CNT-infused fiber and method therefor

Information

  • Patent Grant
  • 8158217
  • Patent Number
    8,158,217
  • Date Filed
    Wednesday, January 3, 2007
    18 years ago
  • Date Issued
    Tuesday, April 17, 2012
    12 years ago
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
FIELD OF THE INVENTION

The present invention relates to carbon nanotubes and fibers.


BACKGROUND OF THE INVENTION

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.


SUMMARY OF THE INVENTION

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 (Publication No. US 2004/0245088) 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.





BRIEF DESCRIPTION OF THE DRAWINGS


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.





DETAILED DESCRIPTION

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 of process 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 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. At this station, any “sizing” that is on fiber 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 in FIG. 2. Station 212 includes catalyst application station 214, fiber pre-heater station 216, plasma spray station 218, and fiber heaters 220.


As depicted in FIG. 2, sizing-free fiber 205 proceeds first to catalyst 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, onto fiber 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 at fiber 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 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. In some embodiments, heaters 220 are disposed above fiber 207 at the plasma sprayers to maintain the elevated temperature of the fiber.


After CNT-infusion, 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.


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 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. Again, 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 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 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.


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 without nanotube 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 with FIG. 2.


After passing through nanotube infusion section 226, 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. 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 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. As fiber tow 307 is pulled over the top of cylinder 330, it contacts the resin film and wets out. In some other embodiments, 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.


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 2309 separate until they are brought together in a single combined band on rotating mandrel 332.


Example

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
  • 1. A method of infusing carbon nanotubes on a parent fiber, the method comprising: spreading said parent fiber before disposing a carbon nanotube-forming catalyst on a surface of said parent fiber, thereby forming a catalyst-laden fiber;actively heating said catalyst-laden fiber to a nanotube-synthesis temperature;transporting said catalyst-laden fiber through a carbon plasma at atmospheric pressure, thereby synthesizing carbon nanotubes directly on said catalyst-laden fiber while being transported; andre-bundling the spread parent fiber after synthesizing carbon nanotubes thereon.
  • 2. The method of claim 1 further comprising removing a sizing material from said parent fiber before disposing said catalyst on said parent fiber.
  • 3. The method of claim 1 wherein said catalyst is a transition metal catalyst.
  • 4. The method of claim 1 wherein the operation of disposing said catalyst on said parent fiber further comprises: forming a solution of said catalyst in a liquid; andspraying said solution on to said parent fiber.
  • 5. The method of claim 1, wherein actively heating said catalyst-laden fiber comprises heating said catalyst-laden fiber to a softening temperature.
  • 6. The method of claim 1, wherein actively heating said catalyst-laden fiber comprises heating said catalyst-laden fiber to a temperature that is between about 500° C. and 1000° C.
  • 7. The method of claim 1 wherein said parent fiber is a carbon fiber and wherein actively heating said catalyst-laden fiber comprises heating to about 800° C.
  • 8. The method of claim 1 further comprising applying resin to said carbon nanotube-infused fiber.
  • 9. The method of claim 8 further comprising winding said carbon nanotube-infused fiber about a mandrel after applying said resin.
  • 10. The method of claim 8 wherein said parent fiber is selected from the group consisting of graphite tow and glass roving.
  • 11. The method of claim 1 further comprising synthesizing a first amount of said carbon nanotubes on said parent fiber, wherein said first amount is selected so that said carbon nanotube-infused fiber exhibits a second group of properties that differ from a first group of properties exhibited by said parent fiber.
  • 12. The method of claim 11 wherein said first group of properties and said second group of properties include at least some of the same properties, and further wherein a value of at least one of said same properties differs between said first group and said second group.
  • 13. The method of claim 11 wherein said second group of properties of said carbon nanotube-infused fiber includes a property that is not included among said first group of properties exhibited by said parent fiber.
  • 14. The method of claim 1 further comprising depositing a first amount of said carbon nanotubes, wherein said first amount is selected so that a value of at least one property selected from the group consisting of tensile strength, Young's Modulus, density, electrical conductivity, and thermal conductivity of said carbon nanotube-infused fiber differs from a value of said at least one property of said parent fiber.
  • 15. A method of infusing carbon nanotubes on a parent fiber having a sizing material, the method comprising: removing sizing material from said parent fiber;spreading said parent fiber before applying a carbon nanotube-forming catalyst on a surface of said parent fiber after sizing material removal, thereby forming a catalyst-laden fiber;heating said catalyst-laden fiber to at least 500° C.;synthesizing carbon nanotubes on said catalyst-laden fiber while the catalyst-laden fiber is being transported; andre-bundling the spread parent fiber after synthesizing carbon nanotubes thereon.
  • 16. The method of claim 1, wherein the carbon nanotubes are covalently bonded to the parent fiber.
  • 17. The method of claim 1, further comprising: generating the carbon plasma by passing a carbon containing gas through an electric field that is capable of ionizing the gas.
US Referenced Citations (234)
Number Name Date Kind
4515107 Fournier et al. May 1985 A
4530750 Alsenberg et al. Jul 1985 A
4707349 Hjersted Nov 1987 A
4920917 Nakatani et al. May 1990 A
5093155 Miyazaki et al. Mar 1992 A
5130194 Baker et al. Jul 1992 A
5173367 Liimatta et al. Dec 1992 A
5221605 Bard et al. Jun 1993 A
5238808 Bard et al. Aug 1993 A
5246794 Blomgren et al. Sep 1993 A
5310687 Bard et al. May 1994 A
5470408 Nielson et al. Nov 1995 A
5514217 Niino et al. May 1996 A
5547525 Bennett et al. Aug 1996 A
5571749 Matsuda et al. Nov 1996 A
5639984 Nielson Jun 1997 A
5714089 Bard et al. Feb 1998 A
5731147 Bard et al. Mar 1998 A
5908585 Shibuta Jun 1999 A
5968274 Fujioka et al. Oct 1999 A
5997832 Lieber et al. Dec 1999 A
6140138 Bard et al. Oct 2000 A
6184280 Shibuta Feb 2001 B1
6221154 Lee et al. Apr 2001 B1
6232706 Dai et al. May 2001 B1
6251520 Blizzard et al. Jun 2001 B1
6331209 Jang et al. Dec 2001 B1
6333016 Resasco et al. Dec 2001 B1
6361861 Gao et al. Mar 2002 B2
6413487 Resasco et al. Jul 2002 B1
6420293 Chang et al. Jul 2002 B1
6455021 Saito Sep 2002 B1
6465057 Nakahigashi et al. Oct 2002 B1
6479028 Kaner et al. Nov 2002 B1
6491789 Niu Dec 2002 B2
6495258 Chen et al. Dec 2002 B1
6528572 Patel et al. Mar 2003 B1
6564744 Nakahigashi et al. May 2003 B2
6653619 Chin et al. Nov 2003 B2
6673392 Lee et al. Jan 2004 B2
6692717 Smalley et al. Feb 2004 B1
6765949 Chang Jul 2004 B2
6790425 Smalley et al. Sep 2004 B1
6818821 Fujieda et al. Nov 2004 B2
6837928 Zhang et al. Jan 2005 B1
6852410 Veedu et al. Feb 2005 B2
6863942 Ren et al. Mar 2005 B2
6887451 Dodelet et al. May 2005 B2
6900264 Kumar et al. May 2005 B2
6900580 Dai et al. May 2005 B2
6908572 Derbyshire et al. Jun 2005 B1
6913075 Knowles et al. Jul 2005 B1
6934600 Jang et al. Aug 2005 B2
6936653 McElrath et al. Aug 2005 B2
6955800 Resasco et al. Oct 2005 B2
6962892 Resasco et al. Nov 2005 B2
6967013 Someya et al. Nov 2005 B2
6979709 Smalley et al. Dec 2005 B2
6986853 Glatkowski et al. Jan 2006 B2
6986877 Takikawa et al. Jan 2006 B2
6994907 Resasco et al. Feb 2006 B2
7011760 Wang et al. Mar 2006 B2
7018600 Yanagisawa et al. Mar 2006 B2
7022776 Bastiaens et al. Apr 2006 B2
7045108 Jiang et al. May 2006 B2
7056452 Niu et al. Jun 2006 B2
7074294 Dubrow Jul 2006 B2
7094386 Resasco et al. Aug 2006 B2
7105596 Smalley et al. Sep 2006 B2
7108841 Smalley et al. Sep 2006 B2
7118693 Glatkowski et al. Oct 2006 B2
7125534 Smalley et al. Oct 2006 B1
7132621 Kumar et al. Nov 2006 B2
7144563 Rao et al. Dec 2006 B2
7148619 Den et al. Dec 2006 B2
7151129 Ishikawa et al. Dec 2006 B2
7153452 Ogale et al. Dec 2006 B2
7157068 Li et al. Jan 2007 B2
7160532 Liu et al. Jan 2007 B2
7211320 Cooper et May 2007 B1
7226643 Juang et al. Jun 2007 B2
7235159 Gu et al. Jun 2007 B2
7253442 Huang et al. Aug 2007 B2
7261779 Gardner Aug 2007 B2
7265174 Carroll et al. Sep 2007 B2
7265175 Winey et al. Sep 2007 B2
7278324 Smits et al. Oct 2007 B2
7294302 Koide et al. Nov 2007 B2
7329698 Noguchi et al. Feb 2008 B2
7338684 Curliss et al. Mar 2008 B1
7354881 Resasco et al. Apr 2008 B2
7354988 Charati et al. Apr 2008 B2
7372880 Jablonski et al. May 2008 B2
7384663 Olry et al. Jun 2008 B2
7399794 Harmon et al. Jul 2008 B2
7407640 Barrera et al. Aug 2008 B2
7407901 Bystricky et al. Aug 2008 B2
7410628 Bening et al. Aug 2008 B2
7419601 Cooper et al. Sep 2008 B2
7431965 Grigorian et al. Oct 2008 B2
7445817 Kumar et al. Nov 2008 B2
7448441 Hendricks et al. Nov 2008 B2
7448931 Liu et al. Nov 2008 B2
7459627 Lee et al. Dec 2008 B2
7465605 Raravikar et al. Dec 2008 B2
7473466 Muradov Jan 2009 B1
7479052 Kim et al. Jan 2009 B2
7488455 Dai et al. Feb 2009 B2
7504078 Jacques et al. Mar 2009 B1
7510695 Smalley et al. Mar 2009 B2
7534486 Boerstoel et al. May 2009 B2
7563411 Jiang et al. Jul 2009 B2
7563428 Resasco et al. Jul 2009 B2
7569425 Huang et al. Aug 2009 B2
7588700 Kwon et al. Sep 2009 B2
7592248 Ventzek et al. Sep 2009 B2
7597869 Hsiao Oct 2009 B2
7608798 Kumar et al. Oct 2009 B2
7611579 Lashmore et al. Nov 2009 B2
7615204 Ajayan et al. Nov 2009 B2
7615205 Jiang et al. Nov 2009 B2
7632550 Mizuno et al. Dec 2009 B2
7632569 Smalley et al. Dec 2009 B2
7700943 Raravikar et al. Apr 2010 B2
7709087 Majidi et al. May 2010 B2
7718220 D'Silva et al. May 2010 B2
7771798 Grosse et al. Aug 2010 B1
7776777 Kim et al. Aug 2010 B2
7811632 Eres Oct 2010 B2
7815820 Tan et al. Oct 2010 B2
7816709 Balzano et al. Oct 2010 B2
7862795 Zhang et al. Jan 2011 B2
7871591 Harutyunyan et al. Jan 2011 B2
7880376 Takai et al. Feb 2011 B2
7927701 Curliss et al. Apr 2011 B2
20020035170 Glatkowski et al. Mar 2002 A1
20020085968 Smalley et al. Jul 2002 A1
20030042147 Talin et al. Mar 2003 A1
20030102585 Poulin et al. Jun 2003 A1
20030111333 Montgomery et al. Jun 2003 A1
20040007955 Yaniv et al. Jan 2004 A1
20040026234 Vanden Brande et al. Feb 2004 A1
20040082247 Desai et al. Apr 2004 A1
20040105807 Fan et al. Jun 2004 A1
20040184981 Liu et al. Sep 2004 A1
20040245088 Gardner Dec 2004 A1
20040253167 Silva et al. Dec 2004 A1
20050090176 Dean et al. Apr 2005 A1
20050100501 Veedu et al. May 2005 A1
20050112052 Gu et al. May 2005 A1
20050119371 Drzal et al. Jun 2005 A1
20050172370 Haq et al. Aug 2005 A1
20050176329 Olry et al. Aug 2005 A1
20050188727 Greywall Sep 2005 A1
20050260412 Gardner Nov 2005 A1
20050263456 Cooper et al. Dec 2005 A1
20050287064 Mayne et al. Dec 2005 A1
20060052509 Saitoh Mar 2006 A1
20060062944 Gardner et al. Mar 2006 A1
20060110599 Honma et al. May 2006 A1
20060121275 Poulin et al. Jun 2006 A1
20060159916 Dubrow et al. Jul 2006 A1
20060177602 Dijon et al. Aug 2006 A1
20060198956 Eres Sep 2006 A1
20070020167 Han et al. Jan 2007 A1
20070048521 Istvan Mar 2007 A1
20070054105 Hsiao Mar 2007 A1
20070092431 Resasco et al. Apr 2007 A1
20070110977 Al-Haik et al. May 2007 A1
20070128960 Nejhad et al. Jun 2007 A1
20070135588 Diakoumakos et al. Jun 2007 A1
20070189953 Bai et al. Aug 2007 A1
20070259128 Parsapour Nov 2007 A1
20080014431 Lashmore et al. Jan 2008 A1
20080020193 Jang et al. Jan 2008 A1
20080048364 Armeniades et al. Feb 2008 A1
20080053922 Honsinger, Jr. et al. Mar 2008 A1
20080075954 Wardle et al. Mar 2008 A1
20080118753 Poulin et al. May 2008 A1
20080160286 Asrar et al. Jul 2008 A1
20080160302 Asrar et al. Jul 2008 A1
20080170982 Zhang et al. Jul 2008 A1
20080182108 Curliss et al. Jul 2008 A1
20080187648 Hart et al. Aug 2008 A1
20080247938 Tsai et al. Oct 2008 A1
20080279753 Harutyunyan Nov 2008 A1
20080286564 Tsotsis Nov 2008 A1
20090017301 Moireau Jan 2009 A1
20090020734 Jang et al. Jan 2009 A1
20090047453 Folaron et al. Feb 2009 A1
20090047502 Folaron et al. Feb 2009 A1
20090068387 Panzer et al. Mar 2009 A1
20090068461 Reneker et al. Mar 2009 A1
20090072222 Radisic et al. Mar 2009 A1
20090081383 Alberding et al. Mar 2009 A1
20090081441 Shah et al. Mar 2009 A1
20090092832 Moireau Apr 2009 A1
20090099016 Carruthers et al. Apr 2009 A1
20090121219 Song et al. May 2009 A1
20090126783 Lin et al. May 2009 A1
20090136707 Ueno May 2009 A1
20090140098 Lengsfeld et al. Jun 2009 A1
20090176100 Higashi et al. Jul 2009 A1
20090176112 Kruckenberg et al. Jul 2009 A1
20090186214 Lafdi et al. Jul 2009 A1
20090191352 DuFaux et al. Jul 2009 A1
20090192241 Raravikar et al. Jul 2009 A1
20090212430 Wyland Aug 2009 A1
20090214800 Saito Aug 2009 A1
20090220409 Curliss et al. Sep 2009 A1
20090258164 Nakai et al. Oct 2009 A1
20090286079 Barker et al. Nov 2009 A1
20090294753 Hauge et al. Dec 2009 A1
20090311166 Hart et al. Dec 2009 A1
20100000770 Gupta et al. Jan 2010 A1
20100059243 Chang Mar 2010 A1
20100074834 Kim Mar 2010 A1
20100098931 Daniel et al. Apr 2010 A1
20100099319 Lashmore et al. Apr 2010 A1
20100178825 Shah et al. Jul 2010 A1
20100188833 Liang et al. Jul 2010 A1
20100192851 Shah et al. Aug 2010 A1
20100196697 D 'Silva et al. Aug 2010 A1
20100197848 Verghese et al. Aug 2010 A1
20100206504 Akiyama et al. Aug 2010 A1
20100210159 Zhu Aug 2010 A1
20100221424 Malecki et al. Sep 2010 A1
20100224129 Malecki et al. Sep 2010 A1
20100227134 Shah et al. Sep 2010 A1
20100254885 Menchhofer et al. Oct 2010 A1
20100272891 Malecki et al. Oct 2010 A1
20100276072 Shah et al. Nov 2010 A1
20100279569 Shah et al. Nov 2010 A1
20100311866 Huang et al. Dec 2010 A1
Foreign Referenced Citations (17)
Number Date Country
101698975 Apr 2010 CN
01900DE2008 Mar 2010 IN
100829001 May 2008 KR
200833861 Aug 2008 TW
03082733 Oct 2003 WO
WO2006048531 May 2006 WO
WO2006115486 Nov 2006 WO
WO 2007015710 Feb 2007 WO
WO2007061854 May 2007 WO
WO2007089118 Aug 2007 WO
WO2007149109 Dec 2007 WO
WO2008041183 Apr 2008 WO
WO2008054541 May 2008 WO
WO2008085634 Jul 2008 WO
WO2008115640 Sep 2008 WO
WO 2009004346 Jan 2009 WO
2009110885 Sep 2009 WO
Related Publications (1)
Number Date Country
20100276072 A1 Nov 2010 US