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US3177094A - Method for coating a molybdenum wire with a carbon layer and the coated article - Google Patents

Method for coating a molybdenum wire with a carbon layer and the coated article Download PDF

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Publication number
US3177094A
US3177094A US202829A US20282962A US3177094A US 3177094 A US3177094 A US 3177094A US 202829 A US202829 A US 202829A US 20282962 A US20282962 A US 20282962A US 3177094 A US3177094 A US 3177094A
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Prior art keywords
layer
coating
wire
carbon
molybdenum wire
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US202829A
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Dijksterhuis Popko Reinder
Melsert Hans
Zuidema Poppe
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US Philips Corp
North American Philips Co Inc
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US Philips Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J19/00—Details of vacuum tubes of the types covered by group H01J21/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2893/00—Discharge tubes and lamps
    • H01J2893/0001—Electrodes and electrode systems suitable for discharge tubes or lamps
    • H01J2893/0012—Constructional arrangements
    • H01J2893/0019—Chemical composition and manufacture
    • H01J2893/0022—Manufacture
    • H01J2893/0023—Manufacture carbonising and other surface treatments
    • 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
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/19—Inorganic fiber
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y10T428/292—In coating or impregnation
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/296—Rubber, cellulosic or silicic material in coating

Definitions

  • the invention relates to a method of coating at low temperature (approximately 1100 C.) a molybdenum wire with a satisfactorily adhering carbon layer, and to a grid electrode for an electric discharge tube provided with such a wire.
  • a carbon layer reacts with a molybdenum substratum so that the carbon disappears into the surface.
  • an intermediate layer of a carbide for example silicon carbide
  • silica and a carbon-containing substance by coating the core with silica and a carbon-containing substance and by heating in an inert atmosphere to from 1700 to 2000 C. to reduce the oxides and to produce a carbide layer.
  • a carbon layer could be applied, for example in the form of powdered graphite.
  • the molybdenum core becomes very brittle as a result of the strong heating.
  • the electrodes must generally be formed first prior to the application of the layers of carbide and carbon respectively. A strong heating was then always necessary, since otherwise no intermediate carbide layer was formed. When the carbides were applied to the electrodes in this manner, it was necessary to heat to temperatures above 2000 C. in order to melt the carbides and to obtain a satisfactory adhesion of the carbon layer.
  • the molybdenum wire is first passed through an atmosphere of silicon chloride (SiCl at a temperature of approximately 900 C. and subsequently through an atmosphere of carbon tetrachloride (CCl at approximately 1100 C.
  • SiCl silicon chloride
  • CCl carbon tetrachloride
  • the molybdenum core is coated with a very satisfactorily adhering intermediate layer of silicon and thereon a carbon layer and that it can be wound to grids without the use of further provision, since the applied layers are so thin that they substantially do not affect the mechanical properties of the molybdenum. It is assumed that the satisfactory adhesion is obtained in that from the Mo-core to the outside the following layers are found: Mosi Si; SiC; C. It is surprising to find that the reaction between Si and C which generally takes place at a high temperature, can now occur already at approximately 1100 C., which 3,177,094 Patented Apr. 6, 1965 is probably due to the purifying effect of the carbon tetrachloride.
  • the coating process can be carried out very rapidly. A stay of approximately 1 /2 seconds in each gas atmosphere is suflicient for the wire to be coated with an assembly, of the said layers having a total thickness of approximately 1,u..
  • the speed of the wire may be from approximately 1000 to 2000 metres per hour, while the length of the furnaces in which the gas atmospheres prevail is approximately 1 m.
  • FIG. 1 diagrammatically illustrates the method
  • FIG. 2 shows a grid manufactured with a molybdenum wire coated in accordance with the invention.
  • FIG. 3 shows an enlarged sectional view of the wire.
  • reference numeral 1 denotes the Mo-wire which travels from a supply reel 2 to a supply reel 3 through the furnaces 4 and 5.
  • the wire is heated by means of passage of current through the wire 1, forexample by means of sliding contacts 6.
  • a suitable speed at which the wire passes through the furnaces is approximately 1000 m./hour, the total layer thickness on the wire being approximately 1 Silicon tetrachloride (SiCl is supplied to the furnace 4 and carbon tetrachloride to the furnace 5, both in a gaseous form.
  • the wire thickness may be from'40 to microns.
  • the grid 9 shown in FIG. 2 has a satisfactory radiation of heat and a low primary and secondary emission as a result of the black carbon layer 8 on the surface of the wire 1, shown in FIG. 3.
  • the intermediate silicon layer is designated by 7.
  • the boundary films (not shown) between the core 1 and the layer 7 and between the layers 7 and 8 probably consist of the compounds MoSi and SiC, as was already indicated.
  • a method of coating a molybdenum wire with a satisfactorily adhering carbon layer comprising the steps of passing the molybdenum Wire through an atmosphere of silicon tetrachloride heated to a temperature of approximately 900 C. to deposit a layer of silicon thereon and subsequently passing the silicon-coated molybdenum Wire through an atmosphere of carbon tetrachloride heated to approximately 1100 C. to deposit a coating of carbon thereon.
  • a carbon-coated molybdenum wire for a grid electrode of an electric discharge tube comprising a core of molybdenum, a layer of MoSi adjacent said core, a layer of silicon adjacent the layer of MoSi a layer of silicon carbide adjacent said silicon layer, and an outer layer of carbon covering said silicon carbide layer.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Resistance Heating (AREA)
  • Carbon And Carbon Compounds (AREA)

Description

p 1955 P. R. DIJKSTERHUIS ETAL 3,177,094
METHOD FOR COATING A MOLYBDENUM WIRE WITH A CARBQN LAYER AND THE COATED ARTICLE Filed June 15, 1962 Si CI. CCl
INVENTOR RDgKETERHUIS United States Patent 6 2 Claims. (Cl. 117-216) The invention relates to a method of coating at low temperature (approximately 1100 C.) a molybdenum wire with a satisfactorily adhering carbon layer, and to a grid electrode for an electric discharge tube provided with such a wire.
It is known that, at approximately 900 C. to 1000 C., a carbon layer reacts with a molybdenum substratum so that the carbon disappears into the surface. In order to prevent this, it has already been suggested to apply an intermediate layer of a carbide, for example silicon carbide, by coating the core with silica and a carbon-containing substance and by heating in an inert atmosphere to from 1700 to 2000 C. to reduce the oxides and to produce a carbide layer. On this layer, a carbon layer could be applied, for example in the form of powdered graphite. However, it has been found that the molybdenum core becomes very brittle as a result of the strong heating. Consequently, in the known method, the electrodes must generally be formed first prior to the application of the layers of carbide and carbon respectively. A strong heating was then always necessary, since otherwise no intermediate carbide layer was formed. When the carbides were applied to the electrodes in this manner, it was necessary to heat to temperatures above 2000 C. in order to melt the carbides and to obtain a satisfactory adhesion of the carbon layer.
Contrary to all expectations, it has been found, however, that the formation of a satisfactorily adhering intermediate layer under a carbon layer on a molybdenum wire is already possible at a temperature of approximately 1100 C., so that the coated molybdenum wire fully preserves its mechanical properties and can be worked up to grid electrodes without the use of further means, if, according to the invention, the molybdenum wire is first passed through an atmosphere of silicon chloride (SiCl at a temperature of approximately 900 C. and subsequently through an atmosphere of carbon tetrachloride (CCl at approximately 1100 C.
It then appears that after this treatment, the molybdenum core is coated with a very satisfactorily adhering intermediate layer of silicon and thereon a carbon layer and that it can be wound to grids without the use of further provision, since the applied layers are so thin that they substantially do not affect the mechanical properties of the molybdenum. It is assumed that the satisfactory adhesion is obtained in that from the Mo-core to the outside the following layers are found: Mosi Si; SiC; C. It is surprising to find that the reaction between Si and C which generally takes place at a high temperature, can now occur already at approximately 1100 C., which 3,177,094 Patented Apr. 6, 1965 is probably due to the purifying effect of the carbon tetrachloride.
The coating process can be carried out very rapidly. A stay of approximately 1 /2 seconds in each gas atmosphere is suflicient for the wire to be coated with an assembly, of the said layers having a total thickness of approximately 1,u.. The speed of the wire may be from approximately 1000 to 2000 metres per hour, while the length of the furnaces in which the gas atmospheres prevail is approximately 1 m.
At a lower travelling speed, the layers become thicker, as a matter of fact.
The invention will now be described more fully with reference to the accompanying drawing in which:
FIG. 1 diagrammatically illustrates the method;
FIG. 2 shows a grid manufactured with a molybdenum wire coated in accordance with the invention; and
FIG. 3 shows an enlarged sectional view of the wire.
Referring now to FIG. 1, reference numeral 1 denotes the Mo-wire which travels from a supply reel 2 to a supply reel 3 through the furnaces 4 and 5. The wire is heated by means of passage of current through the wire 1, forexample by means of sliding contacts 6. A suitable speed at which the wire passes through the furnaces is approximately 1000 m./hour, the total layer thickness on the wire being approximately 1 Silicon tetrachloride (SiCl is supplied to the furnace 4 and carbon tetrachloride to the furnace 5, both in a gaseous form. The wire thickness may be from'40 to microns.
The grid 9 shown in FIG. 2 has a satisfactory radiation of heat and a low primary and secondary emission as a result of the black carbon layer 8 on the surface of the wire 1, shown in FIG. 3. The intermediate silicon layer is designated by 7. The boundary films (not shown) between the core 1 and the layer 7 and between the layers 7 and 8 probably consist of the compounds MoSi and SiC, as was already indicated.
What is claimed is:
1. A method of coating a molybdenum wire with a satisfactorily adhering carbon layer comprising the steps of passing the molybdenum Wire through an atmosphere of silicon tetrachloride heated to a temperature of approximately 900 C. to deposit a layer of silicon thereon and subsequently passing the silicon-coated molybdenum Wire through an atmosphere of carbon tetrachloride heated to approximately 1100 C. to deposit a coating of carbon thereon.
2. A carbon-coated molybdenum wire for a grid electrode of an electric discharge tube comprising a core of molybdenum, a layer of MoSi adjacent said core, a layer of silicon adjacent the layer of MoSi a layer of silicon carbide adjacent said silicon layer, and an outer layer of carbon covering said silicon carbide layer.
References Cited by the Examiner UNITED STATES PATENTS 876,331 l/08 Clark et al 117231 FOREIGN PATENTS 219,925 2/62 Austria.
RICHARD D. NEVIUS, Primary Examiner.

Claims (1)

1. A METHOD OF COATING A MOLYBDENUM WIRE WITH A SATISFACTORILY ADHERING CARBON LAYER COMPRISING THE STEPS OF PASSING THE MOLYBDENUM WIRE THROUGH AN ATMOSPHERE OF SILICON TETRACHLORIDE HEATED TO A TEMPERATURE OF APPROXIMATELY 900*C. TO DEPOSIT A LAYER OF SILICON THEREON AND SUBSEQUENTLY PASSING THE SILICON-COATED MOLYBDENUM WIRE THROUGH AN ATMOSPHERE OF CARBON TETRACLORIDE HEATED TO APPROXIMATELY 1100*C. TO DEPOSIT A COATING OF CARBON THEREON.
US202829A 1961-07-14 1962-06-15 Method for coating a molybdenum wire with a carbon layer and the coated article Expired - Lifetime US3177094A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3479205A (en) * 1966-10-14 1969-11-18 Gen Electric Process for producing boron filament
US3549413A (en) * 1969-07-28 1970-12-22 Gen Technologies Corp Reinforcing filaments comprising coated tungsten wires
US3604970A (en) * 1968-10-14 1971-09-14 Varian Associates Nonelectron emissive electrode structure utilizing ion-plated nonemissive coatings
US4212933A (en) * 1977-03-23 1980-07-15 Chloride Silent Power Limited Current collector for electrochemical cells and method of making
EP0450760A1 (en) * 1990-03-31 1991-10-09 The Secretary Of State For Defence Process for the manufacture of ceramic fibres
US5252359A (en) * 1990-03-31 1993-10-12 The British Petroleum Company P.L.C. CVD process for the manufacture of ceramic fibers
US20090114797A1 (en) * 2003-10-15 2009-05-07 Beals James T Refractory metal core coatings

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9022267D0 (en) * 1990-10-13 1990-11-28 British Petroleum Co Plc Process for depositing a coating on a fibre
FR2682125A1 (en) * 1991-10-07 1993-04-09 Nitruvid PROCESSING PROCESS FOR DEPOSITING A CARBON LAYER IN A STEAM PHASE ON THE SURFACE OF A METAL PART AND A PART THUS OBTAINED.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US876331A (en) * 1906-11-30 1908-01-14 Parker Clark Electric Company Process of making electric-lamp filaments.
AT219925B (en) * 1960-04-02 1962-02-26 Philips Nv Process for coating molybdenum wire with a layer of carbon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US876331A (en) * 1906-11-30 1908-01-14 Parker Clark Electric Company Process of making electric-lamp filaments.
AT219925B (en) * 1960-04-02 1962-02-26 Philips Nv Process for coating molybdenum wire with a layer of carbon

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3479205A (en) * 1966-10-14 1969-11-18 Gen Electric Process for producing boron filament
US3604970A (en) * 1968-10-14 1971-09-14 Varian Associates Nonelectron emissive electrode structure utilizing ion-plated nonemissive coatings
US3549413A (en) * 1969-07-28 1970-12-22 Gen Technologies Corp Reinforcing filaments comprising coated tungsten wires
US4212933A (en) * 1977-03-23 1980-07-15 Chloride Silent Power Limited Current collector for electrochemical cells and method of making
EP0450760A1 (en) * 1990-03-31 1991-10-09 The Secretary Of State For Defence Process for the manufacture of ceramic fibres
US5252359A (en) * 1990-03-31 1993-10-12 The British Petroleum Company P.L.C. CVD process for the manufacture of ceramic fibers
US20090114797A1 (en) * 2003-10-15 2009-05-07 Beals James T Refractory metal core coatings
US7575039B2 (en) * 2003-10-15 2009-08-18 United Technologies Corporation Refractory metal core coatings

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GB979467A (en) 1965-01-06

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