US3846224A - Boron filaments with a boron carbide antidiffusion coating,and metal matrix made therefrom - Google Patents

Boron filaments with a boron carbide antidiffusion coating,and metal matrix made therefrom Download PDF

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Publication number
US3846224A
US3846224A US00250287A US25028772A US3846224A US 3846224 A US3846224 A US 3846224A US 00250287 A US00250287 A US 00250287A US 25028772 A US25028772 A US 25028772A US 3846224 A US3846224 A US 3846224A
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US
United States
Prior art keywords
boron
filament
coating
filaments
cell
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Expired - Lifetime
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US00250287A
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English (en)
Inventor
M Damien
M Andreani
M Leclercq
D Morin
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PONDRES ET EXPLOSIFS SOC NAT D
SOC NAT DES PONDRES ET EXPLOSIFS FR
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PONDRES ET EXPLOSIFS SOC NAT D
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    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • 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
    • 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
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/268—Monolayer with structurally defined element
    • 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]

Definitions

  • An apparatus for production of the filaments comprises a tubular cell provided with gas inlet and outlet conduits and electrically-insulating plugs closing the ends of the cell.
  • Each plug is provided with a passageway therethrough for the filament and is supplied with mercury from a supply conduit.
  • the ends of each passageway are narrowed to substantially the diameter of the filament so that in use the mercury acts as an electrical contact with the filament to enable the latter to be heated by resistance heating yet is retained in the passageway by the narrowed ends to act as a gasket against gas flow through the passageway.
  • This invention is concerned with coated boron filaments and with a process and apparatus for the production thereof.
  • boron filaments have mechanical properties which make them suitable for use as reinforcing agents in composite materials.
  • Composite materials consisting of a synthetic resin matrix reinforced with boron filaments are already in use in certain specialised industries (such as the aerospace industry), but their use remains limited because of the low mechanical strength of the resin,..particularly at high temperatures.
  • metal and metal alloy matrices in filament-reinforced composite materials, but the chemical reactivity of boron with metal matrices, for example aluminium, magnesium, nickel and titanium, makes it impossible to incorporate boron filaments directly in such matrices, irrespective of whether molten metal processing methods or metal spraying by means of plasma arcs are used.
  • contact between aluminium and a boron filament at a temperature of about 650 0. results in degradation of the filament because of the formation of aluminium boride.
  • spraying of this metal by a plasma arc torch. A boron filament borided in this way loses 80% of its tenstile strength.
  • boron carbide (B C) coatings provided on boron filaments reduce the diffusion between the boron and the metal matrix yet do not substantially affect the mechanical properties of the filament.
  • boron filament having a boron carbide coating thereon of a coating thickness of no more than 15 microns, and preferably from 3 to 8 microns.
  • a method of producing a boron filament having a boron carbide coating thereon which comprises heating a boron filament at a temperature of from 900 to 1300 C. (preferably 1150 to 1300 C.) in the presence of a gaseous mixture of hydrogen, a hydrocarbon (such as methane), and a boron halide (such as boron trichloride), the proportions of the gases being sufiicient to form B C, for a sufficient length of time to provide a boron carbide coating on the filament of no more than 15 microns in thickness.
  • the contact time of the filament with the gaseous mixture is preferably from 4 to 6 seconds. If desired, the proportion of the hydrocarbon and/or hydrogen in the gas mixture may be in excess of that stoichiometrically required to form B 0.
  • an apparatus for providing a boron filament with a boron carbide coating thereon which comprises a tubular cell provided with inlet and outlet conduits for the supply and removal of gas, the cell being closed at each end with a plug of electrically-insulating material, each plug having a passageway for the boron filament to pass therethrough, each passageway communicating with a conduit for the supply of mercury thereto and the ends of each passageway being narrowed such that, in use, mercury supplied to the passageway provides an electrical contact with the boron filament passing therethrough but is retained therein by the narrowed ends so as to act as a gasket against flow of gas through the passageway.
  • the boron carbide coating creates an effective antidiffusion barrier and enables practically all the mechanical properties of the initial boron filament to be retainedafterv aluminium has been sprayed thereon by a plasmaarc torch, so as to give boron filament-reinforced aluminium matrix composite material.
  • a study of X-ray diffraction spectra has shown that there is nointeraction between the coated boron filaments and the aluminium matrix...
  • the antidiifusion effect of the boron filaments accord;- ing to the invention may be evaluated as follows:
  • This thickness of the boron carbide coating is defined as the ditference between the diameter of the boron carbidecoated boron filament and the diameter of the bare, initial boron filament.
  • the ratio R/R is approximately equal to 1 when the thickness of the B coating is from 3 to 8 microns; it is slightly less than 1 for other thickness values of less than or equal to microns.
  • the tensile strength of the coated filaments according to the invention is greater than that of the initial uncoated filaments when the thickness of the B C coating is from 3 to 8 microns, and is comparable to that of the initial uncoated filaments for other thickness values of less than or equal to 15 microns.
  • the tensile strength of the coated filaments drops considerably, however, when the B 6 coating is greater than 15 microns. It is surprising that the boron carbide deposit on the filament does not substantially reduce the tensile strength of the initial boron filament in the above-mentioned thickness range, and that in some cases it even improves the tensile strength.
  • any excess of hydrocarbon in the gaseous mixture may be as much as or more (compared to the stoichiometric amount), and, if desired, any excess of hydrogen may be as much as 100% compared to the stoichiometric amount.
  • the boron filament is heated to the required temperature by passing an electric current through the filament and causing resistance heating.
  • the filament is typically passed through a chamber which is continuously supplied with the gaseous mixture, the reaction taking place in this chamber.
  • the apparatus of the invention is preferably located downstream of the reaction chamber of a boron filament production machine wherein a tungsten wire is heated in the presence of a mixture of boron halide and hydrogen as described in French Patent Application No. 6,901,287 to form a boron coating on the tungsten wire.
  • the reaction cell comprises, in addition to gas inlet and outlet conduits, disposed at, or adjacent, the plugs, an inlet conduit for hydrocarbon disposed intermediate the ends of the cell.
  • This apparatus is particularly suited to depositing boron on a tungsten wire in the same chamber as the deposition of the boron carbide: a mixture of boron halide and hydrogen is introduced to the cell via the gas inlet conduit at the upstream end of the cell (to produce a zone for deposition of boron on to, for example, a tungsten wire entering the cell) and the hydrocarbon (e.g. methane) is introduced through the additional conduit (to complete the gas mixture so as to provide a zone for deposition of boron carbide downstream of the boron deposition zone).
  • the hydrocarbon e.g. methane
  • FIG. 1 is a cross-section through an apparatus according to the invention for the deposition of a boron carbide antiditfusion' coating on to a boron filament;
  • FIG. 2 is a modification of the apparatus shown in FIG. 1 and provides for the deposition of boron and then boron carbide in one reaction chamber;
  • FIG. 3 is a diagram of an installation for the continuous production of boron filaments and then the coating thereof with boron carbide.
  • the apparatus shown in FIG. 1 comprises a cell consisting of a Pyrex cylindrical glass tube 1 closed at the ends by Teflon plugs 2 having flanges 2a over which the ends of the tube are force-fitted with the interposition of ring gaskets 3.
  • Each plug is formed with a longitudinal passage 4 for the boron filament being coated and is pro- 7 vided with glass half-capillaries 5, the free ends of which are narrowed to leave an aperture corresponding roughly to the diameter of the filament passing therethrough.
  • a radial conduit 6 is provided at the lower part of each plug, communicates with the passage 4, and is intended for the supply of mercury 7 to the passage 4 from a reservoir (not shown).
  • the mercury supply is connected to an electrical current source and acts both as a gasket. for the cell and as an electrical contact for the filament tional tensioning device which forms part of the boron filament production machine.
  • Typical operating conditions were as follows: using a cell 30 cm. in length, the boron filament 10 was heated by the Joule elfect (electrical resistance heating) to a.
  • the tube 1 of the coating cell is additionally provided with a conduit 12 for the admission of methane (or other hydrocarbon such as ethane, benzene, or toluene), this conduit 12 is situated at a suitable distance from the rear end of the cell, for example cm. therefrom.
  • methane or other hydrocarbon such as ethane, benzene, or toluene
  • this conduit 12 is situated at a suitable distance from the rear end of the cell, for example cm. therefrom.
  • the mixture of boron trichloride (or other boron halide, such as boron tribromide) and hydrogen is admitted to the cell via con duit 9 and the gases are discharged via conduit 8 after reaction in the cell.
  • the portion of the cell situated upstream of conduit 12 forms a boron deposition Zone while the portion downstream of conduit 12 acts as a boron carbide deposition zone.
  • FIG. 3 shows a complete schematic installation for the production of boron filaments coated with a boron carbide antidiffusion coating from a tungsten wire.
  • This installation comprises the following, in a manner known per se:
  • the resulting coated filament had a total diameter of 105 microns, a 5 micron thick boron carbide deposit, and a tensile strength of t./cm.
  • Cell B which is optional, is connected to cell C by means of a connection 2' (see FIG. 2), produced by modifying plug 2 by adding a reaction gas discharge duct 8 and flanges Z'a.
  • the cells are fed with boron trifiuoride (or other boron halide) through circuit D, with hydrogen through circuit E, and with methane (or other hydrocarbon) through circuit G, via the calibrated flow meters F. After reaction, the gases are discharged through circuit H.
  • boron trifiuoride or other boron halide
  • the tungsten wire is taken from the feed spool 13 through the different cells by the take-up spool 15 which is driven by a variable-speed motor.
  • the mechanical ten sion of this wire is controlled by a tensioning device 14 situated immediately after the feed spool.
  • a filament as claimed in claim 1 wherein said coating thickness is from 3 to 8 microns.
  • a filament as claimed in claim 1 wherein said boron filament consists of a tungsten boride core provided with a boron coating thereon.
  • a filament as claimed in claim 3 wherein said boron filament has a diameter of at least 98 microns.
  • a composite material which comprises a metal matrix reinforced with one or more of said boron filaments as claimed in claim 1.
  • a composite material as claimed in claim 5 wherein said metal matrix is selected from the group consisting of aluminium or an aluminium alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Chemical Vapour Deposition (AREA)
  • Inorganic Fibers (AREA)
  • Wire Processing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
US00250287A 1971-05-11 1972-05-04 Boron filaments with a boron carbide antidiffusion coating,and metal matrix made therefrom Expired - Lifetime US3846224A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR717116885A FR2136978B1 (https=) 1971-05-11 1971-05-11

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US3846224A true US3846224A (en) 1974-11-05

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Country Link
US (1) US3846224A (https=)
JP (1) JPS5237996B1 (https=)
BE (1) BE783279A (https=)
CA (1) CA967065A (https=)
DE (1) DE2221943C3 (https=)
FR (1) FR2136978B1 (https=)
GB (1) GB1334476A (https=)
IT (1) IT960382B (https=)
NL (1) NL157354B (https=)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888661A (en) * 1972-08-04 1975-06-10 Us Army Production of graphite fiber reinforced metal matrix composites
US3993818A (en) * 1975-02-28 1976-11-23 United Technologies Corporation Resin bonded composite articles and process for fabrication thereof
US4029838A (en) * 1975-09-24 1977-06-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Hybrid composite laminate structures
US4287259A (en) * 1979-12-05 1981-09-01 The United States Of America As Represented By The United States Department Of Energy Preparation and uses of amorphous boron carbide coated substrates
US4358473A (en) * 1981-05-22 1982-11-09 Avco Corporation Process control system
US4877649A (en) * 1987-09-08 1989-10-31 United Technologies Corporation Coating of boron particles
US4942062A (en) * 1984-06-27 1990-07-17 Coating Development Societe Anonyme Process for producing boron carbide coatings of controlled hardness
US5429870A (en) * 1992-12-17 1995-07-04 United Technologies Corporation Boron carbide coated refractory fibers
US6235675B1 (en) * 1998-09-22 2001-05-22 Idaho Research Foundation, Inc. Methods of forming materials containing carbon and boron, methods of forming catalysts, filaments comprising boron and carbon, and catalysts

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2508381A1 (fr) * 1981-06-26 1982-12-31 Poudres & Explosifs Ste Nale Procede de fabrication de tubes composites a matrice metallique renforcee par des fibres
CN112553603A (zh) * 2020-12-04 2021-03-26 安徽贝意克设备技术有限公司 一种内加热型氮化硼复合纤维化学气相沉积设备
CN112553602A (zh) * 2020-12-04 2021-03-26 安徽贝意克设备技术有限公司 一种氮化硼复合纤维的化学气相沉积设备

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888661A (en) * 1972-08-04 1975-06-10 Us Army Production of graphite fiber reinforced metal matrix composites
US3993818A (en) * 1975-02-28 1976-11-23 United Technologies Corporation Resin bonded composite articles and process for fabrication thereof
US4029838A (en) * 1975-09-24 1977-06-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Hybrid composite laminate structures
US4287259A (en) * 1979-12-05 1981-09-01 The United States Of America As Represented By The United States Department Of Energy Preparation and uses of amorphous boron carbide coated substrates
US4358473A (en) * 1981-05-22 1982-11-09 Avco Corporation Process control system
US4942062A (en) * 1984-06-27 1990-07-17 Coating Development Societe Anonyme Process for producing boron carbide coatings of controlled hardness
US4877649A (en) * 1987-09-08 1989-10-31 United Technologies Corporation Coating of boron particles
US5429870A (en) * 1992-12-17 1995-07-04 United Technologies Corporation Boron carbide coated refractory fibers
US6235675B1 (en) * 1998-09-22 2001-05-22 Idaho Research Foundation, Inc. Methods of forming materials containing carbon and boron, methods of forming catalysts, filaments comprising boron and carbon, and catalysts

Also Published As

Publication number Publication date
BE783279A (fr) 1972-11-10
NL7206305A (https=) 1972-11-14
IT960382B (it) 1973-11-20
DE2221943C3 (de) 1978-04-27
DE2221943A1 (de) 1972-12-21
FR2136978B1 (https=) 1973-05-11
CA967065A (en) 1975-05-06
GB1334476A (en) 1973-10-17
FR2136978A1 (https=) 1972-12-29
DE2221943B2 (de) 1977-08-25
JPS5237996B1 (https=) 1977-09-26
NL157354B (nl) 1978-07-17

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