US3666636A - Electrolytic codeposition of fine particles with copper - Google Patents
Electrolytic codeposition of fine particles with copper Download PDFInfo
- Publication number
- US3666636A US3666636A US834891A US3666636DA US3666636A US 3666636 A US3666636 A US 3666636A US 834891 A US834891 A US 834891A US 3666636D A US3666636D A US 3666636DA US 3666636 A US3666636 A US 3666636A
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- US
- United States
- Prior art keywords
- particles
- bath
- copper
- codeposition
- fine
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- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
Definitions
- This invention relates to the cathodic codeposition of multitudinous fine particles of bath-insoluble, non-conducting,inorganic and organic powders dispersed in aqueous acidic copper plating baths. More particularly this invention provides a means to improve and uniformly increase-the degree of codeposition of bath-dispersed inorganic and organic particles throughout the electrodeposited copper plate.
- the densely codeposited inorganic fine particles in the matrix of the electrodeposited copper can increase the tensile strength of the copper and its resistance to high temperature creep, and the inorganic and organic particles can greatly decrease the tendency for copper surfaces to stick and seize, yet without causing any appreciable loss in electrical or heat conductivity.
- these copper deposits can be used for various engineering purposes either as a composite copper plate on top of a basis metal, including wire or strip, or as an electroform.
- amines especially aliphatic amines, promote the codeposition of bath-insoluble, nonconducting particles dispersed (for example, by air agitation) in the acidlcopper electroplating baths.
- the most effective aliphatic amines for promoting the codeposition are'polyamines and polyimines such as ethylene diamine, diethylene .triamine, tetraethylenepentamine, polyethylene' imine, etc.
- the most effective aliphatic amines are the polyamines.
- 0.1 g./l. of ethylene diamine is at least as effective as 50 g./l. of ethyl amine in promoting the codeposition of the fine, insoluble particles on vertical surfaces.
- a concentration as low as 1 mg./l.- will make possible the codeposition of about 3.5 wt. percent of fine barium sulfate particles dispersed in the acid copper sulfate plating bath.
- the amines present in the bath practically no particles of the type shown above are codeposited on a vertical surface from acid copper plating baths. This is very unlike codeposition of these fine particles dispersed in acidic nickel baths where codeposition on vertical cathode surfaces occurs without the need of special organic additives.
- amino acids such as alanine, N,N-diethyl glycine, asparagine, N- methyl taurine, ethylene diamine tetra-acetic acid (-EDTA), and other amino acid and sequesterin agents, especially those with more than one amino group, give excellent results in promoting codeposition of fine, bathinsoluble, non-conducting particles in the acid copper plating baths.
- the bath-insoluble, fine powders are kept suspended and dispersed in the acid copper plating baths by means of mechanical or air agitation.
- air agitation is preferred, and of course, the air must not be contaminated with oil.
- Optimum codeposition results are usually reached with concentrations of particles of about 25 to 150 g./l., though higher concentration produce no troubles, and with some particles such as barium sulfate and strontium sulfate, concentrations of 500 g./l. can be used. It is important that the fine particles are clean. For example, some commercial grades of talc (a hydrous magnesium silicate) had to be washed with alcohol or acetone before the best codeposition results could be obtained.
- the particle sizes may be from about 10 microns down to 0.01 micron for the inorganic particles with the preferred range of about 5 microns down to 0.01 micron. With particles much greater than about 10 microns, roughness from the inorganic particles is obtained on areas on which settling can occur.
- Some agglomerated powders may have apparent larger particle size than the preferred size, but with agitation in the copper bath, the larger agglomerates are usually broken down and particles of about 5 microns diameter and under may then be the predominant size. With organic resin powders the particle size may be as high as 50 microns size and still codeposit smoothly on vertical surfaces.
- the maximum codeposition was about 5.5 wt. percent on vertical surfaces with higher concentrations on settling surfaces.
- Example I if fine zirconium oxide powder is used in concentrations of about 1-30() g./l. instead of the barium sulfate powder, a maximum of about 6 wt. percent was obtained on vertical surfaces. With fine titania powder the maximum codeposition on vertical surfaces was about 4%.
- Cerium oxide fine powder -150 Cerium oxide fine powder -150.
- the maximum codeposition was about 3.5 wt. percent on vertical surfaces. If fine silicon carbide powder (0.1 to 7 microns) is used instead of the cerium oxide in Example II, the maximum codeposition on vertical surfaces was around 4 Wt. percent, but on settling surfaces it was much higher.
- Example III The procedure of Example I is repeated with the exception that finely divided polyvinyl chloride (PVC), of a particle size Within the range of about l-20 microns, is substituted for the barium sulfate. Using this procedure, comparable results are obtained.
- PVC polyvinyl chloride
- the codeposition of the same dispersed inorganic particles in general proceeds very well, however, the addition of the amines or amino acids maximizes the codeposition rate.
- the codeposition proceeds very readily in the acidic copper plating baths, and it would seem that there is no need to use the amines or amino acid promoters. Nevertheless with these promoters present, lower concentrations of these fine particles may be used which in these cases tend to minimize roughness troubles. That is, with these powders it is difficult to get smooth plate with their codeposition, though with the use of the promoters and with the use of the finest particles, the plate is them much smoother. With fine particles of such powders as barium sulfate, titania, alumina, silicon carbide, the plates are very smooth.
- mixtures of particles for codeposition are desirable, for example, barium sulfate with strontium sulfate, mica with barium sulfate, graphite or molybdenum sulfide with barium sulfate, or strontium sulfate.
- Surfactants and brightening agents may be present in the acid copper plating baths which do not appreciably affect the ductility and adhesion of the deposits.
- the surfactants should not cause overfoaming, and preferably an eight carbon chain length should be used, such as sodium Z-ethyl hexyl sulfate, and sodium n-oetyl sulfonate.
- the most effective amine compounds for promoting codeposition of particles are those where the amino group is attached to an aliphatic group, that is, the aliphatic amino compounds, and this designation would apply even if an aromatic ring is in the molecule, as in benzyl amine.
- the most elfective amino compounds are the polyamino or polyimine compounds such as ethylene diamine, diethylene triamine, tetraethylene pentarnine, etc.
- the aliphatic amino acids may have carboxyl groups as in alanine and EDTA, sulfonic groups as in N-methyl taurine and phosphonic groups as in N(CH PO (OH)
- Saran is intended to refer to polyvinylidene chlorides
- nylon is intended to refer to polyamides
- Teflon and Kel-F are intended to refer to fluorocarbon resins, such as the polytetrafluoroethylenes.
- bath-insoluble particles are barium sulfate particles in concentrations of at least about 1 gram/liter and of particle size less than about 5 microns.
- bath-insoluble particles are silicon carbide particles in concentrations of at least about 1 gram/liter and par-,
- ticle size less than about 7 microns.
- bath-insoluble particles are aluminum oxide particles in concentrations of at least about 1 gram/liter and particle size less than about 5 microns.
- bath-insoluble particles are polyvinylchloride (PVC) "particles in concentrations of at least about 1 gram/liter and particle size less than about 50 microns.
- PVC polyvinylchloride
- An electroplating bath comprising anaqueous acidic copper electroplating bath containing dispersed therein fine bath-insoluble, non-conducting particles and said cop per bath containing dissolved therein additionally atleast one organic compound which contains at least one aliphatic amino group.
- a bath in accordance with claim 9 wherein said amino compound is tetraethylene pentarnine in a concentration greater than about 1 milligram per liter.
- a bath in accordance with claim 9 wherein said concentration amino compound is an amino acid in a greater than about 0.1 gram/liter.
- bath-insoluble particles are barium sulfate particles fin concentrations of at least about 1 gram/liter and of article size less than about 5 microns.
- bath-insoluble particles are boron particles in concentra? tions of at least about 1 gram per liter and pai ticle sizie less:
- a bath in accordancewith claim 9 wheri i fsaiti bath-insoluble particles are sil icon carbide particles concentrations of at least about :1 gram/liter a'ridfpafticle size less than about 7 microns; j
- a bath in accordance withjclaim 9 iwhereinlsaidl bath-insoluble particles are polyvinylchloride ⁇ Pl/C particles in concentrations of at least about 1 ;gram/liter.
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US83489169A | 1969-06-19 | 1969-06-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3666636A true US3666636A (en) | 1972-05-30 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US834891A Expired - Lifetime US3666636A (en) | 1969-06-19 | 1969-06-19 | Electrolytic codeposition of fine particles with copper |
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US (1) | US3666636A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3884772A (en) * | 1971-09-25 | 1975-05-20 | Furukawa Electric Co Ltd | Method for producing a heat exchanger element |
US3898148A (en) * | 1970-11-05 | 1975-08-05 | Ahmad Sam | Apparatus for making abrasive articles |
US3945893A (en) * | 1972-12-30 | 1976-03-23 | Suzuki Motor Company Limited | Process for forming low-abrasion surface layers on metal objects |
US4010005A (en) * | 1973-06-23 | 1977-03-01 | Mitsui-Anaconda Electro Copper Sheet Co., Ltd. | Copper foil having bond strength |
US4139424A (en) * | 1972-06-02 | 1979-02-13 | Montblanc-Simplo Gmbh | Socket structure for the ball of a ball point pen refill |
US4267476A (en) * | 1979-06-25 | 1981-05-12 | Westinghouse Electric Corp. | Metal-solid lubricant brushes for high-current rotating electrical machinery |
DE3121826A1 (en) * | 1981-06-02 | 1983-01-13 | Robert Bosch Gmbh, 7000 Stuttgart | Method of depositing a copper/phosphorus layer on copper materials and application of the method |
US4601795A (en) * | 1985-03-27 | 1986-07-22 | The United States Of America As Represented By Secretary Of Interior | Alloy coating method |
US5512163A (en) * | 1992-06-08 | 1996-04-30 | Motorola, Inc. | Method for forming a planarization etch stop |
US5611905A (en) * | 1995-06-09 | 1997-03-18 | Shipley Company, L.L.C. | Electroplating process |
WO2015091863A1 (en) * | 2013-12-19 | 2015-06-25 | Schlenk Metallfolien Gmbh & Co. Kg | Method for electrolytic surface modification of flat metal workpieces in copper-sulfate treatment liquid containing sulfate-metallates |
-
1969
- 1969-06-19 US US834891A patent/US3666636A/en not_active Expired - Lifetime
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898148A (en) * | 1970-11-05 | 1975-08-05 | Ahmad Sam | Apparatus for making abrasive articles |
US3884772A (en) * | 1971-09-25 | 1975-05-20 | Furukawa Electric Co Ltd | Method for producing a heat exchanger element |
US4139424A (en) * | 1972-06-02 | 1979-02-13 | Montblanc-Simplo Gmbh | Socket structure for the ball of a ball point pen refill |
US3945893A (en) * | 1972-12-30 | 1976-03-23 | Suzuki Motor Company Limited | Process for forming low-abrasion surface layers on metal objects |
US4010005A (en) * | 1973-06-23 | 1977-03-01 | Mitsui-Anaconda Electro Copper Sheet Co., Ltd. | Copper foil having bond strength |
US4267476A (en) * | 1979-06-25 | 1981-05-12 | Westinghouse Electric Corp. | Metal-solid lubricant brushes for high-current rotating electrical machinery |
DE3121826A1 (en) * | 1981-06-02 | 1983-01-13 | Robert Bosch Gmbh, 7000 Stuttgart | Method of depositing a copper/phosphorus layer on copper materials and application of the method |
US4601795A (en) * | 1985-03-27 | 1986-07-22 | The United States Of America As Represented By Secretary Of Interior | Alloy coating method |
US5512163A (en) * | 1992-06-08 | 1996-04-30 | Motorola, Inc. | Method for forming a planarization etch stop |
US5611905A (en) * | 1995-06-09 | 1997-03-18 | Shipley Company, L.L.C. | Electroplating process |
WO2015091863A1 (en) * | 2013-12-19 | 2015-06-25 | Schlenk Metallfolien Gmbh & Co. Kg | Method for electrolytic surface modification of flat metal workpieces in copper-sulfate treatment liquid containing sulfate-metallates |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
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AS | Assignment |
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
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AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |