US2831803A - Electro-deposition of alloys - Google Patents
Electro-deposition of alloys Download PDFInfo
- Publication number
- US2831803A US2831803A US625208A US62520856A US2831803A US 2831803 A US2831803 A US 2831803A US 625208 A US625208 A US 625208A US 62520856 A US62520856 A US 62520856A US 2831803 A US2831803 A US 2831803A
- Authority
- US
- United States
- Prior art keywords
- indium
- lead
- bath
- controlling agent
- hydrazine
- 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
Links
- 229910045601 alloy Inorganic materials 0.000 title description 7
- 239000000956 alloy Substances 0.000 title description 7
- 238000004070 electrodeposition Methods 0.000 title description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 22
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 20
- 229910052738 indium Inorganic materials 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910000978 Pb alloy Inorganic materials 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical class OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- LKRFCKCBYVZXTC-UHFFFAOYSA-N dinitrooxyindiganyl nitrate Chemical class [In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LKRFCKCBYVZXTC-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- DGAHKUBUPHJKDE-UHFFFAOYSA-N indium lead Chemical compound [In].[Pb] DGAHKUBUPHJKDE-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Definitions
- 2,751,341 it has been proposed to effect electrodeposition of lead or a lead alloy, or of antimony or an antimony alloy, from a solution containing an alkali metal salt of ethylenediaminetetraacetic acid, which is said to give a smooth, lustrous, even, bright deposit of metal; electrodeposition of lead-indium alloys from such a solution is said to give most satisfactory results when the bath is operated with a cathode current density of 10- 20' amperes per square foot.
- the present invention is concerned with electrodeposition of alloys of lead and indium particularly at high cathode current densities, up to 120 amperes per square foot.
- controlling agents ethylenediaminetetraacetic acid which for the sake of brevity is hereinafter sometimes called enta.
- Other controlling agents suitable for our purpose are the propylenediaminetetraacetic acids and cyclohexane 1.2 diaminotetraacetic acid.
- the baths in which these controlling agents are used are preferably neutral, or nearly neutral, the controlling agents being then in fact present in the form of salts, which may be the sodium, potassium or ammonium salts, or mixtures of such salts.
- 2' zine in a solution containing enta is preferentially oxidised by an insoluble anode, thus minimising the destruction of enta.
- the decomposition products of hydrazine are not harmful in any way in contrast to the case when enta alone is oxidised. Hydrazine also destroys any formaldehyde which would otherwise gradually accumulate in the electrolyte, despite the greatly retarded oxidation of enta. It is therefore possible by the addition of hydrazine to our electrolytes to maintain the meta ion concentration at the desired value by the periodic use of insoluble anodes without excessive loss of controlling agent by oxidation.
- Electrolytes used in the practice of the present invention thus contain compounds of lead and indium, one of the above mentioned controlling agents, and also hydrazine. With advantage they also contain citric acid (or alternatively tartaric acid), a small proportion of gelatin, triethylenetetramine (or alternatively diethylenetriamine or ethylenediamine), and ammonium chloride.
- Citric acid 45-55 Hydrazine 9.5-625 Ammonium chloride 5-30 Gelatin 0.2-2.0 Triethylenetetramine 1-10 If tartaric acid is employed in place of citric acid, the
- the lead and indium may be introduced into the electrolyte as the hydroxide, sulphate, acetate, chloride or carbonate. Lead and indium nitrates may also be used but we prefer to exclude the presence of the nitrate ion from our electrolytes because of its action as a cathode inhibitor with respect to the deposition of indium.
- the bath is adjusted to have a pH value in the range 5.0 to 7.0, 6.0 being preferred, and is operated with an insoluble anode (and preferably also with a soluble anode) at a temperature in the range 45 to 70 C., about 60 C. being preferred, and with a current density in the range 60 to amperes/square foot.
- the leadindium alloy deposited contains from about 7% to about 10% indium, depending upon the precise operating conditions used. For example, raising the temperature will decrease the indium content of the alloy deposited. An increase in pH value will increase the indium content of the alloy deposited, as also will an increase in current density.
- the constituents of the bath other than lead and indium need only be added as often as is necessary to combat the effects of drag-out.
- the rate of decomposition of the controlling agent is reduced to a very small value.
- soluble anodes In order to maintain the metal content of the bath, it is preferable to use soluble anodes together with the insoluble anodes.
- the soluble anodes may be of pure indium and pure lead, or of the appropriate indium-lead alloy.
- the insoluble anodes are preferably of graphite.
- a rotating or other type of commutator may be employed, which is adjustable so that the times for which the respective anodes are connected and the frequency with which they are changed over may be varied as desired, to maintain the correct metal balance in the bath.
- the bath contains also a polyarnine selected from the group consisting of triethylenetetramine, diethylenetriamine and ethylenediamine.
- the bath contains the following constituents in quantities within the respective ranges stated, in grams per litre: lead 15 to 25; indium 10 to 15; a water-soluble salt of ethylenediaminetetraacetic acid 85 to 115; an organic acid selected from the group consisting of citric acid to and tartaric acid 35 to 45; hydrazine 9.5 to 62.5; ammonium chloride 5 to 30; gelatin 0.2 to 2 and triethylenetetramine 1 to 10.
Landscapes
- 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)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB354644X | 1955-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2831803A true US2831803A (en) | 1958-04-22 |
Family
ID=10378017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US625208A Expired - Lifetime US2831803A (en) | 1955-12-02 | 1956-11-30 | Electro-deposition of alloys |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US2831803A (de) |
| BE (1) | BE553110A (de) |
| CH (1) | CH354644A (de) |
| DE (1) | DE1053275B (de) |
| FR (1) | FR1160985A (de) |
| GB (1) | GB799280A (de) |
| NL (1) | NL111650C (de) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3067110A (en) * | 1961-03-23 | 1962-12-04 | Vandervell Products Ltd | Electrodeposition |
| WO1983003266A1 (en) * | 1982-03-15 | 1983-09-29 | Gsp Metals Chemicals Corp | Chelating metals |
| US9435376B2 (en) | 2014-01-31 | 2016-09-06 | Miba Gleitlager Austria Gmbh | Multi-layered plain bearing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2751341A (en) * | 1952-06-03 | 1956-06-19 | Gen Motors Corp | Electrodeposition of lead and lead alloys |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE731102C (de) * | 1941-12-13 | 1943-02-03 | Dr Herbert Brintzinger | Verfahren zur Erzeugung metallischer UEberzuege |
| US2750333A (en) * | 1952-06-03 | 1956-06-12 | Gen Motors Corp | Electrodeposition of antimony and antimony alloys |
-
0
- BE BE553110D patent/BE553110A/xx unknown
- NL NL111650D patent/NL111650C/xx active
-
1955
- 1955-12-02 GB GB34550/55A patent/GB799280A/en not_active Expired
-
1956
- 1956-11-30 CH CH354644D patent/CH354644A/fr unknown
- 1956-11-30 US US625208A patent/US2831803A/en not_active Expired - Lifetime
- 1956-11-30 DE DEV11591A patent/DE1053275B/de active Pending
- 1956-11-30 FR FR1160985D patent/FR1160985A/fr not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2751341A (en) * | 1952-06-03 | 1956-06-19 | Gen Motors Corp | Electrodeposition of lead and lead alloys |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3067110A (en) * | 1961-03-23 | 1962-12-04 | Vandervell Products Ltd | Electrodeposition |
| WO1983003266A1 (en) * | 1982-03-15 | 1983-09-29 | Gsp Metals Chemicals Corp | Chelating metals |
| US9435376B2 (en) | 2014-01-31 | 2016-09-06 | Miba Gleitlager Austria Gmbh | Multi-layered plain bearing |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1160985A (fr) | 1958-08-18 |
| GB799280A (en) | 1958-08-06 |
| NL111650C (de) | |
| CH354644A (fr) | 1961-05-31 |
| BE553110A (de) | |
| DE1053275B (de) | 1959-03-19 |
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