US3692641A - Electrodeposition of low stress ruthenium alloy - Google Patents
Electrodeposition of low stress ruthenium alloy Download PDFInfo
- Publication number
- US3692641A US3692641A US126886A US3692641DA US3692641A US 3692641 A US3692641 A US 3692641A US 126886 A US126886 A US 126886A US 3692641D A US3692641D A US 3692641DA US 3692641 A US3692641 A US 3692641A
- Authority
- US
- United States
- Prior art keywords
- ruthenium
- metal
- bath
- deposits
- alloy
- 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
- 229910000929 Ru alloy Inorganic materials 0.000 title abstract description 11
- 238000004070 electrodeposition Methods 0.000 title description 6
- 230000000737 periodic effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 229910052707 ruthenium Inorganic materials 0.000 description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 19
- 238000009713 electroplating Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 229910052738 indium Inorganic materials 0.000 description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- 229910052703 rhodium Inorganic materials 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 alkalis Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002659 electrodeposit Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 150000004695 complexes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-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
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
Definitions
- Thick electrodeposits of ruthenium alloy can be obtained by adding an element of Group III-A of the Periodic Table. The deposits obtained are primarily characterized by their low stress and absence of surface cracks at thicknesses up to about 10 millimicrons.
- the present invention concerns the electrodeposition of ruthenium-base alloys and more particularly the codeposition of ruthenium, at least one metal of Column III-A of the Periodic Table and at least one other metal of the platinum family which results in the formation of deposits of superior quality and highly resistant to corrosion.
- the invention also relates to the electroplating solutions or baths for carrying out such electrodeposition and to the use of said baths for the plating of conducting articles and work-parts.
- Electroplating aqueous baths for the deposition of ruthenium and ruthenium alloys are known that contain the ruthenium as water soluble derivatives, e.g. the hydrobromide (see for instance British Pat. No. 1,108,051). These baths have been operated at various temperatures and current densities; however, deposition rates and cathode yields were very low and such plating baths have furnished generally highly strained ruthenium deposits. The stress which was present generally caused the formation of cracks in the deposits when the thickness was greater than 1.5 to 2.5 p.111. This and the low energetic yields represent an "important drawback in most industrial applications; for instance for the manufacture of corrosion resistant electrodes, thicker deposits are required with no visible cracks or other faults.
- ruthenium alloy means an alloy of, at least, ruthenium and a platinum metal.
- platinum metal means a metal selected from the group consisting of rhodium, palladium, platinum, osmium, and irridium.
- the electroplating bath of this invention comprises about 0.5 to 50 g./l. of ruthenium, preferably about 2 to 25 g./1. of ruthenium, as the complex at least one metal of Column III-A of the Periodic Table in the form of a water soluble compound in an amount from about 0.01 g. metal/l. to the saturation concentration of said water soluble compound in the bath, preferably from about 1 g./l.; and at least one other metal of the platinum group in the form of a water soluble compound in concentrations from about 0.05 to 20 g. metal/1., preferably about 0.10 to 10 g. metal/l.
- the preferred Group III-A metals are indium, gallium and thallium.
- the preferred platinum metals are rhodium, palladium and platinum.
- the water soluble compounds of Group III-A metals and platinum metals can be the salts of said metals with most common strong organic and inorganic acids such as for instance sulfuric acid, phosphoric acid, hydrogen halide (chloride and bromide), perchloric acid, tn'chloracetic acid, trifluoracetic acid and the like.
- Said compounds can also be the water soluble complex chelates of the ions of the above metals with usual metal chelating agents.
- the electrodeposits of ruthenium alloys obtained with the baths of the invention are shiny, corrosion resistant and more ductile than other ruthenium alloy deposits obtained previously. Maximum thicknesses of about 2.5 un. can be attained without the metals of Column III-A whereas thicknesses of 10 m. or more can be attained with the co-deposition of Column IIIA metals before the formation of cracks becomes visible with the naked eye or with 500 fold magnification.
- the use of the bath also leads to other improvements such as for instance faster deposition rate, better cathode yield and better microand macro-distribution of the plated metals over the ruthenium plating baths known previously.
- the baths of the invention can be used to plate a great variety of objects, parts, articles and work-pieces which are either self-conductors of electricity (metallic items) or rendered conductors by the application of a conduct-
- ruthenium, one metal of Column III-A, e.g. indium, and one platinum metal has the following additional consequence; the ruthenium content of the deposits can be varied as a function of the concentration ratio of ruthenium to indium, said content being decreased with decreasing ratio of ruthenium to indium.
- Temperature, current density, pH and other operating conditions are relevant only as far as they influence the basic characteristics of the plating bath in a known manner. Thus, operating conditions commonly employed with conventional ruthenium plating solutions may be employed in the practice of this invention.
- the baths are generally operated at current densities between about 0.1 and 40 a./dm. and preferentially between about 0.5 and 4 a./dm.
- the baths are generally operated at a temperature between 15 and 95 C. It is preferred however, to operate between 40 and 70 C.
- the pH of the baths is preferably maintained at 3.0, or below, most preferably 1.5 or below. If necessary, the pH is adjusted with acids such as for example HCl, H SO H PO sulfamic acids, benzene sulfonic acids or salts which might have a buffering action in the bath, e.g., NaH PO or Na HPO or salts of strong acids and weak bases.
- acids such as for example HCl, H SO H PO sulfamic acids, benzene sulfonic acids or salts which might have a buffering action in the bath, e.g., NaH PO or Na HPO or salts of strong acids and weak bases.
- the weight percent of ruthenium, platinum metal and Group III-A metal in the electrodeposit will vary depending upon the composition of the particular electroplating solution used. In general, the amount of ruthenium in the deposit ranges from about 20 to 80%, preferably from about 30 to 75%; the amount of platinum metal ranges from about 15 to 75%, preferably from about 25 to 70%; and the Group III-A metal ranges from about 0.1 to 10%, preferably from about 0.5 to 5%.
- EXAMPLE 1 An electroplating bath for deposition of a rutheniumbase alloy was prepared by mixing the following ingredients (the concentrations of the metal salts or complexes are given in g. of free metal).
- the bath was adjusted to pH 2.0 with 20% ammonia, then it was operated at 1.0 a./dm. and 55 C.
- Gold plated brass samples were plated for various periods.
- the deposits obtained (A) were shiny, with no cracks discernible with the eye or the microscope with thickness up to ,um.
- the plating rate was 12 mg./a.min., i.e. 0.1 pJJL/ min.
- the alloy contained 66% Ru, 33% and 1% indium.
- EXAMPLE 2 An electroplating bath for the deposition of rutheniumbase alloy has been prepared as described in Example 1 but with 2 g./l. of rhodium metal as the sulfate instead of 1 g./ 1. The bath was operated as described in Example 1.
- Example 2 Deposits containing 40% Ru, 59% Rh and 1% indium were obtained. As in Example 1, they showed no cracks or other defects even with thicknesses of up to 10 ,am.
- a corrosion control experiment carried out as described in Example 1 showed that the above deposit with 59% Rh were even more corrosion resistant than the 33% Rh deposit, when it was used as an anode in an alkaline electrolytic bath.
- EXAMPLE 3 An electroplating bath for the deposition of a ruthenium-base alloy was prepared by mixing the following ingredients (the concentrations of the metal salts or com plexes are given in g./1. of free metal).
- the bath was adjusted to pH 1.5 and operated at 1.0 a./dm. at 6 5 C.
- the samples were prepared as described in Example 1 and the cathode-yield was 8 mg./a.min. The samples were shiny and had good corrosion resistance.
- EXAMPLE 4 An electroplating bath was prepared as described in Example 3 but replacement of the platinum by 0.05 g./l. of palladium in the form of a HCl solution of PdClg- The conditions of operation were the same as for Example 3. Corrosion resistant deposits were obtained at a rate of 9.4 mg./a.min.
- An aqueous acid electroplating bath for the electrodeposition of ruthenium alloy comprising about 0.5 to 50 g./l. of ruthenium, as the complex at least one metal selected from indium, gallium, or thallium in an amount from about 0.01 g. metal/l. to saturation; and at least one other platinum metal in an amount from about 0.05 to 20 g. metal/l.
- a method of electrodepositing a low stress ruthenium alloy which comprises passing a current through the aqueous acid bath of claim 1.
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- 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)
- Chemically Coating (AREA)
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH423570A CH512590A (en) | 1970-03-20 | 1970-03-20 | Process for the electrolytic deposition of ruthenium alloys, aqueous bath for carrying out this process, and article coated with a ruthenium alloy obtained by this process |
Publications (1)
Publication Number | Publication Date |
---|---|
US3692641A true US3692641A (en) | 1972-09-19 |
Family
ID=4272323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US126886A Expired - Lifetime US3692641A (en) | 1970-03-20 | 1971-03-22 | Electrodeposition of low stress ruthenium alloy |
Country Status (8)
Country | Link |
---|---|
US (1) | US3692641A (en) |
BE (1) | BE764153A (en) |
CA (1) | CA927313A (en) |
CH (1) | CH512590A (en) |
DE (1) | DE2114119C2 (en) |
FR (1) | FR2083474B1 (en) |
GB (1) | GB1328928A (en) |
NL (1) | NL7103762A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3892638A (en) * | 1973-06-21 | 1975-07-01 | Oxy Metal Industries Corp | Electrolyte and method for electrodepositing rhodium-ruthenium alloys |
US4082625A (en) * | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
US4297178A (en) * | 1979-04-10 | 1981-10-27 | The International Nickel Company, Inc. | Ruthenium electroplating and baths and compositions therefor |
US4938851A (en) * | 1984-12-14 | 1990-07-03 | De Nora Permelec S.P.A. | Method for preparing an electrode and use thereof in electrochemical processes |
US20100051468A1 (en) * | 2007-03-28 | 2010-03-04 | Philip Schramek | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
US20110236720A1 (en) * | 2008-11-21 | 2011-09-29 | Joachim Grimm | Noble metal-containing layer sequence for decorative articles |
WO2020250174A1 (en) * | 2019-06-11 | 2020-12-17 | Legor Group Spa | Galvanic bath and process for producing a ruthenium/platinum alloy by means of electro-galvanic deposition |
WO2022112379A1 (en) | 2020-11-26 | 2022-06-02 | Umicore Galvanotechnik Gmbh | Ruthenium alloy layer and its layer combinations |
IT202100003875A1 (en) * | 2021-02-19 | 2022-08-19 | Legor Group S P A | GALVANIC BATH AND PROCESS FOR PRODUCING A PLATINUM-RUTHENIUM ALLOY THROUGH ELECTROGALVANIC DEPOSITION |
US11421335B2 (en) * | 2019-04-08 | 2022-08-23 | Umicore Galvanotechnik Gmbh | Electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5544157B2 (en) * | 1971-08-21 | 1980-11-11 | ||
AU523857B2 (en) * | 1978-07-14 | 1982-08-19 | International Nickel Inc. | Alloys and electrodes |
AT523922B1 (en) * | 2020-09-08 | 2022-01-15 | Iwg Ing W Garhoefer Ges M B H | Electrolyte bath for palladium-ruthenium coatings |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL43163C (en) * | 1935-01-16 |
-
1970
- 1970-03-20 CH CH423570A patent/CH512590A/en not_active IP Right Cessation
-
1971
- 1971-03-12 BE BE764153A patent/BE764153A/en unknown
- 1971-03-18 FR FR7111003A patent/FR2083474B1/fr not_active Expired
- 1971-03-19 DE DE2114119A patent/DE2114119C2/en not_active Expired
- 1971-03-19 CA CA108185A patent/CA927313A/en not_active Expired
- 1971-03-19 NL NL7103762A patent/NL7103762A/xx unknown
- 1971-03-22 US US126886A patent/US3692641A/en not_active Expired - Lifetime
- 1971-04-19 GB GB2390071*A patent/GB1328928A/en not_active Expired
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3892638A (en) * | 1973-06-21 | 1975-07-01 | Oxy Metal Industries Corp | Electrolyte and method for electrodepositing rhodium-ruthenium alloys |
US4082625A (en) * | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
US4297178A (en) * | 1979-04-10 | 1981-10-27 | The International Nickel Company, Inc. | Ruthenium electroplating and baths and compositions therefor |
US4938851A (en) * | 1984-12-14 | 1990-07-03 | De Nora Permelec S.P.A. | Method for preparing an electrode and use thereof in electrochemical processes |
US8211286B2 (en) * | 2007-03-28 | 2012-07-03 | Umicore Galvotechnik GmbH | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
US20100051468A1 (en) * | 2007-03-28 | 2010-03-04 | Philip Schramek | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
US20110236720A1 (en) * | 2008-11-21 | 2011-09-29 | Joachim Grimm | Noble metal-containing layer sequence for decorative articles |
US11421335B2 (en) * | 2019-04-08 | 2022-08-23 | Umicore Galvanotechnik Gmbh | Electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers |
TWI825262B (en) * | 2019-04-08 | 2023-12-11 | 德商烏明克葛凡諾科技有限公司 | Electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers |
WO2020250174A1 (en) * | 2019-06-11 | 2020-12-17 | Legor Group Spa | Galvanic bath and process for producing a ruthenium/platinum alloy by means of electro-galvanic deposition |
WO2022112379A1 (en) | 2020-11-26 | 2022-06-02 | Umicore Galvanotechnik Gmbh | Ruthenium alloy layer and its layer combinations |
DE102020131371A1 (en) | 2020-11-26 | 2022-06-02 | Umicore Galvanotechnik Gmbh | Ruthenium alloy layer and their layer combinations |
DE102020131371B4 (en) | 2020-11-26 | 2024-08-08 | Umicore Galvanotechnik Gmbh | Use of an electrolyte to produce a ruthenium alloy layer |
IT202100003875A1 (en) * | 2021-02-19 | 2022-08-19 | Legor Group S P A | GALVANIC BATH AND PROCESS FOR PRODUCING A PLATINUM-RUTHENIUM ALLOY THROUGH ELECTROGALVANIC DEPOSITION |
Also Published As
Publication number | Publication date |
---|---|
CH512590A (en) | 1971-09-15 |
DE2114119C2 (en) | 1982-07-01 |
BE764153A (en) | 1971-08-02 |
CA927313A (en) | 1973-05-29 |
FR2083474B1 (en) | 1974-10-11 |
NL7103762A (en) | 1971-09-22 |
FR2083474A1 (en) | 1971-12-17 |
GB1328928A (en) | 1973-09-05 |
DE2114119A1 (en) | 1971-10-07 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
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 |
|
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 |