US3867191A - Carbon-boron surfaced carbon filament - Google Patents

Carbon-boron surfaced carbon filament Download PDF

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Publication number
US3867191A
US3867191A US228953A US22895372A US3867191A US 3867191 A US3867191 A US 3867191A US 228953 A US228953 A US 228953A US 22895372 A US22895372 A US 22895372A US 3867191 A US3867191 A US 3867191A
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United States
Prior art keywords
carbon
boron
filament
approximately
mil
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Expired - Lifetime
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US228953A
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English (en)
Inventor
Francis S Galasso
Richard D Veltri
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Raytheon Technologies Corp
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United Aircraft Corp
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Publication date
Application filed by United Aircraft Corp filed Critical United Aircraft Corp
Priority to US228953A priority Critical patent/US3867191A/en
Priority to GB312873A priority patent/GB1398815A/en
Priority to DE2303407A priority patent/DE2303407A1/de
Priority to FR7303888A priority patent/FR2172999B1/fr
Priority to JP2172973A priority patent/JPS5432401B2/ja
Priority to IT20779/73A priority patent/IT979415B/it
Application granted granted Critical
Publication of US3867191A publication Critical patent/US3867191A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • 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
    • Y10T428/298—Physical dimension

Definitions

  • ABSTRACT F 16 3 A high strength composite filament suitable for use as [5]] [m Cl "/08 a reinforcement in metal matrices comprises a fila- [58] Fieid Cc)? l mentary carbon substrate having a continuous essen- 117/228 H5 111 b tially amorphous carbon alloy coating adhered H 69 led/Mi 5 6 3l3/341' thereto, the coating consisting essentially of approximately 43-60 atomic percent carbon, remainder bo- [56] References Cited UNITED STATES PATENTS 6 Claims, 2 Drawing Figures 1,019,391 3/l912 Wcintraub 117/228 PATENTEU 3 1975 F76. Z i
  • the present invention relates to carbon-base filaments and, more particularly, to carbon-base monol'ilaments at least two mils in diameter suitable for use as reinforcement for metal matrix composites.
  • the present invention contemplates the production of a high strength. high modulus composite filament comprising a carbon filamentary core at least one mil in diameter, preferably l to 2 mils in diameter. having an adherent continuous essentially amorphous coating consisting essentially of a carbon-boron alloy consisting of approximately 43-60 atomic percent carbon. remainder boron. It has been found that such a carbonboron alloy coating composition. to a thickness of approximately 2 mils, will not only provide a diffusion barrier to the carbon and metal matrix materials but, in addition, will impart high strength and modulus thereto.
  • the present invention also contemplates the method for making such a filament and. in general. comprises continuously passing a carbon filament through a reactor, heating the filament to 1050l250C and exposing the heated filament to a reactant gas mixture consisting essentially of methane, boron trichloride and hydrogen.
  • a reactant gas mixture consisting essentially of methane, boron trichloride and hydrogen.
  • the mass flow ratios of methane/boron trichloride and hydrogen/boron trichloride being l.l6 to 8.08 and 0.5 to 2.0 respectively.
  • FIG. I is a simple sketch, taken in elevation. of apparatus used in the production of the carbon-boron alloy coating of the carbon filaments of the present invention.
  • FIG. 2 is an enlarged cross-sectional view through one of the filaments of the present invention.
  • the carbonboron alloy coating is produced on a resistively heated carbon monofilament 4 which is drawn downwardly through a reactor 6 comprising a tubular containment vessel 8, having a gas inlet I0 at the upper end of the reactor and a single exhaust port 12 at the lower end thereofv
  • a reactant gas mixture consisting essentially of methane. boron trichloride and hydrogen is fed to the reactor through inlet I0.
  • the containment vessel may be formed of Py rex. although a number of other materials including Vycor and quartz will be found satisfactory.
  • the gas inlet 10 and the exhaust l2 penetrate and are elcctrically connected to the metallic end plugs 14 and [6 which provide the end closures 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 pur pose of providing a gas seal around the wire where it penctrates the and plugs. and further providing electrical contact between the moving wire and the respective end plugs which are in turn electrically connected through the tubes 10 and I2 and the leads 26 and 28 to a suitable DC power source 30.
  • the upper plug I4 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 accommodate the free passage ofthe wire 2 thercthrough but which, in combination with the wire. is small enough to retain the mercury, through surface tension forces. in their respective wells.
  • the hydrogen is considered necessary in the reactant mixture since it acts not only as a coolant for the end plugs I4 and I6 but also acts to even temperature distribution and to catalyze the methane reaction.
  • the relative proportions. expressed in flow rate ratios of the constituent methane and boron trichloride gases are critical to the formation of useful filaments. It is considered, for example. that with the hydrogcn/- boron trichloride ratio in the range of0.5 to 2.0, preferably at 1.0, the methane/boron trichloride ratio must be greater than l0 but less than approximately l0, preferably [.16 to 8.08. and optimally 2.34. At a mass flow ratio of methane/boron trichloride of 1.0 carbonboron deposition resulted in embrittled filaments which could not be handled without breaking.
  • essentially amorphous for purposes ofthe present inven tion is intended to mean that degree ofamorphousness which is represented by the appearance of one or two utilizing 1900 volts and I40 milliamps at a power setting of 252 watts to a temperature of llC while moving through the reactor at a rate of 40 ft/hr and achieved a final diameter of 3.3 mils.
  • substrate filament speed was ft/hr and a substrate temperature of l00C was ohs carbon reflecuo s1 t fraction stud t I: i i fzfi i tamed by 2 l 00 volts.
  • EXAMPLE l EXAMPLES 12-27 ln a reactor of the type illustrated utilizing a 24 inch [11 the reactor apparatus of Example l. a CH IBCI long reactor formed from l2 mm Pyrex tubing and a ratio of 2.34 and an H /BCl ratio of l.(l was mainreactant gas mixture of methane. boron trichloride and taincd by a methane gas flow of 407 cc/min. a BCl; gas hydrogen. a carbon-boron alloy coating was produced flow of I74 cc/min and an H gas flow of I74 cc/min. on a L68 mil carbon monofilament.
  • the substrate was resistively heated utilizing I6l0 volts. I05 ma and I69 watts to ll85C while moving through the reactor at a rate of 40 ft/hr and achieved a final diameter of 42 mils. Several runs were made and the average UTS was 247,000 psi. The coating appeared to be an adherent single phase carbon-boron layer having a composition calculated to consist of 43 atomic percent C. 57 percent B.
  • the coated filaments had a final diameter of 2.6-4.3 mils and a total average UTS of 99,000 psi.
  • the coating was adherent single phase carbon-boron alloy with a composition consisting essentially of 64 atomic percent C, 36 percent B.
  • the carbon-boron coated carbon filaments are suitable for use in the reinforcement of not only resin, such as epoxy, but also metal matrices such as. for example. aluminum. magnesium and when properly coated. titanium and nickel.
  • the filaments of Example l9 were subjected to testing in aluminum matrices.
  • Composites were prepared by winding the coated fialment around 1 mil 2024 Al foil wrapped around a l2 inch diameter mandrel, spraying with polystyrene. removing from the mandrel and cutting into I X 5 inch pieces. A plurality of pieces (6 to 8) were laid up and diffusion bonded in a hot press at a temperature of 480C and pressure of I0,000 psi for 20 minutes. The resulting composite had a fiber loading of 45 vol. percent, a UTS of 98.000 psi and a Young's Modulus of 23 X l0..- psi.
  • a composite filament at least two mils in diameter having a tensile strength of at least 150.000 psi for use as reinforcement in metal matrix composite articles comprising:
  • a substrate consisting essentially of carbon filament
  • a continuous coating adhered to said substrate consisting essentially of carbon-boron alloy.
  • said coating consisting essentially of approximately 43-60 atomic percent carbon. remainder boron.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Ceramic Products (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Inorganic Fibers (AREA)
  • Chemical Vapour Deposition (AREA)
  • Resistance Heating (AREA)
US228953A 1972-02-24 1972-02-24 Carbon-boron surfaced carbon filament Expired - Lifetime US3867191A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US228953A US3867191A (en) 1972-02-24 1972-02-24 Carbon-boron surfaced carbon filament
GB312873A GB1398815A (en) 1972-02-24 1973-01-22 Carbon-boron surfaced carbon filament
DE2303407A DE2303407A1 (de) 1972-02-24 1973-01-24 Beschichteter kohlenstoffaden und verfahren zu seiner herstellung
FR7303888A FR2172999B1 (pl) 1972-02-24 1973-01-31
JP2172973A JPS5432401B2 (pl) 1972-02-24 1973-02-22
IT20779/73A IT979415B (it) 1972-02-24 1973-02-23 Filamento di carbonio con rivesti mento di carbonio boro

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US228953A US3867191A (en) 1972-02-24 1972-02-24 Carbon-boron surfaced carbon filament

Publications (1)

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US3867191A true US3867191A (en) 1975-02-18

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US228953A Expired - Lifetime US3867191A (en) 1972-02-24 1972-02-24 Carbon-boron surfaced carbon filament

Country Status (6)

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US (1) US3867191A (pl)
JP (1) JPS5432401B2 (pl)
DE (1) DE2303407A1 (pl)
FR (1) FR2172999B1 (pl)
GB (1) GB1398815A (pl)
IT (1) IT979415B (pl)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3967029A (en) * 1973-03-02 1976-06-29 United Technologies Corporation Boron-carbon alloy tape
US4225355A (en) * 1979-02-16 1980-09-30 United Technologies Corporation Amorphous boron-carbon alloy in bulk form and methods of making the same
US4524106A (en) * 1983-06-23 1985-06-18 Energy Conversion Devices, Inc. Decorative carbon coating and method
US4590031A (en) * 1983-09-23 1986-05-20 Energy Conversion Devices, Inc. Molding tool and method
US4594294A (en) * 1983-09-23 1986-06-10 Energy Conversion Devices, Inc. Multilayer coating including disordered, wear resistant boron carbon external coating
US4716083A (en) * 1983-09-23 1987-12-29 Ovonic Synthetic Materials Company Disordered coating
US5088202A (en) * 1988-07-13 1992-02-18 Warner-Lambert Company Shaving razors
US5162159A (en) * 1991-11-14 1992-11-10 The Standard Oil Company Metal alloy coated reinforcements for use in metal matrix composites
US5429870A (en) * 1992-12-17 1995-07-04 United Technologies Corporation Boron carbide coated refractory fibers
DE4018939C2 (de) * 1990-06-13 2000-09-21 Fraunhofer Ges Forschung Verfahren zur laserinduzierten Beschichtung von Fasern
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
WO2016073504A1 (en) * 2014-11-04 2016-05-12 Dynetics, Inc. High-strength refractory fibrous materials
US11499230B2 (en) 2014-08-18 2022-11-15 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1019391A (en) * 1909-10-27 1912-03-05 Gen Electric Boronized conductor and method of manufacture.
US3131089A (en) * 1961-01-25 1964-04-28 Union Carbide Corp Carbon article coated with boron carbide and boron nitride, and process of making the same
US3565683A (en) * 1968-03-21 1971-02-23 Gen Electric Coated filaments
US3668006A (en) * 1969-06-02 1972-06-06 Gen Electric Formation of high-strength high-modulus coated filaments
US3671306A (en) * 1969-11-28 1972-06-20 Nat Res Corp Boron carbide film product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1019391A (en) * 1909-10-27 1912-03-05 Gen Electric Boronized conductor and method of manufacture.
US3131089A (en) * 1961-01-25 1964-04-28 Union Carbide Corp Carbon article coated with boron carbide and boron nitride, and process of making the same
US3565683A (en) * 1968-03-21 1971-02-23 Gen Electric Coated filaments
US3668006A (en) * 1969-06-02 1972-06-06 Gen Electric Formation of high-strength high-modulus coated filaments
US3671306A (en) * 1969-11-28 1972-06-20 Nat Res Corp Boron carbide film product

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3967029A (en) * 1973-03-02 1976-06-29 United Technologies Corporation Boron-carbon alloy tape
US4225355A (en) * 1979-02-16 1980-09-30 United Technologies Corporation Amorphous boron-carbon alloy in bulk form and methods of making the same
US4524106A (en) * 1983-06-23 1985-06-18 Energy Conversion Devices, Inc. Decorative carbon coating and method
US4590031A (en) * 1983-09-23 1986-05-20 Energy Conversion Devices, Inc. Molding tool and method
US4594294A (en) * 1983-09-23 1986-06-10 Energy Conversion Devices, Inc. Multilayer coating including disordered, wear resistant boron carbon external coating
US4716083A (en) * 1983-09-23 1987-12-29 Ovonic Synthetic Materials Company Disordered coating
US5088202A (en) * 1988-07-13 1992-02-18 Warner-Lambert Company Shaving razors
DE4018939C2 (de) * 1990-06-13 2000-09-21 Fraunhofer Ges Forschung Verfahren zur laserinduzierten Beschichtung von Fasern
US5162159A (en) * 1991-11-14 1992-11-10 The Standard Oil Company Metal alloy coated reinforcements for use in metal matrix composites
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
US10167555B2 (en) 2014-08-18 2019-01-01 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US10683574B2 (en) 2014-08-18 2020-06-16 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US10947622B2 (en) 2014-08-18 2021-03-16 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US11499230B2 (en) 2014-08-18 2022-11-15 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
WO2016073504A1 (en) * 2014-11-04 2016-05-12 Dynetics, Inc. High-strength refractory fibrous materials

Also Published As

Publication number Publication date
JPS4899093A (pl) 1973-12-15
IT979415B (it) 1974-09-30
DE2303407A1 (de) 1973-08-30
JPS5432401B2 (pl) 1979-10-15
FR2172999B1 (pl) 1978-03-03
GB1398815A (en) 1975-06-25
FR2172999A1 (pl) 1973-10-05

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