WO1995002564A1 - Procede de densification carbone-carbone utilisant des precurseurs a matrice de brai mesophase - Google Patents

Procede de densification carbone-carbone utilisant des precurseurs a matrice de brai mesophase Download PDF

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Publication number
WO1995002564A1
WO1995002564A1 PCT/US1994/007365 US9407365W WO9502564A1 WO 1995002564 A1 WO1995002564 A1 WO 1995002564A1 US 9407365 W US9407365 W US 9407365W WO 9502564 A1 WO9502564 A1 WO 9502564A1
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WO
WIPO (PCT)
Prior art keywords
pitch
carbon
accordance
mesophase
approximately
Prior art date
Application number
PCT/US1994/007365
Other languages
English (en)
Inventor
Lawrence Edward Mcallister
Shrikant Awasthi
Original Assignee
Alliedsignal, Inc.
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 Alliedsignal, Inc. filed Critical Alliedsignal, Inc.
Priority to AU73195/94A priority Critical patent/AU7319594A/en
Publication of WO1995002564A1 publication Critical patent/WO1995002564A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
    • F16D69/02—Composition of linings ; Methods of manufacturing
    • F16D69/023—Composite materials containing carbon and carbon fibres or fibres made of carbonizable material
    • 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
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds

Definitions

  • the present invention relates generally to carbon- carbon composites, and in particular to a carbon-carbon composite utilizing a mesophase pitch matrix precursor which is converted to a mesomorphic form in order to 5 infiltrate the fibers prior to conversion at a higher temperature to a carbon matrix.
  • Carbon-carbon composites comprise a class of materials containing carbon (graphite) fibers with a carbon
  • the matrix in such composites is 0 derived from organic precursors such as resins or pitches which convert to carbon upon pyrolysis, or hydrocarbon gasses that undergo pyrolytic cracking to deposit carbon onto a fibrous substrate. It is highly desirable to simplify the process of providing a carbon-carbon composite 5 and reduce the time necessary for such fabrication. It is highly desirable for the fabrication of a carbon-carbon composite to be effected by a single step densification process utilizing readily available materials. Such a process should be very short compared to carbon-carbon 0 composite fabrication processes which use chemical vapor deposition (CVD) . It is highly desirable that the densification process provide a high density carbon-carbon composite which, after final heat treatment, may be utilized as an aircraft brake disc. Both military and 5 commercial aircraft are experiencing an increased utilization of carbon-carbon composite aircraft brake discs because of the lightweight nature of the composites and wear rates which, over a period of time, render carbon- carbon composite aircraft brake discs economically 0 acceptable for use on both military and commercial
  • the present invention provides solutions to the above by providing a densification process for producing a carbon-carbon composite, comprising the steps of providing 5 one of a carbon fiber material and a carbon fiber precursor material and combining therewith a pitch, heating the combination to approximately 450°C in order to convert the pitch to a mesomorphic condition pitch which infiltrates the material, and further heating the combination to a temperature of at least approximately 460°C while under pressure in a range of approximately 1000-20.00 psi in order to convert the mesomorphic condition pitch to a char comprising a carbon matrix of a high density carbon-carbon composite.
  • the present invention comprises the utilization of hot pressing of a combination of a carbon fiber and mesophase pitch to form a carbon-carbon composite in a single densification process step.
  • the precursor for this process can be 1) a carbon fiber preform impregnated with a pitch, 2) a chopped carbon fiber/pitch molding compound, or 3) a carbon fiber/pitch prepreg.
  • the combination is thermally treated to convert the pitch to its mesomorphic or mesophase form.
  • the mesophase pitch matrix precursor initially softens and flows around the fibers to form the final shape. Finally, as the temperature is increased to over 460°C, the mesophase pitch is converted to a carbon matrix.
  • the result of this densification process is a high density carbon-carbon composite which, after final heat treatment, may be utilized as a carbon aircraft brake disc.
  • the objective of the invention is to simplify the densification process and reduce the time necessary to fabricate carbon- carbon composites, and accomplish this by using mesophase pitch as the precursor for the carbon matrix phase of the composite.
  • Mesophase pitch has a liquid crystal microstructure in the form of highly oriented microspheres. These microspheres soften and coalesce under heat and pressure to form a precursor to the crystalline (graphitic) structure desired in the final carbon-carbon composite.
  • the crystalline nature and high char yield (85-90% by weight) of mesophase or mesomorphic condition pitch make it an ideal candidate for the fabrication of high density carbon-carbon composites.
  • chopped fiber or carbon fabric a woven or mat type material
  • the liquid pitch is applied thereto.
  • moderate heat approximately 100-
  • This portion of the single step densification process comprises the heating of the combined fiber material and pitch to a temperature necessary to convert the pitch to its mesophase or mesomorphic form. Temperatures of 400-450°C for up to several hours are usually adequate to accomplish this conversion.
  • the pitch material is converted in situ in the carbon fiber material in order to effect the mesophase form of the pitch.
  • the mesophase material can blended with fiber by utilizing a direct die fill at greater than 350°C.
  • Yet another method would be to convert pitch in the chopped fiber molding compound to the mesophase condition before consolidation (preforming or molding) wherein the pitch is placed in the loose fibers, heated to effect conversion, and then pressed via a direct die fill at greater than
  • This phase of the single step densification process is accomplished with heat and pressure.
  • the mesophase will soften and flow at temperatures of up to approximately 600°C depending on the pitch material used and the heating rate.
  • Table 1 shows that coal tar pitch and petroleum pitches can convert to char at approximately 460°C.
  • the mesophase converts to char which is accompanied by a loss of plasticity.
  • pressure of approximately 1000-2000 psi is applied while heating the preform to 600°C or higher.
  • the mesophase condition pitch (pitch in the mesomorphic condition) will flow around the fibers.
  • the mesophase condition pitch will convert to char (carbon) .
  • a further increase in temperature of up to approximately 1000°C under pressure may result in additional compaction (higher density) and remove most of the noncarbon species by pyrolysis.
  • the carbon-carbon composite is then final heat treated to produce a composite having the desired degree of crystalinity needed for a carbon aircraft brake disc.
  • a needled nonwoven preform was placed in a can and covered with an excess amount of crushed 15V coal tar pitch made by AlliedSignal.
  • the can was heated in an oven to 250°C in air atmosphere. As the pitch melted, it infiltrated into the preform by capillary action.
  • the pitch impregnated part was held at 250°C for 48 hours to stabilize the pitch.
  • the part was removed from the oven and stored at room temperature.
  • the part was loaded in a graphite die which had been preheated to 450°C.
  • a contact pressure of 10-20 psi was applied to the part for two hours to convert the pitch to mesophase condition.
  • the part reached a temperature of about 425°C.
  • the temperature was then slowly increased to 637°C at which time the run had to be aborted because of heater failure. As the temperature increased, the pressure was also increased slowly to 2000 psi on the part.
  • Stabilized polyacrilonitrile (PAN) fiber or stabilized pitch fiber can be used in place of carbon 5 fiber. Both of these types of fibers are precursors of carbon fibers.
  • the carbon fiber precursor and the matrix precursor (mesophase pitch) will pyrolyze and 0 convert to carbon at the same time. Because the fiber and matrix component will pyrolyze (and shrink) simultaneously, porosity in the composite will be minimized and density will be maximized.
  • a possible problem with this approach is potential interaction between the fiber and matrix 5 during pyrolysis, which would tend to reduce the crack stopping (toughening) capability of the fiber/matrix interface.
  • a fugitive coating is zinc sulfide. This compound can be applied to the fiber from acid solution.
  • Another approach to maintain the fiber/matrix interface is to treat the oxidized PAN fiber with a glassy carbon producing resin prior to pitch impregnation.
  • the difference in properties between the glassy carbon and the more graphitic fibers and matrix in the final composite should minimize crack propagation and maximize fracture toughness.
  • Coal tar and petroleum pitches and mesophase pitches are thermoplastic materials, i.e., they soften and flow when heated and pressurized. It may be desirable to stabilize the pitch prior to and during mesophase formation. This can be accomplished by controlled chemical crosslinking. This type of stabilization will, require oxidative crosslinking of the pitch in the preform stage of the process. Exposure to air at elevated temperature will stabilize (crosslink) pitches. This approach will not be practical for large preforms because air will not easily diffuse into the preform. The desired-approach will be to incorporate an oxidative crosslinking agent into the pitch prior to impregnation of the fibers and formation of the preform.
  • An example inorganic peroxide such as ammonium peroxydisulfate or an organic peroxide such as dicumyl peroxide, can be used for this purpose.
  • This approach will prevent pitch from flowing out of the preform prior to mesophase formation. It will also increase char (carbon) yield of the pitch by reducing formation of low molecular weigh volatile fractions during pyrolysis of the pitch.
  • Conversion of coal tar or petroleum pitch to mesophase is a function of time at temperature. At temperatures of around 400°C it takes several hours to achieve full conversion. Catalysts can be used to increase the rate of mesophase conversion.
  • Lewis acids are useful for this purpose.
  • An example of a Lewis acid that has practical utility for this purpose is boron trifluoride- monoethylamine complex. This material can be incorporated into the pitch used to make a preform.
  • the complex is dissociated to release boron trifluoride (a Lewis acid) as a catalyst.
  • the mesophase formation catalyst can be used in conjunction with the peroxide stabilization catalyst discussed above to allow optimization of the overall process. THERMAL ANALYSIS OF PITCHES

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Ceramic Products (AREA)

Abstract

Ce procédé permet de produire un composite carbone-carbone au moyen d'un procédé de densification par chauffage et pressurisation en une seule étape. Un brai (goudron de charbon, brais de pétrole ou brais mésophases), est ajouté à des fibres de carbone puis chauffé à environ 450 °C pour faire passer le brai à l'état mésomorphe et ainsi infiltrer les fibres de carbone. Le chauffage de cette combinaison est ensuite poursuivi jusqu'à au moins 460 °C, sous une pression comprise entre environ 1000 et 2000 psi. Le brai mésomorphe passe ainsi à l'état de matrice de carbone ou se carbonise, ce qui donne un composite carbone-carbone de très haute densité. Ce composite peut subir un traitement thermique final pour la confection de disques de freins d'avions au carbone.
PCT/US1994/007365 1993-07-12 1994-06-30 Procede de densification carbone-carbone utilisant des precurseurs a matrice de brai mesophase WO1995002564A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73195/94A AU7319594A (en) 1993-07-12 1994-06-30 Carbon-carbon densification process utilizing mesophase pitch matrix precursors

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9060493A 1993-07-12 1993-07-12
US08/090,604 1993-07-12

Publications (1)

Publication Number Publication Date
WO1995002564A1 true WO1995002564A1 (fr) 1995-01-26

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AU (1) AU7319594A (fr)
WO (1) WO1995002564A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752398A1 (fr) * 1995-07-07 1997-01-08 FIAT AUTO S.p.A. Procédé de fabrication d'un produit composite fritté et produit composite intermédiaire frittable
EP2363619A3 (fr) * 2001-05-11 2014-08-06 Koppers Delaware, Inc. Préforme de frein d'avion saturée comprenant de brai de goudron de houille et sa préparation
WO2017068002A1 (fr) * 2015-10-20 2017-04-27 Tribotecc Gmbh Fibre pour applications tribologiques
CN114369475A (zh) * 2021-11-29 2022-04-19 清华大学 制备碳化中间相沥青的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629379A (en) * 1969-11-06 1971-12-21 Kureha Chemical Ind Co Ltd Production of carbon filaments from low-priced pitches
DE2714364A1 (de) * 1977-03-31 1978-10-12 Schunk & Ebe Gmbh Verfahren zur herstellung von kohlenstoffaserverstaerkten kohlenstoffkoerpern
EP0323750A1 (fr) * 1987-12-28 1989-07-12 Kawasaki Heavy Industries Ltd. Procédé de production d'un matériau en carbone et de matériaux composites de carbone/carbone
EP0402915A2 (fr) * 1989-06-16 1990-12-19 Akebono Brake Industry Co., Ltd. Matériau composite hybride carbone/carbone
US5205888A (en) * 1990-07-03 1993-04-27 Mitsubishi Gas Chemical Company, Inc. Process for producing carbon fiber reinforced carbon materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629379A (en) * 1969-11-06 1971-12-21 Kureha Chemical Ind Co Ltd Production of carbon filaments from low-priced pitches
DE2714364A1 (de) * 1977-03-31 1978-10-12 Schunk & Ebe Gmbh Verfahren zur herstellung von kohlenstoffaserverstaerkten kohlenstoffkoerpern
EP0323750A1 (fr) * 1987-12-28 1989-07-12 Kawasaki Heavy Industries Ltd. Procédé de production d'un matériau en carbone et de matériaux composites de carbone/carbone
EP0402915A2 (fr) * 1989-06-16 1990-12-19 Akebono Brake Industry Co., Ltd. Matériau composite hybride carbone/carbone
US5205888A (en) * 1990-07-03 1993-04-27 Mitsubishi Gas Chemical Company, Inc. Process for producing carbon fiber reinforced carbon materials

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752398A1 (fr) * 1995-07-07 1997-01-08 FIAT AUTO S.p.A. Procédé de fabrication d'un produit composite fritté et produit composite intermédiaire frittable
EP2363619A3 (fr) * 2001-05-11 2014-08-06 Koppers Delaware, Inc. Préforme de frein d'avion saturée comprenant de brai de goudron de houille et sa préparation
WO2017068002A1 (fr) * 2015-10-20 2017-04-27 Tribotecc Gmbh Fibre pour applications tribologiques
US10890226B2 (en) 2015-10-20 2021-01-12 Tribotecc Gmbh Fiber for tribological applications
CN114369475A (zh) * 2021-11-29 2022-04-19 清华大学 制备碳化中间相沥青的方法

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Publication number Publication date
AU7319594A (en) 1995-02-13

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