US3053741A - Deposition of metals - Google Patents

Deposition of metals Download PDF

Info

Publication number
US3053741A
US3053741A US101115A US10111561A US3053741A US 3053741 A US3053741 A US 3053741A US 101115 A US101115 A US 101115A US 10111561 A US10111561 A US 10111561A US 3053741 A US3053741 A US 3053741A
Authority
US
United States
Prior art keywords
solution
palladium
silver
sample
nitrate
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
Application number
US101115A
Other languages
English (en)
Inventor
Victor E Medina
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leesona Corp
Original Assignee
Leesona Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to NL276877D priority Critical patent/NL276877A/xx
Application filed by Leesona Corp filed Critical Leesona Corp
Priority to US101115A priority patent/US3053741A/en
Priority to GB12429/62A priority patent/GB960338A/en
Priority to DEL41658A priority patent/DE1221874B/de
Priority to FR893570A priority patent/FR1319205A/fr
Application granted granted Critical
Publication of US3053741A publication Critical patent/US3053741A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
    • 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
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention relates to the electrodeposition of palladium-silver alloys. More particularly, the invention relates to the electrodeposition of a non-porous film of palladium-silver alloy from an ammoniacal solution of the nitrate.
  • electrodeposition is used extensively in industry as a means of putting down a decorative finish on a metal, as well as to supply a surface which is highly protective against destructive atmospheres. More recently, electrodeposition has been used to lay down a highly conductive surface of copper, silver or gold onto metals such as steel or the like which are not good electrical conductors. However, up until now, no convenient and economical method of depositing a non-porous film of palladium-silver alloy onto a metallic or plastic surface has been known.
  • the objects of this invention are accomplished by preparing an ammoniacal nitrate solution of palladium and silver, placing the sample to be coated in the solution and applying an electric current across the solution to carry out the deposition.
  • an electric current across the solution to carry out the deposition.
  • the surface of the sample must be free from oils, greases and similar substances. This is accomplished by methods known in the art.
  • nitrate solutions employed are conveniently prepared by dissolving a palladium-silver alloy in nitric acid and then rendering the solutions basic, i.e., to a pH of from about 75-11, by adding ammonia to the solution.
  • the solution can be prepared by admixing nitrates of silver and palladium and thereafter rendering the solutions ammoniacal.
  • concentration of the solution is not particularly critical, however, it has been found that solutions containing from 0.5 to about grams of the metal or metals per liter of solution give good results, although solutions containing up to about 150 grams and higher of the metals per liter are conveniently used.
  • the plating process is carried out at temperatures ranging from about 3590 C. with the preferred temperature range being in the neighborhood of 50-60 C.
  • the current density and voltage of the deposition determine the composition of the deposits. It has been observed, surprisingly, that the composition of the film deposited is not dependent upon the concentration of the palladium-silver alloy solution, but is a function of the current density of deposition. Thus, starting out with a solution of given concentration the composition of the film deposited is varied by changing the current density.
  • Non-porous films have been deposited having thicknesses ranging from about 5 to 100 microns. If the coating is less than about 5 microns, the films were found to be porous.
  • anodes In the instant electrodepositi-on process, various anodes can be used, however, platinum anodes are particularly satisfactory. Other operable anodes are electrodes made of silver-palladium alloy or stainless steel.
  • Example 1 This example illustrates the uniform coating of a silverized porous polyethylene plastic sheet with a nonporous film of a palladium-silver alloy.
  • the silverized polyethylene sheet was prepared by immersing a 20 cm. square polyethylene porous plastic sheet 5 mils thick having a porosity of 80% and having of the pores in the range of from one to about five microns in a 5% aqueous potassium hydroxide solution and agitating for one minute.
  • the sample is washed in distilled water, and thereafter immersed, with agitation, for one minute in a sensitized solution composed of grams stannous chloride, 500 ml. concentrated hydrochloric acid and 4000 ml. of water.
  • the sample is again washed in distilled water.
  • the sensitized polyethylene sample is placed in a fiat bottom, glass container only slightly larger than the polyethylene sample.
  • the polyethylene sample is spread flat and attached to the bottom of the container by taping so that the surface of the plastic to be silvered is in a horizontal plane and faces upward.
  • the sample is spread in a fixture so that the surface of the sample is elevated A; to inch from the bottom of the container, thus, any sludge produced during the operation will tend to accumulate at the bottom of the bath container rather than on the surface of the sample.
  • the silverizing solution is prepared by dissolving 40 grams silver nitrate in 800 ml. of water and then dissolving 20 grams of potassium hydroxide in the solution.
  • the reducing solution is prepared as follows: 90 grams of granulated sugar is dissolved in 1 liter of water and then 4 ml. of nitric acid is added. The solution is boiled for five minutes, cooled and 157 ml. of ethyl alcohol is added as a preservative.) The bath is agitated for nine minutes after the addition of the reducing solution and then the polyethylene sample is removed from the bath using care to avoid touching the silvered surface. The sample is quickly washed twice with water to remove any smudge from the silvered surface. The silvered surface is then lightly wiped with a wet absorbent cellulose sponge to remove any stains. The sample is thoroughly washed with water.
  • the silverized porous polyethylene sheet is coated with a thin film of palladium-silver alloy by immersing the sheet in a solution prepared by dissolving 41 milligrams of a 25% silver and 75% palladium alloy in 10 cc. of nitric acid. Ammonium hydroxide is added to the solution to obtain a pH of nine and the volume adjusted to 100 cc.
  • the solution contains 10 milligrams of silver and 31 milligrams of palladium per 120 cc.
  • the plating is carried out at a current density of 7.5 ma./cm. a voltage of 1.9 volts and a temperature of 50 C.
  • the anode was platinum.
  • the deposition which is completed in approximately 80 minutes provides a thin film which exhibits good adhesion to the silverized surface as well as good flexibility. An analysis of the film showed the concentration of palladium to be 32% and silver 68%.
  • Example 2 A sintered porous nickel matrix having a porosity of 85% and an average pore size of eight microns is coated on one surface with a non-porous film of palladium-silver alloy as follows: 10 grams of a palladium nitrate solution containing three grams of palladium nitrate per 100 cc. of Water and 10 grams of silver nitrate containing three grams of silver nitrate per 100 cc. of water are added to 100 cc. of ammonia hydroxide and filtered. The volume is adjusted to give a concentration of six grams of palladium and silver per liter of solution. The porous nickel sample was immersed in the solution and plating is carried out at a current density of 14 ma./cm.
  • the sample to be coated can be replaced by a matrix of any plastic polymer material such as polystyrene, Teflon, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, etc. which is coated with a conductive metallic layer such as copper, nickel, cadmium, platinum, gold or lead.
  • plastic polymer material such as polystyrene, Teflon, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, etc.
  • a conductive metallic layer such as copper, nickel, cadmium, platinum, gold or lead.
  • the porous matrix can be a metal such as silver, gold, nickel, copper, zirconium, rhodium, iridium, ruthenium, or cadmium. The proper selection of these materials depends upon the end use of the coated material and is within the ability of one skilled in the art.
  • the method of electrodepositing a non-porous layer of palladium-silver alloy onto an article comprising the steps of (l) forming an ammoniacal nitrate solution of the palladium and silver, said solution having a pH of from about 7.5 to 11, (2) immersing the article to be coated in the solution, and (3) applying an electrical current to the solution and plating out said metals.
  • nitrate solution is formed by dissolving a palladium-silver alloy in nitric acid and adding ammonium hydroxide to render the solution basic.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemically Coating (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
US101115A 1961-04-06 1961-04-06 Deposition of metals Expired - Lifetime US3053741A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL276877D NL276877A (enrdf_load_stackoverflow) 1961-04-06
US101115A US3053741A (en) 1961-04-06 1961-04-06 Deposition of metals
GB12429/62A GB960338A (en) 1961-04-06 1962-03-30 Improvements in or relating to the electrodeposition of palladium-silver alloys
DEL41658A DE1221874B (de) 1961-04-06 1962-04-04 Verfahren zum galvanischen Abscheiden von Palladium-Silber-Legierungsueberzuegen
FR893570A FR1319205A (fr) 1961-04-06 1962-04-06 Procédé pour déposer électrolytiquement sur un objet une couche non poreuse d'unalliage palladium-argent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US101115A US3053741A (en) 1961-04-06 1961-04-06 Deposition of metals

Publications (1)

Publication Number Publication Date
US3053741A true US3053741A (en) 1962-09-11

Family

ID=22283103

Family Applications (1)

Application Number Title Priority Date Filing Date
US101115A Expired - Lifetime US3053741A (en) 1961-04-06 1961-04-06 Deposition of metals

Country Status (5)

Country Link
US (1) US3053741A (enrdf_load_stackoverflow)
DE (1) DE1221874B (enrdf_load_stackoverflow)
FR (1) FR1319205A (enrdf_load_stackoverflow)
GB (1) GB960338A (enrdf_load_stackoverflow)
NL (1) NL276877A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3130072A (en) * 1961-09-22 1964-04-21 Sel Rex Corp Silver-palladium immersion plating composition and process
US3446393A (en) * 1967-08-25 1969-05-27 Uniroyal Inc Storage container for pressurized fluids
US4269671A (en) * 1979-11-05 1981-05-26 Bell Telephone Laboratories, Incorporated Electroplating of silver-palladium alloys and resulting product
WO1984002538A1 (en) * 1982-12-22 1984-07-05 Learonal Inc Electrodeposition of palladium-silver alloys
US4465563A (en) * 1982-12-22 1984-08-14 Learonal, Inc. Electrodeposition of palladium-silver alloys
US4628165A (en) * 1985-09-11 1986-12-09 Learonal, Inc. Electrical contacts and methods of making contacts by electrodeposition
WO1989004556A1 (en) * 1987-11-07 1989-05-18 Thomas Allmendinger Electrochemical process for manufacturing a pore-free membrane based on palladium and supported by a porous metallic element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT989422B (it) * 1973-06-25 1975-05-20 Oronzio De Nora Impianti Catodo per l uso in celle elettro litiche formato da nuovi materiali catodici e metodo per la sua preparazione
EP0693579B1 (de) * 1994-07-21 1997-08-27 W.C. Heraeus GmbH Bad zum galvanischen Abscheiden von Palladium-Silber-Legierungen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1903860A (en) * 1930-04-25 1933-04-18 Ig Farbenindustrie Ag Preparation of metallic coatings
US1921941A (en) * 1931-03-12 1933-08-08 Johnson Matthey Co Ltd Electrodeposition of palladium
US2452308A (en) * 1946-02-28 1948-10-26 George C Lambros Process of plating palladium and plating bath therefor

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE688398C (de) * 1937-12-19 1940-02-20 Siebert G M B H G Verfahren zur Herstellung silberhaltiger, galvanischer Niederschlaege

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1903860A (en) * 1930-04-25 1933-04-18 Ig Farbenindustrie Ag Preparation of metallic coatings
US1921941A (en) * 1931-03-12 1933-08-08 Johnson Matthey Co Ltd Electrodeposition of palladium
US2452308A (en) * 1946-02-28 1948-10-26 George C Lambros Process of plating palladium and plating bath therefor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3130072A (en) * 1961-09-22 1964-04-21 Sel Rex Corp Silver-palladium immersion plating composition and process
US3446393A (en) * 1967-08-25 1969-05-27 Uniroyal Inc Storage container for pressurized fluids
US4269671A (en) * 1979-11-05 1981-05-26 Bell Telephone Laboratories, Incorporated Electroplating of silver-palladium alloys and resulting product
WO1984002538A1 (en) * 1982-12-22 1984-07-05 Learonal Inc Electrodeposition of palladium-silver alloys
US4465563A (en) * 1982-12-22 1984-08-14 Learonal, Inc. Electrodeposition of palladium-silver alloys
US4628165A (en) * 1985-09-11 1986-12-09 Learonal, Inc. Electrical contacts and methods of making contacts by electrodeposition
WO1989004556A1 (en) * 1987-11-07 1989-05-18 Thomas Allmendinger Electrochemical process for manufacturing a pore-free membrane based on palladium and supported by a porous metallic element

Also Published As

Publication number Publication date
GB960338A (en) 1964-06-10
DE1221874B (de) 1966-07-28
NL276877A (enrdf_load_stackoverflow)
FR1319205A (fr) 1963-02-22

Similar Documents

Publication Publication Date Title
US5178745A (en) Acidic palladium strike bath
US3162512A (en) Immersion plating with noble metals and the product thereof
US4749626A (en) Whisker resistant tin coatings and baths and methods for making such coatings
US4326930A (en) Method for electrolytic deposition of metals
US3053741A (en) Deposition of metals
US3486928A (en) Bath and process for platinum and platinum alloys
US2639997A (en) Metallization of nonmetallic surfaces
US2814589A (en) Method of plating silicon
US3674675A (en) Platinized plastic electrodes
US3272728A (en) Method of producing activated electrodes
US3963841A (en) Catalytic surface preparation for electroless plating
EP0280918A2 (en) Process for metal plating of substrates
US2162789A (en) Method of preparing metal surface for plating
DE2949104C2 (enrdf_load_stackoverflow)
US4242183A (en) Highly active silver cathode, preparation of same and use to make 2,3,5-trichloropyridine
US3321328A (en) Coating of aluminum substrates with a magnetic material
US3622470A (en) Continuous plating method
US3698939A (en) Method and composition of platinum plating
US2834724A (en) Method of electroplating plastic articles
US4196061A (en) Direct nickel-plating of aluminum
ES2477589T3 (es) Proceso de metalizado que no contiene cianuro de cobre para cinc y aleaciones de cinc
US2351940A (en) Method of making plated articles
RU2398049C2 (ru) Усовершенствованные стабилизация и рабочие характеристики автокаталитических способов нанесения покрытия методом химического восстановления
KR900702541A (ko) 귀금속 도금된 금속입자 및 이러한 입자로 얻은 전도성 재료의 제조방법
US4450187A (en) Immersion deposited cathodes