US20120065300A1 - Cnt-infused fiber and method therefor - Google Patents
Cnt-infused fiber and method therefor Download PDFInfo
- Publication number
- US20120065300A1 US20120065300A1 US13/298,259 US201113298259A US2012065300A1 US 20120065300 A1 US20120065300 A1 US 20120065300A1 US 201113298259 A US201113298259 A US 201113298259A US 2012065300 A1 US2012065300 A1 US 2012065300A1
- Authority
- US
- United States
- Prior art keywords
- fiber
- catalyst
- carbon nanotube
- station
- carbon
- 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.)
- Abandoned
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 216
- 238000000034 method Methods 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 49
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims description 30
- 238000004513 sizing Methods 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 238000001802 infusion Methods 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 2
- 230000007723 transport mechanism Effects 0.000 claims 1
- 239000002071 nanotube Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 description 20
- 238000009730 filament winding Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- -1 etc.) Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000003677 Sheet moulding compound Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011554 ferrofluid Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 210000000329 smooth muscle myocyte Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to carbon nanotubes and fibers.
- Fibers are used for many different applications in a wide variety of industries, such as the commercial aviation, recreation, industrial and transportation industries. Commonly-used fibers for these and other applications include cellulosic fiber (e.g., viscose rayon, cotton, etc.), glass fiber, carbon fiber, and aramid fiber, to name just a few.
- cellulosic fiber e.g., viscose rayon, cotton, etc.
- glass fiber e.g., glass fiber
- carbon fiber e.g., aramid fiber
- the fibers are present in the form of a composite material (e.g., fiberglass, etc.).
- a composite material is a heterogeneous combination of two or more constituents that differ in form or composition on a macroscopic scale. While the composite material exhibits characteristics that neither constituent alone possesses, the constituents retain their unique physical and chemical identities within the composite.
- Two key constituents of a composite include a reinforcing agent and a resin matrix.
- the fibers are the reinforcing agent.
- the resin matrix keeps the fibers in a desired location and orientation and also serves as a load-transfer medium between fibers within the composite.
- Fibers are characterized by certain properties, such as mechanical strength, density, electrical resistivity, thermal conductivity, etc.
- the fibers “lend” their characteristic properties, in particular their strength-related properties, to the composite. Fibers therefore play an important role in determining a composite's suitability for a given application.
- sizing provides an all important physico-chemical link between fiber and the resin matrix and thus has a significant impact on the mechanical and chemical properties of the composite.
- the sizing is applied to fibers during their manufacture.
- Substantially all conventional sizing has lower interfacial strength than the fibers to which it's applied. As a consequence, the strength of the sizing and its ability to withstand interfacial stress ultimately determines the strength of the overall composite. In other words, using conventional sizing, the resulting composite cannot have a strength that is equal to or greater than that of the fiber.
- the illustrative embodiment of the present invention is a carbon nanotube-infused (“CNT-infused”) fiber.
- the carbon nanotubes are “infused” to the parent fiber.
- infused means physically or chemically bonded and “infusion” means the process of physically or chemically bonding.
- the physical bond between the carbon nanotubes and parent fiber is believed to be due, at least in part, to van der Waals forces.
- the chemical bond between the carbon nanotubes and the parent fiber is believed to be a covalent bond.
- the bond that is formed between the carbon nanotubes and the parent fiber is quite robust and is responsible for CNT-infused fiber being able to exhibit or express carbon nanotube properties or characteristics.
- This is in stark contrast to some prior-art processes, wherein nanotubes are suspended/dispersed in a solvent solution and applied, by hand, to fiber. Because of the strong van der Waals attraction between the already-formed carbon nanotubes, it is extremely difficult to separate them to apply them directly to the fiber. As a consequence, the lumped nanotubes weakly adhere to the fiber and their characteristic nanotube properties are weakly expressed, if at all.
- infused carbon nanotubes disclosed herein effectively function as a replacement for conventional “sizing.” It has been found that infused carbon nanotubes are far more robust molecularly and from a physical properties perspective than conventional sizing materials. Furthermore, the infused carbon nanotubes improve the fiber-to-matrix interface in composite materials and, more generally, improve fiber-to-fiber interfaces.
- the CNT-infused fiber disclosed herein is itself similar to a composite material in the sense that its properties will be a combination of those of the parent fiber as well as those of the infused carbon nanotubes. Consequently, embodiments of the present invention provide a way to impart desired properties to a fiber that otherwise lacks such properties or possesses them in insufficient measure. Fibers can therefore be tailored or engineered to meet the requirements of a specific application. In this fashion, the utility and value of virtually any type of fiber can be improved.
- nanotubes are synthesized in place on the parent fiber itself. It is important that the carbon nanotubes are synthesized on the parent fiber. If not, the carbon nanotubes will become highly entangled and infusion does not occur. As seen from the prior art, non-infused carbon nanotubes impart little if any of their characteristic properties.
- the parent fiber can be any of a variety of different types of fibers, including, without limitation: carbon fiber, graphite fiber, metallic fiber (e.g., steel, aluminum, etc.), ceramic fiber, metallic-ceramic fiber, glass fiber, cellulosic fiber, aramid fiber.
- nanotubes are synthesized on the parent fiber by applying or infusing a nanotube-forming catalyst, such as iron, nickel, cobalt, or a combination thereof, to the fiber.
- a nanotube-forming catalyst such as iron, nickel, cobalt, or a combination thereof
- operations of the CNT-infusion process include:
- the infused carbon nanotubes are single-wall nanotubes. In some other embodiments, the infused carbon nanotubes are multi-wall nanotubes. In some further embodiments, the infused carbon nanotubes are a combination of single-wall and multi-wall nanotubes. There are some differences in the characteristic properties of single-wall and multi-wall nanotubes that, for some end uses of the fiber, dictate the synthesis of one or the other type of nanotube. For example, single-walled nanotubes can be excellent conductors of electricity while multi-walled nanotubes are not.
- acetylene gas is ionized to create a jet of cold carbon plasma.
- the plasma is directed toward the catalyst-bearing parent fiber.
- carbon nanotubes lend their characteristic properties (e.g., exceptional mechanical strength, low to moderate electrical resistivity, high thermal conductivity, etc.) to the CNT-infused fiber.
- the extent to which the resulting CNT-infused fiber expresses these characteristics is a function of the extent and density of coverage of the parent fiber by the carbon nanotubes.
- CNT infusion is used to provide an improved filament winding process:
- carbon nanotubes are formed on fibers (e.g., graphite tow, glass roving, etc.), as described above, and are then passed through a resin bath to produce resin-impregnated, CNT-infused fiber. After resin impregnation, the fiber is positioned on the surface of a rotating mandrel by a delivery head. The fiber then winds onto the mandrel in a precise geometric pattern in known fashion.
- the filament winding process described above provides pipes, tubes, or other forms as are characteristically produced via a male mold. But the forms made from the filament winding process disclosed herein differ from those produced via conventional filament winding processes. Specifically, in the process disclosed herein, the forms are made from composite materials that include CNT-infused fibers. Such forms will therefore benefit from enhanced strength, etc., as provided by the CNT-infused fibers.
- CNT-infused fiber Any of a variety of different parent fibers can be used to form CNT-infused fiber.
- CNT-infused carbon fiber addresses this problem by providing a fiber that is sized with infused nanotubes, which provides the desired broad applicability with a variety of resins and processes.
- FIG. 1 depicts a method for producing CNT-infused fiber in accordance with the illustrative embodiment of the present invention.
- FIG. 2 depicts a system for implementing the illustrative method for producing CNT-infused fiber.
- FIG. 3 depicts a system for filament winding in accordance with a variation of the illustrative embodiment.
- fiber As the definitions that are provided above indicate, terms such as “fiber,” “filament,” “yarn,” etc., have distinct meanings. But for the purposes of the specification and the appended claims, and unless otherwise indicated, the term “fiber” is used in this specification as a generic term to refer to filament, yarn, tow, roving, fabric, etc., as well as fiber itself.
- the phrase “CNT-infused fiber” is therefore understood to encompass “CNT-infused fiber,” “CNT-infused filament,” “CNT-infused tow,” CNT-infused roving,” etc.
- FIG. 1 depicts a flow diagram of process 100 for producing. CNT-infused fiber in accordance with the illustrative embodiment of the present invention.
- Process 100 includes the operations of:
- the carbon nanotubes are synthesized directly on the parent fiber. In the illustrative embodiment, this is accomplished by disposing nanotube-forming catalyst on the parent fiber, as per operation 102 .
- Suitable catalysts for carbon nanotube formation include, without limitation, transition metal catalysts (e.g., iron, nickel, cobalt, combinations thereof, etc.).
- the catalyst is prepared as a liquid solution that contains nano-sized particles of catalyst.
- the diameters of the synthesized nanotubes are related to the size of the metal particles.
- carbon nanotube synthesis is based on a plasma-enhanced chemical vapor deposition process and occurs at elevated temperatures.
- the temperature is a function of catalyst, but will typically be in a range of about 500 to 1000° C. Accordingly, operation 104 requires heating the parent fiber to a temperature in the aforementioned range to support carbon nanotube synthesis.
- carbon plasma is sprayed onto the catalyst-laden parent fiber.
- the plasma can be generated, for example, by passing a carbon containing gas (e.g., acetylene, ethylene, ethanol, etc.) through an electric field that is capable of ionizing the gas.
- a carbon containing gas e.g., acetylene, ethylene, ethanol, etc.
- Nanotubes grow at the sites of the metal catalyst.
- the presence of the strong plasma-creating electric field can affect nanotube growth. That is, the growth tends to follow the direction of the electric field.
- vertically-aligned carbon nanotubes i.e., perpendicular to the fiber
- closely-spaced nanotubes will maintain a vertical growth direction resulting in a dense array of tubes resembling a carpet or forest.
- FIG. 2 depicts system 200 for producing CNT-infused fiber in accordance with the illustrative embodiment of the present invention.
- System 200 includes fiber payout and tensioner station 202 , fiber spreader station 208 , sizing removal station 210 , CNT-infusion station 212 , fiber bundler station 222 , and fiber uptake bobbin 224 , interrelated as shown.
- Payout and tension station 202 includes payout bobbin 204 and tensioner 206 .
- the payout bobbin delivers fiber 201 to the process; the fiber is tensioned via tensioner 206 .
- Fiber 201 is delivered to fiber spreader station 208 .
- the fiber spreader separates the individual elements of the fiber.
- Various techniques and apparatuses can be used to spread fiber, such as pulling the fiber over and under flat, uniform-diameter bars, or over and under variable-diameter bars, or over bars with radially-expanding grooves and a kneading roller, over a vibratory bar, etc.
- Spreading the fiber enhances the effectiveness of downstream operations, such as catalyst application and plasma application, by exposing more fiber surface area.
- Payout and tension station 202 and fiber spreader station 208 are routinely used in the fiber industry; those skilled in the art will be familiar with their design and use.
- Fiber 201 then travels to sizing removal station 210 .
- any “sizing” that is on fiber 201 is removed. Typically, removal is accomplished by burning the sizing off of the fiber.
- heating means can be used for this purpose, including, without limitation, an infrared heater, a muffle furnace, etc. Generally, non-contact heating methods are preferred. In some alternative embodiments, sizing removal is accomplished chemically.
- the temperature and time required for burning off the sizing vary as a function of (1) the sizing material (e.g., silane, etc.); and (2) the identity of parent fiber 201 (e.g., glass, cellulosic, carbon, etc.).
- the burn-off temperature is a minimum of about 650° C. At this temperature, it can take as long as 15 minutes to ensure a complete burn off of the sizing. Increasing the temperature above a minimum burn temperature should reduce burn-off time. Thermogravimetric analysis can be used to determine minimum burn-off temperature for sizing.
- sizing removal is the slow step in the overall CNT-infusion process.
- a sizing removal station is not included in the CNT-infusion process proper; rather, removal is performed separately (e.g., in parallel, etc.).
- an inventory of sizing-free fiber can be accumulated and spooled for use in a CNT-infused fiber production line that does not include a fiber removal station).
- sizing-free fiber is spooled in payout and tension station 202 .
- This production line can be operated at higher speed than one that includes sizing removal.
- Sizing-free fiber 205 is delivered to CNT-infusion station 212 , which is the “heart” of the process and system depicted in FIG. 2 .
- Station 212 includes catalyst application station 214 , fiber pre-heater station 216 , plasma spray station 218 , and fiber heaters 220 .
- sizing-free fiber 205 proceeds first to catalyst application station 214 .
- fiber 205 is cooled prior to catalyst application.
- the nanotube-forming catalyst is a liquid solution of nanometer-sized particles (e.g., 10 nanometers in diameter, etc.) of a transition metal.
- Typical transition metals for use in synthesizing nanotubes include, without limitation, iron, iron oxide, cobalt, nickel, or combinations thereof. These transition metal catalysts are readily commercially available from a variety of suppliers, including Ferrotech of Nashua, N.H.
- the liquid is a solvent such as toluene, etc.
- the catalyst solution is sprayed, such as by air sprayer 214 , onto fiber 205 .
- the transition metal catalyst is deposited on the parent fiber using evaporation techniques, electrolytic deposition techniques, suspension dipping techniques and other methods known to those skilled in the art.
- the transition metal catalyst is added to the plasma feedstock gas as a metal organic, metal salt or other composition promoting gas phase transport.
- the catalyst can be applied at room temperature in the ambient environment (neither vacuum nor an inert atmosphere is required).
- Catalyst-laden fiber 207 is then heated at fiber preheater station 216 .
- the fiber should be heated until it softens.
- a good estimate of the softening temperature for any particular fiber is readily obtained from reference sources, as is known to those skilled in the art. To the extent that this temperature is not a priori known for a particular fiber, it can be readily determined by experimentation.
- the fiber is typically heated to a temperature that is in the range of about 500 to 1000° C. Any of a variety of heating elements can be used as the fiber preheater, such as, without limitation, infrared heaters, a muffle furnace, and the like.
- fiber 207 is finally advanced to plasma spray station having spray nozzles 218 .
- a carbon plasma is generated, for example, by passing a carbon containing gas (e.g., acetylene, ethylene, ethanol, etc.) through an electric field that is capable of ionizing the gas.
- This cold carbon plasma is directed, via spray nozzles 218 , to fiber 207 .
- the fiber is disposed within about 1 centimeter of the spray nozzles to receive the plasma.
- heaters 220 are disposed above fiber 207 at the plasma sprayers to maintain the elevated temperature of the fiber.
- CNT-infused fiber 209 is re-bundled at fiber bundler 222 . This operation recombines the individual strands of the fiber, effectively reversing the spreading operation that was conducted at station 208 .
- the bundled, CNT-infused fiber 209 is wound about uptake fiber bobbin 224 for storage. CNT-infused fiber 209 is then ready for use in any of a variety of applications, including, without limitation, for use as the reinforcing material in composite materials.
- FIG. 3 depicts a further embodiment of the invention wherein CNT-infused fiber is created as a sub-operation of a filament winding process being conducted via filament winding system 300 .
- System 300 comprises fiber creel 302 , carbon nanotube infusion section 226 , resin bath 328 , and filament winding mandrel 332 , interrelated as shown.
- the various elements of system 300 with the exception of carbon nanotube infusion section 226 , are present in conventional filament winding processes.
- the “heart” of the process and system depicted in FIG. 3 is the carbon nanotube infusion section 226 , which includes fiber spreader station 208 , (optional) sizing-removal station 210 , and CNT-infusion station 212 .
- Fiber creel 302 includes plural spools 204 of parent fiber 201 A through 201 H.
- the untwisted group of fibers 201 A through 201 H is referred to collectively as “tow 303 .”
- the term “tow” generally refers to a group of graphite fibers and the term “roving” usually refers to glass fibers.
- the term “tow” is meant to refer, generically, to any type of fiber.
- creel 302 holds spools 204 in a horizontal orientation.
- the fiber from each spool 206 moves through small, appropriately situated rollers/tensioners 206 that change the direction of the fibers as they move out of creel 302 and toward carbon nanotube infusion section 226 .
- the spooled fiber that is used in system 300 is CNT-infused fiber (i.e., produced via system 200 ). In such embodiments, system 300 is operated without nanotube infusion section 226 .
- tow 303 is spread, sizing is removed, nanotube-forming catalyst is applied, the tow is heated, and carbon plasma is sprayed on the fiber, as described in conjunction with FIG. 2 .
- CNT-infused tow 307 is delivered to resin bath 328 .
- the resin bath contains resin for the production of a composite material comprising the CNT-infused fiber and the resin.
- Some important commercially-available resin-matrix families include general purpose polyester (e.g., orthophthalic polyesters, etc.), improved polyester (e.g., isophthalic polyesters, etc.), epoxy, and vinyl ester.
- Resin bath can be implemented in a variety of ways, two of which are described below.
- resin bath 328 is implemented as a doctor blade roller bath wherein a polished rotating cylinder (e.g., cylinder 330 ) that is disposed in the bath picks up resin as it turns.
- the doctor bar (not depicted in FIG. 3 ) presses against the cylinder to obtain a precise resin film thickness on cylinder 330 and pushes excess resin back into the bath.
- fiber tow 307 is pulled over the top of cylinder 330 , it contacts the resin film and wets out.
- resin bath 328 is realized as an immersion bath wherein fiber tow 307 is simply submerged into resin and then pulled through a set of wipers or roller that remove excess resin.
- resin-wetted, CNT-infused fiber tows 309 is passed through various rings, eyelets and, typically, a multi-pin “comb” (not depicted) that is disposed behind a delivery head (not depicted).
- the comb keeps the fiber tows 309 separate until they are brought together in a single combined band on rotating mandrel 332 .
- a CNT-infused carbon fiber was formed in accordance with the illustrative embodiment.
- a current was passed through carbon fiber (the parent fiber) to heat it to approximately 800° C. to remove epoxy sizing material. The fiber was then cooled to room temperature and left clamped between electrodes.
- a ferro-fluid catalyst was applied to the fiber using an aerosol spray technique. The fiber was allowed to dry and the chamber was closed, evacuated and filled with argon.
- a current was passed through the carbon fiber again to heat it to approximately 800° C. for carbon nanotube synthesis.
- a carbon plasma was generated from acetylene precursor using 13.56 MHz microwave energy using an atmospheric pressure plasma jet.
- the carrier gas in the plasma jet was helium at 20 standard liters per minute (slm) and the argon was provided at 1.2 slm.
- the plasma jet was fixtured to a robotic motion control system allowing the plasma jet to move over the length of the fiber at a speed between 6 and 12 inches per minute.
- the CNT-infused fiber was then cooled to room temperature and removed from the chamber. Scanning Electron Microscopy showed carbon nanotube formation on the surface of the parent carbon fiber.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Inorganic Fibers (AREA)
- Reinforced Plastic Materials (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
A carbon nanotube-infused fiber and a method for its production are disclosed. Nanotubes are synthesized directly on a parent fiber by first applying a catalyst to the fiber. The properties of the carbon nanotube-infused fiber will be a combination of those of the parent fiber as well as those of the infused carbon nanotubes.
Description
- This application is a continuation of U.S. patent application Ser. No. 11/619,327, filed on Jan. 3, 2007.
- The present invention relates to carbon nanotubes and fibers.
- Fibers are used for many different applications in a wide variety of industries, such as the commercial aviation, recreation, industrial and transportation industries. Commonly-used fibers for these and other applications include cellulosic fiber (e.g., viscose rayon, cotton, etc.), glass fiber, carbon fiber, and aramid fiber, to name just a few.
- In many fiber-containing products, the fibers are present in the form of a composite material (e.g., fiberglass, etc.). A composite material is a heterogeneous combination of two or more constituents that differ in form or composition on a macroscopic scale. While the composite material exhibits characteristics that neither constituent alone possesses, the constituents retain their unique physical and chemical identities within the composite.
- Two key constituents of a composite include a reinforcing agent and a resin matrix. In a fiber-based composite, the fibers are the reinforcing agent. The resin matrix keeps the fibers in a desired location and orientation and also serves as a load-transfer medium between fibers within the composite.
- Fibers are characterized by certain properties, such as mechanical strength, density, electrical resistivity, thermal conductivity, etc. The fibers “lend” their characteristic properties, in particular their strength-related properties, to the composite. Fibers therefore play an important role in determining a composite's suitability for a given application.
- To realize the benefit of fiber properties in a composite, there must be a good interface between the fibers and the matrix. This is achieved through the use of a surface coating, typically referred to as “sizing.” The sizing provides an all important physico-chemical link between fiber and the resin matrix and thus has a significant impact on the mechanical and chemical properties of the composite. The sizing is applied to fibers during their manufacture.
- Substantially all conventional sizing has lower interfacial strength than the fibers to which it's applied. As a consequence, the strength of the sizing and its ability to withstand interfacial stress ultimately determines the strength of the overall composite. In other words, using conventional sizing, the resulting composite cannot have a strength that is equal to or greater than that of the fiber.
- The illustrative embodiment of the present invention is a carbon nanotube-infused (“CNT-infused”) fiber.
- In CNT-infused fiber disclosed herein, the carbon nanotubes are “infused” to the parent fiber. As used herein, the term “infused” means physically or chemically bonded and “infusion” means the process of physically or chemically bonding. The physical bond between the carbon nanotubes and parent fiber is believed to be due, at least in part, to van der Waals forces. The chemical bond between the carbon nanotubes and the parent fiber is believed to be a covalent bond.
- Regardless of its true nature, the bond that is formed between the carbon nanotubes and the parent fiber is quite robust and is responsible for CNT-infused fiber being able to exhibit or express carbon nanotube properties or characteristics. This is in stark contrast to some prior-art processes, wherein nanotubes are suspended/dispersed in a solvent solution and applied, by hand, to fiber. Because of the strong van der Waals attraction between the already-formed carbon nanotubes, it is extremely difficult to separate them to apply them directly to the fiber. As a consequence, the lumped nanotubes weakly adhere to the fiber and their characteristic nanotube properties are weakly expressed, if at all.
- The infused carbon nanotubes disclosed herein effectively function as a replacement for conventional “sizing.” It has been found that infused carbon nanotubes are far more robust molecularly and from a physical properties perspective than conventional sizing materials. Furthermore, the infused carbon nanotubes improve the fiber-to-matrix interface in composite materials and, more generally, improve fiber-to-fiber interfaces.
- The CNT-infused fiber disclosed herein is itself similar to a composite material in the sense that its properties will be a combination of those of the parent fiber as well as those of the infused carbon nanotubes. Consequently, embodiments of the present invention provide a way to impart desired properties to a fiber that otherwise lacks such properties or possesses them in insufficient measure. Fibers can therefore be tailored or engineered to meet the requirements of a specific application. In this fashion, the utility and value of virtually any type of fiber can be improved.
- In accordance with the illustrative embodiment of a CNT-infused fiber-forming process, nanotubes are synthesized in place on the parent fiber itself. It is important that the carbon nanotubes are synthesized on the parent fiber. If not, the carbon nanotubes will become highly entangled and infusion does not occur. As seen from the prior art, non-infused carbon nanotubes impart little if any of their characteristic properties.
- The parent fiber can be any of a variety of different types of fibers, including, without limitation: carbon fiber, graphite fiber, metallic fiber (e.g., steel, aluminum, etc.), ceramic fiber, metallic-ceramic fiber, glass fiber, cellulosic fiber, aramid fiber.
- In the illustrative embodiment, nanotubes are synthesized on the parent fiber by applying or infusing a nanotube-forming catalyst, such as iron, nickel, cobalt, or a combination thereof, to the fiber.
- In some embodiments, operations of the CNT-infusion process include:
-
- Removing sizing from the parent fiber;
- Applying nanotube-forming catalyst to the parent fiber;
- Heating the fiber to nanotube-synthesis temperature; and
- Spraying carbon plasma onto the catalyst-laden parent fiber.
- In some embodiments, the infused carbon nanotubes are single-wall nanotubes. In some other embodiments, the infused carbon nanotubes are multi-wall nanotubes. In some further embodiments, the infused carbon nanotubes are a combination of single-wall and multi-wall nanotubes. There are some differences in the characteristic properties of single-wall and multi-wall nanotubes that, for some end uses of the fiber, dictate the synthesis of one or the other type of nanotube. For example, single-walled nanotubes can be excellent conductors of electricity while multi-walled nanotubes are not.
- Methods and techniques for forming carbon nanotubes, as disclosed in co-pending U.S. patent application Ser. No. 10/455,767 (now U.S. Pat. No. 7,261,779) and which is incorporated herein by reference, can be adapted for use with the process described herein. In the illustrative embodiment, acetylene gas is ionized to create a jet of cold carbon plasma. The plasma is directed toward the catalyst-bearing parent fiber.
- As previously indicated, carbon nanotubes lend their characteristic properties (e.g., exceptional mechanical strength, low to moderate electrical resistivity, high thermal conductivity, etc.) to the CNT-infused fiber. The extent to which the resulting CNT-infused fiber expresses these characteristics is a function of the extent and density of coverage of the parent fiber by the carbon nanotubes.
- In a variation of the illustrative embodiment, CNT infusion is used to provide an improved filament winding process: In this variation, carbon nanotubes are formed on fibers (e.g., graphite tow, glass roving, etc.), as described above, and are then passed through a resin bath to produce resin-impregnated, CNT-infused fiber. After resin impregnation, the fiber is positioned on the surface of a rotating mandrel by a delivery head. The fiber then winds onto the mandrel in a precise geometric pattern in known fashion.
- The filament winding process described above provides pipes, tubes, or other forms as are characteristically produced via a male mold. But the forms made from the filament winding process disclosed herein differ from those produced via conventional filament winding processes. Specifically, in the process disclosed herein, the forms are made from composite materials that include CNT-infused fibers. Such forms will therefore benefit from enhanced strength, etc., as provided by the CNT-infused fibers.
- Any of a variety of different parent fibers can be used to form CNT-infused fiber.
- Of late, there has been a demand for carbon fiber forms that are compatible with a broad range of resins and processes, and the sizing material is an important determinant of this compatibility. For example, sizing is critically important for providing an even distribution of chopped carbon fiber in sheet molding compounds (“SMCs”), such as are used in some automotive body panels.
- Notwithstanding this demand for carbon fiber and its potentially broad applicability, carbon fiber has historically been sized for compatibility with only epoxy resin. CNT-infused carbon fiber, as produced according to the method disclosed herein, addresses this problem by providing a fiber that is sized with infused nanotubes, which provides the desired broad applicability with a variety of resins and processes.
-
FIG. 1 depicts a method for producing CNT-infused fiber in accordance with the illustrative embodiment of the present invention. -
FIG. 2 depicts a system for implementing the illustrative method for producing CNT-infused fiber. -
FIG. 3 depicts a system for filament winding in accordance with a variation of the illustrative embodiment. - The following terms are defined for use in this Specification, including the appended claims:
-
- Carding—The process by which the fibers are opened out into an even film.
- Carded Fibers—Fibers that have been carded which opens them up.
- Cloth—A reinforcement material made by weaving strands of fiber yarns.
- Continuous Filament Strand—A fiber bundle composed of many filaments.
- Also, when referring to gun roving; a collection of string-like fiber or yarn, which is fed through a chopper gun in a spray-up process.
- Continuous Strand Roving—A bundle of filaments which are fed through a chopper gun in a spray-up process.
- Fabric—A planar textile structure produced by interlacing yarns, fibers, or filaments.
- Fiber—A unit of matter, either natural, or manufactured, which forms the basic element of fabrics and other textile structures.
- Fiber orientation—Fiber alignment in a non-woven or a mat laminate where the majority of fibers are in the same direction, resulting in a higher strength in that direction.
- Fiber Pattern—Visible fibers on the surface of laminates or moldings; the thread size and weave of glass cloth.
- Filament—A single fiber of an indefinite or extreme length, either natural (e.g., silk, etc.) or manufactured. Typically microns in diameter, manufactured fibers are extruded into filaments that are converted into filament yarn, staple, or tow.
- Filament Winding—A process which involves winding a resin-saturated strand of glass filament around a rotating mandrel.
- Filament Yarn—A yarn composed of continuous filaments assembled with, or without twist.
- Infuse—To form a chemical bond.
- Male Mold—A convex mold where the concave surface of the part is precisely defined by the mold surface.
- Matrix—The liquid component of a composite or laminate.
- Mandrel—The core around which paper-, fabric-, or resin-impregnated fiber is wound to form pipes, tubes, or vessels; in extrusion, the central finger of a pipe or tubing die.
- Pultrusion—Reversed “extrusion” of resin-impregnated roving in the manufacture of rods, tubes and structural shapes of a permanent cross-section. The roving, after passing through the resin dip tank, is drawn through a die to form the desired cross-section.
- Resin—A liquid polymer that, when catalyzed, cures to a solid state.
- Roving—The soft strand of carded fiber that has been twisted, attenuated, and freed of foreign matter preparatory to spinning.
- Sizing—A surface treatment that is applied to filaments immediately after their formation for the purpose of promoting good adhesion between those filaments and the matrix, to the extent the filaments are to be used as the reinforcing agent in a composite material.
- Spray-up—The process of spraying fibers, resin and catalyst simultaneously into a mold using a chopper gun.
- Strands—A primary bundle of continuous filaments (or slivers) combined in a single compact unit without twist. These filaments (usually 51, 102 or 204) are gathered together in the forming operations.
- Tape—A narrow-width reinforcing fabric or mat.
- Tow—A loose strand of filaments without twist.
- Twist—A term that applies to the number of turns and the direction that two yarns are turned during the manufacturing process.
- Woven Roving Fabric—Heavy fabrics woven from continuous filament in roving form. Usually in weights between 18-30 oz. per square yard.
- Yarn—A generic term for a continuous strand of textile fibers, filaments, or material in a form suitable for knitting, weaving, braiding, or otherwise intertwining to form a textile fabric.
- As the definitions that are provided above indicate, terms such as “fiber,” “filament,” “yarn,” etc., have distinct meanings. But for the purposes of the specification and the appended claims, and unless otherwise indicated, the term “fiber” is used in this specification as a generic term to refer to filament, yarn, tow, roving, fabric, etc., as well as fiber itself. The phrase “CNT-infused fiber” is therefore understood to encompass “CNT-infused fiber,” “CNT-infused filament,” “CNT-infused tow,” CNT-infused roving,” etc.
-
FIG. 1 depicts a flow diagram ofprocess 100 for producing. CNT-infused fiber in accordance with the illustrative embodiment of the present invention. -
Process 100 includes the operations of: -
- 102: Applying nanotube-forming catalyst to the parent fiber.
- 104: Heating the parent fiber to a temperature that is sufficient for carbon nanotube synthesis.
- 106: Spraying carbon plasma onto the catalyst-laden parent fiber.
- To infuse carbon nanotubes into a parent fiber, the carbon nanotubes are synthesized directly on the parent fiber. In the illustrative embodiment, this is accomplished by disposing nanotube-forming catalyst on the parent fiber, as per
operation 102. Suitable catalysts for carbon nanotube formation include, without limitation, transition metal catalysts (e.g., iron, nickel, cobalt, combinations thereof, etc.). - As described further in conjunction with
FIG. 2 , the catalyst is prepared as a liquid solution that contains nano-sized particles of catalyst. The diameters of the synthesized nanotubes are related to the size of the metal particles. - In the illustrative embodiment, carbon nanotube synthesis is based on a plasma-enhanced chemical vapor deposition process and occurs at elevated temperatures. The temperature is a function of catalyst, but will typically be in a range of about 500 to 1000° C. Accordingly,
operation 104 requires heating the parent fiber to a temperature in the aforementioned range to support carbon nanotube synthesis. - In
operation 106, carbon plasma is sprayed onto the catalyst-laden parent fiber. The plasma can be generated, for example, by passing a carbon containing gas (e.g., acetylene, ethylene, ethanol, etc.) through an electric field that is capable of ionizing the gas. - Nanotubes grow at the sites of the metal catalyst. The presence of the strong plasma-creating electric field can affect nanotube growth. That is, the growth tends to follow the direction of the electric field. By properly adjusting the geometry of the plasma spray and electric field, vertically-aligned carbon nanotubes (i.e., perpendicular to the fiber) are synthesized. Under certain conditions, even in the absence of a plasma, closely-spaced nanotubes will maintain a vertical growth direction resulting in a dense array of tubes resembling a carpet or forest.
-
FIG. 2 depictssystem 200 for producing CNT-infused fiber in accordance with the illustrative embodiment of the present invention.System 200 includes fiber payout andtensioner station 202,fiber spreader station 208, sizingremoval station 210, CNT-infusion station 212,fiber bundler station 222, andfiber uptake bobbin 224, interrelated as shown. - Payout and
tension station 202 includespayout bobbin 204 andtensioner 206. The payout bobbin deliversfiber 201 to the process; the fiber is tensioned viatensioner 206. -
Fiber 201 is delivered tofiber spreader station 208. The fiber spreader separates the individual elements of the fiber. Various techniques and apparatuses can be used to spread fiber, such as pulling the fiber over and under flat, uniform-diameter bars, or over and under variable-diameter bars, or over bars with radially-expanding grooves and a kneading roller, over a vibratory bar, etc. Spreading the fiber enhances the effectiveness of downstream operations, such as catalyst application and plasma application, by exposing more fiber surface area. - Payout and
tension station 202 andfiber spreader station 208 are routinely used in the fiber industry; those skilled in the art will be familiar with their design and use. -
Fiber 201 then travels to sizingremoval station 210. At this station, any “sizing” that is onfiber 201 is removed. Typically, removal is accomplished by burning the sizing off of the fiber. - Any of a variety of heating means can be used for this purpose, including, without limitation, an infrared heater, a muffle furnace, etc. Generally, non-contact heating methods are preferred. In some alternative embodiments, sizing removal is accomplished chemically.
- The temperature and time required for burning off the sizing vary as a function of (1) the sizing material (e.g., silane, etc.); and (2) the identity of parent fiber 201 (e.g., glass, cellulosic, carbon, etc.). Typically, the burn-off temperature is a minimum of about 650° C. At this temperature, it can take as long as 15 minutes to ensure a complete burn off of the sizing. Increasing the temperature above a minimum burn temperature should reduce burn-off time. Thermogravimetric analysis can be used to determine minimum burn-off temperature for sizing.
- In any case, sizing removal is the slow step in the overall CNT-infusion process. For this reason, in some embodiments, a sizing removal station is not included in the CNT-infusion process proper; rather, removal is performed separately (e.g., in parallel, etc.). In this way, an inventory of sizing-free fiber can be accumulated and spooled for use in a CNT-infused fiber production line that does not include a fiber removal station). In such embodiments, sizing-free fiber is spooled in payout and
tension station 202. This production line can be operated at higher speed than one that includes sizing removal. - Sizing-
free fiber 205 is delivered to CNT-infusion station 212, which is the “heart” of the process and system depicted inFIG. 2 .Station 212 includescatalyst application station 214,fiber pre-heater station 216,plasma spray station 218, andfiber heaters 220. - As depicted in
FIG. 2 , sizing-free fiber 205 proceeds first tocatalyst application station 214. In some embodiments,fiber 205 is cooled prior to catalyst application. - In some embodiments, the nanotube-forming catalyst is a liquid solution of nanometer-sized particles (e.g., 10 nanometers in diameter, etc.) of a transition metal. Typical transition metals for use in synthesizing nanotubes include, without limitation, iron, iron oxide, cobalt, nickel, or combinations thereof. These transition metal catalysts are readily commercially available from a variety of suppliers, including Ferrotech of Nashua, N.H. The liquid is a solvent such as toluene, etc.
- In the illustrative embodiment, the catalyst solution is sprayed, such as by
air sprayer 214, ontofiber 205. In some other embodiments, the transition metal catalyst is deposited on the parent fiber using evaporation techniques, electrolytic deposition techniques, suspension dipping techniques and other methods known to those skilled in the art. In some further embodiments, the transition metal catalyst is added to the plasma feedstock gas as a metal organic, metal salt or other composition promoting gas phase transport. The catalyst can be applied at room temperature in the ambient environment (neither vacuum nor an inert atmosphere is required). - Catalyst-
laden fiber 207 is then heated atfiber preheater station 216. For the infusion process, the fiber should be heated until it softens. Generally, a good estimate of the softening temperature for any particular fiber is readily obtained from reference sources, as is known to those skilled in the art. To the extent that this temperature is not a priori known for a particular fiber, it can be readily determined by experimentation. The fiber is typically heated to a temperature that is in the range of about 500 to 1000° C. Any of a variety of heating elements can be used as the fiber preheater, such as, without limitation, infrared heaters, a muffle furnace, and the like. - After preheating,
fiber 207 is finally advanced to plasma spray station havingspray nozzles 218. A carbon plasma is generated, for example, by passing a carbon containing gas (e.g., acetylene, ethylene, ethanol, etc.) through an electric field that is capable of ionizing the gas. This cold carbon plasma is directed, viaspray nozzles 218, tofiber 207. The fiber is disposed within about 1 centimeter of the spray nozzles to receive the plasma. In some embodiments,heaters 220 are disposed abovefiber 207 at the plasma sprayers to maintain the elevated temperature of the fiber. - After CNT-infusion, CNT-infused
fiber 209 is re-bundled atfiber bundler 222. This operation recombines the individual strands of the fiber, effectively reversing the spreading operation that was conducted atstation 208. - The bundled, CNT-infused
fiber 209 is wound aboutuptake fiber bobbin 224 for storage. CNT-infusedfiber 209 is then ready for use in any of a variety of applications, including, without limitation, for use as the reinforcing material in composite materials. - It is noteworthy that some of the operations described above should be conducted under inert atmosphere or vacuum, such that environmental isolation is required. For example, if sizing is being burned off of the fiber, the fiber must be environmentally isolated to contain off-gassing and prevent oxidation. Furthermore, the infusion process should be conducted under an inert atmosphere (e.g., nitrogen, argon, etc.) to prevent oxidation of the carbon. For convenience, in some embodiments of
system 200, environmental isolation is provided for all operations, with the exception of fiber payout and tensioning (at the beginning of the production line) and fiber uptake (at the end of the production line). -
FIG. 3 depicts a further embodiment of the invention wherein CNT-infused fiber is created as a sub-operation of a filament winding process being conducted viafilament winding system 300. -
System 300 comprisesfiber creel 302, carbonnanotube infusion section 226,resin bath 328, andfilament winding mandrel 332, interrelated as shown. The various elements ofsystem 300, with the exception of carbonnanotube infusion section 226, are present in conventional filament winding processes. Again, the “heart” of the process and system depicted inFIG. 3 is the carbonnanotube infusion section 226, which includesfiber spreader station 208, (optional) sizing-removal station 210, and CNT-infusion station 212. -
Fiber creel 302 includesplural spools 204 of parent fiber 201A through 201H. The untwisted group of fibers 201A through 201H is referred to collectively as “tow 303.” Note that the term “tow” generally refers to a group of graphite fibers and the term “roving” usually refers to glass fibers. Here, the term “tow” is meant to refer, generically, to any type of fiber. - In the illustrative embodiment,
creel 302 holdsspools 204 in a horizontal orientation. The fiber from eachspool 206 moves through small, appropriately situated rollers/tensioners 206 that change the direction of the fibers as they move out ofcreel 302 and toward carbonnanotube infusion section 226. - It is understood that in some alternative embodiments, the spooled fiber that is used in
system 300 is CNT-infused fiber (i.e., produced via system 200). In such embodiments,system 300 is operated withoutnanotube infusion section 226. - In carbon
nanotube infusion section 226,tow 303 is spread, sizing is removed, nanotube-forming catalyst is applied, the tow is heated, and carbon plasma is sprayed on the fiber, as described in conjunction withFIG. 2 . - After passing through
nanotube infusion section 226, CNT-infusedtow 307 is delivered toresin bath 328. The resin bath contains resin for the production of a composite material comprising the CNT-infused fiber and the resin. Some important commercially-available resin-matrix families include general purpose polyester (e.g., orthophthalic polyesters, etc.), improved polyester (e.g., isophthalic polyesters, etc.), epoxy, and vinyl ester. - Resin bath can be implemented in a variety of ways, two of which are described below. In the illustrative embodiment,
resin bath 328 is implemented as a doctor blade roller bath wherein a polished rotating cylinder (e.g., cylinder 330) that is disposed in the bath picks up resin as it turns. The doctor bar (not depicted inFIG. 3 ) presses against the cylinder to obtain a precise resin film thickness oncylinder 330 and pushes excess resin back into the bath. Asfiber tow 307 is pulled over the top ofcylinder 330, it contacts the resin film and wets out. In some other embodiments,resin bath 328 is realized as an immersion bath whereinfiber tow 307 is simply submerged into resin and then pulled through a set of wipers or roller that remove excess resin. - After leaving
resin bath 328, resin-wetted, CNT-infused fiber tows 309 is passed through various rings, eyelets and, typically, a multi-pin “comb” (not depicted) that is disposed behind a delivery head (not depicted). The comb keeps the fiber tows 309 separate until they are brought together in a single combined band onrotating mandrel 332. - A CNT-infused carbon fiber was formed in accordance with the illustrative embodiment. A current was passed through carbon fiber (the parent fiber) to heat it to approximately 800° C. to remove epoxy sizing material. The fiber was then cooled to room temperature and left clamped between electrodes. A ferro-fluid catalyst was applied to the fiber using an aerosol spray technique. The fiber was allowed to dry and the chamber was closed, evacuated and filled with argon. A current was passed through the carbon fiber again to heat it to approximately 800° C. for carbon nanotube synthesis. A carbon plasma was generated from acetylene precursor using 13.56 MHz microwave energy using an atmospheric pressure plasma jet. The carrier gas in the plasma jet was helium at 20 standard liters per minute (slm) and the argon was provided at 1.2 slm. The plasma jet was fixtured to a robotic motion control system allowing the plasma jet to move over the length of the fiber at a speed between 6 and 12 inches per minute. The CNT-infused fiber was then cooled to room temperature and removed from the chamber. Scanning Electron Microscopy showed carbon nanotube formation on the surface of the parent carbon fiber.
- It is to be understood that the above-described embodiments are merely illustrative of the present invention and that many variations of the above-described embodiments can be devised by those skilled in the art without departing from the scope of the invention. For example, in this Specification, numerous specific details are provided in order to provide a thorough description and understanding of the illustrative embodiments of the present invention. Those skilled in the art will recognize, however, that the invention can be practiced without one or more of those details, or with other methods, materials, components, etc.
- Furthermore, in some instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the illustrative embodiments. It is understood that the various embodiments shown in the Figures are illustrative, and are not necessarily drawn to scale. Reference throughout the specification to “one embodiment” or “an embodiment” or “some embodiments” means that a particular feature, structure, material, or characteristic described in connection with the embodiment(s) is included in at least one embodiment of the present invention, but not necessarily all embodiments. Consequently, the appearances of the phrase “in one embodiment,” “in an embodiment,” or “in some embodiments” in various places throughout the Specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics can be combined in any suitable manner in one or more embodiments. It is therefore intended that such variations be included within the scope of the following claims and their equivalents.
Claims (23)
1. A method of infusing carbon nanotubes on a parent fiber, the method comprising:
applying a carbon nanotube-forming catalyst on a surface of a parent fiber comprising a plurality of filaments, thereby forming a catalyst-laden fiber;
pre-heating the catalyst-laden fiber to a temperature between about 500° C. and about 1000° C. prior to synthesizing carbon nanotubes on the catalyst-laden fiber; and
while maintaining the catalyst-laden fiber at a temperature ranging between about 500° C. and about 1000° C., synthesizing carbon nanotubes on the catalyst-laden fiber while the catalyst-laden fiber is being transported, thereby forming a carbon nanotube-infused fiber.
2. The method of claim 1 , further comprising:
removing a sizing material from the parent fiber prior to applying a carbon nanotube-forming catalyst thereto.
3. The method of claim 1 , further comprising:
applying a resin to the carbon nanotube-infused fiber.
4. The method of claim 3 , further comprising:
winding the carbon nanotube-infused fiber about a mandrel after applying the resin.
5. The method of claim 1 , further comprising:
spreading the filaments of the parent fiber.
6. The method of claim 5 , re-bundling the filaments of the spread parent fiber.
7. The method of claim 1 , wherein the carbon nanotube-forming catalyst comprises a transition metal.
8. The method of claim 1 , wherein the carbon nanotubes are synthesized in a carbon plasma at atmospheric pressure.
9. The method of claim 1 , wherein the parent fiber comprises a fiber tow.
10. A system for producing carbon nanotube-infused fibers, the system comprising:
a carbon nanotube infusion station comprising, in series, a catalyst application station, a heater, and a plasma spray station; and
a transport mechanism operable for conveying a fiber comprising a plurality of filaments through the carbon nanotube infusion station.
11. The system of claim 10 , further comprising:
a station for spreading the fiber before the carbon nanotube infusion station.
12. The system of claim 11 , further comprising:
a station for re-bundling the spread fiber after the carbon nanotube infusion station.
13. The system of claim 10 , further comprising:
a station for removing a sizing material from the fiber before the carbon nanotube infusion station.
14. The system of claim 13 , wherein the station for removing a sizing material comprises a heater.
15. The system of claim 10 , wherein the plasma spray station comprises a plurality of carbon plasma sprayers.
16. The system of claim 15 , wherein the plasma spray station further comprises heaters at the carbon plasma sprayers.
17. The system of claim 10 , further comprising:
a resin bath after the carbon nanotube infusion station.
18. A composition comprising a carbon nanotube-infused fiber, wherein the carbon nanotube-infused fiber comprises:
a parent fiber comprising a plurality of filaments; and
a plurality of carbon nanotubes covalently bonded to the parent fiber.
19. The composition of claim 18 , further comprising a resin.
20. The composition of claim 18 , wherein the parent fiber comprises a fiber tow.
21. The composition of claim 18 , wherein the carbon nanotube-infused fiber is prepared by a process comprising:
applying a carbon nanotube-forming catalyst on a surface of a parent fiber comprising a plurality of filaments, thereby forming a catalyst-laden fiber;
pre-heating the catalyst-laden fiber to a temperature between about 500° C. and about 1000° C. prior to synthesizing carbon nanotubes on the catalyst-laden fiber; and
while maintaining the catalyst-laden fiber at a temperature ranging between about 500° C. and about 1000° C., synthesizing carbon nanotubes on the catalyst-laden fiber while the catalyst-laden fiber is being transported.
22. The composition of claim 18 , wherein the parent fiber comprises a carbon fiber lacking a sizing material.
23. The composition of claim 18 , wherein the electrical resistivity of the carbon nanotube-infused fiber is lower than the electrical resistivity of the parent fiber.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/298,259 US20120065300A1 (en) | 2007-01-03 | 2011-11-16 | Cnt-infused fiber and method therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/619,327 US8158217B2 (en) | 2007-01-03 | 2007-01-03 | CNT-infused fiber and method therefor |
US13/298,259 US20120065300A1 (en) | 2007-01-03 | 2011-11-16 | Cnt-infused fiber and method therefor |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/619,327 Continuation US8158217B2 (en) | 2007-01-03 | 2007-01-03 | CNT-infused fiber and method therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
US20120065300A1 true US20120065300A1 (en) | 2012-03-15 |
Family
ID=39321521
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/619,327 Active 2029-01-27 US8158217B2 (en) | 2007-01-03 | 2007-01-03 | CNT-infused fiber and method therefor |
US13/298,259 Abandoned US20120065300A1 (en) | 2007-01-03 | 2011-11-16 | Cnt-infused fiber and method therefor |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/619,327 Active 2029-01-27 US8158217B2 (en) | 2007-01-03 | 2007-01-03 | CNT-infused fiber and method therefor |
Country Status (11)
Country | Link |
---|---|
US (2) | US8158217B2 (en) |
EP (3) | EP2290139B1 (en) |
JP (3) | JP5079819B2 (en) |
KR (1) | KR101218487B1 (en) |
AT (1) | ATE557118T1 (en) |
AU (1) | AU2007342249B2 (en) |
CA (1) | CA2673891C (en) |
DK (3) | DK2290139T3 (en) |
ES (3) | ES2392558T3 (en) |
WO (1) | WO2008085634A1 (en) |
ZA (1) | ZA200904640B (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090081383A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Carbon Nanotube Infused Composites via Plasma Processing |
US20090081441A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Fiber Tow Comprising Carbon-Nanotube-Infused Fibers |
US20100178825A1 (en) * | 2007-01-03 | 2010-07-15 | Lockheed Martin Corporation | Cnt-infused carbon fiber materials and process therefor |
US20100221424A1 (en) * | 2009-02-27 | 2010-09-02 | Lockheed Martin Corporation | Low temperature cnt growth using gas-preheat method |
US20100227134A1 (en) * | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | Method for the prevention of nanoparticle agglomeration at high temperatures |
US20100260998A1 (en) * | 2009-04-10 | 2010-10-14 | Lockheed Martin Corporation | Fiber sizing comprising nanoparticles |
US20100279569A1 (en) * | 2007-01-03 | 2010-11-04 | Lockheed Martin Corporation | Cnt-infused glass fiber materials and process therefor |
US20110028308A1 (en) * | 2009-08-03 | 2011-02-03 | Lockheed Martin Corporation | Incorporation of nanoparticles in composite fibers |
US20110168083A1 (en) * | 2007-01-03 | 2011-07-14 | Lockheed Martin Corporation | Cnt-infused ceramic fiber materials and process therefor |
US20110171469A1 (en) * | 2009-11-02 | 2011-07-14 | Applied Nanostructured Solutions, Llc | Cnt-infused aramid fiber materials and process therefor |
CN103088648A (en) * | 2013-01-25 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
US20210164104A1 (en) * | 2017-09-25 | 2021-06-03 | Raytheon Technologies Corporation | Continuous multiple tow coating reactor |
Families Citing this family (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8337979B2 (en) | 2006-05-19 | 2012-12-25 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
EP2385016B1 (en) * | 2006-05-19 | 2018-08-08 | Massachusetts Institute of Technology | Continuous process for the production of nanostructures |
US8158217B2 (en) | 2007-01-03 | 2012-04-17 | Applied Nanostructured Solutions, Llc | CNT-infused fiber and method therefor |
US9725314B2 (en) * | 2008-03-03 | 2017-08-08 | Performancy Polymer Solutions, Inc. | Continuous process for the production of carbon nanofiber reinforced continuous fiber preforms and composites made therefrom |
JP5577356B2 (en) * | 2009-02-17 | 2014-08-20 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Composite material composed of carbon nanotubes on the fiber |
BRPI1014162A2 (en) * | 2009-04-10 | 2016-04-26 | Applied Nanostructured Sols | Method and apparatus for using a vertical furnace to infuse carbon nanotubes into the fiber |
US9111658B2 (en) | 2009-04-24 | 2015-08-18 | Applied Nanostructured Solutions, Llc | CNS-shielded wires |
CA2758570A1 (en) | 2009-04-24 | 2010-12-16 | Applied Nanostructured Solutions, Llc | Cnt-based signature control material |
WO2010129234A2 (en) * | 2009-04-27 | 2010-11-11 | Lockheed Martin Corporation | Cnt-based resistive heating for deicing composite structures |
US20100279010A1 (en) * | 2009-04-30 | 2010-11-04 | Lockheed Martin Corporation | Method and system for close proximity catalysis for carbon nanotube synthesis |
US8257678B2 (en) | 2009-07-31 | 2012-09-04 | Massachusetts Institute Of Technology | Systems and methods related to the formation of carbon-based nanostructures |
US8409768B2 (en) * | 2009-10-12 | 2013-04-02 | Board Of Regents, The University Of Texas Systems | Tuning of Fe catalysts for growth of spin-capable carbon nanotubes |
US20110089958A1 (en) * | 2009-10-19 | 2011-04-21 | Applied Nanostructured Solutions, Llc | Damage-sensing composite structures |
US20110123735A1 (en) * | 2009-11-23 | 2011-05-26 | Applied Nanostructured Solutions, Llc | Cnt-infused fibers in thermoset matrices |
CA2776752A1 (en) * | 2009-11-23 | 2011-10-13 | Applied Nanostructured Solutions, Llc | Cnt-tailored composite sea-based structures |
US20110124253A1 (en) * | 2009-11-23 | 2011-05-26 | Applied Nanostructured Solutions, Llc | Cnt-infused fibers in carbon-carbon composites |
CA2775619A1 (en) * | 2009-11-23 | 2011-05-26 | Applied Nanostructured Solutions, Llc | Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof |
BR112012012525A2 (en) * | 2009-12-01 | 2019-09-24 | Applied Nanostructured Sols | electrical matrix composite materials containing carbon nanotube infused fiber materials and methods for their production |
CN103079805B (en) * | 2009-12-14 | 2015-02-11 | 应用纳米结构方案公司 | Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials |
US9167736B2 (en) | 2010-01-15 | 2015-10-20 | Applied Nanostructured Solutions, Llc | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
US20110180478A1 (en) * | 2010-01-22 | 2011-07-28 | Applied Nanostructured Solutions, Llc | Filtration systems and methods related thereto using carbon nanotube-infused fiber materials of spoolable length as a moving filtration medium |
BR112012018244A2 (en) * | 2010-02-02 | 2016-05-03 | Applied Nanostructured Sols | carbon nanotube infused fiber materials containing parallel aligned carbon nanotubes, methods for producing them and composite materials derived therefrom |
JP2013521656A (en) | 2010-03-02 | 2013-06-10 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Electrical device wound around spiral including carbon nanotube leaching electrode material, production method and production apparatus thereof |
KR101818640B1 (en) | 2010-03-02 | 2018-01-15 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Electrical devices containing carbon nanotube-infused fibers and methods for production thereof |
US8780526B2 (en) | 2010-06-15 | 2014-07-15 | Applied Nanostructured Solutions, Llc | Electrical devices containing carbon nanotube-infused fibers and methods for production thereof |
CN102372252B (en) * | 2010-08-23 | 2016-06-15 | 清华大学 | Carbon nano tube compound line and preparation method thereof |
US9017854B2 (en) | 2010-08-30 | 2015-04-28 | Applied Nanostructured Solutions, Llc | Structural energy storage assemblies and methods for production thereof |
AU2011305751A1 (en) | 2010-09-23 | 2012-06-21 | Applied Nanostructured Solutions, Llc | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
US9233492B2 (en) * | 2010-10-12 | 2016-01-12 | Florida State University Research Foundation, Inc. | Composite materials reinforced with carbon nanotube yarns |
US9663368B2 (en) | 2010-10-28 | 2017-05-30 | Massachusetts Institute Of Technology | Carbon-based nanostructure formation using large scale active growth structures |
US20130072077A1 (en) | 2011-09-21 | 2013-03-21 | Massachusetts Institute Of Technology | Systems and methods for growth of nanostructures on substrates, including substrates comprising fibers |
US8822057B2 (en) | 2011-10-17 | 2014-09-02 | Lockheed Martin Corporation | High surface area flow battery electrodes |
US9893363B2 (en) | 2011-10-17 | 2018-02-13 | Lockheed Martin Corporation | High surface area flow battery electrodes |
US9085464B2 (en) | 2012-03-07 | 2015-07-21 | Applied Nanostructured Solutions, Llc | Resistance measurement system and method of using the same |
US8470946B1 (en) | 2012-08-20 | 2013-06-25 | The Regents Of The University Of California | Enhanced strength carbon nanotube yarns and sheets using infused and bonded nano-resins |
WO2014089001A1 (en) | 2012-12-05 | 2014-06-12 | Ocv Intellectual Capital, Llc | Post-coated carbon enhanced reinforcement tow and chopped strands and method for forming same |
FR3000691B1 (en) * | 2013-01-10 | 2015-02-13 | Univ Haute Alsace | PROCESS FOR PREPARING AN EXTENDED MATERIAL WITH GRAFT CARBON NANOSTRUCTURES, APPARATUS AND PRODUCT THEREOF |
WO2014134484A1 (en) | 2013-02-28 | 2014-09-04 | N12 Technologies, Inc. | Cartridge-based dispensing of nanostructure films |
GB201412656D0 (en) | 2014-07-16 | 2014-08-27 | Imp Innovations Ltd | Process |
JP6489519B2 (en) * | 2014-10-23 | 2019-03-27 | ニッタ株式会社 | Method for producing reinforcing fiber |
JP2018012741A (en) * | 2014-11-25 | 2018-01-25 | 学校法人同志社 | Carbon fiber-reinforced plastic |
US9908978B2 (en) | 2015-04-08 | 2018-03-06 | Arevo Inc. | Method to manufacture polymer composite materials with nano-fillers for use in additive manufacturing to improve material properties |
US10829872B2 (en) * | 2015-05-20 | 2020-11-10 | University Of Maryland, College Park | Composite materials with self-regulated infrared emissivity and environment responsive fibers |
US11117311B2 (en) | 2015-10-05 | 2021-09-14 | Arevo, Inc. | Amorphous polyaryletherketone and blends thereof for use in additive manufacturing |
CN109311239A (en) | 2016-05-31 | 2019-02-05 | 麻省理工学院 | Composite article including non-linear elongated nanostructure is with and related methods |
JP2018065358A (en) * | 2016-10-21 | 2018-04-26 | 泰英 楠原 | Surface treatment agent removal method, and injection molding method and pellet production using same |
WO2019055155A1 (en) | 2017-09-15 | 2019-03-21 | Massachusetts Institute Of Technology | Low-defect fabrication of composite materials |
EP3718157A4 (en) | 2017-11-28 | 2021-09-29 | Massachusetts Institute of Technology | Separators comprising elongated nanostructures and associated devices and methods for energy storage and/or use |
US10427985B1 (en) | 2018-03-06 | 2019-10-01 | Lockheed Martin Corporation | Engineered micro-voids for toughening ceramic composites |
KR102104879B1 (en) * | 2018-11-23 | 2020-04-27 | 울산과학기술원 | 3-dimensional strain sensor and manufacturing method of the same |
US20220119988A1 (en) * | 2020-10-21 | 2022-04-21 | NanoTubeTec Co., LTD | Fabric with carbon nanotube fiber |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050176329A1 (en) * | 2002-09-12 | 2005-08-11 | Pierre Olry | Three-dimensional fiber structure of refractory fibers, a method of making it, and thermostructural composite materials, in particular friction parts, made therefrom |
US20080020193A1 (en) * | 2006-07-24 | 2008-01-24 | Jang Bor Z | Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes |
US20080075954A1 (en) * | 2006-05-19 | 2008-03-27 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
Family Cites Families (222)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5939527B2 (en) * | 1981-01-14 | 1984-09-25 | 昭和電工株式会社 | Method for producing carbon fiber with branches |
US4530750A (en) | 1981-03-20 | 1985-07-23 | A. S. Laboratories, Inc. | Apparatus for coating optical fibers |
JPS58156512A (en) * | 1982-03-08 | 1983-09-17 | Nippon Steel Corp | Fibrous carbon material having thickly grown fine carbon cilium |
US4515107A (en) | 1982-11-12 | 1985-05-07 | Sovonics Solar Systems | Apparatus for the manufacture of photovoltaic devices |
US4790052A (en) * | 1983-12-28 | 1988-12-13 | Societe Europeenne De Propulsion | Process for manufacturing homogeneously needled three-dimensional structures of fibrous material |
US5221605A (en) | 1984-10-31 | 1993-06-22 | Igen, Inc. | Luminescent metal chelate labels and means for detection |
US5238808A (en) | 1984-10-31 | 1993-08-24 | Igen, Inc. | Luminescent metal chelate labels and means for detection |
US5310687A (en) | 1984-10-31 | 1994-05-10 | Igen, Inc. | Luminescent metal chelate labels and means for detection |
US4707349A (en) | 1986-02-28 | 1987-11-17 | Hjersted Norman B | Process of preparing a preferred ferric sulfate solution, and product |
US4920917A (en) | 1987-03-18 | 1990-05-01 | Teijin Limited | Reactor for depositing a layer on a moving substrate |
US5130194A (en) | 1988-02-22 | 1992-07-14 | The Boeing Company | Coated ceramic fiber |
US5093155A (en) | 1988-11-29 | 1992-03-03 | Tonen Corporation | Process for sizing reinforcing fiber by applying sulfone compounds containing sulfonyl groups and sized reinforcing fibers obtained thereby |
JP2824808B2 (en) | 1990-11-16 | 1998-11-18 | キヤノン株式会社 | Apparatus for continuously forming large-area functional deposited films by microwave plasma CVD |
US5173367A (en) | 1991-01-15 | 1992-12-22 | Ethyl Corporation | Ceramic composites |
US5246794A (en) | 1991-03-19 | 1993-09-21 | Eveready Battery Company, Inc. | Cathode collector made from carbon fibrils |
US20020085974A1 (en) | 1992-01-15 | 2002-07-04 | Hyperion Catalysis International, Inc. | Surface treatment of carbon microfibers |
US5946587A (en) | 1992-08-06 | 1999-08-31 | Canon Kabushiki Kaisha | Continuous forming method for functional deposited films |
US5547525A (en) | 1993-09-29 | 1996-08-20 | Thiokol Corporation | Electrostatic discharge reduction in energetic compositions |
US5470408A (en) | 1993-10-22 | 1995-11-28 | Thiokol Corporation | Use of carbon fibrils to enhance burn rate of pyrotechnics and gas generants |
JP3571785B2 (en) | 1993-12-28 | 2004-09-29 | キヤノン株式会社 | Method and apparatus for forming deposited film |
WO1996029564A2 (en) | 1995-03-14 | 1996-09-26 | Thiokol Corporation | Infrared tracer compositions |
JP3119172B2 (en) | 1995-09-13 | 2000-12-18 | 日新電機株式会社 | Plasma CVD method and apparatus |
JPH09111135A (en) | 1995-10-23 | 1997-04-28 | Mitsubishi Materials Corp | Conductive polymer composition |
JPH09115334A (en) | 1995-10-23 | 1997-05-02 | Mitsubishi Materiais Corp | Transparent conductive film and composition for film formation |
US5997832A (en) | 1997-03-07 | 1999-12-07 | President And Fellows Of Harvard College | Preparation of carbide nanorods |
US6683783B1 (en) | 1997-03-07 | 2004-01-27 | William Marsh Rice University | Carbon fibers formed from single-wall carbon nanotubes |
US6205016B1 (en) | 1997-06-04 | 2001-03-20 | Hyperion Catalysis International, Inc. | Fibril composite electrode for electrochemical capacitors |
JP3740295B2 (en) | 1997-10-30 | 2006-02-01 | キヤノン株式会社 | Carbon nanotube device, manufacturing method thereof, and electron-emitting device |
EP0933343B1 (en) * | 1998-01-29 | 2003-06-25 | Coi Ceramics, Inc. | Method for producing sized, coated ceramic fibers |
EP1089938A1 (en) | 1998-06-19 | 2001-04-11 | The Research Foundation Of State University Of New York | Free-standing and aligned carbon nanotubes and synthesis thereof |
US6455021B1 (en) | 1998-07-21 | 2002-09-24 | Showa Denko K.K. | Method for producing carbon nanotubes |
US6692717B1 (en) | 1999-09-17 | 2004-02-17 | William Marsh Rice University | Catalytic growth of single-wall carbon nanotubes from metal particles |
US7150864B1 (en) | 1998-09-18 | 2006-12-19 | William Marsh Rice University | Ropes comprised of single-walled and double-walled carbon nanotubes |
US6232706B1 (en) | 1998-11-12 | 2001-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
US6265466B1 (en) | 1999-02-12 | 2001-07-24 | Eikos, Inc. | Electromagnetic shielding composite comprising nanotubes |
US6221154B1 (en) | 1999-02-18 | 2001-04-24 | City University Of Hong Kong | Method for growing beta-silicon carbide nanorods, and preparation of patterned field-emitters by chemical vapor depositon (CVD) |
CN1174916C (en) | 1999-04-21 | 2004-11-10 | 张震 | Forming method for carbon nano-tube |
US20030091496A1 (en) | 2001-07-23 | 2003-05-15 | Resasco Daniel E. | Method and catalyst for producing single walled carbon nanotubes |
US7816709B2 (en) | 1999-06-02 | 2010-10-19 | The Board Of Regents Of The University Of Oklahoma | Single-walled carbon nanotube-ceramic composites and methods of use |
US6333016B1 (en) | 1999-06-02 | 2001-12-25 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes |
US6913075B1 (en) | 1999-06-14 | 2005-07-05 | Energy Science Laboratories, Inc. | Dendritic fiber material |
US6361861B2 (en) | 1999-06-14 | 2002-03-26 | Battelle Memorial Institute | Carbon nanotubes on a substrate |
KR100673367B1 (en) | 1999-10-27 | 2007-01-24 | 윌리엄 마쉬 라이스 유니버시티 | Macroscopic ordered assembly of carbon nanotubes |
US6506037B1 (en) * | 1999-11-17 | 2003-01-14 | Carrier Corporation | Screw machine |
DE19958473A1 (en) | 1999-12-04 | 2001-06-07 | Bosch Gmbh Robert | Process for the production of composite layers with a plasma beam source |
FR2805179B1 (en) | 2000-02-23 | 2002-09-27 | Centre Nat Rech Scient | PROCESS FOR OBTAINING MACROSCOPIC FIBERS AND TAPES FROM COLLOIDAL PARTICLES, IN PARTICULAR CARBON NANOTUBES |
WO2001067821A1 (en) | 2000-03-07 | 2001-09-13 | Chang Robert P H | Carbon nanostructures and methods of preparation |
KR100360470B1 (en) | 2000-03-15 | 2002-11-09 | 삼성에스디아이 주식회사 | Method for depositing a vertically aligned carbon nanotubes using thermal chemical vapor deposition |
US6479028B1 (en) | 2000-04-03 | 2002-11-12 | The Regents Of The University Of California | Rapid synthesis of carbon nanotubes and carbon encapsulated metal nanoparticles by a displacement reaction |
US6653005B1 (en) | 2000-05-10 | 2003-11-25 | University Of Central Florida | Portable hydrogen generator-fuel cell apparatus |
US6413487B1 (en) | 2000-06-02 | 2002-07-02 | The Board Of Regents Of The University Of Oklahoma | Method and apparatus for producing carbon nanotubes |
US6908572B1 (en) | 2000-07-17 | 2005-06-21 | University Of Kentucky Research Foundation | Mixing and dispersion of nanotubes by gas or vapor expansion |
US6451175B1 (en) * | 2000-08-15 | 2002-09-17 | Wisconsin Alumni Research Foundation | Method and apparatus for carbon nanotube production |
EP1182272A1 (en) | 2000-08-23 | 2002-02-27 | Cold Plasma Applications C.P.A. | Process and apparatus for continuous cold plasma deposition of metallic layers |
US6420293B1 (en) | 2000-08-25 | 2002-07-16 | Rensselaer Polytechnic Institute | Ceramic matrix nanocomposites containing carbon nanotubes for enhanced mechanical behavior |
US6653619B2 (en) | 2000-09-15 | 2003-11-25 | Agilent Technologies, Inc. | Optical motion encoder with a reflective member allowing the light source and sensor to be on the same side |
US6495258B1 (en) | 2000-09-20 | 2002-12-17 | Auburn University | Structures with high number density of carbon nanotubes and 3-dimensional distribution |
JP3912583B2 (en) | 2001-03-14 | 2007-05-09 | 三菱瓦斯化学株式会社 | Method for producing oriented carbon nanotube film |
JP3981566B2 (en) | 2001-03-21 | 2007-09-26 | 守信 遠藤 | Method for producing expanded carbon fiber body |
US7265174B2 (en) | 2001-03-22 | 2007-09-04 | Clemson University | Halogen containing-polymer nanocomposite compositions, methods, and products employing such compositions |
EP1385481A4 (en) | 2001-03-26 | 2006-06-07 | Eikos Inc | Carbon nanotubes in structures and repair compositions |
AUPR421701A0 (en) | 2001-04-04 | 2001-05-17 | Commonwealth Scientific And Industrial Research Organisation | Process and apparatus for the production of carbon nanotubes |
US7160531B1 (en) | 2001-05-08 | 2007-01-09 | University Of Kentucky Research Foundation | Process for the continuous production of aligned carbon nanotubes |
WO2002095097A1 (en) | 2001-05-21 | 2002-11-28 | Trustees Of Boston College, The | Varied morphology carbon nanotubes and methods for their manufacture |
US7341498B2 (en) | 2001-06-14 | 2008-03-11 | Hyperion Catalysis International, Inc. | Method of irradiating field emission cathode having nanotubes |
US6783702B2 (en) | 2001-07-11 | 2004-08-31 | Hyperion Catalysis International, Inc. | Polyvinylidene fluoride composites and methods for preparing same |
CN1325372C (en) | 2001-07-27 | 2007-07-11 | 萨里大学 | Production of carbon nanotubes |
EP1444701A4 (en) | 2001-07-27 | 2005-01-12 | Eikos Inc | Conformal coatings comprising carbon nanotubes |
CN1195793C (en) | 2001-08-06 | 2005-04-06 | 昭和电工株式会社 | Conductive curable resin composition and separator for fuel cell |
US6656339B2 (en) | 2001-08-29 | 2003-12-02 | Motorola, Inc. | Method of forming a nano-supported catalyst on a substrate for nanotube growth |
ATE414675T1 (en) | 2001-08-29 | 2008-12-15 | Georgia Tech Res Inst | COMPOSITIONS COMPRISING ROD-SHAPED POLYMERS AND NANOTUBE-SHAPED STRUCTURES AND METHODS FOR PRODUCING THE SAME |
US7070472B2 (en) | 2001-08-29 | 2006-07-04 | Motorola, Inc. | Field emission display and methods of forming a field emission display |
US6837928B1 (en) | 2001-08-30 | 2005-01-04 | The Board Of Trustees Of The Leland Stanford Junior University | Electric field orientation of carbon nanotubes |
US6528572B1 (en) | 2001-09-14 | 2003-03-04 | General Electric Company | Conductive polymer compositions and methods of manufacture thereof |
US20030072942A1 (en) * | 2001-10-17 | 2003-04-17 | Industrial Technology Research Institute | Combinative carbon material |
US7022776B2 (en) | 2001-11-07 | 2006-04-04 | General Electric | Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom |
US6921462B2 (en) | 2001-12-17 | 2005-07-26 | Intel Corporation | Method and apparatus for producing aligned carbon nanotube thermal interface structure |
AU2002367020B2 (en) | 2001-12-21 | 2008-11-20 | Battelle Memorial Institute | Structures containing carbon nanotubes and a porous support, methods of making the same, and related uses |
JP4404961B2 (en) | 2002-01-08 | 2010-01-27 | 双葉電子工業株式会社 | A method for producing carbon nanofibers. |
TWI236505B (en) | 2002-01-14 | 2005-07-21 | Nat Science Council | Thermal cracking chemical vapor deposition process for nanocarbonaceous material |
JP3972674B2 (en) * | 2002-02-14 | 2007-09-05 | 東レ株式会社 | Carbon fiber manufacturing method and carbon fiber reinforced resin composition |
JP3922039B2 (en) | 2002-02-15 | 2007-05-30 | 株式会社日立製作所 | Electromagnetic wave absorbing material and various products using the same |
JP4168676B2 (en) | 2002-02-15 | 2008-10-22 | コニカミノルタホールディングス株式会社 | Film forming method |
CN1176014C (en) | 2002-02-22 | 2004-11-17 | 清华大学 | Process for directly synthesizing ultra-long single-wall continuous nano carbon tube |
JP4107475B2 (en) * | 2002-02-22 | 2008-06-25 | 三菱レイヨン株式会社 | Reinforcing fibers for fiber reinforced composites |
US6546744B1 (en) * | 2002-02-28 | 2003-04-15 | Billy Cavender | Recreational vehicle heat transfer apparatus |
WO2003078317A1 (en) | 2002-03-14 | 2003-09-25 | Carbon Nanotechnologies, Inc. | Composite materials comprising polar polyers and single-wall carbon naotubes |
US6934600B2 (en) | 2002-03-14 | 2005-08-23 | Auburn University | Nanotube fiber reinforced composite materials and method of producing fiber reinforced composites |
US7405854B2 (en) | 2002-03-21 | 2008-07-29 | Cornell Research Foundation, Inc. | Fibrous micro-composite material |
US6887451B2 (en) | 2002-04-30 | 2005-05-03 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government | Process for preparing carbon nanotubes |
US7445817B2 (en) | 2002-05-08 | 2008-11-04 | Btu International Inc. | Plasma-assisted formation of carbon structures |
US7227097B2 (en) | 2002-05-08 | 2007-06-05 | Btu International, Inc. | Plasma generation and processing with multiple radiation sources |
FR2841233B1 (en) | 2002-06-24 | 2004-07-30 | Commissariat Energie Atomique | METHOD AND DEVICE FOR PYROLYSIS DEPOSITION OF CARBON NANOTUBES |
US6852410B2 (en) | 2002-07-01 | 2005-02-08 | Georgia Tech Research Corporation | Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same |
US6979947B2 (en) | 2002-07-09 | 2005-12-27 | Si Diamond Technology, Inc. | Nanotriode utilizing carbon nanotubes and fibers |
US7153452B2 (en) | 2002-09-12 | 2006-12-26 | Clemson University | Mesophase pitch-based carbon fibers with carbon nanotube reinforcements |
CN100411979C (en) | 2002-09-16 | 2008-08-20 | 清华大学 | Carbon nano pipe rpoe and preparation method thereof |
AU2002334664A1 (en) | 2002-09-17 | 2004-04-08 | Midwest Research Institute | Carbon nanotube heat-exchange systems |
JP3735651B2 (en) | 2002-10-08 | 2006-01-18 | 独立行政法人 宇宙航空研究開発機構 | Carbon nanofiber dispersed resin fiber reinforced composite material |
US7645400B2 (en) | 2002-11-01 | 2010-01-12 | Mitsubishi Rayon Co., Ltd. | Composition containing carbon nanotubes having a coating |
US7431965B2 (en) | 2002-11-01 | 2008-10-07 | Honda Motor Co., Ltd. | Continuous growth of single-wall carbon nanotubes using chemical vapor deposition |
JP3969650B2 (en) | 2002-11-19 | 2007-09-05 | 日精樹脂工業株式会社 | Method for controlling skin layer thickness in composite resin molded products |
EP1581586B1 (en) | 2002-11-27 | 2010-11-03 | William Marsh Rice University | Functionalized carbon nanotube-polymer composites and interactions with radiation |
CN1290763C (en) | 2002-11-29 | 2006-12-20 | 清华大学 | Process for preparing nano-carbon tubes |
JP4514130B2 (en) | 2002-12-20 | 2010-07-28 | 株式会社アルネアラボラトリ | Optical pulse laser |
TWI304321B (en) | 2002-12-27 | 2008-12-11 | Toray Industries | Layered products, electromagnetic wave shielding molded articles and method for production thereof |
CN1867392B (en) | 2003-03-07 | 2010-06-09 | 塞尔顿技术公司 | Purification of fluids with nanomaterials |
US7419601B2 (en) | 2003-03-07 | 2008-09-02 | Seldon Technologies, Llc | Nanomesh article and method of using the same for purifying fluids |
CN1286716C (en) | 2003-03-19 | 2006-11-29 | 清华大学 | Method for growing carbon nano tube |
US7579077B2 (en) | 2003-05-05 | 2009-08-25 | Nanosys, Inc. | Nanofiber surfaces for use in enhanced surface area applications |
US7074294B2 (en) | 2003-04-17 | 2006-07-11 | Nanosys, Inc. | Structures, systems and methods for joining articles and materials and uses therefor |
FR2854409B1 (en) | 2003-04-30 | 2005-06-17 | Centre Nat Rech Scient | PROCESS FOR OBTAINING FIBERS HAVING A HIGH CONTENT OF COLLOIDAL PARTICLES AND COMPOSITE FIBERS OBTAINED |
US7261779B2 (en) * | 2003-06-05 | 2007-08-28 | Lockheed Martin Corporation | System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes |
US7354988B2 (en) | 2003-08-12 | 2008-04-08 | General Electric Company | Electrically conductive compositions and method of manufacture thereof |
EP1506975A1 (en) | 2003-08-13 | 2005-02-16 | Vantico GmbH | Nanocomposites based on polyurethane or polyurethane-epoxy hybrid resins prepared avoiding isocyanates |
WO2005025734A2 (en) | 2003-09-17 | 2005-03-24 | Molecular Nanosystems, Inc. | Methods for producing and using catalytic substrates for carbon nanotube growth |
US20050119371A1 (en) | 2003-10-15 | 2005-06-02 | Board Of Trustees Of Michigan State University | Bio-based epoxy, their nanocomposites and methods for making those |
KR100570634B1 (en) | 2003-10-16 | 2006-04-12 | 한국전자통신연구원 | Electromagnetic shielding materials manufactured by filling carbon tube and metallic powder as electrical conductor |
WO2005044723A2 (en) * | 2003-10-16 | 2005-05-19 | The University Of Akron | Carbon nanotubes on carbon nanofiber substrate |
US7265175B2 (en) | 2003-10-30 | 2007-09-04 | The Trustees Of The University Of Pennsylvania | Flame retardant nanocomposite |
JP2006516944A (en) | 2003-11-07 | 2006-07-13 | ビ−エイイ− システムズ パブリック リミテッド カンパニ− | Formation of nanostructures |
US7611579B2 (en) | 2004-01-15 | 2009-11-03 | Nanocomp Technologies, Inc. | Systems and methods for synthesis of extended length nanostructures |
US20070189953A1 (en) * | 2004-01-30 | 2007-08-16 | Centre National De La Recherche Scientifique (Cnrs) | Method for obtaining carbon nanotubes on supports and composites comprising same |
JP2005213700A (en) * | 2004-01-30 | 2005-08-11 | National Institute For Materials Science | Diameter-different composite type fibrous carbon and method for producing the same |
JP2005219950A (en) * | 2004-02-04 | 2005-08-18 | Nikon Corp | Carbon material, method of manufacturing carbon material, gas adsorption apparatus and composite material |
US7338684B1 (en) | 2004-02-12 | 2008-03-04 | Performance Polymer Solutions, Inc. | Vapor grown carbon fiber reinforced composite materials and methods of making and using same |
US7628041B2 (en) | 2004-02-27 | 2009-12-08 | Alcatel-Lucent Usa Inc. | Carbon particle fiber assembly technique |
CN100543074C (en) | 2004-03-20 | 2009-09-23 | 帝人阿拉米德有限公司 | The matrix material that comprises PPTA and nanotube |
CN100383213C (en) | 2004-04-02 | 2008-04-23 | 清华大学 | Thermal interface material and its manufacturing method |
US7144563B2 (en) | 2004-04-22 | 2006-12-05 | Clemson University | Synthesis of branched carbon nanotubes |
WO2006073454A2 (en) | 2004-04-28 | 2006-07-13 | University Of South Florida | Polymer/carbon nanotube composites, methods of use and methods of synthesis thereof |
US20050260412A1 (en) * | 2004-05-19 | 2005-11-24 | Lockheed Martin Corporation | System, method, and apparatus for producing high efficiency heat transfer device with carbon nanotubes |
CN1705059B (en) | 2004-05-26 | 2012-08-29 | 清华大学 | Carbon nano tube field emission device and preparation method thereof |
KR20050121426A (en) | 2004-06-22 | 2005-12-27 | 삼성에스디아이 주식회사 | Method for preparing catalyst for manufacturing carbon nano tubes |
FR2872826B1 (en) | 2004-07-07 | 2006-09-15 | Commissariat Energie Atomique | LOW-TEMPERATURE GROWTH OF CARBON NANOTUBES ORIENTED |
JP5173418B2 (en) | 2004-07-22 | 2013-04-03 | ウィリアム・マーシュ・ライス・ユニバーシティ | Polymer / carbon nanotube interpenetrating network structure and manufacturing process thereof |
US8080487B2 (en) | 2004-09-20 | 2011-12-20 | Lockheed Martin Corporation | Ballistic fabrics with improved antiballistic properties |
FR2877262B1 (en) | 2004-10-29 | 2007-04-27 | Centre Nat Rech Scient Cnrse | COMPOSITE FIBERS AND DISSYMETRIC FIBERS FROM CARBON NANOTUBES AND COLLOIDAL PARTICLES |
TW200631111A (en) | 2004-11-04 | 2006-09-01 | Koninkl Philips Electronics Nv | Nanotube-based circuit connection approach |
US6988853B1 (en) * | 2004-11-04 | 2006-01-24 | Nehalem Marine Manufacturing | Muted tidal regulator |
AU2005335123B2 (en) | 2004-11-09 | 2011-02-03 | Board Of Regents, The University Of Texas System | The fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns |
AU2005307779A1 (en) | 2004-11-16 | 2006-05-26 | Hyperion Catalysis International, Inc. | Method for preparing single walled carbon nanotubes |
US7871591B2 (en) | 2005-01-11 | 2011-01-18 | Honda Motor Co., Ltd. | Methods for growing long carbon single-walled nanotubes |
US7407901B2 (en) | 2005-01-12 | 2008-08-05 | Kazak Composites, Incorporated | Impact resistant, thin ply composite structures and method of manufacturing same |
US7811632B2 (en) | 2005-01-21 | 2010-10-12 | Ut-Battelle Llc | Molecular jet growth of carbon nanotubes and dense vertically aligned nanotube arrays |
US20060198956A1 (en) | 2005-03-04 | 2006-09-07 | Gyula Eres | Chemical vapor deposition of long vertically aligned dense carbon nanotube arrays by external control of catalyst composition |
CN100500555C (en) | 2005-04-15 | 2009-06-17 | 清华大学 | Carbon nanotube array structure and its preparation process |
CN100376478C (en) | 2005-04-22 | 2008-03-26 | 清华大学 | Apparatus for preparing carbon nano tube array structure |
CN101198542A (en) | 2005-04-22 | 2008-06-11 | 塞尔顿技术公司 | Product including carbon nano-tube and method for purifying fluid with the carbon nano-tube |
JP2006342011A (en) * | 2005-06-08 | 2006-12-21 | Bridgestone Corp | Carbon nanotube-carbon fiber composite and method for producing the same |
US7278324B2 (en) | 2005-06-15 | 2007-10-09 | United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Carbon nanotube-based sensor and method for detection of crack growth in a structure |
CA2613203C (en) | 2005-06-28 | 2013-08-13 | The Board Of Regents Of The University Of Oklahoma | Methods for growing and harvesting carbon nanotubes |
US8313723B2 (en) | 2005-08-25 | 2012-11-20 | Nanocarbons Llc | Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers |
US20070110977A1 (en) | 2005-08-29 | 2007-05-17 | Al-Haik Marwan S | Methods for processing multifunctional, radiation tolerant nanotube-polymer structure composites |
SG165338A1 (en) | 2005-09-01 | 2010-10-28 | Seldon Technologies Inc | Large scale manufacturing of nanostructured material |
CN1927988A (en) | 2005-09-05 | 2007-03-14 | 鸿富锦精密工业(深圳)有限公司 | Heat interfacial material and method for making the same |
CN100482580C (en) | 2005-10-13 | 2009-04-29 | 鸿富锦精密工业(深圳)有限公司 | Preparation device of carbon nano-tube and its method |
WO2008054378A2 (en) | 2005-10-25 | 2008-05-08 | Massachusetts Institute Of Technology | Apparatus and methods for controlled growth and assembly of nanostructures |
US7709087B2 (en) | 2005-11-18 | 2010-05-04 | The Regents Of The University Of California | Compliant base to increase contact for micro- or nano-fibers |
US8148276B2 (en) | 2005-11-28 | 2012-04-03 | University Of Hawaii | Three-dimensionally reinforced multifunctional nanocomposites |
KR101007621B1 (en) | 2005-11-30 | 2011-01-12 | 시마네켄 | Metal-based composite material containing both micron-size carbon fiber and nano-size carbon fiber |
US7592248B2 (en) | 2005-12-09 | 2009-09-22 | Freescale Semiconductor, Inc. | Method of forming semiconductor device having nanotube structures |
KR100745735B1 (en) | 2005-12-13 | 2007-08-02 | 삼성에스디아이 주식회사 | Method for growing carbon nanotubes and manufacturing method of field emission device therewith |
US7465605B2 (en) | 2005-12-14 | 2008-12-16 | Intel Corporation | In-situ functionalization of carbon nanotubes |
WO2008045109A2 (en) | 2005-12-19 | 2008-04-17 | University Of Virginia Patent Foundation | Conducting nanotubes or nanostructures based composites, method of making them and applications |
US8562937B2 (en) | 2005-12-19 | 2013-10-22 | Nantero Inc. | Production of carbon nanotubes |
US20090176100A1 (en) | 2005-12-22 | 2009-07-09 | Showa Denko K.K. | Vapor-grown carbon fiber and production process thereof |
FR2895397B1 (en) | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN AND STRUCTURES OF GLASS YARNS HAVING A COATING COMPRISING NANOPARTICLES |
FR2895398B1 (en) | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN COATED WITH AN ENSIMAGE COMPRISING NANOPARTICLES. |
JP5550833B2 (en) | 2006-01-30 | 2014-07-16 | 本田技研工業株式会社 | Method and apparatus for high quality single-walled carbon nanotube growth |
KR100749886B1 (en) | 2006-02-03 | 2007-08-21 | (주) 나노텍 | Heating element using Carbon Nano tube |
US8124503B2 (en) | 2006-03-03 | 2012-02-28 | William Marsh Rice University | Carbon nanotube diameter selection by pretreatment of metal catalysts on surfaces |
EP2013408B2 (en) | 2006-05-02 | 2016-09-28 | Rohr, Inc. | Nacelles and components thereof using nanoreinforcements |
US7687981B2 (en) | 2006-05-05 | 2010-03-30 | Brother International Corporation | Method for controlled density growth of carbon nanotubes |
US20090186214A1 (en) | 2006-05-17 | 2009-07-23 | University Of Dayton | Method of growing carbon nanomaterials on various substrates |
EP2385016B1 (en) | 2006-05-19 | 2018-08-08 | Massachusetts Institute of Technology | Continuous process for the production of nanostructures |
US7534648B2 (en) | 2006-06-29 | 2009-05-19 | Intel Corporation | Aligned nanotube bearing composite material |
US9095639B2 (en) | 2006-06-30 | 2015-08-04 | The University Of Akron | Aligned carbon nanotube-polymer materials, systems and methods |
US8389119B2 (en) | 2006-07-31 | 2013-03-05 | The Board Of Trustees Of The Leland Stanford Junior University | Composite thermal interface material including aligned nanofiber with low melting temperature binder |
US20080053922A1 (en) | 2006-09-01 | 2008-03-06 | Honsinger Charles P Jr | Nanostructured materials comprising support fibers coated with metal containing compounds and methods of using the same |
JP2008056546A (en) | 2006-09-01 | 2008-03-13 | Ihi Corp | Production device and production method for carbon structure |
AU2007303821B9 (en) | 2006-10-05 | 2013-06-20 | Technion Research & Development Foundation Ltd. | Microtubes and methods of producing same |
KR100829001B1 (en) | 2006-12-07 | 2008-05-14 | 한국에너지기술연구원 | The manufacturing method of reinforced composite using the method of synthesizing carbon nanowire directly on the glass fiber or the carbon fiber |
US20080160286A1 (en) | 2006-12-27 | 2008-07-03 | Jawed Asrar | Modified discontinuous glass fibers for use in the formation of thermoplastic fiber-reinforced composite articles |
US20080160302A1 (en) | 2006-12-27 | 2008-07-03 | Jawed Asrar | Modified fibers for use in the formation of thermoplastic fiber-reinforced composite articles and process |
US20100279569A1 (en) | 2007-01-03 | 2010-11-04 | Lockheed Martin Corporation | Cnt-infused glass fiber materials and process therefor |
US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
US8158217B2 (en) | 2007-01-03 | 2012-04-17 | Applied Nanostructured Solutions, Llc | CNT-infused fiber and method therefor |
TW200833861A (en) | 2007-02-05 | 2008-08-16 | Nat Univ Tsing Hua | Method for growing carbon nanotubes directly on the carbon fiber |
US20080247938A1 (en) | 2007-04-05 | 2008-10-09 | Ming-Chi Tsai | Process of growing carbon nanotubes directly on carbon fiber |
CN101286384B (en) | 2007-04-11 | 2010-12-29 | 清华大学 | Electromagnetic shielding cable |
US8388795B2 (en) | 2007-05-17 | 2013-03-05 | The Boeing Company | Nanotube-enhanced interlayers for composite structures |
US7718220B2 (en) | 2007-06-05 | 2010-05-18 | Johns Manville | Method and system for forming reinforcing fibers and reinforcing fibers having particulate protuberances directly attached to the surfaces |
EP2011572B1 (en) | 2007-07-06 | 2012-12-05 | Imec | Method for forming catalyst nanoparticles for growing elongated nanostructures |
US7785498B2 (en) | 2007-07-19 | 2010-08-31 | Nanotek Instruments, Inc. | Method of producing conducting polymer-transition metal electro-catalyst composition and electrodes for fuel cells |
CN101821448A (en) | 2007-07-27 | 2010-09-01 | 道康宁公司 | Fiber structure and method of making same |
WO2009018193A1 (en) | 2007-08-02 | 2009-02-05 | Dow Global Technologies Inc. | Amphiphilic block copolymers and inorganic nanofillers to enhance performance of thermosetting polymers |
US20090047453A1 (en) | 2007-08-13 | 2009-02-19 | Smart Nanomaterials, Llc | Nano-enhanced smart panel |
WO2009023643A1 (en) | 2007-08-13 | 2009-02-19 | Smart Nanomaterials, Llc | Nano-enhanced modularly constructed composite panel |
US20090081383A1 (en) | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Carbon Nanotube Infused Composites via Plasma Processing |
US20090081441A1 (en) | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Fiber Tow Comprising Carbon-Nanotube-Infused Fibers |
US7815820B2 (en) | 2007-10-18 | 2010-10-19 | General Electric Company | Electromagnetic interference shielding polymer composites and methods of manufacture |
EP2204493A4 (en) | 2007-10-23 | 2010-11-10 | Tokushu Paper Mfg Co Ltd | Sheet-like article and method for producing the same |
KR20090041765A (en) | 2007-10-24 | 2009-04-29 | 삼성모바일디스플레이주식회사 | Carbon nanotubes and method of growing the same, hybrid structure and method of growing the same and light emitting device |
US20090126783A1 (en) | 2007-11-15 | 2009-05-21 | Rensselaer Polytechnic Institute | Use of vertical aligned carbon nanotube as a super dark absorber for pv, tpv, radar and infrared absorber application |
US8146861B2 (en) | 2007-11-29 | 2012-04-03 | Airbus Deutschland Gmbh | Component with carbon nanotubes |
KR100878751B1 (en) | 2008-01-03 | 2009-01-14 | 한국에너지기술연구원 | Catalyst support using cellulose fiber, preparation method thereof, supported catalyst supporting nano metal catalyst on carbon nanotubes directly grown on surface of the catalyst support, and preparation method of the supported catalyst |
US20090191352A1 (en) | 2008-01-24 | 2009-07-30 | Nanodynamics, Inc. | Combustion-Assisted Substrate Deposition Method For Producing Carbon Nanosubstances |
JP2009184892A (en) | 2008-02-08 | 2009-08-20 | Dainippon Screen Mfg Co Ltd | Carbon nanotube forming device, and carbon nanotube forming method |
US9725314B2 (en) | 2008-03-03 | 2017-08-08 | Performancy Polymer Solutions, Inc. | Continuous process for the production of carbon nanofiber reinforced continuous fiber preforms and composites made therefrom |
WO2009110885A1 (en) | 2008-03-03 | 2009-09-11 | Performance Polymer Solutions, Inc. | Continuous process for the production of carbon nanotube reinforced continuous fiber preforms and composites made therefrom |
US7837905B2 (en) | 2008-05-16 | 2010-11-23 | Raytheon Company | Method of making reinforced filament with doubly-embedded nanotubes |
US20110159270A9 (en) | 2008-06-02 | 2011-06-30 | Texas A & M University System | Carbon nanotube fiber-reinforced polymer composites having improved fatigue durability and methods for production thereof |
US20100059243A1 (en) | 2008-09-09 | 2010-03-11 | Jin-Hong Chang | Anti-electromagnetic interference material arrangement |
KR101420680B1 (en) | 2008-09-22 | 2014-07-17 | 삼성전자주식회사 | Apparatus and method for surface treatment of carbon fiber using resistive heating |
US8351220B2 (en) | 2009-01-28 | 2013-01-08 | Florida State University Research Foundation | Electromagnetic interference shielding structure including carbon nanotube or nanofiber films and methods |
BRPI1008131A2 (en) | 2009-02-27 | 2016-03-08 | Applied Nanostructured Sols | "low temperature carbon nanotube growth using gas preheat method". |
US20100224129A1 (en) | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
US8052951B2 (en) | 2009-04-03 | 2011-11-08 | Ut-Battelle, Llc | Carbon nanotubes grown on bulk materials and methods for fabrication |
US20100272891A1 (en) | 2009-04-10 | 2010-10-28 | Lockheed Martin Corporation | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
US20100311866A1 (en) | 2009-06-05 | 2010-12-09 | University Of Massachusetts | Heirarchial polymer-based nanocomposites for emi shielding |
CN101698975B (en) | 2009-09-23 | 2011-12-28 | 北京航空航天大学 | Method for modifying carbonized pre-oxidized fiber preform interface by carbon nanotube |
-
2007
- 2007-01-03 US US11/619,327 patent/US8158217B2/en active Active
- 2007-12-07 ES ES07869060T patent/ES2392558T3/en active Active
- 2007-12-07 EP EP10012747A patent/EP2290139B1/en not_active Not-in-force
- 2007-12-07 DK DK10012747.1T patent/DK2290139T3/en active
- 2007-12-07 AU AU2007342249A patent/AU2007342249B2/en not_active Ceased
- 2007-12-07 WO PCT/US2007/086875 patent/WO2008085634A1/en active Application Filing
- 2007-12-07 DK DK07869060.9T patent/DK2115191T3/en active
- 2007-12-07 CA CA2673891A patent/CA2673891C/en not_active Expired - Fee Related
- 2007-12-07 AT AT10012747T patent/ATE557118T1/en active
- 2007-12-07 EP EP10009621A patent/EP2261404B1/en not_active Not-in-force
- 2007-12-07 ES ES10009621T patent/ES2389402T3/en active Active
- 2007-12-07 JP JP2009544866A patent/JP5079819B2/en not_active Expired - Fee Related
- 2007-12-07 EP EP07869060A patent/EP2115191B1/en not_active Not-in-force
- 2007-12-07 ES ES10012747T patent/ES2387950T3/en active Active
- 2007-12-07 DK DK10009621.3T patent/DK2261404T3/en active
- 2007-12-07 KR KR1020097013883A patent/KR101218487B1/en active IP Right Grant
-
2009
- 2009-07-02 ZA ZA200904640A patent/ZA200904640B/en unknown
-
2011
- 2011-11-16 US US13/298,259 patent/US20120065300A1/en not_active Abandoned
-
2012
- 2012-05-07 JP JP2012105624A patent/JP6066584B2/en not_active Expired - Fee Related
-
2015
- 2015-02-20 JP JP2015031950A patent/JP6113769B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050176329A1 (en) * | 2002-09-12 | 2005-08-11 | Pierre Olry | Three-dimensional fiber structure of refractory fibers, a method of making it, and thermostructural composite materials, in particular friction parts, made therefrom |
US20080075954A1 (en) * | 2006-05-19 | 2008-03-27 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
US20080020193A1 (en) * | 2006-07-24 | 2008-01-24 | Jang Bor Z | Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110168083A1 (en) * | 2007-01-03 | 2011-07-14 | Lockheed Martin Corporation | Cnt-infused ceramic fiber materials and process therefor |
US9574300B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
US20100178825A1 (en) * | 2007-01-03 | 2010-07-15 | Lockheed Martin Corporation | Cnt-infused carbon fiber materials and process therefor |
US20110168089A1 (en) * | 2007-01-03 | 2011-07-14 | Lockheed Martin Corporation | Cnt-infused carbon fiber materials and process therefor |
US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
US9573812B2 (en) | 2007-01-03 | 2017-02-21 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
US20100279569A1 (en) * | 2007-01-03 | 2010-11-04 | Lockheed Martin Corporation | Cnt-infused glass fiber materials and process therefor |
US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
US20090081383A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Carbon Nanotube Infused Composites via Plasma Processing |
US20090081441A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Fiber Tow Comprising Carbon-Nanotube-Infused Fibers |
US8580342B2 (en) | 2009-02-27 | 2013-11-12 | Applied Nanostructured Solutions, Llc | Low temperature CNT growth using gas-preheat method |
US20100221424A1 (en) * | 2009-02-27 | 2010-09-02 | Lockheed Martin Corporation | Low temperature cnt growth using gas-preheat method |
US20100227134A1 (en) * | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | Method for the prevention of nanoparticle agglomeration at high temperatures |
US10138128B2 (en) | 2009-03-03 | 2018-11-27 | Applied Nanostructured Solutions, Llc | System and method for surface treatment and barrier coating of fibers for in situ CNT growth |
US20100224129A1 (en) * | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
US20100260998A1 (en) * | 2009-04-10 | 2010-10-14 | Lockheed Martin Corporation | Fiber sizing comprising nanoparticles |
US8969225B2 (en) | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
US20110028308A1 (en) * | 2009-08-03 | 2011-02-03 | Lockheed Martin Corporation | Incorporation of nanoparticles in composite fibers |
US20110171469A1 (en) * | 2009-11-02 | 2011-07-14 | Applied Nanostructured Solutions, Llc | Cnt-infused aramid fiber materials and process therefor |
US8784937B2 (en) | 2010-09-14 | 2014-07-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
US8815341B2 (en) | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
CN103088648A (en) * | 2013-01-25 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Preparation method for carbon fiber material with composite nano structure |
US20210164104A1 (en) * | 2017-09-25 | 2021-06-03 | Raytheon Technologies Corporation | Continuous multiple tow coating reactor |
US11697878B2 (en) * | 2017-09-25 | 2023-07-11 | Raytheon Technologies Corporation | Continuous multiple tow coating reactor |
Also Published As
Publication number | Publication date |
---|---|
KR20090086277A (en) | 2009-08-11 |
JP2010531934A (en) | 2010-09-30 |
EP2115191A1 (en) | 2009-11-11 |
ES2392558T3 (en) | 2012-12-11 |
JP2012193105A (en) | 2012-10-11 |
AU2007342249B2 (en) | 2012-08-23 |
DK2261404T3 (en) | 2012-09-17 |
ATE557118T1 (en) | 2012-05-15 |
JP2015110859A (en) | 2015-06-18 |
JP6113769B2 (en) | 2017-04-12 |
ES2387950T3 (en) | 2012-10-04 |
EP2261404B1 (en) | 2012-08-22 |
ZA200904640B (en) | 2010-04-28 |
DK2115191T3 (en) | 2012-10-22 |
AU2007342249A1 (en) | 2008-07-17 |
EP2290139A1 (en) | 2011-03-02 |
KR101218487B1 (en) | 2013-01-04 |
CA2673891A1 (en) | 2008-07-17 |
CA2673891C (en) | 2014-08-19 |
WO2008085634A1 (en) | 2008-07-17 |
US8158217B2 (en) | 2012-04-17 |
ES2389402T3 (en) | 2012-10-25 |
US20100276072A1 (en) | 2010-11-04 |
DK2290139T3 (en) | 2012-07-23 |
EP2290139B1 (en) | 2012-05-09 |
JP5079819B2 (en) | 2012-11-21 |
EP2261404A1 (en) | 2010-12-15 |
EP2115191B1 (en) | 2012-10-03 |
JP6066584B2 (en) | 2017-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8158217B2 (en) | CNT-infused fiber and method therefor | |
US9573812B2 (en) | CNT-infused metal fiber materials and process therefor | |
AU2010328139B2 (en) | CNT-infused fibers in thermoplastic matrices | |
US20110171469A1 (en) | Cnt-infused aramid fiber materials and process therefor | |
AU2010313613A1 (en) | CNT-infused ceramic fiber materials and process therefor | |
AU2012241120B2 (en) | CNT-infused fibre and method therefor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |