US3630856A - Electrodeposition of ruthenium - Google Patents
Electrodeposition of ruthenium Download PDFInfo
- Publication number
- US3630856A US3630856A US21533A US3630856DA US3630856A US 3630856 A US3630856 A US 3630856A US 21533 A US21533 A US 21533A US 3630856D A US3630856D A US 3630856DA US 3630856 A US3630856 A US 3630856A
- Authority
- US
- United States
- Prior art keywords
- ruthenium
- indium
- electrodeposition
- coatings
- gallium
- 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title abstract description 27
- 229910052707 ruthenium Inorganic materials 0.000 title abstract description 24
- 238000004070 electrodeposition Methods 0.000 title description 6
- 229910052738 indium Inorganic materials 0.000 abstract description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052733 gallium Inorganic materials 0.000 abstract description 8
- 229910052716 thallium Inorganic materials 0.000 abstract description 7
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002659 electrodeposit Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
Definitions
- Thick electrodeposits of ruthenium can be obtained by adding an element selected from gallium, indium, and thallium in a stable and soluble form. The deposits obtained are primarily characterized by their low stress and absence of surface cracks at thicknesses up to about millimicrons.
- the present invention relates to a method for the electrodeposition of ruthenium and to an aqueous bath for carrying out this method.
- the ruthenium coatings so obtained are characterized by severe inner stress, so that they show cracks when their thickness is above 1.0 to 1.5 m.
- Today most commercial applications of parts plated with ruthenium require substantially thicker coatings, usually of the order of a minimum thickness of 2.5 ,um. to 5 ,um. or even, on occasion, somewhat thicker, up to about 10 m.
- the object of the present invention is to permit the electrodeposition of ruthenium coatings of a thickness sufficient to meet contemporary industrial needs.
- This invention is based on the discovery that the addition of one of the elements selected from gallium, indium and thallium in the form of a stable, soluble compound to a ruthenium plating solution, serves to severely reduce inner surface stress of the plated ruthenium to the point where relatively thick deposits of ruthenium electroplate can be obtained.
- one of the elements selected from gallium, indium and thallium is added in concentration from 50 mg./l. up to saturation to an aqueous solution of a ruthenium compound which contains from about 0.5 g./l. to about 50 g./l. of ruthenium metal.
- Ruthenium 10 g./l. as a complex of containing 34.4% in weight of ruthenium metal
- Indium 5 g./l. (as sulfate)
- Ammonium sulfamate 15 g./l. (conductivity salt) pH adjusted to 1.5 by means of NH OH or HCl or H 80 Temperature of the bath: 60 C. Current density: 1 amp.dm.
- the light coatings produced on samples of brass precoated with a flash of gold, showing no visible cracks or micro-cracks, to thicknesses up to about 10 ,uI'IL, have been obtained at a plating rate of 12 mg./amp.min., that represent 1 ,um. in 9 minutes. These deposits contained about 1.2 to 1.5% indium.
- Ruthenium 10 -g./l. as a complex of Indium: 3 g./l. (as sulfamate) Ammonium sulfamate: 5 g./l.
- Bright coatings of ruthenium were obtained on brass samples precoated with a flash of gold which showed no visible cracks or micro-cracks, and for this thicknesses up to 10 ,um. These coatings were obtained at a plating rate of 11 m-g./amp.min. These deposits contained about 1.0 to 1.3% indium.
- ruthenium Along with the deposit of ruthenium there will be a codeposit of the Group III-B metal chosen. That codeposit will generally be on the order of about 0.1% to 10.0% of the total content of the electrodeposit. At about 5 g./l. of a Group III-B metal, the metal will codeposit with ruthenium in a range of about 1.0 to 2.0%.
- the cathodic efliciency increases with the temperature. Between 6.0 and it is practically constant. On the other hand, it shows a tendency to decrease while the current density increases.
- the plating can be effected on any support permitting an electrodeposition, especially on the same supports as those which permit the coating of gold, like brass, nickel, titanium, etc.
- a method for electrodepositing ruthenium by passing a current through an aqueous solution containing from about 0.5 g./l. to about 50 g./L of ruthenium and at least one element selected from the group consisting of gallium, indium and thallium in a stable and soluble form and in a concentration from about 50 mg./l. up to saturation, whereby ruthenium is deposited on the cathode.
- An aqueous electroplating solution containing from about 0.5 g./1. to about 50 g./l. of ruthenium and at least one element selected from the group consisting of gallium,
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)
- Electrolytic Production Of Metals (AREA)
Abstract
THICK ELECTRODEPOSITS OF RUTHENIUM CAN BE OBTAINED BY ADDING AN ELEMENT SELECTED FROM GALLIUM, INDIUM, AND THALLIUM IN A STABLE AND SOLUBLE FORM. THE DEPOSITS OBTAINED ARE PRIMARILY CHARACTERIZED BY THEIR LOW STRESS AND ABSENCE OF SURFACE CRACKS AT THICKNESS UP TO ABOUT 10 MILLIMICRONS.
Description
United States Patent @fice 3,630,856 ELECTRODEPOSITION OF RUTHENIUM Andre Meyer, Geneva, Switzerland, assignor to Sel-Rex Corporation, Nutley, NJ.
No Drawing. Filed Mar. 20, 1970, Ser. No. 21,533 Claims priority, application Switzerland, Mar. 21, 1969, 4,277 69 Int. Cl. C23b /32 US. Cl. 204-43 2 Claims ABSTRACT OF THE DISCLOSURE Thick electrodeposits of ruthenium can be obtained by adding an element selected from gallium, indium, and thallium in a stable and soluble form. The deposits obtained are primarily characterized by their low stress and absence of surface cracks at thicknesses up to about millimicrons.
The present invention relates to a method for the electrodeposition of ruthenium and to an aqueous bath for carrying out this method.
It is known to electrolytically produce ruthenium coatings by using, as an electrolyte, a complex having the formula (NH [Ru Cl (H O') N], containing 34.4% in Weight of ruthenium metal, at several current densities.
The ruthenium coatings so obtained are characterized by severe inner stress, so that they show cracks when their thickness is above 1.0 to 1.5 m. Today most commercial applications of parts plated with ruthenium require substantially thicker coatings, usually of the order of a minimum thickness of 2.5 ,um. to 5 ,um. or even, on occasion, somewhat thicker, up to about 10 m.
The object of the present invention is to permit the electrodeposition of ruthenium coatings of a thickness sufficient to meet contemporary industrial needs. In particular, it is an object of the present invention to permit the production of ruthenium coatings of a thickness of up to about 10 ,um. while comprising no visible cracks even at a magnification of 500 times.
This invention is based on the discovery that the addition of one of the elements selected from gallium, indium and thallium in the form of a stable, soluble compound to a ruthenium plating solution, serves to severely reduce inner surface stress of the plated ruthenium to the point where relatively thick deposits of ruthenium electroplate can be obtained. In general, one of the elements selected from gallium, indium and thallium is added in concentration from 50 mg./l. up to saturation to an aqueous solution of a ruthenium compound which contains from about 0.5 g./l. to about 50 g./l. of ruthenium metal.
The addition of at least one metal selected from gallium, indium and thallium, as stable and water soluble compounds, results in coatings which are more ductile. These metallic compounds which appear in the cathodic film during the electrolysis modify the cathodic polarization and the crystallization phenomena, and produce coatings which are completely dilferent from those heretofore obtained by known methods, in their appearance (brighter and clearer), in their mechanical characteristics (more ductile, without cracks), and in their composition, the metals of addition being co-deposited with the ruthenium during the electrolysis. Some secondary eflfects due to the addition of these metals have also been found, especially a slight improvement of the cathodic elficiency, almost at high current density, and a higher power of macro and micro-repartition.
3,630,856 Patented Dec. 28, 1971 EXAMPLES (1) A bath has been prepared containing:
Ruthenium: 10 g./l. as a complex of containing 34.4% in weight of ruthenium metal Indium: 5 g./l. (as sulfate) Ammonium sulfamate: 15 g./l. (conductivity salt) pH adjusted to 1.5 by means of NH OH or HCl or H 80 Temperature of the bath: 60 C. Current density: 1 amp.dm.
The light coatings, produced on samples of brass precoated with a flash of gold, showing no visible cracks or micro-cracks, to thicknesses up to about 10 ,uI'IL, have been obtained at a plating rate of 12 mg./amp.min., that represent 1 ,um. in 9 minutes. These deposits contained about 1.2 to 1.5% indium.
(2) Deposits have been effected by means of the following bath:
Ruthenium: 10 -g./l. as a complex of Indium: 3 g./l. (as sulfamate) Ammonium sulfamate: 5 g./l.
Sulphamic acid: 5 g./l.
Sulfuric acid up to a pH of 1.0 to 1.5
Temperature of bath: 65 to C.
Current density: 1 amp.dm.
Bright coatings of ruthenium were obtained on brass samples precoated with a flash of gold which showed no visible cracks or micro-cracks, and for this thicknesses up to 10 ,um. These coatings were obtained at a plating rate of 11 m-g./amp.min. These deposits contained about 1.0 to 1.3% indium.
Along with the deposit of ruthenium there will be a codeposit of the Group III-B metal chosen. That codeposit will generally be on the order of about 0.1% to 10.0% of the total content of the electrodeposit. At about 5 g./l. of a Group III-B metal, the metal will codeposit with ruthenium in a range of about 1.0 to 2.0%.
The above examples have only an illustrative purpose and are not to be considered, in any way, as being limitative.
Experience has shown that indium and gallium give the best result, thallium being less soluble and presenting a tendency to crystallize partially.
The effects of the addition are substantial from a concentration of about 100 mg./l. the maximum eifect being obtained, however, with an addition of 5 g./l. of indium, for instance. Above this concentration, no substantial supplementary effect appears.
At pH higher than 1.5, the deposits obtained are less bright and have a greater tendency to present micro-cracks and pits which alter its appearance.
The cathodic efliciency increases with the temperature. Between 6.0 and it is practically constant. On the other hand, it shows a tendency to decrease while the current density increases.
The plating can be effected on any support permitting an electrodeposition, especially on the same supports as those which permit the coating of gold, like brass, nickel, titanium, etc.
So as to produce a better adherence and for limiting the formation of porous deposits, it is advantageous, in some cases, to apply on the support, before the electrodeposition of ruthenium, a flash of gold.
I claim:
1. A method for electrodepositing ruthenium by passing a current through an aqueous solution containing from about 0.5 g./l. to about 50 g./L of ruthenium and at least one element selected from the group consisting of gallium, indium and thallium in a stable and soluble form and in a concentration from about 50 mg./l. up to saturation, whereby ruthenium is deposited on the cathode.
2. An aqueous electroplating solution containing from about 0.5 g./1. to about 50 g./l. of ruthenium and at least one element selected from the group consisting of gallium,
References Cited Frederick A. Lowenheim: Modern Electroplating, p. 6, 1968.
GERALD L. KAPLAN, Primary Examiner US. Cl. X.R. 75172; 20447
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH427769A CH508055A (en) | 1969-03-21 | 1969-03-21 | Process for the electrolytic plating of ruthenium, and aqueous bath for the implementation of this process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3630856A true US3630856A (en) | 1971-12-28 |
Family
ID=4273098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US21533A Expired - Lifetime US3630856A (en) | 1969-03-21 | 1970-03-20 | Electrodeposition of ruthenium |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US3630856A (en) |
| JP (1) | JPS4926175B1 (en) |
| AT (1) | AT301977B (en) |
| BE (1) | BE747595A (en) |
| CA (1) | CA920084A (en) |
| CH (1) | CH508055A (en) |
| DE (1) | DE2014122C3 (en) |
| DK (1) | DK124960B (en) |
| ES (1) | ES377773A1 (en) |
| FR (1) | FR2037241B1 (en) |
| GB (1) | GB1300153A (en) |
| NL (1) | NL7004066A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793162A (en) * | 1971-12-17 | 1974-02-19 | Int Nickel Co | Electrodeposition of ruthenium |
| US4082625A (en) * | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
| US4082622A (en) * | 1977-04-20 | 1978-04-04 | Gte Automatic Electric Laboratories Incorporated | Electrodeposition of ruthenium |
| US4375392A (en) * | 1981-06-02 | 1983-03-01 | Occidental Chemical Corporation | Bath and process for the electrodeposition of ruthenium |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19741990C1 (en) * | 1997-09-24 | 1999-04-29 | Degussa | Electrolyte for low-stress, crack-free ruthenium coatings |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB959052A (en) * | 1962-01-02 | 1964-05-27 | Johnson Matthey Co Ltd | Improvements in and relating to the electro-deposition of rhodium |
-
1969
- 1969-03-21 CH CH427769A patent/CH508055A/en not_active IP Right Cessation
-
1970
- 1970-03-17 GB GB02824/70A patent/GB1300153A/en not_active Expired
- 1970-03-19 BE BE747595D patent/BE747595A/en unknown
- 1970-03-19 DE DE2014122A patent/DE2014122C3/en not_active Expired
- 1970-03-20 DK DK143670AA patent/DK124960B/en unknown
- 1970-03-20 AT AT264370A patent/AT301977B/en active
- 1970-03-20 FR FR707010260A patent/FR2037241B1/fr not_active Expired
- 1970-03-20 NL NL7004066A patent/NL7004066A/xx unknown
- 1970-03-20 US US21533A patent/US3630856A/en not_active Expired - Lifetime
- 1970-03-20 JP JP45023234A patent/JPS4926175B1/ja active Pending
- 1970-03-20 CA CA077959A patent/CA920084A/en not_active Expired
- 1970-03-21 ES ES377773A patent/ES377773A1/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793162A (en) * | 1971-12-17 | 1974-02-19 | Int Nickel Co | Electrodeposition of ruthenium |
| US4082625A (en) * | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
| US4082622A (en) * | 1977-04-20 | 1978-04-04 | Gte Automatic Electric Laboratories Incorporated | Electrodeposition of ruthenium |
| US4375392A (en) * | 1981-06-02 | 1983-03-01 | Occidental Chemical Corporation | Bath and process for the electrodeposition of ruthenium |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2014122C3 (en) | 1979-05-10 |
| DK124960B (en) | 1972-12-11 |
| CH508055A (en) | 1971-05-31 |
| BE747595A (en) | 1970-08-31 |
| DE2014122A1 (en) | 1970-10-22 |
| NL7004066A (en) | 1970-09-23 |
| GB1300153A (en) | 1972-12-20 |
| AT301977B (en) | 1972-09-25 |
| FR2037241B1 (en) | 1973-03-16 |
| FR2037241A1 (en) | 1970-12-31 |
| DE2014122B2 (en) | 1978-10-05 |
| JPS4926175B1 (en) | 1974-07-06 |
| CA920084A (en) | 1973-01-30 |
| ES377773A1 (en) | 1972-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3677909A (en) | Palladium-nickel alloy plating bath | |
| US2830014A (en) | Electroplating process | |
| US3354059A (en) | Electrodeposition of nickel-iron magnetic alloy films | |
| US2436316A (en) | Bright alloy plating | |
| US3697391A (en) | Electroplating processes and compositions | |
| US3692641A (en) | Electrodeposition of low stress ruthenium alloy | |
| US3764489A (en) | Electrodeposition of gold alloys | |
| US2176668A (en) | Silver plating process | |
| US4411965A (en) | Process for high speed nickel and gold electroplate system and article having improved corrosion resistance | |
| US3620936A (en) | Electroplating a decorative chromium-plating resistant to corrosion | |
| US4617096A (en) | Bath and process for the electrolytic deposition of gold-indium alloys | |
| US3630856A (en) | Electrodeposition of ruthenium | |
| US3892638A (en) | Electrolyte and method for electrodepositing rhodium-ruthenium alloys | |
| US4119502A (en) | Acid zinc electroplating process and composition | |
| JPS6141999B2 (en) | ||
| US3522155A (en) | Method of electrodepositing a tinbismuth alloy and compositions therefor | |
| US3574067A (en) | Electroforming metals and electrolytes therefor | |
| US3668083A (en) | Process of electroplating rhenium and bath for this process | |
| JPH1171695A (en) | Low-stress nickel electroplating | |
| US4411744A (en) | Bath and process for high speed nickel electroplating | |
| US4435254A (en) | Bright nickel electroplating | |
| US4416740A (en) | Method and bath for the electrodeposition of palladium/nickel alloys | |
| US3969399A (en) | Electroplating processes and compositions | |
| JPS6112038B2 (en) | ||
| US3514380A (en) | Chromium plating from a fluosilicate type bath containing sodium,ammonium and/or magnesium ions |
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 |
|
| 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 |
|
| 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 |