US3414427A - Coating catalyst - Google Patents

Coating catalyst Download PDF

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Publication number
US3414427A
US3414427A US453497A US45349765A US3414427A US 3414427 A US3414427 A US 3414427A US 453497 A US453497 A US 453497A US 45349765 A US45349765 A US 45349765A US 3414427 A US3414427 A US 3414427A
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US
United States
Prior art keywords
solution
acetone
plating
complex
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US453497A
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English (en)
Inventor
Levy Joseph Peppo
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BAE Systems PLC
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Sperry Rand Ltd
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Assigned to BRITISH AEROSPACE PUBLIC LIMITED COMPANY reassignment BRITISH AEROSPACE PUBLIC LIMITED COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SPERRY LIMITED
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions

Definitions

  • the invention relates to processes for plating surfaces with metals.
  • a surface is coated with metal by immersing it in a plating bath containing a salt of the metal and a suitable reducing agent.
  • the solution is unstable or metastable, and the surface to be plated is pretreated with a catalyst for the reduction reaction so that the metal is reduced and deposited on the treated surface, and only slowly, or not at all,- on the walls of the plating bath or homogeneously throughout the solution.
  • An example of such a chemical reduction plating process is plating with nickel from a solution containing soluble nickel salts and hypophosphites.
  • the present invention utilises a catalyst solution which gives a striking improvement in this respect.
  • a chemical reduction plating process includes the step of treating the surface to be plated before immersion in the plating bath with a catalyst comprising a solution of a complex of palladium chloride with hydrogen halide and water, dissolved in an organic solvent.
  • the hydrogen halide is preferably hydrogen chloride.
  • the treatment is more effective if the surface to be plated is preheated, being brought before treatment to a temperature not substantially below the boiling point of the highest boiling constituent of the catalyst solvents.
  • the treatment is of the nature of a quenching step.
  • the composition of the solution may be chosen with reference to the highest temperature at which heat treatment may be carried out without damaging or distorting the article to be plated.
  • glass or metal may be treated with a solution containing relatively high boiling point solvents whereas for plastics which cannot be heated substantially above room temperature the solvent should contain more volatile constituents, for example acetaldehyde, which boils at approximately room temperature.
  • the surface to be plated is preferably again heated to a temperature not substantially below the boiling point of the highest boiling constituent of the catalyst solvents.
  • the treatment with the catalyst solution is preferably repeated a number of times, being carried out, for example, from three to six times before plating.
  • the treatment is applicable to plating on both metals and non-metals, and in particular to plating with nickel or cobalt from a hypophosphite bath, but the treatment with the catalyst solution may be employed in any chemical reduction platin process where deposition is catalysed by the presence of palladium compounds.
  • Preferred concentrations of the catalyst solution are those containing up to one gram per litre of palladium chloride, and a solution containing 0.2 gram per litre has proved generally satisfactory.
  • Acetone is a suitable organic solvent for the palladium chloride complex in many cases, or where boiling point of acetone is not ideal for the proposed condition of heat treatment, mixtures of acetone with other substances may be employed.
  • at least one constituent of the catalyst solution is a liquid having some slight softening or etching effect on the surface of the plastic, and many organic esters having suitable boiling points are effective.
  • a preferred composition of the catalyst solution comprises up to one gram of palladium chloride per litre converted to the complex, and dissolved in a mixture of acetone with one or more of the substances specified in Table III below. This is to 'be used on conjunction with a plastic substrate which can be safely heated to a temperature within the range indicated in that table.
  • the mixture contains about 40% acetone and of the substance by volume.
  • Palladium chloride is reported in the chemical literature to exist in the form of delaquesent needles readily soluble in water. However, the commercially available form of palladium chloride is virtually insoluble in water, but is readily soluble in small quantities of concentrated hydrochloric acid.
  • a method of preparing a solution of a palladium chloride complex in an organic solvent comprises dissolving palladium chloride in a concentrated aqueous solution of a hydrogen halide, preferably hydrogen chloride, evaporating the solution to drive off the greater part of the excess hydrogen halide and water, and dissolving the residue in an organic solvent.
  • evaporation is continued until the solution is concentrated to a thick syrup.
  • This syrup after cooling, is readily soluble in many organic solvents, including acetone, either cold, or with gentle warming. It still contains a small quantity of excess acid, and if this is objectionable and a neutral solution is required the acid may be neutralized by repeated small additions of solid sodium bicarbonate to the acetone solution.
  • the sodium hali e formed, together with any excess sodium bi-carbonate, both of which are insoluble in acetone, are separated by filtering the. solution.
  • evaporation may be continued beyond the syrup stage until the complex forms a pasty mass, and driving off even more of the excess acid and water. This mass decomposes above 115 C., but even if this temperature is not exceeded some of the complex may be converted to an insoluble form, so that the mass cannot be completely dissolved in the organic solvent.
  • the complex may be first formed as above with hydrogen chloride and evaporated to a syrupy liquid, dissolved in a limited quantity of acetone, and then the required amount of an aqueous solution of hydrogen fluoride is added. This may constitute, for example, 5-10 percent by volume of the total bulk of catalyst solution.
  • a palladium chloride complex prepared as a syrup by the above method was found to be soluble in the following liquids:
  • the solution consisted of 0.2 gram of palladium chloride formed into the hydrochloric acid complex and dissolved in 40 parts of acetone and 60 parts of the ester.
  • a mixture of 600 ml. methyl salicylate and 350 ml. acetone was prepared in a 2-litre beaker and very vigorously stirred with a mechanical stirrer, while the palladium chloride-acetone concentrate was slowly added.
  • This solution may usefully be employed for articles of the more heat resistant materials such as higher temperature stoving epoxy resin varnish films, glass, and ceramics and a pretreatment temperature of 200 C. is suitable with such a solution.
  • the object which may be of any of these materials or any other material which will withstand heating to 200 C., is first thoroughly cleaned by chemical cleaning, etching or vapour blasting as may be appropriate.
  • the article is then heated to a temperature of 200 C., immersed in the 60% methyl salicylate-acetone solution prepared as described above, removed and dried in an oven at a temperature of 200 C. The process is then repeated, a total of 2-6 treatments being given. Since the article is above the temperature at which the acetonemethyl salicylate mixture begins to boil, boiling takes place at the surface on immersion, producing a quenching action. At each treatment the article is allowed to stand in the solution for a minute or so if it is porous, and for a longer period if it is non-porous.
  • the article is then immersed in a nickel plating solution of which the following is a typical example:
  • the temperature of the solution is maintained between 65 and 75 C.
  • the plating bath may be, for example, of the following composition:
  • a sheet of plastic material which will not withstand temperatures much in excess of 110 C. is to be plated with phospho-nickel.
  • the palladium chloride complex is prepared as above, evaporated to a syrupy consistency, and dissolved in 50 ml. of acetone. This solution is then added, with stirring, to a mixture of 600 ml. of n-butyl formate and 350 ml. of acetone in a Z-litre beaker.
  • the plastic sheet is then pre-heated to a temperature of 110 C. and immersed in the catalyst solution for several minutes, then dried off in an oven at 110 C.
  • Petroleum ether Aliphatic hydrocarbon Benzene Aromatic hydrocarbon. Cyclohexane Alicyclic hydrocarbon. Chloroform Halogenated aliphatic hydrocarbon. Nitrobenzene Aromatic nitro-compound. Chlorobenzene Halogenated aromatic hydrocarbon. Di-iso-propyl ether Aliphatic ether.
  • Similar complexes can be prepared from palladium chloride by using hydrobromic or hydriodic acids, instead of hydrochloric acid. It is to be noted, however, that the hydriodic acid complex prevents plating on copper treated with its solutions. This is thought to be due to the formation of a film of cuprous iodide on the surface of the copper.
  • a catalyst solution containing free hydrofluoric acid suitable, for example, for nickel plating silicon Wafers in the manufacture of semi-conductive devices, or for nickel-plating tungsten rods which are required to be soldered, a catalyst solution containing hydrogen fluoride is used.
  • the complex of palladium chloride with hydrogen chloride and water is prepared as above and evaporated to a syrupy consistency by driving off excess water and hydrogen chloride.
  • the syrupy liquid so formed is then dissolved in a small quantity of acetone, and there is added to it with stirring a quantity of an aqueous solution of hydrogen fluoride amounting to about 5% of the calculated quantity of the solution.
  • the catalyst solution is then made up to the calculated quantity by adding acetone.
  • the step of treating the surface to be plated before immersion in the plating bath with a catalyst comprising a solution of a complex of palladium chloride dissolved in an organic solvent, said complex comprising palladium chloride with hydrogen halide and Water evaporated to a condition not dryer than a paste.
  • a method of preparing a catalyst solution for use in a chemical reduction plating process comprising forming a complex of palladium chloride with water and an excess of hydrogen halide, evaporating off excess water and hydrogen halide to a condition not dryer than a paste and dissolving said complex in an organic solvent.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
US453497A 1964-05-07 1965-05-05 Coating catalyst Expired - Lifetime US3414427A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB19002/64A GB1063092A (en) 1964-05-07 1964-05-07 Improvements in metal plating processes

Publications (1)

Publication Number Publication Date
US3414427A true US3414427A (en) 1968-12-03

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US453497A Expired - Lifetime US3414427A (en) 1964-05-07 1965-05-05 Coating catalyst

Country Status (7)

Country Link
US (1) US3414427A (enrdf_load_stackoverflow)
BE (1) BE663599A (enrdf_load_stackoverflow)
DE (1) DE1280016B (enrdf_load_stackoverflow)
GB (1) GB1063092A (enrdf_load_stackoverflow)
IL (1) IL23456A (enrdf_load_stackoverflow)
NL (1) NL6505820A (enrdf_load_stackoverflow)
SE (1) SE319948B (enrdf_load_stackoverflow)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3524754A (en) * 1967-04-28 1970-08-18 Shell Oil Co Metal plating of plastics
US3536443A (en) * 1968-06-07 1970-10-27 Eastman Kodak Co Process for recovering metal compounds
US3622370A (en) * 1969-04-07 1971-11-23 Macdermid Inc Method of and solution for accelerating activation of plastic substrates in electroless metal plating system
US3849177A (en) * 1972-06-26 1974-11-19 Du Pont Process employing catalyst coated yarn processing rolls
US3902234A (en) * 1972-06-26 1975-09-02 Du Pont Catalyst coated yarn handling roll
US3905877A (en) * 1974-02-19 1975-09-16 Du Pont Process for electroplating polyoxymethylene
US4006047A (en) * 1974-07-22 1977-02-01 Amp Incorporated Catalysts for electroless deposition of metals on comparatively low-temperature polyolefin and polyester substrates
US4131692A (en) * 1974-07-11 1978-12-26 Siemens Aktiengesellschaft Method for making ceramic electric resistor
US4734299A (en) * 1984-06-29 1988-03-29 Hitachi Chemical Co. Ltd. Sensitizing agent for electroless plating and method for sensitizing substrate with the agent
US4910072A (en) * 1986-11-07 1990-03-20 Monsanto Company Selective catalytic activation of polymeric films
US5075037A (en) * 1986-11-07 1991-12-24 Monsanto Company Selective catalytic activation of polymeric films
US5079040A (en) * 1988-08-17 1992-01-07 Hoechst Ceramtec Aktiengesellschaft Process for electrolessly depositing nickel
US5384154A (en) * 1991-06-12 1995-01-24 U.S. Philips Corporation Method of selectively providing a pattern of a material other than glass on a glass substrate by electroless metallization
US5411795A (en) * 1992-10-14 1995-05-02 Monsanto Company Electroless deposition of metal employing thermally stable carrier polymers
US20050241949A1 (en) * 2004-04-30 2005-11-03 Kenneth Crouse Selective catalytic activation of non-conductive substrates
US20050241951A1 (en) * 2004-04-30 2005-11-03 Kenneth Crouse Selective catalytic activation of non-conductive substrates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075856A (en) * 1958-03-31 1963-01-29 Gen Electric Copper plating process and solution
US3212918A (en) * 1962-05-28 1965-10-19 Ibm Electroless plating process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075856A (en) * 1958-03-31 1963-01-29 Gen Electric Copper plating process and solution
US3212918A (en) * 1962-05-28 1965-10-19 Ibm Electroless plating process

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3524754A (en) * 1967-04-28 1970-08-18 Shell Oil Co Metal plating of plastics
US3536443A (en) * 1968-06-07 1970-10-27 Eastman Kodak Co Process for recovering metal compounds
US3622370A (en) * 1969-04-07 1971-11-23 Macdermid Inc Method of and solution for accelerating activation of plastic substrates in electroless metal plating system
US3849177A (en) * 1972-06-26 1974-11-19 Du Pont Process employing catalyst coated yarn processing rolls
US3902234A (en) * 1972-06-26 1975-09-02 Du Pont Catalyst coated yarn handling roll
US3905877A (en) * 1974-02-19 1975-09-16 Du Pont Process for electroplating polyoxymethylene
US4131692A (en) * 1974-07-11 1978-12-26 Siemens Aktiengesellschaft Method for making ceramic electric resistor
US4006047A (en) * 1974-07-22 1977-02-01 Amp Incorporated Catalysts for electroless deposition of metals on comparatively low-temperature polyolefin and polyester substrates
US4734299A (en) * 1984-06-29 1988-03-29 Hitachi Chemical Co. Ltd. Sensitizing agent for electroless plating and method for sensitizing substrate with the agent
US4910072A (en) * 1986-11-07 1990-03-20 Monsanto Company Selective catalytic activation of polymeric films
US5075037A (en) * 1986-11-07 1991-12-24 Monsanto Company Selective catalytic activation of polymeric films
US5079040A (en) * 1988-08-17 1992-01-07 Hoechst Ceramtec Aktiengesellschaft Process for electrolessly depositing nickel
US5384154A (en) * 1991-06-12 1995-01-24 U.S. Philips Corporation Method of selectively providing a pattern of a material other than glass on a glass substrate by electroless metallization
US5411795A (en) * 1992-10-14 1995-05-02 Monsanto Company Electroless deposition of metal employing thermally stable carrier polymers
US20050241949A1 (en) * 2004-04-30 2005-11-03 Kenneth Crouse Selective catalytic activation of non-conductive substrates
US20050241951A1 (en) * 2004-04-30 2005-11-03 Kenneth Crouse Selective catalytic activation of non-conductive substrates
WO2005111274A2 (en) 2004-04-30 2005-11-24 Macdermid, Incorporated Selective catalytic activation of non-conductive substrates
US7255782B2 (en) 2004-04-30 2007-08-14 Kenneth Crouse Selective catalytic activation of non-conductive substrates
US20070267298A1 (en) * 2004-04-30 2007-11-22 Macdermid, Incorporated Selective catalytic activation of non-conductive substrates

Also Published As

Publication number Publication date
DE1280016B (de) 1968-10-10
IL23456A (en) 1969-01-29
BE663599A (enrdf_load_stackoverflow) 1965-09-01
GB1063092A (en) 1967-03-30
SE319948B (enrdf_load_stackoverflow) 1970-01-26
NL6505820A (enrdf_load_stackoverflow) 1965-11-08

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Owner name: BRITISH AEROSPACE PUBLIC LIMITED COMPANY; 100 PALL

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SPERRY LIMITED;REEL/FRAME:004073/0175

Effective date: 19820809