US2973283A - Surface treatment - Google Patents

Surface treatment Download PDF

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Publication number
US2973283A
US2973283A US692257A US69225757A US2973283A US 2973283 A US2973283 A US 2973283A US 692257 A US692257 A US 692257A US 69225757 A US69225757 A US 69225757A US 2973283 A US2973283 A US 2973283A
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United States
Prior art keywords
platinum
rhodium
gold
coating
layer
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Expired - Lifetime
Application number
US692257A
Inventor
James S Hill
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Engelhard Industries Inc
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Engelhard Industries Inc
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Filing date
Publication date
Application filed by Engelhard Industries Inc filed Critical Engelhard Industries Inc
Priority to US692257A priority Critical patent/US2973283A/en
Priority to GB14510/58A priority patent/GB829730A/en
Priority to FR1195986D priority patent/FR1195986A/en
Priority to DEE15896A priority patent/DE1106577B/en
Priority to US760061A priority patent/US3065526A/en
Application granted granted Critical
Publication of US2973283A publication Critical patent/US2973283A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
    • C03B37/0805—Manufacturing, repairing, or other treatment of bushings, nozzles or bushing nozzle plates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
    • C03B37/095—Use of materials therefor
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/941—Solid state alloying, e.g. diffusion, to disappearance of an original layer
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12875—Platinum group metal-base component
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12889—Au-base component

Definitions

  • the present invention deals with a surface treatment for articles made from platinum-rhodium alloys, such articles being, more particularly, apparatus for handling molten glass as, for example, glass forming dies or extrusion nozzles for the spinning of glass fibers.
  • Alloys of platinum with up to about 50 percent rhodium have been suggested and used for the manufactureof many types of spinning nozzles for artificial fibers, these alloys combining the required properties for the purpose, to a large extent, such as hardness and corrosion resistance.
  • the desired properties of hardness, and of non-wetting by molten glass can be obtained by depositing, for example by electroplating or any other suitable method, a double coating upon an article of a platinum-rhodium alloy, which may be the portion of an apparatus which contacts molten glass, such as a spinnerette for spinning glass fibers, a die in a press or the like.
  • the article is coated with platinum, and then a coating of gold is applied upon the platinum layer whereupon the article is heated to diffusion temperature, preferably by placing it in a furnace at about 800 C. and gradually raising the temperature to about 1200 C.
  • the heat treatment causes the metals to diffuse into each other whereby, in the different boundary zones, solid solutions are formed, thus insuring that the coatings adhere firmly to each other and to the platinum-rhodium surface.
  • the coatings of platinum and gold may be in the range of about 0.0001 to about 0.001 inch and good results have been obtained with layers of about 0.0005 inch.
  • a surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface with platinum, subsequently applying a coating of gold upon the platinum layer, each of-the coatings being sufliciently thick to allow the formation of boundary zones of solid solutions, and heating to diffusion temperature to harden the outer surface of the article to a hardness at least equal to that of the platinum-rhodium alloy by the formation of said solid solutions.
  • a surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface with platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings being sufficiently thick to allow the formation of boundary zones of solid solutions, heating to about 800 C. and
  • a surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface of the article with a layer of platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings having a thickness of about 0.000110 about 0.001 inch, and, heating to' produce diffusion of platinum metal from the platinum layer into said article and into said gold coating.
  • a surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface of the article with a layer of platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings having a thickness of about 0.0001 to about 0.001 inch, and heating to about 1200 C.
  • a surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface of the article with a layer of platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings having a thickness: of about 0.0001 to about 0.001 inch, heating to about 800 C. and gradually raising the temperature to about 1200 C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Description

United States I atent SURFACE TREATMENT James S. Hill, Cranford, N.J., assignor, by mesne assignments, to Eugelhard Industries, Inc., Newark, N.J., a corporation of Delaware No Drawing. Filed Oct. 25, 1957, Ser. No. 692,257 5 Claims. (Cl. 117-71) The present invention deals with a surface treatment for articles made from platinum-rhodium alloys, such articles being, more particularly, apparatus for handling molten glass as, for example, glass forming dies or extrusion nozzles for the spinning of glass fibers.
Alloys of platinum with up to about 50 percent rhodium have been suggested and used for the manufactureof many types of spinning nozzles for artificial fibers, these alloys combining the required properties for the purpose, to a large extent, such as hardness and corrosion resistance.
However, for apparatus handling molten glass, such as e.g. glass spinnerettes, a further requirement for satisfactory operation becomes important, i.e., the surface which is in contact with the molten glass should not be wetted thereby. This requirement is not satisfactorily met by the platinum-rhodium alloys used heretofore. On the other hand, it is known that platinum-gold alloys show a considerable resistance to wetting by molten glass, but they are mechanically insufiiciently resistant, especially at the high temperatures of molten glass.
It has been found that the desired properties of hardness, and of non-wetting by molten glass, can be obtained by depositing, for example by electroplating or any other suitable method, a double coating upon an article of a platinum-rhodium alloy, which may be the portion of an apparatus which contacts molten glass, such as a spinnerette for spinning glass fibers, a die in a press or the like.
According to the invention, the article is coated with platinum, and then a coating of gold is applied upon the platinum layer whereupon the article is heated to diffusion temperature, preferably by placing it in a furnace at about 800 C. and gradually raising the temperature to about 1200 C. The heat treatment causes the metals to diffuse into each other whereby, in the different boundary zones, solid solutions are formed, thus insuring that the coatings adhere firmly to each other and to the platinum-rhodium surface.
A fiow diagram illustrating the order of steps is as follows:
Platinum Rhodium Alloy Body Coating Step Platinum I Platinum Rhodium Alloy Body with Platinum Coating Platinum Rhodium Alloy Body with Platinum and Gold Coatings Heat Treatment Platinum Rhodium Alloy Body with Diffused Platinum and Gold Coatings The coatings of platinum and gold may be in the range of about 0.0001 to about 0.001 inch and good results have been obtained with layers of about 0.0005 inch.
Moreover, it has been found by tests made with platinum-rhodium alloys containing 10 percent to 40 percent by weight rhodium that the surfaces obtained display a combination of properties which the single components do not shown. The surfaces are extremely repellent to molten glass, due to the predominating content of gold in the outer layer, wherein some platinum but practically no rhodium is present, but at the same time the hardness is increased beyond the hardness the original platinumrhodium alloy would have attained, when subjected to the same heat treatment, without being coated or if coated with one of the components only.
It is believed that this result is due to the formation of solid solutions which are gradually enriched in gold near the surface whereas an increasing content of rhodium is present deeper in the metal. The intermediate layer of platinum prevents undesirable diifusion between the rhodium content of the alloy and the gold coating, thus acting simultaneously as a buffer and as a bonding agent between the platinum-rhodium alloy and the gold layer.
It will be obvious to those skilled in the art that many modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.
What is claimed is:
1. A surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface with platinum, subsequently applying a coating of gold upon the platinum layer, each of-the coatings being sufliciently thick to allow the formation of boundary zones of solid solutions, and heating to diffusion temperature to harden the outer surface of the article to a hardness at least equal to that of the platinum-rhodium alloy by the formation of said solid solutions.
2. A surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface with platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings being sufficiently thick to allow the formation of boundary zones of solid solutions, heating to about 800 C. and
gradually raising the temperature to about 1200" C. to
harden the outer surface of the article to a hardness at least equal to that of the platinum-rhodium alloy by the formation ofv said solid solutions.
3. A surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface of the article with a layer of platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings having a thickness of about 0.000110 about 0.001 inch, and, heating to' produce diffusion of platinum metal from the platinum layer into said article and into said gold coating.
4. A surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface of the article with a layer of platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings having a thickness of about 0.0001 to about 0.001 inch, and heating to about 1200 C.
5. A surface treatment for articles made from platinum-rhodium alloys which comprises coating the surface of the article with a layer of platinum, subsequently applying a coating of gold upon the platinum layer, each of the coatings having a thickness: of about 0.0001 to about 0.001 inch, heating to about 800 C. and gradually raising the temperature to about 1200 C.
References Cited in the file of this patent UNITED STATES PATENTS Fry Mar. 5, 1929 Hostetter Jan. 25, 1938 Stevens Feb. 1, 1949 Davignon l July 28, 1953 Chester et al. June 18, 1957 Klausrnann Aug. 27, 1957 Homer et al. Nov. 19, 1957 Wrotnowski -'Mar. 29, 1960

Claims (1)

1. A SURFACE TREATMENT FOR ARTICLES MADE FROM PLATINUM-RHODIUM ALLOYS WHICH COMPRISES COATING THE SURFACE WITH PLATINUM, SUBSEQUENTLY APPLYING A COATING OF GOLD UPON THE PLATINUM LAYER, EACH OF THE COATINGS BEING SUFFICIENTLY THICK TO ALLOW THE FORMATION OF BOUNDARY ZONES OF SOLID SOLUTIONS, AND HEATING TO DIFFUSION TEMPERATURE TO HARDEN THE OUTER SURFACE OF THE ARTICLE TO A HARDNESS AT LEAST EQUAL TO THAT OF THE PLATINUM-RHODIUM ALLOY BY THE FORMATION OF SAID SOLID SOLUTIONS.
US692257A 1957-10-25 1957-10-25 Surface treatment Expired - Lifetime US2973283A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US692257A US2973283A (en) 1957-10-25 1957-10-25 Surface treatment
GB14510/58A GB829730A (en) 1957-10-25 1958-05-06 Improvements in or relating to the surface treatment of articles made from platinum-rhodium alloys
FR1195986D FR1195986A (en) 1957-10-25 1958-05-19 Process for surface treatment of parts made of platinum and rhodium alloys
DEE15896A DE1106577B (en) 1957-10-25 1958-05-20 Process for the production of objects from a platinum-rhodium alloy, e.g. B. spinnerets for glass
US760061A US3065526A (en) 1957-10-25 1958-09-10 Material for handling molten glass

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3117846A (en) * 1960-01-28 1964-01-14 Pfaudler Permutit Inc Multi layer difusion coatings and method of applying the same
US3137766A (en) * 1957-12-16 1964-06-16 Norton Co Electric wire for use at high temperatures
US3162512A (en) * 1961-03-21 1964-12-22 Engelhard Ind Inc Immersion plating with noble metals and the product thereof
US3208871A (en) * 1962-07-30 1965-09-28 Minnesota Mining & Mfg Method of making stain-resistant roofing granules, and product thereof
US3210167A (en) * 1962-04-19 1965-10-05 Louyot Comptoir Lyon Alemand Metallic appliances and components subjected to contact with molten materials at high temperature
US3219426A (en) * 1961-09-14 1965-11-23 Owens Illinois Glass Co Apparatus and method for drawing glass tubes, rods, or the like
US3221393A (en) * 1961-09-05 1965-12-07 Victory Engineering Corp Method of making bead type thermistors
US3293064A (en) * 1962-07-23 1966-12-20 Ling Temco Vought Inc Method of making heat resistant article
US3371409A (en) * 1964-10-29 1968-03-05 Engelhard Ind Inc Method of making a mandrel for precision-shaping internal surfaces on glass vessels
US3393446A (en) * 1966-05-23 1968-07-23 Philips Corp Method for joining aluminum to metals
US3428476A (en) * 1965-06-22 1969-02-18 Engelhard Min & Chem Method for producing hydrogen diffusion cells
US3457052A (en) * 1965-09-14 1969-07-22 Westinghouse Electric Corp High temperature,electrically conductive hermetic seals
US3514841A (en) * 1967-05-17 1970-06-02 Owens Corning Fiberglass Corp Forming a tip section that feeds streams of heat-softened material
US4525433A (en) * 1981-09-08 1985-06-25 Johnson Matthey Public Limited Company Composite material
EP0470822A1 (en) * 1990-08-10 1992-02-12 Bend Research, Inc. Hydrogen-permeable composite metal membrane

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1704126A (en) * 1924-09-23 1929-03-05 Wilson H A Co Composite precious-metal stock
US2106527A (en) * 1936-06-27 1938-01-25 Corning Glass Works Refractory for contacting molten glass
US2460547A (en) * 1946-10-07 1949-02-01 Glass Fibers Inc Drawing crucible
US2646616A (en) * 1949-09-06 1953-07-28 Metals & Controls Corp Composite metal having precious metal surface and berylliumcopper base
US2796361A (en) * 1953-04-15 1957-06-18 Poor & Co Method of making corrosion protected articles
US2803925A (en) * 1951-10-25 1957-08-27 Baker & Co Inc Glass forming die
US2813803A (en) * 1955-06-22 1957-11-19 Ohio Commw Eng Co Method for the production of composite metallic material
US2930106A (en) * 1957-03-14 1960-03-29 American Felt Co Gaskets

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1704126A (en) * 1924-09-23 1929-03-05 Wilson H A Co Composite precious-metal stock
US2106527A (en) * 1936-06-27 1938-01-25 Corning Glass Works Refractory for contacting molten glass
US2460547A (en) * 1946-10-07 1949-02-01 Glass Fibers Inc Drawing crucible
US2646616A (en) * 1949-09-06 1953-07-28 Metals & Controls Corp Composite metal having precious metal surface and berylliumcopper base
US2803925A (en) * 1951-10-25 1957-08-27 Baker & Co Inc Glass forming die
US2796361A (en) * 1953-04-15 1957-06-18 Poor & Co Method of making corrosion protected articles
US2813803A (en) * 1955-06-22 1957-11-19 Ohio Commw Eng Co Method for the production of composite metallic material
US2930106A (en) * 1957-03-14 1960-03-29 American Felt Co Gaskets

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137766A (en) * 1957-12-16 1964-06-16 Norton Co Electric wire for use at high temperatures
US3117846A (en) * 1960-01-28 1964-01-14 Pfaudler Permutit Inc Multi layer difusion coatings and method of applying the same
US3162512A (en) * 1961-03-21 1964-12-22 Engelhard Ind Inc Immersion plating with noble metals and the product thereof
US3221393A (en) * 1961-09-05 1965-12-07 Victory Engineering Corp Method of making bead type thermistors
US3219426A (en) * 1961-09-14 1965-11-23 Owens Illinois Glass Co Apparatus and method for drawing glass tubes, rods, or the like
US3210167A (en) * 1962-04-19 1965-10-05 Louyot Comptoir Lyon Alemand Metallic appliances and components subjected to contact with molten materials at high temperature
US3293064A (en) * 1962-07-23 1966-12-20 Ling Temco Vought Inc Method of making heat resistant article
US3208871A (en) * 1962-07-30 1965-09-28 Minnesota Mining & Mfg Method of making stain-resistant roofing granules, and product thereof
US3371409A (en) * 1964-10-29 1968-03-05 Engelhard Ind Inc Method of making a mandrel for precision-shaping internal surfaces on glass vessels
US3428476A (en) * 1965-06-22 1969-02-18 Engelhard Min & Chem Method for producing hydrogen diffusion cells
US3457052A (en) * 1965-09-14 1969-07-22 Westinghouse Electric Corp High temperature,electrically conductive hermetic seals
US3393446A (en) * 1966-05-23 1968-07-23 Philips Corp Method for joining aluminum to metals
US3514841A (en) * 1967-05-17 1970-06-02 Owens Corning Fiberglass Corp Forming a tip section that feeds streams of heat-softened material
US4525433A (en) * 1981-09-08 1985-06-25 Johnson Matthey Public Limited Company Composite material
EP0470822A1 (en) * 1990-08-10 1992-02-12 Bend Research, Inc. Hydrogen-permeable composite metal membrane

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