WO2000039043A2 - Microcellular carbon foams and microcellular c/c composites fabricated therefrom - Google Patents
Microcellular carbon foams and microcellular c/c composites fabricated therefrom Download PDFInfo
- Publication number
- WO2000039043A2 WO2000039043A2 PCT/US1999/030884 US9930884W WO0039043A2 WO 2000039043 A2 WO2000039043 A2 WO 2000039043A2 US 9930884 W US9930884 W US 9930884W WO 0039043 A2 WO0039043 A2 WO 0039043A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- foam
- carbon
- carbon fiber
- fiber precursor
- shape
- Prior art date
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Classifications
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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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3325—Including a foamed layer or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3325—Including a foamed layer or component
- Y10T442/3366—Woven fabric is coated, impregnated, or autogenously bonded
Definitions
- the present invention relates to the production and application of a novel class of low-cost microcellular carbon foams and to microcellular carbon/carbon (C/C) composites manufactured therefrom.
- C/C composites in space structures and satellite components because these materials possess very unique characteristics such as: high specific stiffness, high specific strength, excellent dimensional stability, near zero thermal expansion coefficients, no out-gassing and laser and radiation survivability.
- Sandwich structures containing such low density, high temperature core materials have many applications for, for example, high speed transport vehicles such as supersonic aircraft and outerspace structures.
- Conventional carbon foams demonstrate relatively low mechanical properties, such as fracture toughness, due to their amorphous morphology or low level of crystalline orientation. High cost, dictated by the need for long processing times, is also a major shortcoming of these materials.
- thermosetting polymer precursors such as phenolics
- Such materials are therefor used primarily for nonstructural applications such as electrodes.
- the carbon foams of the present invention are preferably crystalline carbon foams produced by the pyrolysis and graphitization of thermoplastic carbon fiber precursors such as mesophase pitch or polyacrylonitrile (PAN). These foams are produced by a process wherein a blowing process aligns the anisotropic pitch molecules along the struts or boundaries of the individual abutting microcells. Such foams are mechanically very strong and can therefore be used in structural applications. They are also good conductors of electricity and heat due to their carbon nature.
- Figure 1 is a block flow diagram of the process for producing the novel foams of the present invention.
- Figure 2 is a cross-sectional view of a C/C composite of the present invention.
- Figure 3 is an SEM photomicrograph of a low to medium density carbon foam of the present invention.
- Figure 4 is another lower magnification SEM photomicrograph of a low to medium density carbon foam of the present invention.
- Figure 5 is an SEM photomicrograph of a high density carbon foam of the present invention.
- Figure 6 is a graph of compression stress versus strain for the carbon foams of the present invention.
- Figure 7 is an SEM photomicrograph of a carbon foam of the present invention having elliptical bubbles.
- Figure 8 is a stress versus strain curve of a carbon foam of the prior art.
- Figure 9 is an SEM photomicrograph of a carbon foam of the prior art.
- the present invention provides a method for the production of and a novel class of 3-D carbon cellular foams that demonstrate extremely high fracture toughness and fracture strain, and C/C composites incorporating such novel cellular foams. Because of the micron size of the bubbles in these novel carbon foams and their crystalline morphology, they form an extremely strong network with unidirectional fibers and woven fabrics. As a consequence, although the C/C composites of the present invention are lighter than prior art such materials, they possess much higher specific mechanical properties and demonstrate higher impact resistance than such prior art C/C composites.
- the fracture toughness and fracture strain of the foams of the present invention are an order of magnitude greater than those of similar prior art carbon foams. For example, existing carbon foams fracture at about 1.2% of strain whereas the carbon foams of the present invention fracture at about 42% of strain under compression loading.
- Impregnation of unidirectional or woven fabrics with the carbon fiber precursor derived microcellular foams of the present invention provides an entirely new class of C/C composites having a carbon microcellular foam matrix as opposed to the glassy carbon matrix of conventional C/C composites.
- the method of the present invention allows this new class of C/C composites to be produced in a in a much faster and less expensive process than those of the prior art.
- the process of the present invention permits the production of novel microcellular foams having ligament or strut dimensions that are similar to those of carbon fibers (5-10 ⁇ m) from carbon fiber precursors such as mesophase pitch or poly aery Ion it rile.
- the process of the present invention comprises compression molding the carbon fiber precursor powder into an appropriate disc or part, saturating the disc or part with high-pressure gas, depressurizing and quenching.
- Conventional processing involving oxygen stabilization, carbonization and, optionally, graphitization complete the fabrication.
- the methods and materials of the present invention can use a variety of carbon fiber precursors.
- a mesophase pitch material is used , however any suitable pitch-based or PAN-based carbon fiber precursor may be used.
- the particular material used for demonstration purposes herein is ARA24ZPP produced by the catalytic polymerization of naphthalene and sold by Mitsubishi Gas Chemical Company, Inc., Mitsubishi Building, 5-2 Marunouchi 2-chome, Chiyoda-ku, Tokyo, Japan. Any carbon fiber precursor that is crystalline is highly preferred in the successful practice of the invention, as this allows ease of aligning of the carbon planes during the blowing or depressurization step.
- the carbon fiber precursor material Before the start of compaction and compression, the carbon fiber precursor material should be in the form of a powder, Hence, if the material is received in the form of pellets, is should be ground to a fine powder before the start of production. Once in powder form, the powder is compression molded into disks or other shapes using a hydraulic press at a pressure over 10 Ksi.
- Foaming is accomplished in a pressure vessel by first saturating the compression molded part with an inert fluid, such as nitrogen, carbon dioxide, helium, argon, etc. while raising the temperature of the reactor.
- Fluid as used in this disclosure is generic to both gas and liquid.
- Heat up can be at a rate of from about 0.5°C/min up to about 5°C/min. Care should be exercised at the higher heat-up rates due to the potential for sample microcracking.
- the pressure is raised to over 800psi, preferably over 3000psi and held for at least 15 minutes. Holding periods of up to 40 minutes have been found useful for conventionally sized parts, however, for larger parts, longer holding periods may be necessary/useful.
- Gas saturation should occur above the glass transition temperature of the carbon fiber precursor material, although the gas can be introduced at any time during the heat-up process. In the case of the material from Mitsubishi Gas and Chemical, saturation was reached in about 15-30 minutes at a temperature of from about 280°C to about 300°C. Gas saturation is relatively poor at temperatures below the glass transition temperature since the crystalline structure of the carbon planes prevents the gas molecules from penetrating into the bulk pitch. Thus, the application of high gas pressure prior to attaining the glass transition temperature does not materially affect the saturation time.
- a part icu late of small particle size on the order of l.S ⁇ m can be used as a nucleating agent.
- Talc powder of this dimension has been found particularly useful in this regard.
- a small amount, about 0.5% to about 2% by weight, of the nucleating agent powder is blended with the dry pitch in a ball mill prior to compression molding the pitch into a disc or preform. The remaining processing steps are the same as those for a foam which contains no nucleating agent.
- the foams are oxygen stabilized in a circulating oven, carbonized in a furnace with a nitrogen atmosphere and, finally, graph itized in a graphite vacuum furnace.
- the graphite planes are cross-linked and become infusible.
- Oxygen stabilization is necessary so that the pitch does not melt during the subsequent carbonization step.
- Oxygen stabilization is preferably performed at between about 220°C and about 240°C in an air or oxygen atmosphere.
- Heat up may be at a constant about l°C/min to about 10°C/ min or stepwise.
- An exemplary stepwise heat-up would be as follows: 5°C/min up to 150°C, hold for 1 hour; 5°C/min up to 180°C, hold for 1 hour, 5°C/ min up to 220°C, hold for 72 hours, then cool down at a rate of 5°C/min or slower to ambient.
- Oxygenation can be accelerated through the use of oxygen gas rather than ambient air in the furnace.
- the time of oxygen stabilization will be dependent upon the thickness of the sample.
- Carbonization can be performed in a furnace in a nitrogen atmosphere. The material is heated up slowly at a rate of from about 10°C/hr to about 5°C/min to from about 600°C to about 1000°C and held for an appropriate length of time, e.g. 1 hour and then cooled down slowly, for example at about 5°C/min to room temperature.
- Graphitization if desired because the foam is to be graphitic, is accomplished in a graphite vacuum furnace using conventional practice for graphitization of carbon fibers.
- a typical such practice involves heating up at about 1 to about 5°C/min to from about 2200 to about 2300°C in a vacuum, holding at this temperature for about 1 hour, then cooling down at less than about 5°C/min.
- Materials produced in accordance with the method of the present invention can be analyzed using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the photomicrographs can be used to obtain an estimation of bubble density, cell size and strut size.
- the mechanical properties are determined using dogbone tensile specimens and cubicle specimens for compression testing.
- the crystal orientations of the foams can be determined using fluorescence and polarized light microscopy.
- Foam samples should be vacuum impregnated with a fluorescent-y-tagged epoxy potting resin and polished using conventional metallographic techniques.
- Optical microscopy can be performed using a microscope equipped with fluorescent illumination or a polarizing microscope.
- the quantitative measurement of bubble size and cross-section can be obtained using an image analysis system taking images directly from a microscope.
- the C/C composites of the present invention comprise graphite fabrics, unidirectional or woven, impregnated with the foamed carbon fiber precursors just described.
- carbon fibers are layered with carbon fiber precursor material, as described below, and formed into discs or preforms and subjected to the same process used to produce the foams described hereinabove, gas saturation followed by pressure release and quenching.
- the combined pitch foam-green carbon fiber forms are then oxygen stabilized in a circulating oven, carbonized in a furnace with a nitrogen atmosphere and, finally, graphitized in a graphite vacuum furnace. Operating parameters for this processing are similar to those described above for the production of the crystalline foams.
- a first category of C/C composites can be fabricated using continuous unidirectional fabrics as the reinforcement for a crystalline carbon foam.
- Any suitable continuous unidirectional carbon fabric may be used for the production of these C/C composites, however, in the examples and diagrams which follow, Torayca, T300, P130 manufactured by Toray Industries, Inc., Toray Building, 2-1 Nihonbashi-Muromachi 2- chome, Chuo-ku, Tokyo 103, Japan was used.
- the unidirectional fabrics are cut to the size of the forming die or part to be formed and placed in one direction in the die.
- a layer of fiber precursor pitch powder (mesophase pitch) of the type described hereinabove is then sprayed evenly over the fabric.
- a second layer of fabric is then layered in the die at right angles to the first and another layer of fiber precursor pitch powder sprayed thereon. This procedure is repeated until the desired thickness is achieved.
- the layered structure has the cross-section depicted generally in Figure 2 wherein composite structure 10 comprising fiber layer 14 layered between two layers 16 of fiber precursor pitch, and fabric layers 12 placed at right angles to fabric layer 14 also covered with layers 18 of fiber precursor pitch.
- This composite structure is then processed as described above for the production of the crystalline foams, i.e. compression molded, saturated with gas at high pressure and elevated temperature, depressurized and quenched, oxygen stabilized, carbonized and graphitized. The process parameters for these various operations is as described above for the processing of the crystalline foams.
- a second class of C/C composites can be fabricated using the same procedures, but using woven fabrics as the reinforcing member.
- the preparation and processing procedures for such materials are the same as those for the unidirectionally reinforced composites. Because of the constraints in both the x and y directions which occur with the woven fabrics, thermal residual stresses can more easily build up in these materials than in the case of the unidirectional fabric. Consequently, it is even more critical in these materials that quenching proceed slowly after the foam has reached its glass transition temperature in the cool down period.
- the quenching step must proceed slowly after the foam has attained its glass transition temperature otherwise, microcracking in the foam or deiamination in the composite will occur.
- Near net shape structural components can be produced by preparing a mold which allows the fiber precursor pitch/PAN to expand in one direction only during the foaming process. During foam expansion, spherical bubbles will be formed in the regions with little constraint whereas elliptical bubbles will be formed in the regions where directional constraint exists. This provides for the ability to tailor mechanical performance directionalhy.
- the foams and C/C composites of the present invention have numerous potential uses in structural and other applications. Among these is as the core for a composite sandwich structure whose skins may be of any material, preferably a high temperature material such as titanium or ceramics. This sandwich material has potential applications in hot structures and cryogenic tanks.
- a graphitized low to medium density fiber precursor foam was produced as described above by saturating with nitrogen at 3000-3800psi. and at a temperature in the range of 280 ⁇ 300°C. As shown in Figures 3 and 4, the cell sizes are on the order of 50-80 ⁇ m and the ligaments or struts are about 7-10 ⁇ m. Cells having struts ranging from about 2 ⁇ m up to about 15 ⁇ m in thickness can be produced by the process of the present invention. By controlling the quench rate, a higher density foam as shown in Figure 5 can be obtained. The stress-strain relationship of the low to medium density foam of Figures 3 and 4 is shown in Figure 6.
- the fracture surfaces of the carbon foams shown in Figures 3-5 exhibit many homeles formations which are considered a sign of high fracture toughness. This is indeed borne out by the stress- strain curve shown in Figure 6.
- Conventional carbon foams and C/C composites have low fracture strains (-1.2%) whereas the carbon foams of the present invention demonstrate fracture strains on the order of about 42%.
- the fracture toughness and fracture strain of the materials of the present invention are an order of magnitude higher than those of conventional glassy or amorphous foams.
- a representative stress strain curve of a typical prior art carbon foam is shown in Figure 8 which demonstrates the significant differences in properties between these materials and those of the current invention.
- Figure 9 is an SEM photomicrograph of a typical carbon foam of the prior art showing the difference in bubble size between the prior art foams and those of the present invention.
- the foams produced in this example have spherical bubbles that result in globally isotropic properties.
- Example 2
- Table 1 shown in Table 1 below are comparative properties of prior art carbon foams and those of the present invention.
- A is a reticulated carbon foam
- B is an earlier cellular carbon foam
- C is the microcellular foam of the present invention.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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AU41650/00A AU4165000A (en) | 1998-12-29 | 1999-12-27 | Microcellular carbon foams and microcellular c/c composites fabricated therefrom |
CA002358306A CA2358306A1 (en) | 1998-12-29 | 1999-12-27 | Microcellular carbon foams and microcellular c/c composites fabricated therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/222,630 | 1998-12-29 | ||
US09/222,630 US6339031B1 (en) | 1998-12-29 | 1998-12-29 | Microcellular carbon foams and microcellular C/C composites fabricated therefrom |
Publications (3)
Publication Number | Publication Date |
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WO2000039043A2 true WO2000039043A2 (en) | 2000-07-06 |
WO2000039043A3 WO2000039043A3 (en) | 2000-09-21 |
WO2000039043A9 WO2000039043A9 (en) | 2002-08-22 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/030884 WO2000039043A2 (en) | 1998-12-29 | 1999-12-27 | Microcellular carbon foams and microcellular c/c composites fabricated therefrom |
Country Status (4)
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US (1) | US6339031B1 (en) |
AU (1) | AU4165000A (en) |
CA (1) | CA2358306A1 (en) |
WO (1) | WO2000039043A2 (en) |
Families Citing this family (60)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100823748B1 (en) * | 2000-09-29 | 2008-04-21 | 트레셀 인코포레이티드 | Fiber-Filled Molded Articles |
US6906164B2 (en) | 2000-12-07 | 2005-06-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
US7033485B2 (en) * | 2001-05-11 | 2006-04-25 | Koppers Industries Of Delaware, Inc. | Coal tar and hydrocarbon mixture pitch production using a high efficiency evaporative distillation process |
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US7135541B2 (en) * | 2003-06-06 | 2006-11-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
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US20080139780A1 (en) * | 2006-12-07 | 2008-06-12 | Debruin Bruce Roger | Polyester production system employing short residence time esterification |
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US7649109B2 (en) * | 2006-12-07 | 2010-01-19 | Eastman Chemical Company | Polyester production system employing recirculation of hot alcohol to esterification zone |
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US7829653B2 (en) * | 2007-07-12 | 2010-11-09 | Eastman Chemical Company | Horizontal trayed reactor |
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US20090172998A1 (en) * | 2008-01-08 | 2009-07-09 | Carbonxt Group Limited | System and method for refining carbonaceous material |
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US20100189627A1 (en) * | 2009-01-27 | 2010-07-29 | Chung-Hua Hu | Carbonization apparatus and method of the same |
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US8137628B2 (en) * | 2011-03-24 | 2012-03-20 | Cool Planet Biofuels, Inc. | System for making renewable fuels |
US8951476B2 (en) | 2011-03-24 | 2015-02-10 | Cool Planet Energy Systems, Inc. | System for making renewable fuels |
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US9493379B2 (en) | 2011-07-25 | 2016-11-15 | Cool Planet Energy Systems, Inc. | Method for the bioactivation of biochar for use as a soil amendment |
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US9216916B2 (en) | 2013-10-25 | 2015-12-22 | Cool Planet Energy Systems, Inc. | System and method for purifying process water produced from biomass conversion to fuels |
US11279662B2 (en) | 2011-06-06 | 2022-03-22 | Carbon Technology Holdings, LLC | Method for application of biochar in turf grass and landscaping environments |
US8568493B2 (en) | 2011-07-25 | 2013-10-29 | Cool Planet Energy Systems, Inc. | Method for producing negative carbon fuel |
US9809502B2 (en) | 2011-06-06 | 2017-11-07 | Cool Planet Energy Systems, Inc. | Enhanced Biochar |
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US9260666B2 (en) | 2011-07-25 | 2016-02-16 | Cool Planet Energy Systems, Inc. | Method for reducing the carbon footprint of a conversion process |
US10472297B2 (en) | 2014-10-01 | 2019-11-12 | Cool Planet Energy System, Inc. | Biochars for use in composting |
CA2963444C (en) | 2014-10-01 | 2023-12-05 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
US10870608B1 (en) | 2014-10-01 | 2020-12-22 | Carbon Technology Holdings, LLC | Biochar encased in a biodegradable material |
US11426350B1 (en) | 2014-10-01 | 2022-08-30 | Carbon Technology Holdings, LLC | Reducing the environmental impact of farming using biochar |
US11097241B2 (en) | 2014-10-01 | 2021-08-24 | Talipot Cool Extract (Ip), Llc | Biochars, biochar extracts and biochar extracts having soluble signaling compounds and method for capturing material extracted from biochar |
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AU2019327091B2 (en) * | 2017-11-01 | 2022-07-14 | Asahi Kasei Kabushiki Kaisha | Carbon foam, complex, and production method |
MX2020006266A (en) | 2017-12-15 | 2021-01-20 | Talipot Cool Extract Ip Llc | Biochars and biochar extracts having soluble signaling compounds and method for capturing material extracted from biochar. |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4892783A (en) * | 1988-11-10 | 1990-01-09 | General Electric Company | Tri-element carbon based heat shield |
US5540996A (en) * | 1983-08-23 | 1996-07-30 | The United States Of America As Represented By The Secretary Of The Air Force | Rigidized, low density, insulation |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4442165A (en) * | 1981-03-26 | 1984-04-10 | General Electric Co. | Low-density thermally insulating carbon-carbon syntactic foam composite |
US4818448A (en) * | 1987-06-17 | 1989-04-04 | The United States Of America As Represented By The United States Department Of Energy | Method for fabricating light weight carbon-bonded carbon fiber composites |
RU2047588C1 (en) * | 1992-05-14 | 1995-11-10 | Капралов Владимир Константинович | Method of making article of porous structure from carbon-carbon composition materials |
-
1998
- 1998-12-29 US US09/222,630 patent/US6339031B1/en not_active Expired - Lifetime
-
1999
- 1999-12-27 CA CA002358306A patent/CA2358306A1/en not_active Abandoned
- 1999-12-27 WO PCT/US1999/030884 patent/WO2000039043A2/en active Application Filing
- 1999-12-27 AU AU41650/00A patent/AU4165000A/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5540996A (en) * | 1983-08-23 | 1996-07-30 | The United States Of America As Represented By The Secretary Of The Air Force | Rigidized, low density, insulation |
US4892783A (en) * | 1988-11-10 | 1990-01-09 | General Electric Company | Tri-element carbon based heat shield |
Also Published As
Publication number | Publication date |
---|---|
CA2358306A1 (en) | 2000-07-06 |
WO2000039043A3 (en) | 2000-09-21 |
AU4165000A (en) | 2000-07-31 |
US6339031B1 (en) | 2002-01-15 |
WO2000039043A9 (en) | 2002-08-22 |
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