US3811920A - Silicon carbide surfaced filaments with titanium carbide coating - Google Patents

Silicon carbide surfaced filaments with titanium carbide coating Download PDF

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Publication number
US3811920A
US3811920A US00215593A US21559372A US3811920A US 3811920 A US3811920 A US 3811920A US 00215593 A US00215593 A US 00215593A US 21559372 A US21559372 A US 21559372A US 3811920 A US3811920 A US 3811920A
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US
United States
Prior art keywords
silicon carbide
titanium
filaments
coating
carbide
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
Application number
US00215593A
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English (en)
Inventor
F Galasso
B Jacob
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raytheon Technologies Corp
Original Assignee
United Aircraft Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Aircraft Corp filed Critical United Aircraft Corp
Priority to US00215593A priority Critical patent/US3811920A/en
Priority to FR7246121A priority patent/FR2166373B1/fr
Priority to JP48003981A priority patent/JPS4879800A/ja
Priority to IT33799/72A priority patent/IT973100B/it
Priority to GB50173A priority patent/GB1386551A/en
Priority to DE2300510A priority patent/DE2300510A1/de
Application granted granted Critical
Publication of US3811920A publication Critical patent/US3811920A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4584—Coating or impregnating of particulate or fibrous ceramic material
    • 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
    • Y10T428/2916—Rod, strand, filament or fiber including boron or compound thereof [not as steel]
    • 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]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • a composite filament suitable for use as a reinforcement in titanium or nickel matrices comprises a filamentary substrate having a silicon carbide I surface layerand a thin, adherent outer layer consisting essentially of titanium carbide.
  • silicon carbide surfaced filaments such as silicon carbide, silicon carbide coated boron and silicon carbide coated carbon are useful as reinforcing materials in composite structures, particularly silicon carbide coated boron filaments such as those taught in US. Pat. No. 3,622,369, commonly owned by the assignee of the present invention.
  • silicon carbide surfaced filaments as reinforcements in the resin matrices and in certain metal matrices such as aluminum and magnesium is recognized in the industry.
  • silicon carbide While the reactivity of silicon carbide is lower than that of, for example, boron, it has itself been sufficiently high to necessitate the use of relatively low temperature or short time at temperature processes during fabrication of the filament reinforced metal composites in order to prevent fiber degradation. In addition, it limits the choice of metal matrix material and further, may well define the temperature to which the structure is limited in operation.
  • the present invention relates to composite filaments and, more particularly to silicon carbide surfaced filaments such as filaments of silicon carbide, silicon carbide coated boron, silicon carbide coated carbon and the like which are provided with a thin, adherent coating of titanium carbide.
  • Titanium carbide has been found to be compatible with silicon carbide surfaced substrates as well as with such metal matrix materials as titanium and nickel. It has been found that a titanium carbide coating on a silicon carbide surfaced filament to a thickness of only 0.03 mil will not only impart oxidation resistance to the filament but, in addition, will provide a diffusion barrier between the silicon carbide surfaced substrate and such matrix metals as titanium and nickel whereby fiber degradation is minimized in processes wherein temperatures above 800C are employed.
  • Titanium carbide is advantageous in several respects. Because it may perform its principal function as surface protection for silicon carbide surfaced filaments, such as the high modulus, high strength, low density silicon carbide coated boron in very thin thicknesses, only a very small weight penalty is paid as a result of its addition. Furthermore, while there is a coefficient of thermal expansion mismatch in the use of titanium carbide, no problem in this regard has been presented in actual practice, primarily because of the thin film aspect.
  • FIG. 1 is a simple sketch, taken in elevation, of apparatus used in the production of the titanium carbide coating on the filaments of the present invention.
  • FIG. 2 is an enlarged cross-sectional view through one of the filaments of the present invention.
  • the titanium carbide coating is produced on a resistively heated silicon carbide surface filament 2 which is drawn downwardly through a reactor 4 comprising a tubular containment vessel 6, having dual gas inlets 8 and 10 at the upper end of the reactor and a single exhaust part 12 at the lower end thereof. Cooling hydrogen is fed to the reactor through inlet 8, and inlet 10 is used for the introduction of a reactant gas mixture comprising methane and titanium chloride (TiCl).
  • the containment vessel may be formed of Pyrex, although a number of other materials including Vycor and quartz will be found satisfactory.
  • the gas inlets 8 and 10 and the exhaust l2 penetrate and are electrically connected to the metallic end plugs l4and 16 which provide the end closure for the containment vessel and, also provide convenient means by which power may be supplied to the wire for resistance heating purposes.
  • the end plugs are each respectively provided with a well 20 and 22, for containing a suitable conductive sealant 24, such as mercury, which serves the dual purpose of providing a gas seal around the wire where it penetrates the end plugs, and furtherproviding electrical contact between the moving wire and the respective end plugs which are in turn electrically connected through the tubes 10 and 12 and the leads 26 and 28 to a suitable DC power source 30.
  • the upper plug 14 is provided with a peripheral groove 34, which communicates with the mercury well 20 through the passageway 36, to provide peripheral sealing around the plug. Sealing between the end plug 16 and the lower end of the containment vessel 6 is provided by mercury contained in an annular well 38.
  • the respective plugs are each formed with a centrally oriented orifice 40 and 42 which is large enough to accomodate the free passage of the wire 2 therethrough but which, in combination with the wire, is small enough to retain the mercury, through surface tension forces, in their respective wells.
  • the hydrogen admitted through the inlet 8 enters the reactant chamber immediately adjacent the wire inlet and is used primarily for cooling purposes at the end plug 14.
  • passage through the reactor results in a composite filament comprising a silicon carbide surfaced substrate 46 having a thin adherent coating of titanium carbide 48.
  • the filaments are consolidated and bonded to the desired matrix material by hot pressing.
  • EXAMPLE I In a reactor of the type illustrated, utilizing an 8 inch long reactor formed from 25 mm Pyrex tubing and a reactant gas mixture of methane, hydrogen and titanium chloride, a titanium carbide coating was produced on silicon carbide coated boron filaments heated to 1 150C and passed through the reactor at a rate of 600 ft./hour (reactor dwell time: 4 seconds).
  • the substrate filaments are commercially available from Hamilton Standard Division of United Aircraft Corporation and comprised 4 mil boron filaments having a 0.15 mil thick coating of silicon carbide and an average UTS of 410,000 psi. The total gas flow through the reactor was maintained at 500 cc/min.
  • the titanium carbide coating was verified by X-ray diffraction and electrical conductivity measurements showed marked decrease in resistance.
  • the coating was found to be thin (0.03 mils) and adherent with the.
  • coated filament exhibiting a UTS of 360,000 psi.
  • EXAMPLE III The same apparatus and conditions were utilized as in Example ll except that substrate temperature was l,lOC and the hydrogen/methane 'ratio was to l. Adherent titanium carbide coatings were approximately 0.02 mils thick, were produced on ten samples and the composite coated filament exhibited an average UTS of 372,000 psi.
  • EXAMPLE IV The same apparatus and conditions were utilized as in Example I except that substrate filament speed was 150 ft./hour (reactor dwell time: 16 seconds), substrate temperature was l,l00C and the hydrogen/methane ratio was 25 to l.
  • the titanium carbide coating was of similar thickness and quality as that produced in Example l and the'filament had a UTS of 325,000 'psi.
  • Example IV was repeated except that substrate temperature was l,l50C and the hydrogen/methane ratio was to l.
  • the titanium carbide coated filament had a UTS of 365,000 psi.
  • Example VI In the reactor apparatus of Example I a thin, adherent titanium carbide coating is produced on a silicon carbide coated carbon filament (1 mil circular cross section carbon monofilainent available from Great Lakes Carbon Corporation) heated to l,100C and passed through a reactant gas mixture of methane, hydrogen and titanium chloride in the reactor at a rate of 240 ft./hour (dwell time: 10 seconds). The total gas flow through the reactor is maintained at 500 cc/min. and the hydrogen/methane ratio is maintained at 5 to l. The methane is saturated with TiCl, as in Example I.
  • EXAMPLE VII Utilizing the apparatus and conditions of Example VI, a titanium carbide coating is produced on a silicon carbide filament p. continuous filament from Dow Corning or General Technologies Corporation).
  • the deposition of titanium carbide doesresult in a small reduction in average strength of the composite filament. This reduction is relatively slight, however, when the proper process conditions are observed.
  • the parameters set forth in Example III show a reduction of only 7 percent (410,000 psi to 372,000 psi) in strength. This reduction is not considered significant in view of the fact that the TiC coated filaments allow bonding with titanium or nickel matrices which normally, at temper atures above 800C, attack and destroy silicon carbide surfaced filaments. In the present case, titanium coated filaments were subjected to compatibility testing in matrices of nickel and titanium.
  • Composites were prepared by hot pressing TiC coated silicon carbide surfaced filaments with Ti powder at 900C and 5,000 psi for 30 minutes. They were also prepared by hot pressing with Ni powder at 850C and 5,000 psi for 3 minutes. In all cases, the TiC coated filament was not attacked by either the titanium or the nickel.
  • a composite filament for use as a reinforcement in matrices of titanium and nickel comprising:
  • a filamentary substrate selected from the group consisting of silicon carbide, silicon carbide coated boron and silicon carbide coated carbon;
  • a thin adherent outer layer which consists essentially of titanium carbide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Products (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Inorganic Fibers (AREA)
US00215593A 1972-01-05 1972-01-05 Silicon carbide surfaced filaments with titanium carbide coating Expired - Lifetime US3811920A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US00215593A US3811920A (en) 1972-01-05 1972-01-05 Silicon carbide surfaced filaments with titanium carbide coating
FR7246121A FR2166373B1 (xx) 1972-01-05 1972-12-20
JP48003981A JPS4879800A (xx) 1972-01-05 1972-12-27
IT33799/72A IT973100B (it) 1972-01-05 1972-12-29 Filamenti per rinforzo metallurgico con strato superficiale di carburo di silicio rivestiti di carburo di titanio
GB50173A GB1386551A (en) 1972-01-05 1973-01-04 Silicon carbide surfaced filaments with titanium carbide coating
DE2300510A DE2300510A1 (de) 1972-01-05 1973-01-05 Verstaerkungsfaser fuer titan- und nickelmatrices

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00215593A US3811920A (en) 1972-01-05 1972-01-05 Silicon carbide surfaced filaments with titanium carbide coating

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US3811920A true US3811920A (en) 1974-05-21

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US00215593A Expired - Lifetime US3811920A (en) 1972-01-05 1972-01-05 Silicon carbide surfaced filaments with titanium carbide coating

Country Status (6)

Country Link
US (1) US3811920A (xx)
JP (1) JPS4879800A (xx)
DE (1) DE2300510A1 (xx)
FR (1) FR2166373B1 (xx)
GB (1) GB1386551A (xx)
IT (1) IT973100B (xx)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993818A (en) * 1975-02-28 1976-11-23 United Technologies Corporation Resin bonded composite articles and process for fabrication thereof
US4068037A (en) * 1976-01-02 1978-01-10 Avco Corporation Silicon carbide filaments and method
US4072516A (en) * 1975-09-15 1978-02-07 Fiber Materials, Inc. Graphite fiber/metal composites
US4139659A (en) * 1975-06-02 1979-02-13 Lumalampan Ab Thin composite wire saw with surface cutting crystals
US4373006A (en) * 1979-08-09 1983-02-08 United Technologies Corporation Silicon carbide coated carbon fibers and composites
US4405685A (en) * 1980-11-13 1983-09-20 Agency Of Industrial Science & Technology, Ministry Of International Trade & Industry Carbon fibers with duplex metal carbide coating and methods for manufacture thereof
US4596741A (en) * 1982-12-06 1986-06-24 Shin-Etsu Chemical Co., Ltd. Carbon fibers having improved surface properties and a method for the preparation thereof
WO1987005831A1 (en) * 1986-03-31 1987-10-08 Spectran Corporation Hermetic coatings for optical fibers
US4772524A (en) * 1986-04-14 1988-09-20 The United States Of America As Represented By The Secretary Of Commerce Fibrous monolithic ceramic and method for production
US4874222A (en) * 1986-03-31 1989-10-17 Spectran Corporation Hermetic coatings for non-silica based optical fibers
US5114785A (en) * 1990-10-09 1992-05-19 The Standard Oil Company Silicon based intermetallic coatings for reinforcements
US5156912A (en) * 1989-12-20 1992-10-20 The Standard Oil Company Multi-layer coatings for reinforcements in high temperature composites
US5162159A (en) * 1991-11-14 1992-11-10 The Standard Oil Company Metal alloy coated reinforcements for use in metal matrix composites
US5227249A (en) * 1991-10-03 1993-07-13 Standard Oil Company Boride coatings for SiC reinforced Ti composites
US5238741A (en) * 1989-10-19 1993-08-24 United Kingdom Atomic Energy Authority Silicon carbide filaments bearing a carbon layer and a titanium carbide or titanium boride layer
US5262235A (en) * 1991-10-28 1993-11-16 General Electric Company Coated ceramic fiber system
US5270112A (en) * 1989-12-20 1993-12-14 Standard Oil Company Hybrid reinforcements for high temperature composites and composites made therefrom
US5273833A (en) * 1989-12-20 1993-12-28 The Standard Oil Company Coated reinforcements for high temperature composites and composites made therefrom
DE3822578A1 (de) * 1987-06-12 1994-01-27 Lanxide Technology Co Ltd Beschichteter keramischer Füllstoff
US5354615A (en) * 1990-06-27 1994-10-11 The Carborundum Company Coated SiC reinforcements and composites containing same
US5571561A (en) * 1992-10-27 1996-11-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Coated filaments
US5645781A (en) * 1994-09-21 1997-07-08 The Regents Of The University Of Michigan Process for preparing textured ceramic composites
US20070110913A1 (en) * 2005-10-05 2007-05-17 Snecma Method for metallic coating of fibres by liquid technique
US8753720B2 (en) 2007-12-27 2014-06-17 Lockheed Martin Corporation Nano-structured refractory metals, metal carbides, and coatings and parts fabricated therefrom

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60232184A (ja) * 1984-05-01 1985-11-18 株式会社　小賀坂スキ−製作所 スキ−
GB8923588D0 (en) * 1989-10-19 1989-12-06 Atomic Energy Authority Uk Coated filaments for composites
GB2264617A (en) * 1991-10-08 1993-09-01 Atomic Energy Authority Uk Porous heating element
FR3036409B1 (fr) * 2015-05-21 2019-08-02 Safran Materiau composite a matrice metallique a base nickel et procede de fabrication d'un tel materiau composite

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993818A (en) * 1975-02-28 1976-11-23 United Technologies Corporation Resin bonded composite articles and process for fabrication thereof
US4139659A (en) * 1975-06-02 1979-02-13 Lumalampan Ab Thin composite wire saw with surface cutting crystals
US4072516A (en) * 1975-09-15 1978-02-07 Fiber Materials, Inc. Graphite fiber/metal composites
US4127659A (en) * 1976-01-02 1978-11-28 Avco Corporation Silicon carbide filaments and method
US4068037A (en) * 1976-01-02 1978-01-10 Avco Corporation Silicon carbide filaments and method
US4373006A (en) * 1979-08-09 1983-02-08 United Technologies Corporation Silicon carbide coated carbon fibers and composites
US4405685A (en) * 1980-11-13 1983-09-20 Agency Of Industrial Science & Technology, Ministry Of International Trade & Industry Carbon fibers with duplex metal carbide coating and methods for manufacture thereof
US4596741A (en) * 1982-12-06 1986-06-24 Shin-Etsu Chemical Co., Ltd. Carbon fibers having improved surface properties and a method for the preparation thereof
US4735856A (en) * 1986-03-31 1988-04-05 Spectran Corporation Hermetic coatings for optical fiber and product
WO1987005831A1 (en) * 1986-03-31 1987-10-08 Spectran Corporation Hermetic coatings for optical fibers
US4874222A (en) * 1986-03-31 1989-10-17 Spectran Corporation Hermetic coatings for non-silica based optical fibers
US4772524A (en) * 1986-04-14 1988-09-20 The United States Of America As Represented By The Secretary Of Commerce Fibrous monolithic ceramic and method for production
DE3822578A1 (de) * 1987-06-12 1994-01-27 Lanxide Technology Co Ltd Beschichteter keramischer Füllstoff
US5238741A (en) * 1989-10-19 1993-08-24 United Kingdom Atomic Energy Authority Silicon carbide filaments bearing a carbon layer and a titanium carbide or titanium boride layer
US5270112A (en) * 1989-12-20 1993-12-14 Standard Oil Company Hybrid reinforcements for high temperature composites and composites made therefrom
US5156912A (en) * 1989-12-20 1992-10-20 The Standard Oil Company Multi-layer coatings for reinforcements in high temperature composites
US5273833A (en) * 1989-12-20 1993-12-28 The Standard Oil Company Coated reinforcements for high temperature composites and composites made therefrom
US5354615A (en) * 1990-06-27 1994-10-11 The Carborundum Company Coated SiC reinforcements and composites containing same
US5114785A (en) * 1990-10-09 1992-05-19 The Standard Oil Company Silicon based intermetallic coatings for reinforcements
US5227249A (en) * 1991-10-03 1993-07-13 Standard Oil Company Boride coatings for SiC reinforced Ti composites
US5262235A (en) * 1991-10-28 1993-11-16 General Electric Company Coated ceramic fiber system
US5162159A (en) * 1991-11-14 1992-11-10 The Standard Oil Company Metal alloy coated reinforcements for use in metal matrix composites
US5571561A (en) * 1992-10-27 1996-11-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Coated filaments
US5645781A (en) * 1994-09-21 1997-07-08 The Regents Of The University Of Michigan Process for preparing textured ceramic composites
US20070110913A1 (en) * 2005-10-05 2007-05-17 Snecma Method for metallic coating of fibres by liquid technique
US7687114B2 (en) * 2005-10-05 2010-03-30 Snecma Method for metallic coating of fibres by liquid technique
CN1944714B (zh) * 2005-10-05 2011-08-10 斯奈克玛 采用液体技术进行纤维的金属包覆方法
US8753720B2 (en) 2007-12-27 2014-06-17 Lockheed Martin Corporation Nano-structured refractory metals, metal carbides, and coatings and parts fabricated therefrom
US9469543B2 (en) 2007-12-27 2016-10-18 Lockheed Martin Corporation Nano-structured refractory metals, metal carbides, and coatings and parts fabricated therefrom

Also Published As

Publication number Publication date
JPS4879800A (xx) 1973-10-25
DE2300510A1 (de) 1973-07-12
FR2166373A1 (xx) 1973-08-17
IT973100B (it) 1974-06-10
FR2166373B1 (xx) 1976-10-29
GB1386551A (en) 1975-03-05

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