WO2014123532A1 - Fibres de verre nanocomposites à résistance élevée - Google Patents

Fibres de verre nanocomposites à résistance élevée Download PDF

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Publication number
WO2014123532A1
WO2014123532A1 PCT/US2013/025251 US2013025251W WO2014123532A1 WO 2014123532 A1 WO2014123532 A1 WO 2014123532A1 US 2013025251 W US2013025251 W US 2013025251W WO 2014123532 A1 WO2014123532 A1 WO 2014123532A1
Authority
WO
WIPO (PCT)
Prior art keywords
nanomaterials
glass fiber
glass
set forth
manufacture
Prior art date
Application number
PCT/US2013/025251
Other languages
English (en)
Inventor
Janet HURST
Original Assignee
United States Of America, As Represented By The Administrator Of The National Aeronautics And Space Administration
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 States Of America, As Represented By The Administrator Of The National Aeronautics And Space Administration filed Critical United States Of America, As Represented By The Administrator Of The National Aeronautics And Space Administration
Priority to PCT/US2013/025251 priority Critical patent/WO2014123532A1/fr
Publication of WO2014123532A1 publication Critical patent/WO2014123532A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/075—Manufacture of non-optical fibres or filaments consisting of different sorts of glass or characterised by shape, e.g. undulated fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/01265—Manufacture of preforms for drawing fibres or filaments starting entirely or partially from molten glass, e.g. by dipping a preform in a melt
    • C03B37/01268—Manufacture of preforms for drawing fibres or filaments starting entirely or partially from molten glass, e.g. by dipping a preform in a melt by casting
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
    • C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
    • C03B37/01807—Reactant delivery systems, e.g. reactant deposition burners
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/025—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from reheated softened tubes, rods, fibres or filaments, e.g. drawing fibres from preforms
    • C03B37/026—Drawing fibres reinforced with a metal wire or with other non-glass material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2203/00—Fibre product details, e.g. structure, shape

Definitions

  • Glass fibers have been used for many years for a variety of applications. These applications range from the inexpensive glass fibers in the form of fiberglass, the mainstay for insulation in the building industry, to optical glass fibers which are extensively used in communications. While these glass fibers possess useful properties, they have not rivaled the mechanical properties of carbon fibers.
  • Carbon fibers are used widely to provide structural reinforcement to many materials. However carbon fibers are difficult to manufacture which renders this useful engineering material a high cost reinforcement. Additionally, carbon fibers also tend to be not oxidatively stable above 500°C, reducing both the potential end-use applications to low temperatures and the potentially available manufacturing methods. Summary
  • nanomaterials as generally used herein is defined to mean a material having nanometric dimensions, I.e. a material at least one of the dimensions of which is at a nanometric scale. For example, a material in at least one of the dimensions of space having a dimension between 1 and 500 nm.
  • the glass matrix provides protection from an oxidative environment to the nanomaterial reinforcing phase.
  • the addition of nanomaterials to several matrix materials have demonstrated enhanced mechanical properties.
  • These enhanced matrices can include a wide variety of materials including polymers, glass, ceramics and metals.
  • FIGURE 1 illustrates a glass pre-form with non-aligned, non- dispersed nanomaterials.
  • FIGURE 2 illustrates a method of forming a glass pre-form with nanomaterials.
  • FIGURE 3 illustrates a method of forming glass fiber having substantially aligned and dispersed nanomaterials.
  • FIGURE 4 illustrates an exemplary glass fiber with improved mechanical properties from aligned and dispersed nanomaterials.
  • Nanomaterials are very light and tend to separate within a glass melt due to differences in density. Nanomaterials typically have densities of around 1 gram/cm3 and glass is typically 4 grams/cm3. This results in difficulty mixing nanomaterials into the glass melt as the density difference causes nanomaterials to float near the surface of a glass melt.
  • Typical glass processing methods utilized for synthesizing glass fibers have not proven useful for developing reinforced glass fibers with nanomaterials.
  • Nanomaterials tend not to be oxidatively stable at the temperatures necessary in glass melting furnaces. These furnaces operate at temperatures which are typically from 1 200 to 1 400°C or even higher and often utilize additional oxygen in the form of oxygen torches to speed melting. Carbon nanotubes and fibers oxidize violently at only 500°C while the higher temperature capability boron nitride nanotubes are still insufficient with oxidative stability to 1 000°C and are not commercially available.
  • One aspect of the disclosure exploits the unexpected stability of carbon nanotubes (CNT) and potentially nanomaterials in general in a glass melt which is processed under inert atmospheres.
  • CNT carbon nanotubes
  • Recent work at NASA Glenn Research Center successfully demonstrated nanotube material (Boron Nitride nanotube (BNNT)) as a structural reinforcement for a barium calcium aluminosilicate glass compositions. Both strength and fracture toughness demonstrated marked improvement.
  • improved dispersion or alignment of the nanomaterials to overcome agglomeration may be achieved by either pulling fibers from a melt or by extrusion pressing to enhance shear mixing.
  • so called E-glass fibers containing carbon nanotubes were aligned with the fiber axis. Average strength of these fibers was two times that of fibers pulled without the nanomaterial reinforcement.
  • CNT appeared to pullout from the glass surface in classical composite behavior. In over 200 individual fiber fracture surfaces which were examined, no regions of CNT agglomeration were detected. Additionally, polished surface sections taken throughout the fiber lengths detected only standard porosity unlike hot pressed samples. This processing method eliminated the porous regions of CNT agglomerations which were not infiltrated by glass which were evident in hot pressed samples and resulted in poorer than hoped for strengths.
  • processing methods are shown to provide oxidative protection to the nanomaterials by processing in well controlled, oxygen-free conditions both during incorporation of the nanomaterials into the glass preform and again in the glass fiber drawing step. Additionally, as previously discussed, the density differences between the glass and the nanomaterials are overcome in synthesizing composites with well distributed nanomaterials, a key requirement for optimized mechanical properties. Finally, nanomaterial "float" is reduced to prevent nanomaterial destruction by oxidation.
  • Equipment to manufacture the composite glass/nanomaterial can include a glass melter within an environment chamber or bell jar, or a glass lathe such as typically used for optical glass manufacturing used to create a
  • Optimized mixing may not be required as additional melting and nanomaterial alignment may be achieved in a
  • dispersed, poorly aligned carbon nanotubes/fibers or other nanomaterials may be created by filling a hollow glass rod 1 02 with glass and nanomaterial 1 04.
  • the glass rod may or may not be transparent as illustrated depending largely on the composition of the glass and the particular nanomaterial 1 04 used.
  • the nanomaterial 1 04 appear as single separate strands for ease of illustration and understanding, those skilled will appreciate that, in practice the nanomaterial agglomorates together into clumps of material.
  • the glass may be deposited by a modified chemical vapor deposition process 200 shown generally.
  • the modified chemical vapor deposition process 200 may use various gases 204 to create a wide array of compositions. This is a process more typically associated with the synthesis of optical fiber.
  • compositions of interest for optical glasses often are mixtures of Si, Ge, and B among others.
  • simpler compositions such as those similar to so- called e-glass and s-glass may be utilized as the one purpose is mechanical property enhancement rather than improved optical qualities.
  • Nanomaterials 1 04 may be co-deposited with glass material or the feedstock may be periodically removed from the glass lathe 202 and nanomaterials may be added as a separate step. Addition of the nanomaterials may be accomplished by a gas carrier or other methods as well.
  • One variation is to grow nanomaterials in- situ during manufacturing of the preform by incorporating steps utilizing gases such as actelyene and FeCI 3 , common reagents for carbon nanotubes.
  • the tube may be collapsed, as is typical in optical glass formation.
  • a polishing step may be useful to remove surface defects.
  • such a feedstock 1 00 may be inserted into a glass fiber drawing tower 300 and pulled into fibers.
  • the tower 300 includes a preform feed 304 where feedstock 1 00 is supplied to a small furnace 308 that may be configured as a laser.
  • the glass melt zone is very small in this process and the length of time material remains in the molten state is short.
  • Inert gas may be incorporated as the processing atmosphere, protecting the nanotubes/fibers from oxidation damage. This method also reduces the opportunity for nanotubes/fibers to separate from the melt.
  • Nanotube alignment is not necessary within the feedstock 1 00, only partial dispersion and distribution will suffice.
  • shear forces urge the nanotubes/fibers toward dispersion and alignment.
  • a laser micrometer 31 2 or other measuring device ensures desired dimensions are maintained by adjusting the tractor pull rate.
  • the fiber passes through a first coating and curing section 31 6 followed by a second coating and curing section 320. Finished fiber 350 is then wound onto a reel 354.
  • the glass/nanoparticle composite 400 defines an axis A. Substantially evenly dispersed within the composite are nanoparticles 41 4 substantially aligned along or parallel to the axis A.
  • nanotubes/fibers can then be utilized in axial fiber direction. Also, by altering the nanotube density in the feedstock, one can tailor the nanotube density in the fiber as well.
  • the composite fibers will likely require surface coatings as damage to the glass surface may lead to strength limiting flaws as in the case of any glass fiber.
  • Carbon nanotubes are pyrophoric at temperatures of around 500°C while boron nitride nanotubes slowly oxidize at temperatures of around 800-1 000°C.
  • connection means both directly, that is, without other intervening elements or components, and indirectly, that is, with another component or components arranged between the items identified or described as being connected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention se rapporte à une fibre de verre composite présentant une résistance élevée et à ses procédés de fabrication. Cette fibre de verre utilise la résistance élevée et le module des nanomatériaux tels que les nanotubes de carbone ou d'autres compositions dignes d'intérêt, telles que le nitrure de bore ou le carbure de silicium, pour synthétiser des fibres de verre nanocomposites à résistance élevée.
PCT/US2013/025251 2013-02-08 2013-02-08 Fibres de verre nanocomposites à résistance élevée WO2014123532A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2013/025251 WO2014123532A1 (fr) 2013-02-08 2013-02-08 Fibres de verre nanocomposites à résistance élevée

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2013/025251 WO2014123532A1 (fr) 2013-02-08 2013-02-08 Fibres de verre nanocomposites à résistance élevée

Publications (1)

Publication Number Publication Date
WO2014123532A1 true WO2014123532A1 (fr) 2014-08-14

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Country Status (1)

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WO (1) WO2014123532A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150093562A1 (en) * 2013-10-01 2015-04-02 Samsung Sdi Co., Ltd. Conductive Thermoplastic Resin Composition
WO2019023801A1 (fr) * 2017-08-02 2019-02-07 National Research Council Of Canada Composites de verre de silice à base de nanotubes de nitrure de bore
DE102020107743A1 (de) 2020-03-20 2021-09-23 Karlsruher Institut für Technologie (Körperschaft des öffentlichen Rechts) Hybridfaser und Verfahren zu ihrer Herstellung
CN113502051A (zh) * 2021-07-29 2021-10-15 浙江鑫辉新材料科技有限公司 一种优良耐漏电性、可紫外激光标识、无卤阻燃聚酰胺复合材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266533A (en) * 1991-04-12 1993-11-30 Allied-Signal Inc. Black glass ceramic from rapid pyrolysis in oxygen-containing atmospheres
US20050188727A1 (en) * 2004-02-27 2005-09-01 Greywall Dennis S. Carbon particle fiber assembly technique
US20100203351A1 (en) * 2006-06-09 2010-08-12 Nayfeh Taysir H High strength composite materials and related processes
US20100279569A1 (en) * 2007-01-03 2010-11-04 Lockheed Martin Corporation Cnt-infused glass fiber materials and process therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266533A (en) * 1991-04-12 1993-11-30 Allied-Signal Inc. Black glass ceramic from rapid pyrolysis in oxygen-containing atmospheres
US20050188727A1 (en) * 2004-02-27 2005-09-01 Greywall Dennis S. Carbon particle fiber assembly technique
US20100203351A1 (en) * 2006-06-09 2010-08-12 Nayfeh Taysir H High strength composite materials and related processes
US20100279569A1 (en) * 2007-01-03 2010-11-04 Lockheed Martin Corporation Cnt-infused glass fiber materials and process therefor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150093562A1 (en) * 2013-10-01 2015-04-02 Samsung Sdi Co., Ltd. Conductive Thermoplastic Resin Composition
WO2019023801A1 (fr) * 2017-08-02 2019-02-07 National Research Council Of Canada Composites de verre de silice à base de nanotubes de nitrure de bore
DE102020107743A1 (de) 2020-03-20 2021-09-23 Karlsruher Institut für Technologie (Körperschaft des öffentlichen Rechts) Hybridfaser und Verfahren zu ihrer Herstellung
CN113502051A (zh) * 2021-07-29 2021-10-15 浙江鑫辉新材料科技有限公司 一种优良耐漏电性、可紫外激光标识、无卤阻燃聚酰胺复合材料及其制备方法
CN113502051B (zh) * 2021-07-29 2023-05-16 浙江鑫辉新材料科技有限公司 一种优良耐漏电性、可紫外激光标识、无卤阻燃聚酰胺复合材料及其制备方法

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