WO2001048282A2 - Production of high surface energy, high surface area vapor grown carbon fiber (vgcf) utilizing carbon dioxide - Google Patents
Production of high surface energy, high surface area vapor grown carbon fiber (vgcf) utilizing carbon dioxide Download PDFInfo
- Publication number
- WO2001048282A2 WO2001048282A2 PCT/US2000/042187 US0042187W WO0148282A2 WO 2001048282 A2 WO2001048282 A2 WO 2001048282A2 US 0042187 W US0042187 W US 0042187W WO 0148282 A2 WO0148282 A2 WO 0148282A2
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- WO
- WIPO (PCT)
- Prior art keywords
- surface energy
- vapor grown
- high surface
- grown carbon
- carbon fiber
- Prior art date
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Classifications
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present invention relates to vapor grown carbon fibers generally, and more particularly to vapor grown carbon fibers having high surface energy and high surface area, and to methods of producing such fibers without post-manufacture treatment.
- VGCF vapor grown carbon fibers
- VGCF VGCF
- iron generally being the predominant constituent, which catalyze the growth of long slender partially graphitic filaments when exposed to a hydrocarbon gas in the temperature range of 600° - 1500° C.
- sulfur enhances the growth
- ammonia results in improved distribution in fiber diameter (Alig, et al. U.S. Patent 5,374,415).
- the iron catalyst required for the reaction is provided by using either liquid zero valent iron compounds such as iron pentacarbonyl or solid zero valent iron compounds dissolved in liquid hydrocarbons.
- An example of the latter is ferrocene.
- Liquid compounds are preferred since their introduction into the reactor is easier to control. They are most readily introduced by bubbling an inert gas through the liquid, thus carrying the catalyst into the reactor in the vapor state.
- the normal inert gases used for this method are argon, helium, and nitrogen.
- VGCF differ substantially from commercial carbon fiber in that VGCF are not continuous. They are about 0.001 to 0.04 mm long. Also, VGCF are much finer than their continuously grown counterparts.
- the fibers upon leaving the reactor, the fibers exist as an entangled mass that is very lightweight with a large apparent volume, from 5 to 50 ftVlb. In other words, the fibers form a lightweight, fluffy entangled mass. In this state, the fibers are very difficult to ship and handle. Such a light and fluffy material is almost impossible to incorporate into mixing equipment that typically processes rubber or plastic. The fly loss and incorporation time are tremendous.
- the VGCF produced by these processes have a surface energy in the range of 25 to 40 mJ/m 2 .
- This surface energy although useful for some applications, is considered low with respect to the ability of resins to wet and, therefore, to adhere to the fiber for purposes of preparing useful composites. Due to the low surface tension, the fibers cannot be easily wetted out or mixed into liquid applications without prior surface treatments. These problems represent a severe limitation on the use of VGCF, as they cannot be readily dispersed into rubbers, plastics or the like. Thus, the development of methods by which the VGCF are wet out is important to the commercialization of these materials.
- the conventional technique for providing the required surface modification of VGCF involves exposure to one or more of a number of oxidizing or etching agents in a post-manufacture processing step.
- "Effect of Surface Treatment on the Bulk Chemistry and Structure of Vapor Grown Carbon Fibers H.Darmstadt et al., CARBON, 35, no. 11 , pp. 1581-1585, 1997.
- Such post-manufacture processing steps have also been demonstrated to provide desired modification of surface properties of VGCF.
- "Effect of Surface Treatment on the Bulk Chemistry and Structure of Vapor Grown Carbon Fibers” H. Darmstadt et al., CARBON, 35, no. 11 , pp. 1581-1585, 1997.
- Carbon fibers may be activated by exposure to a number of oxidizing agents in the gas phase, including H 2 0 and CO 2 .
- oxidizing agents including H 2 0 and CO 2 .
- ammonia as an additive gas during fiber synthesis, as taught by U.S. Patent No. 5,374,415, has been shown to have beneficial impact on the morphology of the fiber, and to modify the surface of the fiber.
- air containing O 2 as a purge gas following the synthesis of the fiber has been shown to provide some degree of oxidation of the fiber.
- the high surface energy VGCF of the present invention have a surface energy greater than about 75 mJ/m 2 with post-manufacture treatment. They preferably have a surface energy in the range of about 125 to about 185 mJ/m 2 and more preferably about 145 to about 185 mJ/m 2 . In addition, they preferably have a total surface area in the range of about 25 to about 200 m 2 /g, and an external surface area greater than 20 m 2 /g. The surface area of the high surface energy vapor grown carbon fibers is preferably increased by a factor of at least 2, more preferably 10 or greater.
- the invention teaches the use of a gaseous oxidant, such as CO 2 , as an additive during fiber synthesis in order to provide the desired surface modification to the fiber, including increased surface area and surface energy.
- a gaseous oxidant such as CO 2
- CO 2 is known to oxidize carbon as well as iron
- the use of CO 2 during fiber synthesis might be expected to poison the fiber synthesis reaction, or to degrade the mechanical properties of the fiber.
- This discovery reduces the cost and complexity of the production of high surface energy VGCF. It provides a one-step fiber synthesis process without the necessity of post-manufacture treatment.
- One method involves forming a mixture comprising a gaseous hydrocarbon, ammonia, and an iron-containing compound decomposable to form iron nucleation sites.
- the hydrocarbon and the ammonia are present in an amount sufficient to provide a ratio of carbon atoms to nitrogen atoms in a range of from about 1 :1 to 30:1.
- the gaseous oxidant is added as a separate stream to the mixture.
- the mixture is heated in a reactor for a time and at a temperature sufficient to cause decomposition of the decomposable compound to form particles of nanometer size iron nucleation sites dispersed and entrained in the gaseous mixture which induce growth of carbon fibers.
- High surface energy VGCF are formed, which have an average diameter of about 0.05 to about 0.5 micron, contain carbon and nitrogen, and have a surface energy greater than about 75 mJ/m 2 .
- the high surface energy VGCF are then recovered.
- the carbon dioxide is introduced into the mixture by using it as a carrier for the iron-containing compound.
- Fig. 1 is a tensile strength contour graph (MPa) of eight composites made with post-manufacture treated carbon fibers.
- the process for the production of VGCF is a modification of the vapor deposition process described in U.S. Patent No. 5,374,415, which is incorporated by reference.
- high surface energy VGCF are formed in a gas phase reaction by first forming a mixture comprising a gaseous hydrocarbon, a iron-containing compound decomposable to form iron nucleation sites and ammonia. The gaseous oxidant is added as a separate stream to the mixture.
- the hydrocarbon and ammonia are present in an amount sufficient to provide a ratio of carbon atoms to nitrogen atoms in a range of from about 1 :1 to 30:1.
- the mixture is heated in the reactor for a time and at a temperature sufficient to decompose the decomposable compound to form nuclei which induce growth of carbon fibers.
- the VGCF are then recovered from the reactor.
- the VGCF produced have a surface energy greater than 75 mJ/m 2 without post- manufacture treatment, preferably in the range of about 125 to about 185 mJ/m 2 , more preferably in the range of about 145 to about 185 mJ/m 2 .
- the VGCF preferably have a surface area in the range of about 10 to about 200 m 2 /g, more preferably about 25 to about 100.
- the gaseous hydrocarbon preferably includes at least one selected from methane, ethane, propane, ethylene, acetylene, natural gas and vaporizable hydrocarbons. Most preferably, the hydrocarbon is selected from methane, high methane natural gas having a methane content of at least 90 volume percent, and mixtures thereof.
- the decomposable iron-containing compound is preferably iron pentacarbonyl.
- Carbon dioxide is the preferred oxidant because it is the mildest of the gaseous oxidants, and therefore, potentially offers a wider operating window, it is relatively inexpensive, it is easy and safe to handle, and it is compatible with iron pentacarbonyl, the preferred catalyst.
- oxidants such as H 2 O and O 2 could be used.
- the oxidizing agent in a separate stream it can be introduced as the carrier for the iron-containing compound.
- the oxidizing gas can be introduced at other points in the reactor system.
- the oxidant gas could be introduced into the exit end of the reactor so that the fibers interacted with it while they were still very hot as they exit the reactor. Under these conditions the fiber-oxidant gas mixture would be very reactive and fiber surface modification could be accomplished in the very short residence times that exist at the reactor exit port.
- the ability to modify the fiber surface is dependent to some extent on the choice of oxidant used to do the modification.
- CO 2 is a mild oxidant that produces a high surface energy fiber along with the modest increases in surface area and little, if any, introduction of fiber surface functional groups.
- air (oxygen) or water as the oxidant provides a more aggressive oxidizing environment which results in the introduction of more functional groups on the fiber surface.
- a sulfur-containing gaseous compound such as hydrogen sulfide, is included in the mixture.
- the number of hydrogen sulfide molecules should be at least as great as the number of atoms of the iron in the decomposable compound.
- the hydrogen sulfide enhances the fiber growth from the iron catalyst and remains with the fiber. Thus, for abundant fiber formation, hydrogen sulfide addition is preferred.
- ammonia, air, and sulfur used in the reaction during formation provide sites on the fiber and can be adjusted and tailored depending upon the desired end use.
- VGCF produced by the process of U.S. Patent No. 5,374,415 were post-treated for comparison with the high surface energy VGCF of the present invention.
- the surface of the VGCF was oxidized by heating in the presence of carbon dioxide, at a temperature and for a time sufficient to produce a high surface energy VGCF having a surface energy greater than about 75 mJ/m 2 .
- Table 1 shows the results of a series of experiments in which the time, temperature, and flow rate of carbon dioxide were varied. Run 11 gives the property values for the fibers as produced, without any additional treatment, for comparison.
- VGCF surface energy and surface area of VGCF can be increased significantly using this oxidation process.
- the amount of the increase can be controlled by controlling the reaction time, temperature, and flow rate of carbon dioxide.
- the adhesion of the post-treated VGCF to a polymer matrix was evaluated using composite tensile strength as a measure of fiber-matrix adhesion.
- Tensile strength is known to have a direct positive relationship to fiber-matrix adhesion.
- eight polypropylene (PP) composites were made, each containing 15-volume % of fiber. Four samples were selected from those shown in
- Fig. 1 shows the results of a contour plot of the tensile strength of the eight composites against the external surface area and surface energy.
- the optimum fiber- matrix adhesion occurs when the fiber surface has not been extensively oxidized, i.e., the increase in surface area is two-fold or less and the surface energy is between about 145 and about 185 mJ/m 2 .
- the high surface energy VGCF of the present invention were tested for comparison with post-treated VGCF.
- the high surface energy VGCF made by the process of adding carbon dioxide as a separate stream were characterized for surface energy and surface area, and the results are shown in Table 2.
- Table 2 includes data for the standard production of VGCF (PR-1 1 ) and for fiber produced using post- production oxidation for comparison. The data shows that the in situ addition of carbon dioxide produces high surface energy VGCF comparable to VGCF produced using post-production oxidation.
- the high surface energy VGCF produced using carbon dioxide as the carrier gas for the iron pentacarbonyl were also analyzed. This process yielded fibers having a surface energy of 124.8 mJ/m 2 (total), and a surface area of 27.8 m 2 /g (total) and 21.0 m 2 /g (external). These values are close to those of the post-treated VGCF fiber used to produce the PP composite with the maximum tensile strength, as shown in Fig. 1.
- the high surface energy VGCF of the present invention can optionally be post- treated by pyrolytic stripping.
- This fiber cleaning operation is readily conducted by heating the high surface energy VGCF fiber to a temperature between about 400° and 1000°C under a slow flow of inert gas (about 2 l/min). The exact time-temperature profile depends on the temperature used.
- the resulting surface energy of fibers produced with post-manufacture pyrolytic stripping is about 135 mJ/m 2 .
- the surface area of these fibers is in the range of 20-35 m 2 /g. These values are in the same range as those which produced the highest levels of adhesion as shown in Fig. 1.
- pyrolytic stripping involves both property enhancement and potential health benefits.
- Fibers produced by pyrolytic stripping are readily wet by both organic liquids and water.
- the high surface energy results in the matrix resin wetting the fiber more efficiently and effectively, which translates into improved adhesion and higher tensile strengths.
- the VGFC fiber produced by the process of U.S. Patent No. 5,374,415 is wet by a variety of organic liquids, but is not wet by water without the use of surfactants.
- the processes of the present invention allow production of high surface energy VGCF without post-manufacture treatment. These fibers should enhance the mechanical properties of composites using a variety of matrix resins. In addition, because of the limited amount of fiber surface modification, other properties of the fiber, such as electrical and thermal conductivity, should not be affected.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Inorganic Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60017799T DE60017799T2 (de) | 1999-11-22 | 2000-11-16 | Herstellung von kohlenstofffasern mit hoher oberflächenenergie und hoher spezifischer oberfläche durch dampf-phase-pyrolise unter verwendung von kohlendioxid |
EP00993155A EP1244830B1 (en) | 1999-11-22 | 2000-11-16 | Production of high surface energy, high surface area vapor grown carbon fiber (vgcf) utilizing carbon dioxide |
AT00993155T ATE287981T1 (de) | 1999-11-22 | 2000-11-16 | Herstellung von kohlenstofffasern mit hoher oberflächenenergie und hoher spezifischen oberfläche durch dampf-phase-pyrolise unter verwendung von kohlendioxid |
JP2001548782A JP2003518563A (ja) | 1999-11-22 | 2000-11-16 | 二酸化炭素を利用して高い表面エネルギーで高い表面積の気相成長炭素繊維を製造する方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/444,877 US6506355B1 (en) | 1999-11-22 | 1999-11-22 | Production of high surface energy, high surface area vapor grown carbon fiber |
US09/444,877 | 1999-11-22 |
Publications (2)
Publication Number | Publication Date |
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WO2001048282A2 true WO2001048282A2 (en) | 2001-07-05 |
WO2001048282A3 WO2001048282A3 (en) | 2001-12-13 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/042187 WO2001048282A2 (en) | 1999-11-22 | 2000-11-16 | Production of high surface energy, high surface area vapor grown carbon fiber (vgcf) utilizing carbon dioxide |
Country Status (6)
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3981567B2 (ja) * | 2001-03-21 | 2007-09-26 | 守信 遠藤 | 炭素繊維の長さ調整方法 |
JP3981565B2 (ja) * | 2001-03-21 | 2007-09-26 | 守信 遠藤 | 触媒金属を担持した気相成長法による炭素繊維 |
JP3981568B2 (ja) * | 2001-03-21 | 2007-09-26 | 守信 遠藤 | 電界電子エミッタ用炭素繊維および電界電子エミッタの製造方法 |
US7132062B1 (en) | 2003-04-15 | 2006-11-07 | Plasticolors, Inc. | Electrically conductive additive system and method of making same |
US7939046B2 (en) * | 2004-06-21 | 2011-05-10 | Raytheon Company | Microporous graphite foam and process for producing same |
US9362560B2 (en) | 2011-03-08 | 2016-06-07 | GM Global Technology Operations LLC | Silicate cathode for use in lithium ion batteries |
US9281515B2 (en) | 2011-03-08 | 2016-03-08 | Gholam-Abbas Nazri | Lithium battery with silicon-based anode and silicate-based cathode |
US8663840B2 (en) | 2011-04-12 | 2014-03-04 | GM Global Technology Operations LLC | Encapsulated sulfur cathode for lithium ion battery |
US11508498B2 (en) | 2019-11-26 | 2022-11-22 | Trimtabs Ltd | Cables and methods thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3378345A (en) * | 1965-03-22 | 1968-04-16 | Union Carbide Corp | Process for producing pyrolytic graphite whiskers |
US5374415A (en) * | 1993-02-03 | 1994-12-20 | General Motors Corporation | Method for forming carbon fibers |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2796331A (en) | 1954-06-09 | 1957-06-18 | Pittsburgh Coke & Chemical Co | Process for making fibrous carbon |
US5024818A (en) | 1990-10-09 | 1991-06-18 | General Motors Corporation | Apparatus for forming carbon fibers |
US5594060A (en) | 1994-07-18 | 1997-01-14 | Applied Sciences, Inc. | Vapor grown carbon fibers with increased bulk density and method for making same |
JPH0978360A (ja) | 1995-09-07 | 1997-03-25 | Nikkiso Co Ltd | 気相成長炭素繊維の製造方法 |
-
1999
- 1999-11-22 US US09/444,877 patent/US6506355B1/en not_active Expired - Fee Related
-
2000
- 2000-11-16 DE DE60017799T patent/DE60017799T2/de not_active Expired - Lifetime
- 2000-11-16 AT AT00993155T patent/ATE287981T1/de not_active IP Right Cessation
- 2000-11-16 WO PCT/US2000/042187 patent/WO2001048282A2/en active IP Right Grant
- 2000-11-16 JP JP2001548782A patent/JP2003518563A/ja active Pending
- 2000-11-16 EP EP00993155A patent/EP1244830B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3378345A (en) * | 1965-03-22 | 1968-04-16 | Union Carbide Corp | Process for producing pyrolytic graphite whiskers |
US5374415A (en) * | 1993-02-03 | 1994-12-20 | General Motors Corporation | Method for forming carbon fibers |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1997, no. 07, 31 July 1997 (1997-07-31) & JP 09 078360 A (NIKKISO CO LTD), 25 March 1997 (1997-03-25) * |
Also Published As
Publication number | Publication date |
---|---|
DE60017799T2 (de) | 2006-01-05 |
ATE287981T1 (de) | 2005-02-15 |
DE60017799D1 (de) | 2005-03-03 |
JP2003518563A (ja) | 2003-06-10 |
WO2001048282A3 (en) | 2001-12-13 |
US6506355B1 (en) | 2003-01-14 |
EP1244830A2 (en) | 2002-10-02 |
EP1244830B1 (en) | 2005-01-26 |
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