US3446682A - Method of making high strength refractory filaments - Google Patents

Method of making high strength refractory filaments Download PDF

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Publication number
US3446682A
US3446682A US453160A US3446682DA US3446682A US 3446682 A US3446682 A US 3446682A US 453160 A US453160 A US 453160A US 3446682D A US3446682D A US 3446682DA US 3446682 A US3446682 A US 3446682A
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United States
Prior art keywords
boron
filaments
high strength
filament
substrate
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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
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US453160A
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English (en)
Inventor
Franklin E Wawner Jr
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Texaco Experiment Inc
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Texaco Experiment Inc
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Publication date
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    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • 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
    • C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
    • C04B41/5338—Etching
    • C04B41/5353—Wet etching, e.g. with etchants dissolved in organic solvents
    • 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
    • C23C16/56—After-treatment
    • 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

Definitions

  • This invention relates to high strength refractory filaments consisting in whole or in part of boron and to methods and apparatus for making the same. More particularly, the invention relates to methods of increasing the strength of vapor-deposited boron filaments, the term filament being used herein to denote elongated elements of various cross-sectional shapes including ribbons.
  • the invention is based on the discovery that the tensile strengths of boron-containing, including boroncoated filaments, may be substantially increased by subjecting the filaments to the action of nitric acid in the vapor or liquid phase.
  • the boron-containing filaments are produced by passing an elongated substrate at substantially constant speed through an ambient gaseous composition containing a vaporizable compound of boron while maintaining the filamentary substrate at a temperature effective to cause deposition of boron on the substrate.
  • the gaseous composition may consist of or comprise a thermally decomposable halide or hydride of boron or a mixture of a boron halide with hydrogen.
  • the gaseous composition may consist of a mixture of a boron halide, such as boron trichloride, and hydrogen, at least a portion of the sub-V strate in contact with the gaseous composition being maintained at a temperature in the range from about 1100 K.
  • Boranes such as BZHS, may also be used as the thermally decomposable substance and are particularly suitable for deposition of boron on substrates of lower melting points, such as aluminum.
  • the speed of lthe substrate through the zone of contact thereof with the gaseous composition is adjusted with respect to the temperature thereof and the rate of deposition of boron to obtain a deposit of the desired thickness.
  • tungsten-containing filaments which can advantageously be used for the preparation of boron-containing filaments are tungsten, rhenium, tantalum, titanium, molybdenum, iron, copper, nickel, Nichrome, aluminum, magnesium, carbon and graphite.
  • X-ray diffraction data indicate that in the deposition of boron by the methods described above the boron combines with the substrate substance to form borides.
  • the compounds WB, or W2B5 may be formed.
  • the 4filaments thus formed may for some purposes be subjected to a moving zone melting operation, for example, by localized electron bombardment, to convert the substance of the filament to substantially monocrystalline condition or to otherwise improve the physical properties of the filaments.
  • the filaments formed by deposition in the manner described above are treated with aqueous nitric acid, at a concentration of about 40% to 50% by Weight, for example, one part by volume of red furning nitric acid to one part by volume of water, at a temperature of about C.
  • aqueous nitric acid at a concentration of about 40% to 50% by Weight, for example, one part by volume of red furning nitric acid to one part by volume of water, at a temperature of about C.
  • This treatment results in increases in the tensile strengths of the filaments in the range of from about 105,000 to ⁇ about 200,000 lb./in.2.
  • the illustrated apparatus comprises a preheating chamber generally designated 10 and a deposition chamber generally designated 11 and an etching bath generally designated 30.
  • a substrate filament 12 is passed continuously at a substantially uniform rate of travel from power-driven feed spool 13 successively through the preheating chamber, the deposition chamber and the etching and rinsing baths to power-driven take-up spool 14.
  • the preheating chamber and deposition chamber are sealed from each other and from the surrounding atmosphere by means of Y-shaped mercury seals 15a, 15b, 15a ⁇ connected by fiexible tubes 24 to separate level adjusting reservoirs 16a, 16b, 16e.
  • the mercury seals also serve as contactors for the supply of heating current to the substrate in the preheating and deposition chambers. Tension on the substrate filament is maintained substantially constant by suspending a tensioning weight 26 in a loop of the filament.
  • Containers 30 and 31 for .the nitric acid etching bath and the rinsing bath are provided with glass rods 32 for guiding the filament beneath the surface of the etching bath and rinsing bath.
  • Ts 17a, 17b, 17e and 17d and associated T-connectors 1-8 serve as inlets and outlets for gases and vapors into and out of the preheating and deposition chambers and also for the support of adjustable guide loops 19 for the substrate filament.
  • Hydrogen or other purging gas may be supplied to preheating chamber 10 through tube 20 and removed through Itube 21 for the purpose of removing adsorbed, absorbed or reacted oxygen from the surface of the substrate filament as it passes through chamber 10. Any lubricants or other surficial impurities are also removed from the filament by evaporation or by reaction with the hydrogen.
  • Boron halide may be supplied to chamber 11 by passing a carrier gas, such as argon, or a reducing gas, such as hydrogen, through a body of liquid halide in reservoir 25, which is maintained by heat transfer means (not shown) at a suitable pre-determined temperature, and passing the gas saturated with halide into the deposition chamber 11 through inlet tube 22. Residual gases and vapors pass out of chamber 11 through tube 23 to recovery or disposal means (not shown).
  • a carrier gas such as argon
  • a reducing gas such as hydrogen
  • Glass is a suitable material of construction for the outgassing and deposition chambers and for the etching bath container and for the connections thereto and therebetween including the Ts 15 and the Ts 17.
  • the flexible tubing 20, 21, 22, 23 and 24 can be made of polyethylene and T-connectors 18 can be of copper.
  • An 0.5 mil tungsten wire is passed through the apparatus at a speed of 2 feet per minute. It is heated to about 1900 F. in a current of hydrogen in the outgassing chamber. In passing through the deposition chamber (about 24 inches in length) it is maintained at about 1900 F. and is contacted With hydrogen gas saturated in vessel 25 with boron tribromide at a temperature of about 77 F. (BBr3 concentration about 8 mole percent). Under these conditions a boron lament about 3 mils in nal diameter is obtained and continuous lengths up to 1000 feet of the boron filament having breaking strengths of the order of 4 105 lb./in.2 may be made.
  • a method of increasing the strength of metallic filaments having a diameter of 3-15 mils and having a surface structure principally containing boron which cornprises etching the laments with aqueous nitric acid at a concentration of from about to 50% by weight at a temperature of about 100 C. until the diameter of such filaments has been reduced by about 0.5 mil.
  • a method of increasing the strength of metallic filaments having a surface structure principally containing boron which comprises treating the filaments with aqueous nitric acid at a concentration of from about 40% to about by weight and at a temperature of about C. until at least about 0.5 mil has been removed from the surface of the filaments.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Vapour Deposition (AREA)
US453160A 1965-05-04 1965-05-04 Method of making high strength refractory filaments Expired - Lifetime US3446682A (en)

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US45316065A 1965-05-04 1965-05-04

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US3446682A true US3446682A (en) 1969-05-27

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US (1) US3446682A (enrdf_load_html_response)
BE (1) BE680427A (enrdf_load_html_response)
DE (1) DE1546044A1 (enrdf_load_html_response)
GB (1) GB1088669A (enrdf_load_html_response)
LU (1) LU51013A1 (enrdf_load_html_response)
NL (1) NL6605997A (enrdf_load_html_response)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4631114A (en) * 1985-04-18 1986-12-23 Siemens Aktiengesellschaft Method for removing a surface layer from a metal fluoride glass
US4770732A (en) * 1983-08-01 1988-09-13 Minnesota Mining And Manufacturing Company Transfer method for applying graphics to a display surface
US4820559A (en) * 1983-08-01 1989-04-11 Minnesota Mining And Manufacturing Company Graphics transfer medium
DE102005062392A1 (de) * 2005-07-10 2007-01-11 Ip2H Ag Lichtquelle, ein Filament und ein Verfahren zur Herstellung eines monokristallinen Metalldrahts
US20100086729A1 (en) * 2008-10-07 2010-04-08 Alliant Techsystems Inc. Multifunctional radiation-hardened laminate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839367A (en) * 1957-04-09 1958-06-17 American Potash & Chem Corp Preparation of crystalline boron

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839367A (en) * 1957-04-09 1958-06-17 American Potash & Chem Corp Preparation of crystalline boron

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4770732A (en) * 1983-08-01 1988-09-13 Minnesota Mining And Manufacturing Company Transfer method for applying graphics to a display surface
US4820559A (en) * 1983-08-01 1989-04-11 Minnesota Mining And Manufacturing Company Graphics transfer medium
US4631114A (en) * 1985-04-18 1986-12-23 Siemens Aktiengesellschaft Method for removing a surface layer from a metal fluoride glass
DE102005062392A1 (de) * 2005-07-10 2007-01-11 Ip2H Ag Lichtquelle, ein Filament und ein Verfahren zur Herstellung eines monokristallinen Metalldrahts
US20100086729A1 (en) * 2008-10-07 2010-04-08 Alliant Techsystems Inc. Multifunctional radiation-hardened laminate
US8460777B2 (en) * 2008-10-07 2013-06-11 Alliant Techsystems Inc. Multifunctional radiation-hardened laminate

Also Published As

Publication number Publication date
NL6605997A (enrdf_load_html_response) 1966-11-07
DE1546044A1 (de) 1970-11-12
LU51013A1 (enrdf_load_html_response) 1966-07-04
BE680427A (enrdf_load_html_response) 1966-10-17
GB1088669A (en) 1967-10-25

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