US3637474A - Electrodeposition of palladium - Google Patents

Electrodeposition of palladium Download PDF

Info

Publication number: US3637474A
Authority: US; United States
Prior art keywords: palladium; solution; bath; complex; approximately
Prior art date: 1967-09-08
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

US755386A

Other languages

English (en)

Inventor

Franco Zuntini

Jean M Gioria

Donald Gardner Foulke

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.)

OMI International Corp

Sel Rex Corp

Original Assignee

Sel Rex 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.)

1967-09-08

Filing date

1968-08-26

Publication date

1972-01-25

1968-08-26 Application filed by Sel Rex Corp filed Critical Sel Rex Corp

1972-01-25 Application granted granted Critical

1972-01-25 Publication of US3637474A publication Critical patent/US3637474A/en

1982-03-16 Assigned to OXY METAL INDUSTRIES CORPORATION reassignment OXY METAL INDUSTRIES CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 4-09-74 Assignors: OXY METAL FINISHING CORPORATION

1982-04-19 Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION

1983-05-05 Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.

1983-10-06 Assigned to OMI INTERNATIONAL CORPORATION reassignment OMI INTERNATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION

1983-11-20 Assigned to MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF reassignment MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL CORPORATION, A CORP OF DE

1989-01-25 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 66
229910052763 palladium Inorganic materials 0.000 title claims abstract description 34
238000004070 electrodeposition Methods 0.000 title description 5
239000004202 carbamide Substances 0.000 claims abstract description 19
238000000034 method Methods 0.000 claims abstract description 14
239000000126 substance Substances 0.000 claims abstract description 8
239000000243 solution Substances 0.000 claims description 31
150000003839 salts Chemical class 0.000 claims description 12
-1 sulfite compound Chemical class 0.000 claims description 8
KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
239000012670 alkaline solution Substances 0.000 claims description 4
229960001484 edetic acid Drugs 0.000 claims description 4
229910021645 metal ion Inorganic materials 0.000 claims description 4
238000000151 deposition Methods 0.000 abstract description 6
238000009713 electroplating Methods 0.000 abstract description 6
230000008021 deposition Effects 0.000 abstract description 2
XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
229910052751 metal Inorganic materials 0.000 description 5
239000002184 metal Substances 0.000 description 5
150000002500 ions Chemical class 0.000 description 4
238000007747 plating Methods 0.000 description 4
LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
239000000908 ammonium hydroxide Substances 0.000 description 3
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
239000003513 alkali Substances 0.000 description 2
238000000576 coating method Methods 0.000 description 2
PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
235000010288 sodium nitrite Nutrition 0.000 description 2
235000010265 sodium sulphite Nutrition 0.000 description 2
239000004254 Ammonium phosphate Substances 0.000 description 1
LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
229910000881 Cu alloy Inorganic materials 0.000 description 1
229910000570 Cupronickel Inorganic materials 0.000 description 1
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 1
229910000990 Ni alloy Inorganic materials 0.000 description 1
229910019142 PO4 Inorganic materials 0.000 description 1
238000013019 agitation Methods 0.000 description 1
229910000148 ammonium phosphate Inorganic materials 0.000 description 1
235000019289 ammonium phosphates Nutrition 0.000 description 1
150000003863 ammonium salts Chemical class 0.000 description 1
239000007864 aqueous solution Substances 0.000 description 1
239000002738 chelating agent Substances 0.000 description 1
230000000536 complexating effect Effects 0.000 description 1
239000008139 complexing agent Substances 0.000 description 1
150000001875 compounds Chemical class 0.000 description 1
238000011109 contamination Methods 0.000 description 1
229910052802 copper Inorganic materials 0.000 description 1
239000010949 copper Substances 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
230000007797 corrosion Effects 0.000 description 1
230000007812 deficiency Effects 0.000 description 1
MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
239000004615 ingredient Substances 0.000 description 1
239000000203 mixture Substances 0.000 description 1
150000002940 palladium Chemical class 0.000 description 1
235000021317 phosphate Nutrition 0.000 description 1
150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
239000002244 precipitate Substances 0.000 description 1
238000001556 precipitation Methods 0.000 description 1
229910052708 sodium Inorganic materials 0.000 description 1
239000011734 sodium Substances 0.000 description 1
UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used

Definitions

This invention relates to an electroplating solution and process for electrodepositing palladium. More particularly, this invention relates to the electrodeposition of palladium onto the surface of another metal which serves as the workpiece or cathode.
Palladium has been electrodeposited from a number of aqueous solutions.
the most popular palladium-electroplating solution utilizes palladium in the form of a salt, particularly palladium diamino-dinitrite, known as palladium P" salt as the source of palladium ions.
deposits obtained from the known plating baths heretofore used suffer from the deficiency of being porous in the thin 2.5 to 5 micron coatings range which is the most desirable range from a commercial standpoint.
the porosity is due primarily to the fact that the deposits from known plating solutions are highly stressed. Porosity results in corrosion of the underlying metal.
a stable pore-free deposit in the thicknesses customarily used for contacts, connectors, printed circuit boards, etc. can be obtained by the electrodeposition of palladium from a solution containing palladium in the form of a palladium-urea complex.
the deposit is not only pore-free in the thin coatings generally used, but remains so when used for heavy, thicker deposits.
the deposits of palladium are bright, and indeed can actually be made white" if a further ingredient, namely a sulfite salt is used in combination with the palladium-urea complex.
a palladium-urea complex salt can be obtained by reacting palladium chloride, or sodium palladium chloride or other soluble palladous salts with a slight excess of urea.
a salt containing approximately 36 percent palladium metal precipitates, which is soluble in alkaline solutions containing urea.
the palladium-urea complex dissolved in a solution containing urea can be used directly for electrodepositing palladiurn.
the solution must be alkaline and that is easily accomplished by using ammonium hydroxide or similar alkalies.
other salts can be any water-soluble salt which does not cause a precipitation in the bath by reacting with the palladium ions or with urea.
phosphates are suitable.
complexing or chelating agents to the solution, such as the sodium salt of ethylenediamine tetra-acetic acid to prevent the contamination of the bath with ions of the metal on which the deposit is effected.
the palladium is deposited over copper, copper alloys or nickel and nickel alloys and there is a certain amount of drag-in of contaminating ions.
Those ions are chelated by EDTA and similar compounds thus preventing codeposition of ions of the metal on which palladium is being deposited.
the pH of the plating bath is not critical, but should be maintained alkaline, preferable above 8 and preferably by the addition of ammonium hydroxide, although other alkalies are suitable.
the current density is not critical and can be varied. One skilled in the art will recognize that the current density can be varied greatly depending upon the amount of agitation and density in the solution. However, the preferred current density range is about 0.1 to about 1.2 amp. dm.
the temperature is not critical and in general it is preferred to operate a temperature of from about 40 to about 60 C.
the palladium content of this bath was increased to 15 g./l. by adding additional palladium-urea complex. Using high This bath gave bright, white deposits at a current density of 0.1 amp./dm. and a temperature of 55 C.
the quantity of sodium sulfite was increased to 75 g./l. and the urea palladium compound was added to the limit of its solubility.
the soluble sulfite compound can be present in a quantity such that the sulfite ion concentration is between ap proximately 1.5 and approximately 70 grams per liter of solution. Under these conditions, bright deposits were obtained at current densities well over 1.0 amp. dmF.
An electroplating bath for depositing palladium therefrom comprising an aqueous alkaline solution of a urea complex of palladium wherein the palladium content of the bath derived from said complex is at least about 2 grams per liter.
a method of electrodepositing palladium on a workpiece which comprises passing an electric current through a chemical solution wherein the workpiece serves as a cathode, said chemical solution comprising an aqueous alkaline solution of a palladium-urea complex wherein the palladium content of the bath derived from said complex is at least about 2 grams per liter.

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)

US755386A 1967-09-08 1968-08-26 Electrodeposition of palladium Expired - Lifetime US3637474A (en)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
CH1261267A CH479715A (fr)	1967-09-08	1967-09-08	Procédé de placage électrolytique de palladium, et bain pour la mise en oeuvre de ce procédé

Publications (1)

Publication Number	Publication Date
US3637474A true US3637474A (en)	1972-01-25

Family

ID=4384706

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US755386A Expired - Lifetime US3637474A (en)	1967-09-08	1968-08-26	Electrodeposition of palladium

Country Status (4)

Country	Link
US (1)	US3637474A (fr)
JP (1)	JPS475401B1 (fr)
CH (1)	CH479715A (fr)
GB (1)	GB1171734A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3933602A (en) *	1973-04-27	1976-01-20	Oxy Metal Industries Corporation	Palladium electroplating bath, process, and preparation
US4076599A (en) *	1975-10-30	1978-02-28	International Business Machines Corporation	Method and composition for plating palladium
US4411743A (en) *	1981-05-13	1983-10-25	Degussa	Electrolytic palladium bath and process
US4545868A (en) *	1981-10-06	1985-10-08	Learonal, Inc.	Palladium plating
US4622110A (en) *	1981-10-06	1986-11-11	Learonal, Inc.	Palladium plating
US4741818A (en) *	1985-12-12	1988-05-03	Learonal, Inc.	Alkaline baths and methods for electrodeposition of palladium and palladium alloys
US5415685A (en) *	1993-08-16	1995-05-16	Enthone-Omi Inc.	Electroplating bath and process for white palladium
US20090038950A1 (en) *	2007-07-20	2009-02-12	Rohm And Haas Electronic Materials Llc	High speed method for plating palladium and palladium alloys
JP2010031300A (ja) *	2008-07-22	2010-02-12	Rohm & Haas Electronic Materials Llc	パラジウムおよびパラジウム合金の高速めっき方法
US20110147225A1 (en) *	2007-07-20	2011-06-23	Rohm And Haas Electronic Materials Llc	High speed method for plating palladium and palladium alloys

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CH597372A5 (fr) *	1976-06-28	1978-03-31	Systemes Traitements Surfaces
US4328286A (en) *	1979-04-26	1982-05-04	The International Nickel Co., Inc.	Electrodeposited palladium, method of preparation and electrical contact made thereby
SE8106693L (sv) *	1980-12-17	1982-06-18	Hooker Chemicals Plastics Corp	Elektropleteringsbad innehallande palladium
US4392921A (en) *	1980-12-17	1983-07-12	Occidental Chemical Corporation	Composition and process for electroplating white palladium

Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US1981715A (en) *	1931-07-11	1934-11-20	Int Nickel Co	Electrodeposition of metals
US3290234A (en) *	1963-10-29	1966-12-06	Technic	Electrodeposition of palladium

1967
- 1967-09-08 CH CH1261267A patent/CH479715A/fr not_active IP Right Cessation
1968
- 1968-07-29 GB GB36111/68A patent/GB1171734A/en not_active Expired
- 1968-08-26 US US755386A patent/US3637474A/en not_active Expired - Lifetime
- 1968-09-09 JP JP6489668A patent/JPS475401B1/ja active Pending

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US1981715A (en) *	1931-07-11	1934-11-20	Int Nickel Co	Electrodeposition of metals
US3290234A (en) *	1963-10-29	1966-12-06	Technic	Electrodeposition of palladium

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3933602A (en) *	1973-04-27	1976-01-20	Oxy Metal Industries Corporation	Palladium electroplating bath, process, and preparation
US4076599A (en) *	1975-10-30	1978-02-28	International Business Machines Corporation	Method and composition for plating palladium
US4411743A (en) *	1981-05-13	1983-10-25	Degussa	Electrolytic palladium bath and process
US4545868A (en) *	1981-10-06	1985-10-08	Learonal, Inc.	Palladium plating
US4622110A (en) *	1981-10-06	1986-11-11	Learonal, Inc.	Palladium plating
US4741818A (en) *	1985-12-12	1988-05-03	Learonal, Inc.	Alkaline baths and methods for electrodeposition of palladium and palladium alloys
US5415685A (en) *	1993-08-16	1995-05-16	Enthone-Omi Inc.	Electroplating bath and process for white palladium
US20090038950A1 (en) *	2007-07-20	2009-02-12	Rohm And Haas Electronic Materials Llc	High speed method for plating palladium and palladium alloys
US20110147225A1 (en) *	2007-07-20	2011-06-23	Rohm And Haas Electronic Materials Llc	High speed method for plating palladium and palladium alloys
US9435046B2 (en)	2007-07-20	2016-09-06	Rohm And Haas Electronics Llc	High speed method for plating palladium and palladium alloys
JP2010031300A (ja) *	2008-07-22	2010-02-12	Rohm & Haas Electronic Materials Llc	パラジウムおよびパラジウム合金の高速めっき方法

Also Published As

Publication number	Publication date
GB1171734A (en)	1969-11-26
DE1796110B2 (de)	1977-04-21
DE1796110A1 (de)	1972-02-24
JPS475401B1 (fr)	1972-02-16
CH479715A (fr)	1969-10-15

Legal Events

Date	Code	Title	Description
1982-03-16	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
1982-04-19	AS	Assignment	Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222
1983-05-05	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
1983-10-06	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
1983-11-20	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

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