a spray
- Weak acids W comprise P b y c ds of this acid is given off thereby rendering the o an acidity of that of tartaric.
- o i c r c plating operation a, possible ur e f danger t benzoic, lactic and like organic acids and also the plater.
- aid a id spray may phosphoric and similar weak inorganic acids.
- rhodium resides in the corrosive action of-the free acid ammonium'lactate and the likeon base metal cathodes which must not there- A peculiarity of these baths which t y far re be i d r left standing in t t cilitates the deposition of the metal therefrom unless the current is on.
- the deand enhances the emflency 0f the electrolysis i posit obtained with this type of bath, is not, the feet that they may be p y wi h great always bright and coherent and in order t success either in an acid, neutral or alkaline tain any satisfactory deposit, very careful regcmditmn-
- the P p D f e bath if it is ulation of the plating conditions must be to be alkaline. may be provided by a din a i t m certain amount of a weak or strong alkali to an si th t of t above precious metal and aqueous solution of the simple or double salts its salts is very high, it can be appreciated that of Said Precious metal.
- the electrolyaqueous baths containing said metal Preferably,- the electrolyaqueous baths containing said metal.
- m the sis lS effected with an inert anode such as platiform of Salts with weak acids nulm ofi a: size sugflentttlo :IEVEIW high electrli); It is comm an b ca ress ance. e ca.
- 0 e o course may provide a g gzgg gg fi mf sfifigx any metal upon which it IS desired to plate, such deposits of rhodium without a careful and exas sflver gold platmum copper brass German pensive control of the plating operation and sllver' pewter and the like of course the I cathode, as in general plating should be clea without subjecting the operator to dangerou and smooth to facilitate the production 0 and disagreeable working conditions.
- the concentration of the metal ions in soluvide a S mp e. eminent. relatively inexpensive tion may vary depending upon the conditions of process for electrolytically obtaining rhodium in temperature, electrical pressure andv cathode dense deposits of a high clarity andbrilliance. current density but need not be high to secure 55 other and further important objects of this good deposits.
- the anode cur 55 rent density is not of great importance but should be less than that 01' the cathode.
- An aqueous solution of a salt of rhodium with a weak acid such' as rhodium oxalate, citrate, tartrate, benzoate, lactate, phosphate or the like or of a double salt of rhodium such as rhodium ammonium oxalate, rhodium ammonium citrate, rhodium ammonium benzoate or the like containing about 1 gram of rhodium per liter of solution is electrolyzed with a platinum anode and a smooth copper cathode which it is desired to plate at a voltage of about 4 volts and a cathodic current density of about 2 amperes per sq. inch.
- the electrolyte is maintained at a temperature of between 60" and 90 C. during the electrolysis. In this way dense, brilliant deposits of rhodium are obtained. 0! course, the usual D. C. current is used.
- the electrolyte may be acid, neutral or alkaline which conditions may be obtained by the use of the proper amount of a suitable acid or alkali. Generally an alkaline electrolyte is preferable. If, however, an acid bath is used, it is obvious that the acidity will not be made so high as to cause deposition of hydrogen to the exclusion of the metal. Likewise, excessive alkalinity should be avoided. These are however obvious details which will be varied at the option of the skilled plater under diiierent desired conditions of plating.
- a process of depositing an adherent coating or layer of rhodium which comprises passing a D. C. current through an aqueous bath containing a rhodium lactate compound.
- a process of depositing an adherent layer or coating of rhodium which comprises passing a D. C. current through a solution containing rhodium ammonium lactate.
- a process of depositing an adherent layer or coating of rhodium which comprises passing a D. C. current through an aqueous alkaline bath containing a rhodium lactate compound.
- a process of depositing an adherent layer or coating of rhodium which comprises passing a D. C. current through an aqueous alkaline bath containing rhodium ammonium lactate.
- a process 01' electroplating rhodium which comprises passing a D. C. current at about 4 volts and a cathode current density of about 2. amperes per sq. inch through a rhodium lactate solution maintained at a temperature of about 60 to 90 C.
- a process of electrodepositing rhodium which comprises passing a D. C. current of about 4 volts at a cathodic current density of 2 amperes per sq. inch from a platinum anode through an alkaline rhodium ammonium lactate solution containing about 1 gram of rhodium per liter of solution.
- An electrolyte for depositing rhodium which contains a rhodium lactate compound.
- An electrolyte for electrodepositing coatings oi, rhodium which comprises an alkaline aqueous solution of rhodium lactate.
- An electrolyte for depositing rhodium which contains rhodium ammonium lactate.
- An electrolyte for electrodepositing coatings of rhodium which comprises an alkaline aqueous solution of rhodium ammonium lactate.
- a process for plating rhodium which comprises passing a direct current through an aqueous bath containing rhodium combined with an organic acid selected from the group consisting of tartaric, oxalic, citric, lactic and benzoic acids.
- a process for plating a brilliant and dense layer of rhodium which comprises passing a D. C. current through an aqueous bath containing rhodium, said rhodium being combined with an organic acid selected from the group consisting of tartaric, oxalic, citric, lactic, and benzoic acids, and maintaining the temperature between about 60 to 90 C. during the plating operation.
- a process for plating a brilliant and dense layer of rhodium which comprises passing a D. C. current through an aqueous bath containing rhodium, said rhodium being in the form of a complex compound with an organic acid selected from the group consisting of tartaric, oxalic, citric, lactic and benzoic acids, and a cation selected from the class consisting of the alkali metals and ammonium, and maintaining the temperature of the bath between about 60 to 90 C. during theplating operation.
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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
SATE i PT ensure I ELECTRODEPOSITION or nnonrcm Sigmund Cohn, New York, N. Y., assignor to Baker 8: Company, Inc, Newark, N. .L, a corporation of New Jersey No Drawing. Original application March 31,
1931, Serial No. 526,786. Divided and this application November 9, 1935, Serial No. 49,029
13 Claims. (El. Zoo-1) This invention relates to a process for the invention will become apparent from the followelectrolytie deposition of rhodium and to a bath ing description and appended claims. for efieeting said deposition. The plating baths with which my process is -The precious metal, rhodium, according to operative, as stated above, comprise essentially 5 general practice is usually plated from strongly aqueous baths containing the precious metal 5 acid aqueous'baths containing said metal in the rhodium in the form of salts of weak acids. form of salts of strong mineral acids, the sulfate Any weak acid whether organic or in n c. bath being that most usually employed. This which forms a salt with the above metal may form of bath in order to be at all effective conbe employ d in connection with said metal for tains a high concentration of free sulfuric acid furnishing e e c on to he ec y e. 10 with the result, that during electrolysis a spray These Weak acids W comprise P b y c ds of this acid is given off thereby rendering the o an acidity of that of tartaric. o i c r c plating operation a, possible ur e f danger t benzoic, lactic and like organic acids and also the plater. In addition, aid a id spray may phosphoric and similar weak inorganic acids. 15 attack base metal objects adjacent to the plating Moreover, Said acids y b C m ed wi h Said tank. While this difiiculty could be overcome by metal either as simple salts or as complex salts providing a hood over the plating tank, the cost With alkali metals and ammonium as for incident. to this construction which must be acid example rhodium ammonium Oxalate, od um proof is a drawback to this process. Still ammonium r e. rhodium ammonium taranother drawback to the use of the above bath irate. rhodium ammonium n oate. rhodium resides in the corrosive action of-the free acid ammonium'lactate and the likeon base metal cathodes which must not there- A peculiarity of these baths which t y far re be i d r left standing in t t cilitates the deposition of the metal therefrom unless the current is on. Furthermore, the deand enhances the emflency 0f the electrolysis i posit obtained with this type of bath, is not, the feet that they may be p y wi h great always bright and coherent and in order t success either in an acid, neutral or alkaline tain any satisfactory deposit, very careful regcmditmn- The P p D f e bath, if it is ulation of the plating conditions must be to be alkaline. may be provided by a din a i t m certain amount of a weak or strong alkali to an si th t of t above precious metal and aqueous solution of the simple or double salts its salts is very high, it can be appreciated that of Said Precious metal. The aiiidity 0f the ath in view of the many objections to the use of the on the other h may be controlled by reguabove bath for plating these metals, the plating lated additions of free, Strong Weak acidsf d metal on commercial scale hasyhardly Obviously, this feature of my invention greatly bt i any degree of importance decreases the necessary skill required by the I have now found that the many objections to workmen operating the plating Processthe plating of aid precious t 1 in the No highly acid proof form of tank such for strongly a id bath above mentioned, can be Web instance, as fused silica, is necessary for concome and clear, brilliant deposits of said metal fining t plating soluti Since t corrosive obtained without a careful manipulation of the action of the same cpntmry to that of the $111- 40 plating process, by depositing said metal from photo bath, is small. Preferably,- the electrolyaqueous baths containing said metal. m the sis lS effected with an inert anode such as platiform of Salts with weak acids nulm ofi a: size sugflentttlo :IEVEIW high electrli); It is comm an b ca ress ance. e ca. 0 e o course may provide a g gzgg gg fi mf sfifigx any metal upon which it IS desired to plate, such deposits of rhodium without a careful and exas sflver gold platmum copper brass German pensive control of the plating operation and sllver' pewter and the like of course the I cathode, as in general plating should be clea without subjecting the operator to dangerou and smooth to facilitate the production 0 and disagreeable working conditions.
clear, dense, brilliant deposits. It s a further object of this invention to The concentration of the metal ions in soluvide a S mp e. eminent. relatively inexpensive tion may vary depending upon the conditions of process for electrolytically obtaining rhodium in temperature, electrical pressure andv cathode dense deposits of a high clarity andbrilliance. current density but need not be high to secure 55 other and further important objects of this good deposits. As a general rule, the anode cur 55 rent density is not of great importance but should be less than that 01' the cathode.
It is also not necessary with the baths of my invention to agitate the solution during plating or provide any other means to efiect depolarization of the electrodes, although a more even plate may be obtained if this is done.
The following example will serve to more fully illustrate the nature of my invention, but it should be borne in mind that my process is not limited to the specific conditions recited therein.
An aqueous solution of a salt of rhodium with a weak acid such' as rhodium oxalate, citrate, tartrate, benzoate, lactate, phosphate or the like or of a double salt of rhodium such as rhodium ammonium oxalate, rhodium ammonium citrate, rhodium ammonium benzoate or the like containing about 1 gram of rhodium per liter of solution is electrolyzed with a platinum anode and a smooth copper cathode which it is desired to plate at a voltage of about 4 volts and a cathodic current density of about 2 amperes per sq. inch. The electrolyte is maintained at a temperature of between 60" and 90 C. during the electrolysis. In this way dense, brilliant deposits of rhodium are obtained. 0! course, the usual D. C. current is used.
As stated above, the electrolyte may be acid, neutral or alkaline which conditions may be obtained by the use of the proper amount of a suitable acid or alkali. Generally an alkaline electrolyte is preferable. If, however, an acid bath is used, it is obvious that the acidity will not be made so high as to cause deposition of hydrogen to the exclusion of the metal. Likewise, excessive alkalinity should be avoided. These are however obvious details which will be varied at the option of the skilled plater under diiierent desired conditions of plating.
' It can thus be seen that I have provided a novel and highly efiicient process for obtaining dense, brilliant deposits of rhodium.
Various details of my process may of course be varied and I therefore do not intend to be limited in the scope of my invention except as necessitated by the prior art.
This application is filed as a division of my application for Electrodeposition of rhodium, Ser. No. 526,786, filed March 31, 1931.
What I claim is:
1. A process of depositing an adherent coating or layer of rhodium which comprises passing a D. C. current through an aqueous bath containing a rhodium lactate compound.
2. A process of depositing an adherent layer or coating of rhodium which comprises passing a D. C. current through a solution containing rhodium ammonium lactate.
3. A process of depositing an adherent layer or coating of rhodium which comprises passing a D. C. current through an aqueous alkaline bath containing a rhodium lactate compound.
4. A process of depositing an adherent layer or coating of rhodium which comprises passing a D. C. current through an aqueous alkaline bath containing rhodium ammonium lactate.
5. A process 01' electroplating rhodium which comprises passing a D. C. current at about 4 volts and a cathode current density of about 2. amperes per sq. inch through a rhodium lactate solution maintained at a temperature of about 60 to 90 C. I
6. A process of electrodepositing rhodium which comprises passing a D. C. current of about 4 volts at a cathodic current density of 2 amperes per sq. inch from a platinum anode through an alkaline rhodium ammonium lactate solution containing about 1 gram of rhodium per liter of solution.
7. An electrolyte for depositing rhodium which contains a rhodium lactate compound.
8. An electrolyte for electrodepositing coatings oi, rhodium which comprises an alkaline aqueous solution of rhodium lactate.
9. An electrolyte for depositing rhodium which contains rhodium ammonium lactate.
10. An electrolyte for electrodepositing coatings of rhodium. which comprises an alkaline aqueous solution of rhodium ammonium lactate.
11. A process for plating rhodium which comprises passing a direct current through an aqueous bath containing rhodium combined with an organic acid selected from the group consisting of tartaric, oxalic, citric, lactic and benzoic acids.
12. A process for plating a brilliant and dense layer of rhodium, which comprises passing a D. C. current through an aqueous bath containing rhodium, said rhodium being combined with an organic acid selected from the group consisting of tartaric, oxalic, citric, lactic, and benzoic acids, and maintaining the temperature between about 60 to 90 C. during the plating operation.
13. A process for plating a brilliant and dense layer of rhodium, which comprises passing a D. C. current through an aqueous bath containing rhodium, said rhodium being in the form of a complex compound with an organic acid selected from the group consisting of tartaric, oxalic, citric, lactic and benzoic acids, and a cation selected from the class consisting of the alkali metals and ammonium, and maintaining the temperature of the bath between about 60 to 90 C. during theplating operation.
SIGMUND COHN.
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US2057476A true US2057476A (en) | 1936-10-13 |
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US2057476D Expired - Lifetime US2057476A (en) | Electrodeposition of rhodium |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2458504A (en) * | 1944-03-06 | 1949-01-11 | Poor & Co | Reaction products of gelatin and aldonic acids and process for making same |
-
0
- US US2057476D patent/US2057476A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2458504A (en) * | 1944-03-06 | 1949-01-11 | Poor & Co | Reaction products of gelatin and aldonic acids and process for making same |
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