EP1648675A2 - Procede de traitement de preformes de fibres de carbone coupees utilisant un liant de brai de houille - Google Patents

Procede de traitement de preformes de fibres de carbone coupees utilisant un liant de brai de houille

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Publication number
EP1648675A2
EP1648675A2 EP04754173A EP04754173A EP1648675A2 EP 1648675 A2 EP1648675 A2 EP 1648675A2 EP 04754173 A EP04754173 A EP 04754173A EP 04754173 A EP04754173 A EP 04754173A EP 1648675 A2 EP1648675 A2 EP 1648675A2
Authority
EP
European Patent Office
Prior art keywords
coal tar
pitch
tar pitch
softening point
preform
Prior art date
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.)
Withdrawn
Application number
EP04754173A
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German (de)
English (en)
Inventor
David R. Snyder
Robert H. Wombles
Thomas A. Golubic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koppers Industries of Delaware Inc
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Koppers Industries of Delaware Inc
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Filing date
Publication date
Application filed by Koppers Industries of Delaware Inc filed Critical Koppers Industries of Delaware Inc
Publication of EP1648675A2 publication Critical patent/EP1648675A2/fr
Withdrawn legal-status Critical Current

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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
    • C04B35/71—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
    • 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
    • C04B35/52—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 carbon, e.g. graphite
    • 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
    • C04B35/52—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 carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6021—Extrusion moulding
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the present invention relates to friction material preforms using a coal tar pitch binder, and more specifically, a chopped carbon fiber preform using a coal tar pitch binder and the method of making thereof .
  • Coal tar is a primary by-product material produced during the destructive distillation or carbonization of coal into coke. While the coke product is utilized as a fuel and reagent source in the steel industry, the coal tar material is distilled ' into a series of fractions, each of which are commercially viable products in their own right . A significant portion of the distilled coal tar material is the pitch residue. This material is utilized in the production of anodes for aluminum smelting, as well as electrodes for electric arc furnaces used in the steel industry. In evaluating the qualitative characteristics of the pitch material, the prior art has been primarily focused on the ability of the coal tar pitch material to provide a suitable binder used in the anode and electrode production processes. Various characteristics such as softening point, specific gravity, percentage of material insoluble in quinoline, also known as QI, and coking value have all served to characterize coal tar pitches for applicability in these various manufacturing processes and industries.
  • Softening point is the basic measurement utilized to determine the distillation process end point in coal tar pitch production and to establish the mixing, forming or impregnating temperatures in carbon product production. All softening points referred to herein are taken according to the Mettler method or ASTM Standard D3104. Additional characteristics described herein include QI, which is utilized to determine the quantity of solid and high molecular weight material in the pitch. QI may also be referred to as ⁇ -resin and the standard test methodology used to determine the QI as a weight percentage include either ASTM Standard D4746 or ASTM Standard D2318. Percentage of material insoluble in toluene, or TI, will also be referred to herein, and is determined through ASTM Standard D4072 or D4312.
  • Estimations of potential toxicity of a pitch material may be made by converting its total PAH content into a B(a)P equivalent which eliminates the necessity of referring to each of the 14 materials individually, providing a useful shorthand for the evaluation of a material's toxicity.
  • a typical coal tar binder pitch is characterized as shown in Table I.
  • High efficiency evaporative distillation processes are known that subject a material to elevated temperatures, generally in the range of 300°C to 450°C, and reduced pressures generally in the range of 5 Torr or less, in a distillation vessel to evolve lower molecular weight, more volatile components from higher molecular weight, less volatile components.
  • Such high efficiency evaporative distillation processes may be carried out using conventional distillation equipment having enhanced vacuum capabilities for operating at the above specified temperature and pressure ranges.
  • high efficiency evaporative distillation processes may be carried out in an apparatus known as a wiped film evaporator, or WFE, and thus such processes are commonly referred to as WFE processes.
  • WFE and thin film evaporator processes are often used as efficient, relatively quick ways to continuously distill a material.
  • WFE and thin film evaporator processes involve forming a thin layer of a material on a heated surface, typically the interior wall of a vessel or chamber, generally in the range of 300°C to 450°C, while simultaneously providing a reduced pressure, generally in the range of 5 Torr or less.
  • the thin layer of material is formed by a rotor in close proximity with the interior wall of the vessel.
  • the thin film evaporator typically has a spinner configuration such that the thin layer of material is formed on the interior wall of the vessel as a result of centrifugal force.
  • WFE and thin film evaporator processes are continuous processes as they involve the continuous ingress of feed material and egress of output material . Both wiped film evaporators and thin film evaporators are well known in the prior art.
  • Baird United States Patent No. 4,093,479.
  • the apparatus described in Baird includes a cylindrical processing chamber or vessel .
  • the processing chamber is surrounded by a temperature control jacket adapted to introduce a heat exchange fluid.
  • the processing chamber includes a feed inlet at one end and a product outlet at the opposite end.
  • the processing chamber of the apparatus described in Baird also includes a vapor chamber having 1 a vapor outlet.
  • a condenser and a vacuum means may be placed in communication with the vapor outlet to permit condensation of the generated vapor under sub- atmospheric conditions.
  • Extending from one end of the processing chamber to the other end is a tube-like motor-driven rotor.
  • Extending axially outward from the rotor shaft are a plurality of radial rotor blades which are non-symmetrically twisted to extend radially from one end of the chamber to the other between the feed inlet and the product outlet .
  • the rotor blades extend into a small but generally uniform closely spaced thin- film relationship with respect to the interior wall of the processing chamber so that, when the rotor rotates, the rotor blades provide a thin, wiped or turbulent film of the processing material on the interior wall of the processing chamber.
  • a material to be processed is introduced into the feed inlet by a pump or by gravity.
  • the material is permitted to move downwardly and is formed into a thin-film on the interior wall of the processing, chamber by the rotating rotor blades.
  • a heat-exchange fluid such as steam, is introduced into the temperature control jacket so that the interior wall of the processing chamber is heated to a steady, preselected temperature to effect the controlled evaporation of the relatively volatile component of the processing material .
  • a relatively non-volatile material is withdrawn from the product outlet, and the vaporized volatile material is withdrawn from the vapor chamber through the vapor outlet .
  • coal tar pitch is the binder for carbon/graphite products. These products range from anodes for the production of aluminum to fine grain graphite products for use in electric discharge machining. Carbon/graphite products contain two major components petroleum coke and coal tar pitch. Coal tar pitch is the binder that holds the structure together. The major steps in production of the finished product are mixing, forming, carbonization for carbon products, and carbonization followed by graphitization for graphite products. The major problem experienced with pitch in the process is evolution of volatiles during the carbonization step. Volatiles evolution causes two major problems: 1) emissions of organic compounds, and 2) reduction of the density of the finished baked product.
  • Volatiles emissions are an environmental concern which must be addressed by either capture or destruction of the organic compounds generated.
  • the reduction of the density of the carbon/graphite product results in an inferior product with reduced strength, increased reactivity, and increased electrical resistivity.
  • Aircraft brakes are produced by carbon impregnation of a carbon fiber preform.
  • the process used for carbon impregnation is called chemical vapor infiltration.
  • Chemical vapor infiltration is performed by coking methane gas in the preform to result in a carbon filled carbon fiber preform.
  • the chemical vapor infiltration process is very time consuming with about 600 hours of processing time required to produce a finished product. An advantage therefore exists for a carbon infiltration process having a reduced time.
  • Natural rubber is used to produce many of the products we use each day.
  • One rubber product which plays a great part in each of our lives is tires.
  • a tire is produced from a number of different rubber formulations. Different formulations are used to produce the tread, sidewalls, belt coating, and rim.
  • One of the most important characteristics of the different rubber formulations used to produce a tire is the adhesive properties for each of the rubber formulations for each other. An advantage therefore exists for a rubber formulation having increased adhesive properties.
  • Mesophase pitch is a highly structured pitch which is used in applications where strength or the ability to conduct heat or electricity is important .
  • Significant work has been performed to produce mesophase pitch from coal tar pitch with limited success because of the quinoline insolubles content of the pitch. It has been shown that the quinoline insolubles particles in coal tar pitch hinder coalescence of the mesophase spheres causing a poor quality mesophase to be formed.
  • Known methods of producing mesophase from coal tar pitch involve a filtration or centrifugation step for removing the quinoline insolubles. While these processes work quite well and allow for production of a high quality mesophase, they result in a very high cost of the mesophase product. An advantage therefore exists for a lower cost production of a high quality mesophase.
  • the present invention relates to a method of making a high softening point coal tar pitch using high efficiency evaporative distillation, as well as the uses and applications of such pitch.
  • a feed coal tar pitch having a softening point in the range of 70°C to 160°C is fed into a processing vessel wherein the processing vessel is heated to a temperature in the range of 300°C to 450°C and wherein a pressure inside the processing vessel is in the range of 5 Torr or less .
  • An output coal tar pitch is withdrawn from the processing vessel .
  • the output coal tar pitch has a softening point in the range of 140°C to 300°C and has less than 5% mesophase.
  • a mesophase content of greater than 5% in the output coal tar pitch will degrade its performance as a binder for carbon-carbon composites, and in the production of graphite electrodes and anodes used for aluminum production.
  • Preferable ranges for the output coal tar pitch include a softening point in the range of 150°C to 250°C and less than 1% mesophase.
  • the output coal tar pitch preferably has a B(a)P Equivalent less than or equal to 24,000 ppm.
  • the feed coal tar pitch may preferably have a softening point in the range of 110°C to 140°C, and the processing vessel may preferably be heated to a temperature in the range of 300°C to 450°C.
  • the output coal tar pitch may also be combined with a plasticizer such as a low viscosity, preferably between 2 and 5 centistokes at 210°F, low B(a)P equivalent, preferably no more than 5,000 ppm B(a)P, coal tar, or such a coal tar in combination with a petroleum oil where the petroleum oil constitutes 30% to 60% of the mixture.
  • a plasticizer such as a low viscosity, preferably between 2 and 5 centistokes at 210°F, low B(a)P equivalent, preferably no more than 5,000 ppm B(a)P, coal tar, or such a coal tar in combination with a petroleum oil where the petroleum oil constitutes 30% to 60% of the mixture.
  • the present invention also relates to a method of making a mesophase coal tar pitch having 10% to 100% mesophase.
  • a feed coal tar pitch having a softening point in the range of 70°C to 160°C is fed into a processing vessel, wherein the processing vessel is heated to a temperature in the range of 300°C to 450°C and wherein a pressure inside the processing vessel is in the range of 5 Torr or less.
  • a quinoline insoluble-free and ash-free distillate having a softening point in the range of 25°C to 60°C is obtained from the • processing vessel .
  • the distillate is heat treated at a temperature in the range of 370 °C to 595°C for between three and eighty hours.
  • the present invention also relates to a method of making a quinoline insoluble-free and ash-free coal tar pitch.
  • the method includes steps of feeding a feed coal tar pitch having a softening point in the range of 70°C to 160°C into a first processing vessel, wherein the first processing vessel is heated to a temperature in the range of 300°C to 450°C and wherein a pressure inside the first processing vessel is in the range of 5 Torr or less, obtaining a quinoline insoluble-free and ash-free distillate having a softening point in the range of 25°C to 60°C from the first processing vessel, heat treating the distillate at a temperature in the range of 350°C to 595°C for between five minutes and forty hours, distilling the heat treated distillate to obtain a pitch having a desired softening point, feeding the pitch having a desired softening point into a second processing vessel, wherein the second processing vessel is heated to a temperature in the range of 300°C to 450°C , and
  • a hydrocarbon mixture such as a mixture of coal tar pitch and petroleum pitch, may be used as a feed material in place of the feed coal tar pitch in each of the methods of the present invention.
  • the hydrocarbon mixture preferably has a coal tar pitch content of at least 50%.
  • Each of the methods of the present invention may be performed using conventional distillation equipment, a wiped film evaporator, or a thin film evaporator.
  • Conventional distillation is limited to a softening point pitch of 180°C.
  • At least one pr esently preferred embodiment of the present invention broadly contemplates output coal tar pitch having a high softening point greater than 170°C used as a "modifier" in the formation of carbon/graphite products.
  • the utilization of high softening point pitch product of the present invention addresses the problems associated with evolution of volatiles during production by yielding a lower number of volatiles.
  • the lower volatiles yield means there are fewer organic compounds to capture or destroy, and the product produced has a higher density with resulting superior properties of the finished carbon/graphite product.
  • the high softening point coal tar pitch portion of the resulting carbon/graphite product shrinks thereby improving product density and strength.
  • the resulting product exhibits increased efficiency to conduct heat and electricity.
  • At least one presently preferred embodiment of the present invention broadly contemplates high softening point coal tar pitch used as a binder in the formation of automobile brakes.
  • the addition of the high softening point pitch product of this invention to brake formulations results in a reduction of fade because the pitch is very stable to high temperatures, therefor it does not decompose and produce the gas bubble responsible for fade.
  • At least one presently preferred embodiment of the present invention broadly contemplates high softening point coal tar pitch used as a saturant in the formation of aircraft brakes.
  • the saturation of carbon fiber preforms can be performed with the high softening point pitch of the present invention resulting in a 95% saturation of the carbon fiber preform in about one hour. This preliminary quick saturation has the potential to reduce the time necessary for complete carbon saturation of the preform by many hours. Also, dynamometer testing results of the finished aircraft brakes produced using high softening point pitch have shown superior friction characteristics.
  • At least one presently preferred embodiment of the present invention broadly contemplates high softening point coal tar pitch used in the production of rubber products. Rubber formulations containing the pitch of this invention have exhibited superior adhesive properties.
  • at least one presently preferred embodiment of the present invention broadly contemplates distillate used to make mesophase pitch.
  • the distillate product of this invention is a quinoline insolubles free coal tar derived material which has been shown to produce high quality mesophase. Also, the economics for mesophase production of the present invention result in a product with a much lower cost .
  • At least one embodiment of the presently preferred invention contemplates using high softening point coal tar pitch as a means to uniformly distribute chopped carbon fibers in a friction material preform without the use of phenolic resin.
  • Aircraft and automobile brake preforms are typically formed using phenolic resin.
  • the phenolic resin used in producing these preforms is replaced by high softening point pitch.
  • Fig. la is a top view of preform mold pan
  • Fig. lb is a cross-sectional view through AA of Fig. 1 of a preform mold pan with removable inside and outside sleeves inserted;
  • FIG. 2a is a cross-sectional view of a preform mold pan with perforated pressing plate
  • Fig. 2b is a top view of perforated pressing plate
  • Fig. 3 is a cross-sectional view of a preform mold pan with removable inside and outside sleeves removed;
  • Fig. 4 is a cross-sectional view of a preform mold pan with vacuum/pressure chamber,-
  • Fig. 5 is a cross-sectional view of a preform mold pan according to another example.
  • Fig. 6 is a top view of a preform removal fixture .
  • a high softening point, low volatility coal tar pitch is produced by processing a feed coal tar pitch having a softening point in the range of 70°C to 160°C , and preferably i'n the range of 110°C to 140°C , using a high efficiency evaporative distillation process carried out in a processing vessel operating at temperatures of 300°C to 450°C and pressures of 5 Torr or less.
  • This temperature range is important because operating below the bottom temperature will not yield the desired softening point in the output material and operating above the top temperature will result in thermal cracking and thermal degradation in the output material.
  • this pressure range is important because if the pressure is higher than the specified top range pressure, higher operating temperatures will be necessary to achieve the desired softening point, which higher temperatures will result in thermal cracking and thermal degradation in the output material .
  • the processing may be performed using a WFE apparatus, and for purposes of illustration and not limitation, the present invention will be described with respect to processing using a WFE apparatus. It will be appreciated, however, that conventional distillation equipment and conventional thin film evaporators may be used so long as such equipment and evaporators may be operated at the temperatures and pressures described herein. In the case where a thin film evaporator is used, the thin film evaporator preferably should form a film on the interior wall thereof having a minimum thickness that is no smaller than the thickness of the largest QI particle contained in the feed material .
  • any known WFE apparatus may be used as long as it is capable of operating at temperatures of 300°C to 450°C and pressures of 5 Torr or less.
  • the WFE apparatus should be capable of processing a minimum film thickness of 1 millimeter, and operating with a wiper speed of 200 rpm to 3000 rpm.
  • the processing chamber or vessel wall of the WFE is heated to a temperature of between 300°C and 450°C, and preferably between 300°C to 400°C.
  • the appropriate feed rate of the feed coal tar pitch into the WFE apparatus will depend on the processing surface area of the vessel.
  • the feed rate should be between 10 and 100 pounds/square foot of surface area/hour, and preferably between 35 and 50 pounds/square foot of surface area/hour.
  • the residence time of the feed coal tar pitch in the WFE apparatus will be approximately 1 to 60 seconds. If the feed coal tar pitch is fed at the preferred rate of between 35 and 50 pounds/square foot/hour, the residence time of the feed coal tar pitch in the WFE apparatus will be approximately 5 to 30 seconds.
  • the residue of the WFE will be an output coal tar pitch having a softening point in the range of 140°C to 300°C , preferably 150°C to 250 °C, and having a minimal formation of mesophase of 0% to 5%, preferably 0% to 1%.
  • the output coal tar pitch will have a softening point in the range of 140°C to 180°C.
  • a high efficiency evaporative distillation process such as a WFE process facilitates the removal of high boiling point PAH's, particularly benzo (a) pyrene, from the feed coal tar pitch, resulting in an output coal tar pitch having a B(a)P equivalent of no more than 24,000 ppm.
  • PAH's particularly benzo (a) pyrene
  • B(a)P equivalent of no more than 24,000 ppm The yield of the output coal tar pitch at a given vessel temperature depends on the softening point of the feed coal tar pitch.
  • a feed coal tar pitch having, a softening point of 109°C is fed into a WFE apparatus having a 1.4 square foot vessel operating at a temperature of 335°C, 18.5mmHg absolute, and at a feed rate of 77 pounds/square foot of surface area/hour.
  • the output coal tar pitch of the WFE apparatus has a pitch yield of 85%.
  • Table II A laboratory analysis of the output coal tar pitch is summarized in the following Table II:
  • a feed coal tar pitch having a softening point of 109°C is fed into a WFE apparatus having a 1.4 square foot vessel operating at a temperature of 335°C, 10.4 mmHg absolute, and at a feed rate of 95 pounds/square foot/hour.
  • the output coal tar pitch of the WFE apparatus has a pitch yield of 73%.
  • Table III A laboratory analysis of the output coal tar pitch is summarized in the following Table III:
  • a feed coal tar pitch having a softening point of 109°C is fed a WFE apparatus having a 1.4 square foot vessel operating at a temperature of 350°C, 5.0 mmHg absolute and at a feed rate of 65 pounds/square foot/hour.
  • the output coal tar pitch of the WFE apparatus has a pitch yield of 74.2%.
  • a laboratory analysis of the output coal tar pitch is summarized in the following Table IV: TABLE IV
  • a feed coal tar pitch having a softening point of 109°C is fed into a WFE apparatus having a 1.4 square foot vessel operating at a temperature of 365°C, 5.0 mmHg absolute, and at a feed rate of 67 pounds/square foot/hour.
  • the output coal tar pitch of the WFE apparatus has a pitch yield of 67%.
  • a laboratory analysis of the output coal tar pitch is summarized in the following Table V: TABLE V
  • the output coal tar pitch having a softening point in the range of 140°C to 300°C , and preferably in the range of 150°C to 250°C may be used as a binder for carbon-carbon composites and friction materials, and in the production of graphite electrodes and anodes used for aluminum production.
  • the output coal tar pitch having a softening, point in the range of 140°C to 300°C , and preferably in the range of 150°C to 250°C may be combined with a plasticizer to produce a pitch having a 110 °C softening point suitable for use in aluminum anode production, including Soderberg binder pitch, and any other industrial application where very low PAH contents are required.
  • the plasticizer may be low viscosity, preferably between 2 and 5 centistokes at 210°F , low B(a)P equivalent, preferably no more than 5,000 ppm B(a)P, coal tar, or such a coal tar in combination with a petroleum oil where the petroleum oil constitutes 30% to 60% of the mixture.
  • low B(a)P equivalent preferably no more than 5,000 ppm B(a)P
  • coal tar or such a coal tar in combination with a petroleum oil where the petroleum oil constitutes 30% to 60% of the mixture.
  • One suitable plasticizer is the coal tar pitch blend described in McHenry et al . , United States Patent No. 5,746,906, the disclosure of which is incorporated herein by reference.
  • a hydrocarbon mixture such as a mixture of coal tar pitch and petroleum pitch, may be used as a feed material in place of the feed coal tar pitch.
  • the hydrocarbon mixture in this embodiment preferably has a coal tar pitch content of at least 50%.
  • the distillate produced when using a hydrocarbon mixture as the feed material may then be used in the methods described below.
  • the distillate evolved by processing the feed coal tar pitch in the WFE apparatus will be quinoline insoluble-free, which as used herein means it has a QI in the range of 0% to 0.5%, and ash-free, which as used herein means it has an ash content in the range of 0% to 0.1%.
  • a quinoline insoluble-free, ash free distillate is desirable for at least two reasons. First, the distillate may be used to create materials that will be used as an impregnating pitch to fill in porosity in carbon structures, and it is known that QI and ash hinders the ability to fill in such porosity. Second, the distillate may be used to create mesophase pitch, and QI is known to hinder the coalescence of mesophase spheres. The distillate will comprise a pitch having a softening point in the range of 25°C to 60°C.
  • the distillate may be used to produce a quinoline insoluble-free and ash-free pitch of a desired higher softening point by first heat treating the distillate at temperatures between 350°C and 595°C for between 5 minutes and 40 hours.
  • the heat treating step may, for example, be performed by placing the distillate in a flask containing a short distillation column, and heating and stirring the distillate therein under a slight vacuum of no more than 600 mmHg Absolute.
  • the step of heat treating the distillate will result in a pitch having a softening point in the range of 60°C to 110°C.
  • the heat treated distillate may then be distilled by known conventional means to obtain a pitch residue of a desired softening point.
  • a narrow boiling range quinoline insoluble-free pitch may be produced by further processing the quinoline insoluble-free and ash- free pitch produced through heat treating and distillation using a high efficiency evaporative distillation process, such as a WFE or a thin film evaporator process, at temperatures in the range of 300°C to 450°C and pressures no greater than 5 Torr, wherein the narrow boiling range pitch is the residue of such processing.
  • a high efficiency evaporative distillation process such as a WFE or a thin film evaporator process
  • a 25-30°C softening point distillate produced from a feed coal tar pitch having a softening point of 110°C is heat treated at 360°C for approximately 8 hours to produce a pitch having a softening point of 60°C.
  • the 60°C softening point pitch is distilled in a batch/pot distillation at an overhead temperature of 400°C to produce a pitch having a softening point of 98.9°C with a 70% yield.
  • a laboratory analysis of the resulting pitch is summarized in the following Table VI: TABLE VI
  • a mesophase pitch having mesophase content in the range of 70% to 100%, and preferably in the range of 75% to 85% may be produced from the distillate by heat treating the distillate at temperatures between 370°C and 595°C for between 3 and 40 hours.
  • the yield of the mesophase pitch is generally in the range of 70% and 100%.
  • the mesophase pitch may be used in carbon fibers, lithium-ion batteries and graphite foam.
  • a hydrocarbon mixture such as a mixture of coal tar pitch and petroleum pitch, may be us ' ed as a feed material in place of the feed coal tar pitch.
  • the hydrocarbon mixture in this embodiment preferably has a coal tar pitch content of at least 50%.
  • the present invention also relates to applications of the output coal tar pitch having a high softening point.
  • output coal tar pitch having a high softening point in the preferred range of 150°C-250°C, more preferably in the range of 160°C-220°C, and most preferably in the range of 170°C- 200°C is used as a "modifier" in the formation of carbon/graphite products which are traditionally formed from coke an 110°C softening point coal tar pitch.
  • One embodiment of the present invention involves substituting the 110°C softening pint coal tar pitch with 160°C softening point coal tar pitch in the production of the carbon/graphite products.
  • the output coal tar pitch having a high softening point is used as a substitute for a portion of the coke in the production of the carbon/graphite products .
  • Pitch having a softening point of 160°C . is used as a replacement for 110°C pitch in the extrusion of 5/16" diameter x 12" long gouging rods.
  • the pitch is mixed with coke at a pitching level of approximately 60% by weight and extruded to form the finished piece.
  • the products are baked and graphitized. The properties of these products are set forth in Table VII. TABLE VII
  • the carbon and graphite products produced had improved density, strength, and resistivity properties using the 160 °C high softening point pitch over the typical 110 °C pitch.
  • the density of the graphite improved 3.8%
  • the graphite strength improved 14.3%.
  • the output coal tar pitch is used in the formation of friction materials, in the brakes of various kinds of vehicles such as aircraft and automobiles.
  • coal tar pitch having a high softening point in the preferred range of 150°C-250°C, more preferably in the range of 170°C-240°C, and most preferably in the range of 180°C-230°C is used as a binder. It is preferred to use a crosslinking additive to further increase the softening point of the pitch during post cure with temperatures in the range of 350°F to 450°F.
  • the 180 °C softening point coal tar pitch can be used as a replacement for 3 wt . % of a total 8 wt . % phenolic resin in a semi-metallic automobile brake pad.
  • a semi-metallic automobile brake pad formulation according to this example has the following composition:
  • a low QI (Quinoline Insoluble) 180°C softening point coal tar pitch can be used to saturate aircraft brake carbon fiber preforms to reduce the porosity of the preform from 75 vol . % to 5 vol . % in the following manner.
  • a carbon fiber preform with approximately 25 vol . % carbon fibers is placed under vacuum ( ⁇ 10 mmHg) and heated to 325°C.
  • Low QI ⁇ 10 wt.% 180°C softening point coal tar pitch at 325 °C is introduced into the carbon fiber preform.
  • the coal tar pitch saturated carbon fiber preform is pressurized with nitrogen at 15 psig.
  • the saturated carbon fiber preform is cooled.
  • the saturated carbon fiber preform is further processed by the initiation of densification steps using Chemical Vapor Infiltration (CVI) .
  • CVI Chemical Vapor Infiltration
  • coal tar pitch having a high softening point in the preferred range of 100°C-200°C, more preferably in the range of 120°C-180°C, and most preferably in the range of 140°C-180°C is used in the production of rubber products such as tire compounds with natural rubber in the formulation.
  • control compound consists of the following: ⁇ 100 parts Natural Rubber ⁇ 55 parts Carbon Black ⁇ 15 parts Silica ⁇ 4 parts Paraffinic Oil ⁇ 2 parts Stearic Acid
  • Resorcinol and HMMM are removed and 6 parts of 140 °C softening point coal tar pitch that has been milled to 50% through 200 mesh and 0.5 parts of additional sulfur is added.
  • a Wire Belt-Coat Compound formulation according to the present example (Coal Tar Pitch Compound) consists of the following: ⁇ 100 parts Natural Rubber
  • Another presently preferred embodiment of the present invention broadly contemplates distillate used to make mesophase pitch.
  • Mesophase can be prepared in concentrations of ⁇ 1 vol% to over 80 vol% by various thermal treatment methods .
  • Example 1 overhead was treated at 440 °C. After 35 hours, the mesophase content was 80.2 vol%.
  • the overhead was vacuum distilled with no heat treatment to a soft pitch (54.0°C SP) .
  • the soft pitch was then heat treated in the 100-ml glass reactor with nitrogen purge. After 39 hours at 400 °C the mesophase was 3.9 vol%.
  • the soft pitch was also heat treated for 31 hours at temperatures ranging from 430 to 455°C for a total of 31 hours; the mesophase content was 82.4 vol%.
  • liquid coal tar pitch 26 having a softening point greater than or equal to 140°C into the mold pan 12, filling the chopped fiber volume with liquid coal tar pitch 26 (Fig.- 4) .
  • Fixture 28 is a steel plate 30 with center sleeve 32.
  • An attachment mechanism 34 disposed on the center sleeve 32 may be used for pulling the preform removal fixture 28.
  • the preform may further include a lip 36 (preferably W ) for locking down when pulling the preform.

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Abstract

L'invention concerne un procédé de formation d'une préforme de fibres de carbone coupées qui fait intervenir un liant de brai de houille, ainsi que le produit obtenu.
EP04754173A 2003-05-30 2004-06-01 Procede de traitement de preformes de fibres de carbone coupees utilisant un liant de brai de houille Withdrawn EP1648675A2 (fr)

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ZA200703561B (en) * 2004-10-05 2009-09-30 Wyeth Corp Methods and compositions for improving recombinant protein production
US7700014B2 (en) 2005-06-08 2010-04-20 Honeywell International Inc. VPI-RTM-CVD brake disc preform densification
JP4750882B2 (ja) * 2008-12-01 2011-08-17 住友ゴム工業株式会社 サイドウォール補強層又はサイドウォール用ゴム組成物及びタイヤ
KR20100062907A (ko) * 2008-12-01 2010-06-10 스미토모 고무 고교 가부시키가이샤 측벽 보강층 또는 측벽용 고무 조성물 및 타이어
JP6529071B2 (ja) * 2015-04-27 2019-06-12 株式会社エコ・アール ディスクブレーキ用材料
CN115404714B (zh) * 2022-08-25 2023-08-25 易高碳材料控股(深圳)有限公司 一种低阻抗碳纤维纸的制备方法

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US2302564A (en) * 1939-03-04 1942-11-17 Allen Bradley Co Insulated resistor making process
US3171720A (en) * 1961-06-23 1965-03-02 Great Lakes Carbon Corp Carbonaceous bodies useful for thermal insulation and processes for preparing same
US3309437A (en) * 1961-08-28 1967-03-14 Great Lakes Carbon Corp Method of producing bodies from raw petroleum coke
US3867491A (en) * 1970-06-22 1975-02-18 Carborundum Co Process for reinforced carbon bodies
US5569417A (en) * 1985-07-11 1996-10-29 Amoco Corporation Thermoplastic compositions comprising filled, B-staged pitch

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ZA200510345B (en) 2006-10-25

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