Systems and methods for formation and harvesting of nanofibrous materials

Information

  • Patent Grant
  • 10029442
  • Patent Number
    10,029,442
  • Date Filed
    Friday, February 27, 2015
    9 years ago
  • Date Issued
    Tuesday, July 24, 2018
    5 years ago
Abstract
A system that receives nanomaterials, forms nanofibrous materials therefrom, and collects these nanofibrous materials for subsequent applications. The system include a housing coupled to a synthesis chamber within which nanotubes are produced. A spindle may extend from within the housing, across the inlet, and into the chamber for collecting nanotubes and twisting them into a yarn. A body portion may be positioned at an intake end of the spindle. The body portion may include a pathway for imparting a twisting force onto the flow of nanotubes and guide them into the spindle for collection and twisting into the nanofibrous yarn. Methods and apparatuses for forming nanofibrous are also disclosed.
Description
TECHNICAL FIELD

The present invention relates to systems for formation and harvesting of nanofibrous materials, and more particularly to the formation of yarns and non-woven sheets from nanotubes, nanowires, or other filamentous structures having nanoscale dimensions.


BACKGROUND ART

Carbon nanotubes are known to have extraordinary tensile strength, including high strain to failure and relatively high tensile modulus. Carbon nanotubes may also be highly resistant to fatigue, radiation damage, and heat. To this end, the addition of carbon nanotubes to composite materials can increase tensile strength and stiffness of the composite materials.


Within the last fifteen (15) years, as the properties of carbon nanotubes have been better understood, interests in carbon nanotubes have greatly increased within and outside of the research community. One key to making use of these properties is the synthesis of nanotubes in sufficient quantities for them to be broadly deployed. For example, large quantities of carbon nanotubes may be needed if they are to be used as high strength components of composites in macroscale structures (i.e., structures having dimensions greater than 1 cm.)


One common route to nanotube synthesis can be through the use of gas phase pyrolysis, such as that employed in connection with chemical vapor deposition. In this process, a nanotube may be formed from the surface of a catalytic nanoparticle. Specifically, the catalytic nanoparticle may be exposed to a gas mixture containing carbon compounds serving as feedstock for the generation of a nanotube from the surface of the nanoparticle.


Recently, one promising route to high-volume nanotube production has been to employ a chemical vapor deposition system that grows nanotubes from catalyst particles that “float” in the reaction gas. Such a system typically runs a mixture of reaction gases through a heated chamber within which the nanotubes may be generated from nanoparticles that have precipitated from the reaction gas. Numerous other variations may be possible, including ones where the catalyst particles may be pre-supplied.


In cases where large volumes of carbon nanotubes may be generated, however, the nanotubes may attach to the walls of a reaction chamber, resulting in the blockage of nanomaterials from exiting the chamber. Furthermore, these blockages may induce a pressure buildup in the reaction chamber, which can result in the modification of the overall reaction kinetics. A modification of the kinetics can lead to a reduction in the uniformity of the material produced.


An additional concern with nanomaterials may be that they need to be handled and processed without generating large quantities of airborne particulates, since the hazards associated with nanoscale materials are not yet well understood.


The processing of nanotubes or nanoscale materials for macroscale applications has steadily increased in recent years. The use of nanoscale materials in textile fibers and related materials has also been increasing. In the textile art, fibers that are of fixed length and that have been processed in a large mass may be referred to as staple fibers. Technology for handling staple fibers, such as flax, wool, and cotton has long been established. To make use of staple fibers in fabrics or other structural elements, the staple fibers may first be formed into bulk structures such as yarns, tows, or sheets, which then can be processed into the appropriate materials.


Long nanotubes, which may have dimensions of 20 nm or less in diameter and 10 microns or more in length, can have relatively high aspect ratios. These nanotube fibers, when produced in large quantities from, for instance, chemical vapor deposition, may be used as a new source of staple fibers despite being smaller than most other textile staple fibers.


Accordingly, it would be desirable to provide a system and an approach to collect and handle synthesized nanotubes that can minimize the generation air-borne particulates, and in such a way as to permit processing of the nanotubes into a fibrous material of high strength for subsequent incorporation into various applications, structural or otherwise.


SUMMARY OF THE INVENTION

The present invention, in one embodiment, provides a system for forming nanofibrous materials, such as yarn. The system includes a housing having an inlet for engaging an independent synthesis chamber within which nanotubes may be produced. The system also includes a spindle having an intake end, an opposing outlet end, and a pathway therebetween. In an embodiment, the spindle extends from within the housing, across the inlet and into the chamber for collecting the nanotubes through the intake end and for subsequently twisting the nanotubes into a nanofibrous yarn. The system further includes a spool positioned within the housing and downstream of the spindle for winding thereonto the yarn from the spindle. A sensor system can also be provided to generate feedback data to control a rate of spin of the spindle and spool, so as to avoid compromising the integrity of the yarn as it is being wound about the spool. In one embodiment, a guide arm may be provided between the spindle and spool to direct the yarn exiting from the spindle onto the spool for subsequent winding.


The present invention provides, in another embodiment, a system for forming a nanofibrous non-woven sheet. The system includes a housing having an inlet for engaging an independent synthesis chamber within which nanotubes may be produced. The system also includes a moving surface positioned adjacent the inlet within the housing for collecting and transporting the nanotubes flowing from the synthesis chamber. A pressure applicator may be situated adjacent the moving surface to apply a force against the collected nanotubes on the moving surface, so as to compact the nanotubes into a non-woven sheet of intermingled nanotubes. The system further includes a spool positioned within the housing and downstream of the pressure applicator for winding thereonto the non-woven sheet. A separator may also be provided to apply a material on to one side of the non-woven sheet prior to the sheet being wound about the spool to minimize bonding of the non-woven sheet to itself. The system can also include a sensor system to generate feedback data to control a rate of spin of the moving surface and spool, so as to avoid compromising the integrity of the yarn as it is being wound about the spool.


The present invention, in a further embodiment, provides a method for forming a nanofibrous yarn. The method includes receiving a plurality of synthesized nanotubes moving substantially in one direction. The environment may be an airtight environment. In an embodiment, prior to receiving, a vortex flow may be imparted on to the nanotubes so as to provide an initial twisting. Next, the nanotubes may be twisted together into a yarn in a direction substantially transverse to the direction of movement of the nanotubes. Thereafter, the yarn may be moved toward an area for harvesting and subsequently harvested by winding the yarn about an axis substantially transverse to a direction of movement of the yarn. The rate of winding may be controlled so as to avoid compromising the integrity of the yarn.


The present invention also provides a method for forming a nanofibrous non-woven sheet. The method includes depositing a plurality of synthesized nanotubes onto a surface and subsequently transporting the nanotubes away from a point of deposition. Next, pressure may be applied onto the plurality of nanotubes against the surface, so as to compact the nanotubes into a non-woven sheet of intermingled nanotubes. The non-woven sheet may then be directed toward an area for harvesting. In an embodiment, a material may be put onto one side of the non-woven sheet to prevent the sheet from bonding to itself. The non-woven sheet may subsequently be harvested by winding the sheet about an axis substantially transverse to a direction of movement of the sheet. In an embodiment, The rate of winding may be controlled so as to avoid compromising the integrity of the non-woven sheet.


The present invention, in a further embodiment, provides an apparatus for presenting synthesized nanotubes in a twisting manner for subsequent formation of nanofibrous materials. The apparatus includes a body portion having a pathway through which synthesized nanotubes may flow. The apparatus may also include a cap portion attached to a distal end of the body portion and having an opening through which the nanotubes may exit. A channel may be situated between the cap portion and the body portion circumferentially about the pathway. The apparatus may further include a plurality of exit ports, positioned within the channel, in fluid communication with the pathway, so as to impart a vortex flow into the pathway. In this way, nanotubes flowing through the pathway can be presented in a twisting manner after exiting the distal end of the body portion.


The present invention also provides another apparatus for presenting synthesized nanotubes for subsequent formation of nanofibrous materials. The apparatus includes a disc having a proximal end and a distal end. A passageway, in one embodiment, extends between the proximal end and a distal end. The apparatus also includes a constricted portion at the distal end of the passageway to permit accumulation of the nanotubes thereat. To that end, the constricted portion at the distal end may provide a source from which nanotubes may be presented for subsequent formation of nanofibrous materials.





BRIEF DESCRIPTION OF DRAWINGS


FIG. 1 illustrates a system for formation and harvesting of nanofibrous materials in accordance with one embodiment of the present invention.



FIG. 2 illustrates a variation of the system shown in FIG. 1.



FIG. 3 A-B illustrate a vortex generator for use in connection with the system shown in FIG. 1.



FIG. 4A illustrates another variation of the system shown in FIG. 1. FIG. 4B illustrates anchor 40 according to some embodiments of the invention.



FIGS. 5-6 illustrate another system of the present invention for formation and harvesting of nanofibrous materials.



FIGS. 7 A-B illustrate another vortex generator for use in connection with the system shown in FIG. 1.





DESCRIPTION OF SPECIFIC EMBODIMENTS

Nanotubes for use in connection with the present invention may be fabricated using a variety of approaches. Presently, there exist multiple processes and variations thereof for growing nanotubes. These include: (1) Chemical Vapor Deposition (CVD), a common process that can occur at near ambient or at high pressures, (2) Arc Discharge, a high temperature process that can give rise to tubes having a high degree of perfection, and (3) Laser ablation. It should be noted that although reference is made below to nanotube synthesized from carbon, other compound(s) may be used in connection with the synthesis of nanotubes for use with the present invention.


The present invention, in one embodiment, employs a CVD process or similar gas phase pyrolysis procedures well known in the industry to generate the appropriate nanotubes. In particular, since growth temperatures for CVD can be comparatively low ranging, for instance, from about 600° C. to about 1300° C., carbon nanotubes, both single wall (SWNT) or multiwall (MWNT), may be grown, in an embodiment, from nanostructural catalyst particles supplied by reagent carbon-containing gases (i.e., gaseous carbon source).


Moreover, the strength of the SWNT and MWNT generated for use in connection with the present invention may be about 30 GPa maximum. Strength, as should be noted, is sensitive to defects. However, the elastic modulus of the SWNT and MWNT fabricated for use with the present invention is typically not sensitive to defects and can vary from about 1 to about 1.5 TPa. Moreover, the strain to failure, which generally can be a structure sensitive parameter, may range from a few percent to a maximum of about 10% in the present invention.


Referring now to FIG. 1, there is illustrated a system 10 for collecting and extended length nanotubes produced by a CVD process within a synthesis chamber 11, and for subsequently forming fibrous structures or materials, such as yarn, from the nanotubes. Synthesis chamber 11, in general, includes an entrance end 111, into which reaction gases may be supplied, a hot zone 112, where synthesis of extended length nanotubes 113 may occur, and an exit end 114 from which the products of the reaction, namely the extended length nanotubes 113 and exhaust gases, may exit and be collected. In one embodiment, synthesis chamber 11 may be a quartz tube 115, extending through a furnace 116, and may include flanges 117 provided at exit end 114 and entrance end 114 for sealing tube 115. Although illustrated as such in FIG. 1, it should be appreciated that other configurations may be employed in the design of synthesis chamber 11.


System 10, in one embodiment of the present invention, includes a housing 12. Housing 12, as illustrated in FIG. 1, may be substantially airtight to minimize the release of potentially hazardous airborne particulates generated from within the synthesis chamber 11 into the environment, and to prevent oxygen from entering into the system 10 and reaching the synthesis chamber 11. It should be appreciated that the presence of oxygen within the synthesis chamber 11 can compromise the production and affect the integrity of the extended nanotubes 113.


System 10 also include an inlet 13 for engaging the flanges 117 at exit end 114 of synthesis chamber 11 in a substantially airtight manner. In one embodiment, inlet 13 may include at least one gas exhaust 131 through which gases and heat may leave the housing 12. Gas exiting from exhaust 131, in an embodiment, may be allowed to pass through a liquid, such as water, or a filter to collect nanomaterials not gathered on to a rotating spindle 14 upstream of the exhaust 10. In addition, the exhaust gas may be exposed to a flame and air in order to de-energize various components of the exhaust gas, for instance, reactive hydrogen may be oxidized to form water.


Rotating spindle 14, as shown in FIG. 1, may be designed to extend from within housing 12, through inlet 13, and into synthesis chamber 11 for collection of extended length nanotubes 113. In an embodiment, rotating spindle 14 may include an intake end 141 into which a plurality of nanotubes may enter and be spun into a yarn 15. In an embodiment, the direction of spin may be substantially transverse to the direction of movement of the nanotubes 113. Rotating spindle 14 may also include a pathway, such as hollow core 142, along which yarn 15 may be guided toward outlet end 143 of spindle 14. The intake end 141 of rotating spindle 14 may include a variety of designs. In one embodiment, intake end 141 may simply include an aperture (not shown) through which the nanotubes 113 may enter. Alternatively, it may include a funnel-like structure 144 that may serve to guide the nanotubes 113 into the intake end 141. Structure 144 can also serve to support yarn 15, should it break, until such time that it might be able to reconstitute itself from the twisting with newly deposited nanotubes 113. In one embodiment, a roller, capstan or other restrictive devices (not shown) may be provided adjacent the intake end 141 of spindle 14 in order to: (1) serve as a point from which yarn 15 may be twisted, and (2) prevent springiness in yarn 15 from pulling the yarn too quickly into the core 142 of spindle 14, which can prevent yarn 15 from re-forming if it were to break.


System 10 further includes a guide arm 16 which may be coupled to the outlet end 143 of rotating spindle 14 to guide and direct yarn 15 toward a spool 17 for gathering thereon. In accordance with one embodiment of the present invention, a set of pulleys 161, eyelets, or hooks may be provided as attachments to the guide arm 16 to define a path on which yarn 15 may be directed along the guide arm 16. Alternatively, yarn 15 may be permitted to pass through a tubular structure (not shown) that can direct yarn 15 from the outlet end 143 of spindle 14 to a point from which yarn 15 may be wound onto spool 17.


Guide arm 16 and rotating spindle 14, in an embodiment, may work together to induce twisting in yarn 15. The rotation of spindle 14 and guide arm 16, as shown in FIG. 1, may be mechanically driven, for example, by an electric motor 18 coupled to the spindle 14 via a belt 181, for instance.


Spool 17, situated within housing 12, may be positioned, in one embodiment, downstream of guide arm 16 for the harvesting of yarn 15. In particular, yarn 15 advancing from guide arm 16 may be directed on to a spinning spool 17, such that yarn 15 may thereafter be wound circumferentially about spool 17. Although shown to be in axial alignment with rotating spindle 14, it should be appreciated that spool 17 may be placed at any other location within housing 12, so long as spool 17 may be spun about its axis to collect yarn 15 from guide arm 16. In an embodiment the axis of spin of spool 17 may be substantially transverse to the direction of movement of yarn 15 onto spool 17.


To impart rotation to spool 17, an additional mechanical drive 19 may be coupled to spool 17. In one embodiment, spool 17 may be synchronized to spin or rotate near or at substantially a similar rotation rate as that of spindle 14 to permit uniform harvesting of yarn 15 on to spool 17. Otherwise, if, for instance, the rate of rotation of spool 17 is faster than that of spindle 14, breakage of yarn 15 from guide arm 16 to spool 17 may occur, or if the rate is slower than that of spindle 14, loose portions from yarn 15 may end up entangled.


To maintain substantial synchronization of rotation rates, movement of mechanical drives 18 and 19 may be adjusted by a control system (not shown). In one embodiment, the control system may be designed to receive data from position sensors, such as optical encoders 182, attached to each of mechanical drives 17 and 18. Subsequently, based on the data, the control system may use a control algorithm in order to modify power supplied to each drive in order to control the rate of each drive so that they substantially match the rate of nanotube synthesis. As a result, the control system can impart: (1) constant yarn velocity controlled by set tension limits, or (2) constant tension controlled by velocity limits. In one embodiment, the yarn velocity can be reset in real time depending on the tension values, so that the tension may be kept within a preset limit. In addition, the yarn tension can be reset in real time depending on the velocity values, so that the tension can be kept within a set value.


The control system can also vary the rate between the spool 17 and spindle 14, if necessary, to control the yarn up-take by the spool 17. In addition, the control system can cause the spool 17 to move back and forth along its axis, so as to permit the yarn 15 to be uniformly wound thereabout.


In operation, under steady-state production using a CVD process of the present invention, extended length nanotubes may be collected from within the synthesis chamber 11 and yarn 15 may thereafter be formed. In particular, as the nanotubes 113 emerge from the synthesis chamber 11, they may be collected into a bundle, fed into the intake end 141 of spindle 14, and subsequently spun or twist into yarn 15 therewithin. It should be noted that a continual twist to yarn 15 can build up sufficient angular stress to cause rotation near a point where new nanotubes 113 arrive at the spindle 14 to further the yarn formation process. Moreover, a continual tension may be applied to yarn 15 or its advancement may be permitted at a controlled rate, so as to allow its uptake circumferentially about spool 17.


Typically, the formation of yarn 15 results from a bundling of nanotubes 113 that may subsequently be tightly spun into a twisting yarn. Alternatively, a main twist of yarn 15 may be anchored at some point within system 10 and the collected nanotubes 113 may be wound on to the twisting yarn 15. Both of these growth modes can be implemented in connection with the present invention.


Looking now at FIG. 2, a vortex generator, such as gas-spinner 20, may be provided toward the exit end 114 of synthesis chamber 11 to generate a substantial vortex flow in order to impart a twisting motion to the nanotubes 113 prior to being directed into spindle 14 and spun into yarn 15. The generation of a vortex to impart twisting motion may also serve to even out an amount of nanotube material used in the formation of yarn 15. Gas-spinner 20, as illustrated in FIGS. 3A-B, may be designed to include a cap portion 31, a body portion 32, and a channel 33 positioned circumferentially about the gas-spinner 20 between the cap portion 31 and body portion 32.


The cap portion 31, in an embodiment, includes a duct 311 through which an inert gas from a supply line 312 may enter into channel 33 of the gas-spinner 30 for subsequent generation of a vortex flow. Examples of an inert gas for use in connection with the gas-spinner 20 includes, He, Ar or any other suitable inert gases.


The body portion 32, on the other hand, includes an axisymmetric pathway 321, through which gas (i.e., fluid) and fibrous nanomaterials (i.e., nanotubes 113) generated from hot zone 112 of the synthesis chamber 11 may flow (arrows 35 in FIG. 3A). In one embodiment, pathway 321 includes a tapered portion 322 adjacent a proximal end 325 of the body portion 32 and a substantially uniform portion 323 adjacent a distal end 326 of the body portion 32. With such a design, the tapered portion 322 and the uniform portion 323 can act together to minimize over-accumulation or build-up of nanotubes 113 upstream of the spindle 14. Specifically, pathway 321 can act to guide the nanotubes 113 into the tapered portion 322 and across the uniform portion 323, so that nanotubes 113 generated from the synthesis chamber 11 may avoid being caught on sharp edges or other protruding obstructions within the synthesis chamber 11. To permit nanotubes to exit from pathway 321, cap portion 31 includes an opening 313, in substantial axial alignment with the uniform portion 323 of pathway 321.


The body portion 32 may also include a recess 324, which upon an engagement between the body portion 32 and cap portion 31, becomes channel 33. The body portion 32 may further include exit ports 325 positioned within recess 324. In one embodiment, exit ports 325 may be symmetrically distributed about the uniform portion 323 to subsequently generate, within the uniform portion 323 of pathway 321, a vortex flow from the inert gas previously introduced into channel 33. It should be appreciated that since vortex flow requires a tangential velocity vector component around a given axis, e.g., axis of symmetry of gas-spinner 30, in order to provide this tangential velocity component, the exit ports 325, as illustrated in FIG. 3B, may need to be positioned in a plane normal to the axis of symmetry, and in such a way that each exit port 325 enters the uniform portion 323 of the pathway 321 at a substantially non-perpendicular angle. In other words, each exit port 325 needs to be in tangential communication with the pathway 321, so that fluid (e.g., inert gas) within channel 33, when permitted to move across each exit port 325, can flow into the uniform portion 323 of pathway 321 in a tangential manner.


It should also be appreciated that by providing a solid constriction to the flow of gas and generated nanomaterials, the gas-spinner 20 can also allow substantial freedom in defining yarn and tow formation modes for system 10 of the present invention. Moreover, to the extent necessary, gas-spinner 20 can provide an area where nanotubes 113 may accumulate, particularly when the gas supplied through the gas-spinner 20 is at a low flow rate to create a source from which nanotubes 113 may be pulled, such as that by a leader (see description below) to subsequently twist into yarn 15.


In an alternate embodiment, a different vortex generator, such electrostatic spinner 70, as illustrated in FIGS. 7A-B, may be used to impart a substantial vortex flow to the nanotubes 113 prior to directing the nanotubes 113 into spindle 14 where they may be spun into yarn 15. Electrostatic spinner 70, in an embodiment, includes a substantially tubular body 71 having an entry end 72, an exit end 73, and a pathway 74 extending therebetween. The electrostatic spinner 70 may also include a plurality of electrical contacts 75 situated circumferentially about the pathway 74. Each contact 75 includes a positive end +V and a negative end −V, and can be made from a metallic material, such as copper. In this regard, a voltage may be applied to each of the contacts 75 to generate an electric field. Moreover, as voltage may be applied to each contact 75 in succession, a rotating electrostatic field may be generated. Since the nanotubes 113 have a substantially high aspect ratio and since they can be conductors, the nanotubes 113 may be attracted to the electrostatic field and move in a vortex or winding manner as the field moves about the pathway 74. It should be noted that the winding motion imparted to the nanotubes 113 may be substantially transverse to the direction along which the nanotubes 113 may move from the entry end 72 to the exit end 73 of the body portion 71. To control the application of voltage to each successive contact 75, any commercially available controller chip or processor may be used.


In accordance with one embodiment of the present invention, at the inception of formation of yarn 15, it may be beneficial to start the yarn with a “leader.” This leader, for example, may be an additional piece of nanotube yarn, some other type of yarn or filament, or a thin wire. In an embodiment, a wire may be used because it can provide the requisite stiffness necessary to transfer the twisting motion of the spindle 14 to the accumulating webbing or bundle of nanotubes 113 until there exist a sufficient build-up, such that the wire can tether an end of a growing yarn. The wire used, in one embodiment, may be, for example, a ferrous wire or nichrome, since these alloys can withstand the temperature within the hot zone (600° C.-1300° C.) of the synthesis chamber 11. Moreover, nanotubes produced via a CVD process have been observed to adhere relatively well to these alloys. In particular, since catalytic nanoparticles at the end of the nanotubes 113 may include ferromagnetic materials, such as Fe, Co, Ni, etc., these nanoparticles can magnetically attract to the magnetic domains on the ferrous alloy materials.


To the extent that a leader is provided, it may be necessary to pre-thread the leader before the start of the reaction. Specifically, a hole, in one embodiment, may provided in the spool 17 to serve as an anchor point for one end of the leader. Additionally, notches or slots may be provided in the guide pulleys 161 to permit the leader to be easily inserted into the guide arm 16. The leader may then be inserted into the spindle 14, and thereafter advanced into the synthesis chamber 11 upstream to gas-spinner 20, should one be employed.


Looking at FIG. 4, when using a leader, an anchor 40 may be provided in place of gas-spinner 20 to provide a source from which the leader can pull nanotubes into the spindle 14 to initiate the yarn making process. In an embodiment, anchor 40 may be positioned toward the exit end 114 of synthesis chamber 11 to constrict the flow of gas and nanotubes 113 so that an accumulation of nanotubes 113 can be generated within the anchor 40. To do so, anchor 40 may be designed as a disc having a distal end 41, a proximal end 42, and a passageway 44 extending therebetween. As illustrated in FIG. 4, passageway 44 may taper from the proximal end 42 toward the distal end 41. In this manner, when nanotubes 113 enter passageway 44 toward constricted portion 45, the constricted portion 45 may act to accumulate nanotubes 113 thereat to provide a source for the leader. Although provided as being tapered or toroidal in shape, it should be appreciated that passageway 44 of anchor 40 may be designed to include a variety of forms, so long as it works to constrict the flow of gas and nanotubes 113 in chamber 11.


To enhance the accumulation of nanotubes there at, projections (not shown) or other similar designs may be provided at the constricted portion 45 to provide a surface to which a webbing or bundle of nanotubes 113 can attach. In one embodiment, anchor 40 can be positioned near furnace 116 where the nanotubes 113 may have a relatively greater tendency to adhere to solid surfaces. As it may be near furnace 16, anchor 40 may be made, in an embodiment, from a graphite material or any other material that would withstanding heat from furnace 16.


Assuming that the nanotubes 113 can be produced at a constant rate, the design and location of anchor 40 near furnace 116 can permit the nanotubes 113 to accumulate thereon at a uniform rate. To that end, a controlled source of nanotubes 113 may be generated for subsequent collection and formation of yarn 15 having substantially uniform properties. Furthermore, anchor 40 can act to provide a point from which the nanotubes 113 can be pulled to permit substantial alignment of the nanotubes 113 in a direction substantially coaxial with yarn 15. The ability to align the nanotubes 113 along an axis of yarn 15 can enhance load transfer between the nanotubes 113 to allow for the formation of a high strength yarn 15. Nevertheless, it should be appreciated that yarn 15 can be formed regardless of whether anchor 40 is present.


Synthesis and harvesting of yarn 15 may subsequently be initiated by causing the spool 17, spindle 14, guide arm 16, and leader to rotate. In one embodiment, after initiating the synthesis of nanotubes 113, the nanotubes 113 may be directed toward the leader to permit build-up or bundling of the nanotubes 113 thereon. Thereafter, once a webbing or bundling of nanotubes 113 begins to build up on the leader, and the leader can be withdrawn by causing the spool 17 to rotate at a slightly different rate than the spindle 14 and guide arm 16. The formation of the nanotube yarn 15, as described above, may proceed automatically thereafter once the leader has been withdrawn sufficiently from the hot zone 112 of synthesis chamber 11. In particular, the webbing of nanotubes 113 may be twisted into a yarn 15 at a point near the intake end 141 of spindle 14. The twisted portions of yarn 15 may then be allowed to move along the core 142 towards the outlet end 143 of spindle 14. Upon exiting the outlet end 143, the yarn 15 may be guided along guide arm 16 and directed toward the spool 17. The yarn 15 may thereafter be wound about spool 17 at a controlled rate.


In accordance with another embodiment, the system 10 may also be used for continuous formation of a tow (not shown) from nanotubes 113 synthesized within synthesis chamber 11. This tow may be later processed into a tightly wound yarn, similar to technologies common in the art of thread and yarn formation. In one embodiment, the tow may be collected using the hollow spindle 14, guide arm 16 and spool 17, as described above. The formed tow may extend from the spool 17, through the guide arm 16 and spindle 14 into the synthesis chamber 11 near the exit end 114. Nanotubes 113, in an embodiment, may accumulate on the tow by winding around the tow, as the tow spins rapidly and is slowly withdrawn. An anchor may not required for this mode of operation. However, should it be necessary to provide a point to which the growing end of the spinning tow may attach, an anchor may be used.


The formation of a yarn or tow in accordance with one embodiment of the present invention provides an approach to producing a relatively long fibrous structure capable of being employed in applications requiring length. In particular, the twisting action during formation of the yarn allows the staple fibers (i.e., nanotubes) to be held together into the larger fibrous structure (i.e., yarn). Additionally, the twisting of axially aligned fibers (i.e., nanotubes) can enhance load transfer between the fibers to allow for the formation of a high strength yarn.


Specifically, staple fibers, such as the nanotubes synthesized by the process of the present invention, can be provided with a high aspect ratio (e.g., >100:1 length:diameter). As a result, they can serve better than those with smaller aspect ratios to transfer structural loads between individual fibers within a yarn. While fibers with essentially infinite aspect ratio would be ideal, the length scale of structures in which the yarn may be incorporated better defines the length and aspect ratios required of the constituent fibers. For example, if it is necessary to bridge a distance of only one to two centimeters, fibers much longer than this distance may not required. Furthermore, within a yarn, load transfer typically occurs as an interaction between each of the contact points of adjacent fibers. At each contact point, each fiber may interact via, for example, a van der Waal's bond, hydrogen bond, or ionic interaction. As such, the presence of a plurality of fibers in the yarn of the present invention can increase the number of contact points and thus the bonding interaction between adjacent fibers to enhance load transfer between the fibers. Moreover, since twisting can further increase the number of contact points between constituent fibers in a yarn by forcing individual fibers closer together, it can be advantageous to the overall strength of the yarn to impart twisting. In this regard, the ability to independently control twisting and up-take velocity can be important in order to optimize strength.


The strength of the yarn can further be enhanced by increasing the bond strength between adjacent fibers. In one embodiment, the yarn may be impregnated with a matrix material, such as a polymer, or a surfactant molecule to crosslink adjacent fibers. Crosslinking the fibers using covalent or ionic chemical bonds can provide an additional means of improving the overall strength of the yarn.


It should be noted that since the number of contact points increases the opportunities for phonon or electron to transfer between adjacent nanotubes, the imparting of a twist to the yarn can also enhance the electrical and thermal conductivity of the yarn of the present invention.


With reference now to FIGS. 5-6, there is illustrated, in accordance with another embodiment of the present invention, a system 50 for collecting synthesized nanotubes made from a CVD process within a synthesis chamber 51, and for subsequently forming bulk fibrous structures or materials from the nanotubes. In particular, system 50 may be used in the formation of a substantially continuous non-woven sheet generated from compacted and intermingled nanotubes and having sufficient structural integrity to be handled as a sheet.


System 50, like system 10, may be coupled to a synthesis chamber 51. Synthesis chamber 51, in general, includes an entrance end, into which reaction gases may be supplied, a hot zone, where synthesis of extended length nanotubes may occur, and an exit end 514 from which the products of the reaction, namely the extended length nanotubes and exhaust gases, may exit and be collected. In one embodiment, synthesis chamber 51 may include a quartz tube 515, extending through in a furnace and may include flanges 517 provided at exit end 514 and entrance end for sealing tube 515. Although illustrated generally in FIG. 5, it should be appreciated that other configurations may be employed in the design of synthesis chamber 51.


System 50, in one embodiment of the present invention, includes a housing 52. Housing 52, as illustrated in FIG. 5, may be substantially airtight to minimize the release of potentially hazardous airborne particulates from within the synthesis chamber 51 into the environment, and to prevent oxygen from entering into the system 50 and reaching the synthesis chamber 51. In particular, the presence of oxygen within the synthesis chamber 51 can affect the integrity and compromise the production of the nanotubes.


System 50 may also include an inlet 53 for engaging the flanges 517 at exit end 514 of synthesis chamber 51 in a substantially airtight manner. In one embodiment, inlet 53 may include at least one gas exhaust 531 through which gases and heat may leave the housing 52. Gas exiting from exhaust 531, in an embodiment, may be allowed to pass through a liquid, such as water, or a filter to collect nanomaterials not gathered upstream of the exhaust 531. In addition, the exhaust gas may be treated in a manner similar to that described above. Specifically, the exhaust gas may be treated with a flame in order to de-energize various components of the exhaust gas, for instance, reactive hydrogen may be oxidized to form water.


System 50 may further include a moving surface, such as belt 54, situated adjacent inlet 53 for collecting and transporting the nanomaterials, i.e., nanotubes, from exit end 514 of synthesis chamber 51. To collect the nanomaterials, belt 54 may be positioned at an angle substantially transverse to the flow of gas carrying the nanomaterials from exit end 514 to permit the nanomaterials to be deposited on to belt 54. In one embodiment, belt 54 may be positioned substantially perpendicularly to the flow of gas and may be porous in nature to allow the flow of gas carrying the nanomaterials to pass therethrough and to exit from the synthesis chamber 51. The flow of gas from the synthesis chamber 51 may, in addition, exit through exhaust 531 in inlet 53.


To carry the nanomaterials away from the inlet 53 of system 50, belt 54 may be designed as a continuous loop similar to a conventional conveyor belt. To that end, belt 54, in an embodiment, may be looped about opposing rotating elements 541 and may be driven by a mechanical device, such as an electric motor 542, in a clockwise manner, as illustrated by arrows 543. Alternatively, a drum (not shown) may be used to provide the moving surface for transporting the nanomaterial. Such a drum may also be driven by a mechanical device, such as electric motor 542. In an embodiment, motors 542 may be controlled through the use of a control system, similar to that used in connection with mechanical drives 18 and 19, so that tension and velocity can be optimized.


Still looking at FIG. 5, system 50 may include a pressure applicator, such as roller 55, situated adjacent belt 54 to apply a compacting force (i.e., pressure) onto the collected nanomaterials. In particular, as the nanomaterials get transported toward roller 55, the nanomaterials on belt 54 may be forced to move under and against roller 55, such that a pressure may be applied to the intermingled nanomaterials while the nanomaterials get compacted between belt 54 and roller 55 into a coherent substantially-bonded non-woven sheet 56 (see FIG. 6). To enhance the pressure against the nanomaterials on belt 54, a plate 544 may be positioned behind belt 54 to provide a hard surface against which pressure from roller 55 can be applied. It should be noted that the use of roller 55 may not be necessary should the collected nanomaterials be ample in amount and sufficiently intermingled, such that an adequate number of contact sites exists to provide the necessary bonding strength to generate the non-woven sheet 56.


To disengage the non-woven sheet 56 of intermingled nanomaterials from belt 54 for subsequent removal from housing 52, a scalpel or blade 57 may be provided downstream of the roller 55 with its edge against surface 545 of belt 54. In this manner, as non-woven sheet 56 moves downstream past roller 55, blade 57 may act to lift the non-woven sheet 56 from surface 545 of belt 54.


Additionally, a spool or roller 58 may be provided downstream of blade 57, so that the disengaged non-woven sheet 56 may subsequently be directed thereonto and wound about roller 58 for harvesting. Of course, other mechanisms may be used, so long as the non-woven sheet 56 can be collected for removal from the housing 52 thereafter. Roller 58, like belt 54, may be driven, in an embodiment, by a mechanical drive, such as an electric motor 581, so that its axis of rotation may be substantially transverse to the direction of movement of the non-woven sheet 56.


In order to minimize bonding of the non-woven sheet 56 to itself as it is being wound about roller 58, a separation material 59 (see FIG. 6) may be applied onto one side of the non-woven sheet 56 prior to the sheet 56 being wound about roller 58. The separation material 59 for use in connection with the present invention may be one of various commercially available metal sheets or polymers that can be supplied in a continuous roll 591. To that end, the separation material 59 may be pulled along with the non-woven sheet 56 onto roller 58 as sheet 56 is being wound about roller 58. It should be noted that the polymer comprising the separation material 59 may be provided in a sheet, liquid, or any other form, so long as it can be applied to one side of non-woven sheet 56. Moreover, since the intermingled nanotubes within the non-woven sheet 56 may contain catalytic nanoparticles of a ferromagnetic material, such as Fe, Co, Ni, etc., the separation material 59, in one embodiment, may be a non-magnetic material, e.g., conducting or otherwise, so as to prevent the non-woven sheet 56 from sticking strongly to the separation material 59.


Furthermore, system 50 may be provided with a control system (not shown), similar to that in system 10, so that rotation rates of mechanical drives 542 and 581 may be adjusted accordingly. In one embodiment, the control system may be designed to receive data from position sensors, such as optical encoders, attached to each of mechanical drives 542 and 581. Subsequently, based on the data, the control system may use a control algorithm in order to modify power supplied to each drive in order to control the rate of each drive so that they substantially match the rate of nanotube collection on belt 54 to avoid compromising the integrity of the non-woven sheet as it is being wound about the spool. Additionally, the control system can act to synchronize a rate of spin of the roller 58 to that of belt 54. In one embodiment, tension of the non-woven sheet 56 can be reset in real time depending on the velocity values, so that the tension between the belt 54 and roller 58 can be kept within a set value.


The control system can also vary the rate between the roller 58 and belt 54, if necessary, to control the up-take of the non-woven sheet 56 by roller 58. In addition, the control system can cause the roller 58 to adjust slightly back and forth along its axis, so as to permit the non-woven sheet 56 to evenly remain on roller 58.


To the extent desired, an electrostatic field (not shown) may be employed to align the nanotubes, generated from synthesis chamber 51, approximately in a direction of belt motion. The electrostatic field may be generated, in one embodiment, by placing, for instance, two or more electrodes circumferentially about the exit end 514 of synthesis chamber 51 and applying a high voltage to the electrodes. The voltage, in an embodiment, can vary from about 10 V to about 100 kV, and preferably from about 4 kV to about 6 kV. If necessary, the electrodes may be shielded with an insulator, such as a small quartz or other suitable insulator. The presence of the electric field can cause the nanotubes moving therethrough to substantially align with the field, so as to impart an alignment of the nanotubes on moving belt 54.


System 50, as noted, can provide bulk nanomaterials of high strength in a non-woven sheet. By providing the nanomaterials in a non-woven sheet, the bulk nanomaterials can be easily handled and subsequently processed for end use applications, including (i) structural systems, such as fabrics, armor, composite reinforcements, antennas, electrical or thermal conductors, and electrodes, (ii) mechanical structural elements, such as plates and I-beams, and (iii) cabling or ropes. Other applications can include hydrogen storage, batteries, or capacitor components.


Moreover, the non-woven sheet may be incorporated into composite structures for additional end use applications, such as sporting goods products, helmets, etc. In one embodiment, a composite material may be formed by impregnating the non-woven sheet with a matrix precursor, such as Krayton, vinyl ester, PEEK, bispolyamide, BMI (bismaleimide), epoxies, or polyamides, and subsequently allowing the matrix to polymerize or thermally cure.


In an alternate embodiment, a layered composite of materials may be formed by sintering non-woven sheets together with a matrix material. For example, adjacent layers of non-woven sheets may be separated with a sheet of matrix precursor and subsequently sintered in a hot press under isostatic pressure.


It should also be noted that, although structural applications are discussed herein, the nanomaterial based yarn and non-woven sheets may be used in numerous other applications which require structures to be formed from nanomaterials. Such structures may be used, for instance, in electrical applications as conducting materials, or as electrodes of a capacitor, or battery or fuel cell. In such an instance, since the nanomaterials provided in the electrode structure has a substantially high surface area, the nanomaterials can provide capacitors or batteries with a substantially large area to which electrons or ions might localize in order to store charge or transfer charge to or from the electrode. The high surface area or surface chemistry of nanomaterials in bulk macroscale structures may also be a useful property in mechanical filtration applications.


Furthermore, because nanomaterials, such as carbon nanotubes are known to have extremely high heat transfer coefficients, bulk structures produced with the system of the present invention may also be useful as conductors of phonons or thermal energy.


It should also be appreciated that yarns and tows made from synthesized nanomaterials of the present invention, especially those with nanotubes preferentially aligned along the axis of the yarn, may be incorporated as bulk assemblies having fibers oriented substantially parallel to one another, such as in a woven fabric. In addition, macroscale structures may be made from non-woven sheets of the present invention having aligned fibers. Since these structures of parallel conducting fibers have controlled spacing based on, for example, the amount of nanomaterials, the spacing of yarns in a weave, or the thickness of individual yarns, the presence of aligned fibers in these assemblies or macroscale structures may impart interesting properties to the assemblies and macroscale structures.


For example, in electrical applications, parallel conductors may be used as polarizing filters, diffraction gratings, and occasionally objects with large backscatter cross-sections. All of these applications may be dependent on the wavelength of incident electromagnetic waves, and the spacing, diameter and length of the parallel conductors which interact with the waves. By controlling the spacing between parallel conducting fibers, the interaction of an assembly of these fibers with electromagnetic radiation of specific frequencies may be controlled. For instance, a polarizing filter for terahertz frequency electromagnetic radiation may be defined by a thread size and tightness of a weave of nanotube yarns. Using, for example, 100 micron diameter yarns woven at a 300 micron pitch should be sufficient to polarize radiation with wavelengths in the vicinity of 300 microns, which corresponds to a 1 THz electromagnetic wave.


As a second example, aligned nanotubes within a non-woven sheet or yarn may have spacings and nanotube diameters on the order of several nanometers, but much longer conducting paths along the axis of the nanotubes. By providing aligned nanotubes in a non-woven sheet or within a continuous yarn, a diffraction grating may be provided that can interact strongly with x-rays. These bulk structures, therefore, can easily be formed to provide diffraction gratings and polarizers for x-rays. Moreover, because perpendicular polarizers can block transmission of the electromagnetic waves incident on the polarizers and with which each polarizer interacts, it may be possible to block x-rays using two non-woven sheets of aligned nanotubes, provided that the nanotubes in the first sheet may be oriented substantially perpendicularly to the nanotubes in the second sheet. A tightly woven fabric of yarns of aligned nanotubes may also have a similar effect. As such, it may be possible to use bulk structures having aligned nanotubes in broad-spectrum electromagnetic absorption shielding for x-rays, ultraviolet, visible light, infrared, terahertz, microwave radiation, and radar and radio frequencies.


In another embodiment, the nanofibrous materials of the present invention having aligned nanotubes may be incorporated for use in anisotropic composites and thermal conductors, and especially in gratings, filters, and shields of electromagnetic radiation, or other waves, such as electrons or neutrons with wavelengths greater than, for instance, 0.1 nm.


While the invention has been described in connection with the specific embodiments thereof, it will be understood that it is capable of further modification. Furthermore, this application is intended to cover any variations, uses, or adaptations of the invention, including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains.

Claims
  • 1. An apparatus for presenting synthesized nanotubes for subsequent formation of nanofibrous materials, the apparatus comprising: disc having a proximal end and a distal end;a passageway extending between the proximal end and the distal end; anda constricted portion at the distal end of the passageway to permit accumulation of the nanotubes thereat for use as a source from which nanotubes may be presented for subsequent formation of nanofibrous materials.
  • 2. An apparatus as set forth in claim 1, wherein the passageway is tapered from the proximal end toward the distal end of the disc.
  • 3. A method for presenting synthesized nanotubes for subsequent formation of nanofibrous materials, the method comprising: positioning, in a flow of synthesized nanotubes, a disc having a proximal end, a distal end, and a passageway therebetween provided with a constricted portion at the distal end;directing a volume of the synthesized nanotubes into the passageway through the proximal end of the disc; andaccumulating the nanotubes at the constricted portion to provide a source from which nanotubes may be presented for subsequent formation of nanofibrous materials.
  • 4. A method of claim 3, wherein, in the step of accumulating, the constricted portion is tapered in design.
RELATED US APPLICATION(S)

The present application is a divisional application of U.S. patent application Ser. No. 13/191,109, filed Jul. 16, 2011, now U.S. Pat. No. 8,999,285, which is a divisional application of U.S. patent application Ser. No. 11/488,387, filed Jul. 17, 2006, now U.S. Pat. No. 7,993,620, which claims priority to U.S. Provisional Patent Application Ser. No. 60/703,328, filed Jul. 28, 2005, each of which is incorporated herein by reference.

US Referenced Citations (179)
Number Name Date Kind
3090876 Hutson May 1963 A
3109712 Redfem Nov 1963 A
3665695 Amato May 1972 A
3706193 Amato Dec 1972 A
3943689 Kunz et al. Mar 1976 A
4384944 Silver et al. May 1983 A
4468922 McCrady et al. Sep 1984 A
4572813 Arakawa Feb 1986 A
4987274 Miller et al. Jan 1991 A
5168004 Daumit et al. Dec 1992 A
5428884 Tsuzuki Jul 1995 A
5488752 Randolph Feb 1996 A
5648027 Tajiri et al. Jul 1997 A
5747161 Iijima May 1998 A
6036774 Lieber et al. Mar 2000 A
6110590 Zarkoob et al. Aug 2000 A
6143412 Schueller et al. Nov 2000 A
6265466 Glatkowski et al. Jul 2001 B1
6299812 Newman et al. Oct 2001 B1
6308509 Scardino et al. Oct 2001 B1
6333016 Resasco et al. Dec 2001 B1
6376971 Pelrine et al. Apr 2002 B1
6426134 Lavin et al. Jul 2002 B1
6452085 Tauchi et al. Sep 2002 B2
6495116 Herman et al. Dec 2002 B1
6541744 Von Arx et al. Apr 2003 B2
6611039 Anthony et al. Aug 2003 B2
6630772 Bower et al. Oct 2003 B1
6682677 Lobovsky et al. Jan 2004 B2
6706402 Rueckes et al. Mar 2004 B2
6723299 Chen et al. Apr 2004 B1
6749827 Smalley et al. Jun 2004 B2
6764874 Zhang et al. Jul 2004 B1
6790426 Ohsaki Sep 2004 B1
6841139 Liu et al. Jan 2005 B2
6842328 Schott et al. Jan 2005 B2
6854602 Oyama et al. Feb 2005 B2
6884861 Keller et al. Apr 2005 B2
6923946 Geohegan et al. Aug 2005 B2
6979709 Smalley et al. Dec 2005 B2
7001556 Shambaugh Feb 2006 B1
7041620 Smalley et al. May 2006 B2
7045108 Jiang et al. May 2006 B2
7048999 Smalley et al. May 2006 B2
7052668 Smalley et al. May 2006 B2
7109581 Dangelo et al. Sep 2006 B2
7182929 Singhal et al. Feb 2007 B1
7205069 Smalley et al. Apr 2007 B2
7247290 Lobovsky et al. Jul 2007 B2
7261779 Gardner Aug 2007 B2
7282191 Choi et al. Oct 2007 B1
7323157 Kinloch et al. Jan 2008 B2
7345242 Chen Mar 2008 B2
7354877 Rosenberger et al. Apr 2008 B2
7413474 Liu et al. Aug 2008 B2
7423084 Marissen et al. Sep 2008 B2
7437938 Chakraborty Oct 2008 B2
7491883 Lee et al. Feb 2009 B2
7553472 Mouli et al. Jun 2009 B2
7611579 Lashmore et al. Nov 2009 B2
7615097 McKechnie et al. Nov 2009 B2
7615204 Ajayan et al. Nov 2009 B2
7641829 Liang et al. Jan 2010 B2
7670970 Ko Mar 2010 B2
7704480 Jiang et al. Apr 2010 B2
7727504 Kittrell et al. Jun 2010 B2
7745810 Rueckes et al. Jun 2010 B2
7750240 Jiang et al. Jul 2010 B2
7846414 Harbec et al. Dec 2010 B2
7897248 Barrera et al. Mar 2011 B2
7906208 Poulin et al. Mar 2011 B2
7938996 Baughman et al. May 2011 B2
7988893 Liao et al. Aug 2011 B2
7993620 Lashmore Aug 2011 B2
8057777 Lashmore Nov 2011 B2
8071906 Smiljanic et al. Dec 2011 B2
8445788 Tsotsis et al. May 2013 B1
8926933 Zhang et al. Jan 2015 B2
8999285 Lashmore et al. Apr 2015 B2
20010003576 Klett et al. Jun 2001 A1
20020004028 Margrave et al. Jan 2002 A1
20020040900 Von Arx et al. Apr 2002 A1
20020113335 Lobovsky et al. Aug 2002 A1
20020130610 Ginzewski et al. Sep 2002 A1
20020136681 Smalley et al. Sep 2002 A1
20020159943 Smalley et al. Oct 2002 A1
20020179564 Geohegan et al. Dec 2002 A1
20030036877 Schietinger et al. Feb 2003 A1
20030109619 Keller et al. Jun 2003 A1
20030122111 Glatkowski Jul 2003 A1
20030133865 Smalley et al. Jul 2003 A1
20030134916 Hrubesh Jul 2003 A1
20030165648 Lobovsky et al. Sep 2003 A1
20030222015 Oyama et al. Dec 2003 A1
20040020681 Hjortstam et al. Feb 2004 A1
20040053780 Jiang et al. Mar 2004 A1
20040081758 Mauthner et al. Apr 2004 A1
20040096389 Lobovsky et al. May 2004 A1
20040124772 Chen Jul 2004 A1
20040150312 McElrath et al. Aug 2004 A1
20040177451 Poulin et al. Sep 2004 A1
20040180157 Ishikawa et al. Sep 2004 A1
20040223901 Smalley et al. Nov 2004 A1
20040240144 Schott et al. Dec 2004 A1
20040265212 Varadan et al. Dec 2004 A1
20040265489 Dubin Dec 2004 A1
20040266065 Zhang et al. Dec 2004 A1
20050006801 Kinloch et al. Jan 2005 A1
20050046019 Dangelo Mar 2005 A1
20050063658 Crowley Mar 2005 A1
20050067406 Rajarajan et al. Mar 2005 A1
20050074569 Lobovsky et al. Apr 2005 A1
20050079119 Kawakami et al. Apr 2005 A1
20050087222 Muller-Werth Apr 2005 A1
20050095938 Rosenberger et al. May 2005 A1
20050104258 Lennhoff May 2005 A1
20050112051 Liu et al. May 2005 A1
20050124246 Ko Jun 2005 A1
20050170089 Lashmore et al. Aug 2005 A1
20050269726 Matabayas, Jr. Dec 2005 A1
20060017191 Liang et al. Jan 2006 A1
20060118158 Zhang et al. Jun 2006 A1
20060127299 Harbec et al. Jun 2006 A1
20060252853 Ajayan et al. Nov 2006 A1
20060269670 Lashmore et al. Nov 2006 A1
20060272701 Ajayan et al. Dec 2006 A1
20070009421 Kittrell et al. Jan 2007 A1
20070029291 Boulos et al. Feb 2007 A1
20070036709 Lashmore et al. Feb 2007 A1
20070048211 Jiang et al. Mar 2007 A1
20070056855 Lo et al. Mar 2007 A1
20070087121 Chang et al. Apr 2007 A1
20070092431 Resasco et al. Apr 2007 A1
20070116627 Collier et al. May 2007 A1
20070116631 Li et al. May 2007 A1
20070140947 Schneider et al. Jun 2007 A1
20070151744 Chen Jul 2007 A1
20070166223 Jiang et al. Jul 2007 A1
20070232699 Russell et al. Oct 2007 A1
20070236325 Bertin et al. Oct 2007 A1
20070237959 Lemaire Oct 2007 A1
20070277866 Sander et al. Dec 2007 A1
20070293086 Liu et al. Dec 2007 A1
20080170982 Zhang et al. Jul 2008 A1
20080238882 Sivarajan et al. Oct 2008 A1
20090042455 Mann et al. Feb 2009 A1
20090044848 Lashmore et al. Feb 2009 A1
20090047513 Lashmore Feb 2009 A1
20090087640 Li et al. Apr 2009 A1
20090117025 Lashmore et al. May 2009 A1
20090127712 Wyland et al. May 2009 A1
20090169819 Drzaic et al. Jul 2009 A1
20090194525 Lee et al. Aug 2009 A1
20090208708 Wei et al. Aug 2009 A1
20090237886 Iwai et al. Sep 2009 A1
20090269511 Zhamu et al. Oct 2009 A1
20090277897 Lashmore et al. Nov 2009 A1
20090282802 Cooper et al. Nov 2009 A1
20090311167 Height et al. Dec 2009 A1
20100041297 Jiang et al. Feb 2010 A1
20100044074 Kim et al. Feb 2010 A1
20100126134 Atkinson et al. May 2010 A1
20100219383 Eklund Sep 2010 A1
20100220074 Irvin, Jr. et al. Sep 2010 A1
20100243295 Allemand et al. Sep 2010 A1
20100270058 Mahoney et al. Oct 2010 A1
20100272978 Kumar et al. Oct 2010 A1
20100297441 Zhu Nov 2010 A1
20100324656 Lashmore et al. Dec 2010 A1
20100328845 Hiralal et al. Dec 2010 A1
20110005808 White et al. Jan 2011 A1
20110007477 Xu et al. Jan 2011 A1
20110110843 Pasquali et al. May 2011 A1
20110316183 Lashmore et al. Dec 2011 A1
20120045385 Lashmore et al. Feb 2012 A1
20120045643 Liu et al. Feb 2012 A1
20120045644 Wei et al. Feb 2012 A1
20120118552 White et al. May 2012 A1
20130316172 Shanov et al. Nov 2013 A1
Foreign Referenced Citations (38)
Number Date Country
1614772 May 2005 CN
1160861 Dec 2001 EP
2365117 Sep 2011 EP
1958-072036 May 1983 JP
58-180615 Oct 1983 JP
60-027700 Feb 1985 JP
8035069 Feb 1996 JP
2000-058228 Feb 2000 JP
2003-298338 Oct 2003 JP
2004-315297 Nov 2004 JP
2005-502792 Jan 2005 JP
2005-075672 Mar 2005 JP
2005-109870 Apr 2005 JP
2005-281672 Oct 2005 JP
2006-335604 Dec 2006 JP
2002-515847 May 2008 JP
2008-108583 May 2008 JP
2008-523254 Jul 2008 JP
20050007886 Jan 2005 KR
1998039250 Sep 1998 WO
2002055769 Jul 2002 WO
2003004741 Jan 2003 WO
2003080905 Oct 2003 WO
2005007926 Jan 2005 WO
2005069412 Jul 2005 WO
2005098084 Oct 2005 WO
2006052039 May 2006 WO
2006069007 Jun 2006 WO
2006073460 Jul 2006 WO
2006099156 Sep 2006 WO
2006137893 Dec 2006 WO
2007003879 Jan 2007 WO
2007015710 Feb 2007 WO
2007089118 Aug 2007 WO
2008036068 Mar 2008 WO
2008048286 Apr 2008 WO
2011005964 Jan 2011 WO
2011091257 Jul 2011 WO
Non-Patent Literature Citations (92)
Entry
U.S. Appl. No. 13/191,109, filed Jul. 26, 2011, System and Methods for Formation and Harvesting of Nanofibrous Materials.
International Search Report based on PCT/US2010/041374 dated Sep. 8, 2010.
International Search Report for International Patent Application No. PCT/US12/33300 dated Jul. 5, 2012.
Japanese Office Action issued for Japanese Patent Application No. 2009-551705 dated May 29, 2012.
Japanese Office Action issued in Japanese Application No. 2011-508688 dated Nov. 19, 2013.
Japanese Office Action issued in Japanese Application No. 2012-519729 dated Nov. 26, 2013.
Non-Final Office Action in U.S. Appl. No. 12/038,408 dated Oct. 14, 2010.
Non-Final Office Action in U.S. Appl. No. 12/140,263 dated Sep. 20, 2010.
Non-Final Office Action in U.S. Appl. No. 12/170,092 dated Nov. 21, 2011.
Non-Final Office Action in U.S. Appl. No. 12/180,300 dated Mar. 16, 2011.
Non-Final Office Action in U.S. Appl. No. 12/187,278 dated Sep. 29, 2010.
Non-Final Office Action in U.S. Appl. No. 12/191,765 dated Apr. 4, 2011.
Non-Final Office Action in U.S. Appl. No. 12/437,537 dated Apr. 7, 2011.
Non-Final Office Action in U.S. Appl. No. 12/437,537 dated Oct. 25, 2010.
Non-Final Office Action in U.S. Appl. No. 12/566,229 dated Apr. 6, 2011.
Non-Final Office Action in U.S. Appl. No. 12/841,768 dated May 26, 2011.
Office Action cited in U.S. Appl. No. 11/413,512 dated Jul. 8, 2010.
Office Action cited in U.S. Appl. No. 11/415,927 dated Feb. 22, 2010.
Office Action cited in U.S. Appl. No. 11/415,927 dated Sep. 9, 2010.
Office Action cited in U.S. Appl. No. 11/818,279 dated Jun. 2, 2010.
Office Action cited in U.S. Appl. No. 12/187,278 dated Jun. 11, 2010.
Office Action cited in U.S. Appl. No. 12/191,765 dated May 14, 2010.
Office Action cited in U.S. Appl. No. 12/390,906 dated Jul. 9, 2010.
Office Action cited in U.S. Appl. No. 11/715,756 dated Jan. 25, 2010.
Office Action issued for Australian Patent Application No. 2008311234 dated Feb. 14, 2012.
Office Action issued for U.S. Appl. No. 12/038,408 dated Feb. 23, 2012.
Office Action issued for U.S. Appl. No. 12/437,535 dated Aug. 22, 2012.
Office Action issued for U.S. Appl. No. 12/437,538 dated Mar. 26, 2012.
Office Action issued for U.S. Appl. No. 12/566,229 dated May 4, 2012.
Office Action issued for U.S. Appl. No. 12/580,994 dated Mar. 12, 2012.
Official Action cited in JP Serial No. 2008-540155 dated Mar. 8, 2011.
Official Action cited in JP Serial No. 2008-540155 dated Nov. 4, 2011.
PCT International Search Report based on PCT/US06/27918 dated Sep. 23, 2008.
PCT International Search Report based on PCT/US2009/043209 dated Mar. 3, 2010.
PCT International Search Report issued in International Application No. PCT/US2012/020194 dated May 1, 2012.
PCT International Search Report issued in International Application No. PCT/US2013/035844 dated Jul. 12, 2013.
Supplementary European Search Report based on EP 06851553.5 dated Nov. 15, 2010.
U.S. Office Action issued in U.S. Appl. No. 12/390,906 dated Sep. 30, 2013.
U.S. Office Action issued in U.S. Appl. No. 12/566,229 dated Jul. 23, 2013.
U.S. Office Action issued in U.S. Appl. No. 13/294,698 dated Jan. 2, 2014.
U.S. Office Action issued in U.S. Appl. No. 12/140,263 dated Aug. 14, 2014.
U.S. Office Action issued in U.S. Appl. No. 13/560,582 dated Jun. 19, 2014.
“Metallurgical & Chemical Engineering,” McGraw Publishing Co., 15(5), pp. 258-259 (Dec. 1916).
Baker et al.; “Nucleation and Growth of Carbon Deposits from Nickel Catalyzed Decomposition of Acetylene,” Journal of Catalysis, 26(1), pp. 51-62 (Jul. 1972).
Bethune et al., “Cobalt-Catalyzed Growth of Carbon Nanotubes With Single-Atomic-Layer Walls,” Letters to Nature, 363, pp. 605-607 (Jun. 1993).
Biro et al., “Direct Synthesis of Multi-Walled and Single-Walled Carbon Nanotubes by Spray-Pyrolysis,” Journal of Optoelectronics and Advanced Materials, 5(3), pp. 661-666 (Sep. 2003).
Ci et al., “Preparation of carbon nanofibers by the floating catalyst method,” Carbon, 38(14), pp. 1933-1937 (Sep. 18, 2000).
Gou, “Passage: Nanotube Bucky Papers and Nanocomposites,” Ph.D. Dissertation, Marburg an Der Lahn, pp. 93-126 (Jan. 2002).
Gou, “Single-Walled Carbon Nanotube Bucky Paper/Epoxy Composites: Molecular Dynamics Simulation and Process Development,” PhD Dissertation, The Florida State University, pp. 1-176 (Fall 2002).
Hanson, “Fundamental Transmitting Properties of Carbon Nanotube Antennas,” IEEE Transactions on Antennas and Propagation, 53(11), pp. 3426-3435 (Nov. 2005).
Iijima, “Helical Microtubules of Graphitic Carbon,” Letters to Nature, 354, pp. 56-58 (Nov. 1991).
Jiang et al., “Spinning Continuous Carbon Nanotube Yams,” Nature, 419, p. 801 (Oct. 2002).
Jose-Yacaman et al., “Catalytic Growth of Carbon Microtubules With Fullerene Structure,” Applied Physics Letters, 62 (6), pp. 657-659 (Feb. 1993).
Kim et al., “Dependence of the Vertically Aligned Growth of Carbon Nanotubes on the Catalysts,” The Journal of Physical Chemistry, 106(36), pp. 9286-9290 (Aug. 2002).
Ko et al., “Electrospinning of Continuous Carbon Nanotube-Filled Nanofiber Yams,” Advanced Materials. 15(14): 1161-1165 (2003).
Kroto et al., “C60: Buckminsterfullerene,” Letters to Nature, 318, pp. 162-163 (Nov. 1985).
Kukovitsky et al., “CVD Growth of Carbon Nanotube Films on Nickel Substrates,” Applied Surface Science, 215(1-4), pp. 201-208 (Jun. 2003).
Lee et al, “Catalytic Decomposition of Acetylene on Fe(001): A First-Principles Study,” Physical Review B, 66(8), 081403-1-081403-4 (Aug. 2002).
Lee et al., “Control of Growth Orientation for Carbon Nanotubes,” Applied Physics Letters, 82(3), pp. 448-450, (Jan. 2003).
Lee et al., “Synthesis of Carbon Nanotubes Over Gold Nanoparticle Supported Catalysts,” Carbon, 43(13), pp. 2654-2663 (May 2005).
Li et al., “Direct Spinning of Carbon Nanotube Fibers from Chemical Vapor Deposition Synthesis,” Science, 304, pp. 276-278 (Apr. 2004).
Merriam Webster Dictionary Definition of “along,” available at <http://merriam-webster.com/dictionary/along> (retrieved Sep. 16, 2010).
Merriarn-Webster, definition “funnel”; http://www.merriam-webster.com/diclionary/funnel; Oct. 21, 2014.
Moisala et al., “Single-walled carbon nanotube synthesis using ferrocene and iron pentacarbonyl in a laminar flow reactor,” Chemical Engineering Science, 61(13), pp. 4393-4402 (Jul. 2006).
Okabe et al., “New Porous Carbon Materials, Woodceramics: Development and Fundamental Properties,” Journal of Porous Materials, 2(3), pp. 207-213 (1996).
“Pipes et al., “Helical carbon nanotube arrays: mechanical properties,” Composities Science and Technology.62: 419-428 (2002).”.
Schaevitz et al., “A Combustion-Based Mems Thermoelectric Power Generator,” The 11th Conference on Solid-State Sensors and Actuators, Munich, Germany, (Jun. 2001).
Seo et al.; “Synthesis and Manipulation of Carbon Nanotubes”; New Journal of Physics 5; 2003.
Su et al.; Continuous Production of Single-Wall Carbon Nanotubes by Spray Pyrolysis of Alcohol with Dissolved Ferrocene; Chemical Physics Letters; 420, pp. 421-425; Jan. 26, 2006.
Tapaszto et al., “Diameter and morphology dependence on experimental conditions of carbon nanotube arrays grown by spray pyrolysis,” Carbon, 43(5), pp. 970-977 (2005).
Tibbetts, “Vapor-grown carbon fibers: Status and prospects,” Carbon, 27(5), pp. 745-747 (1989).
Vigolo et al.; “Improved Structure and Properties of Single-Wall Carbon Nanotube Spun Fibers”; Applied Physics Letters; vol. 81, No. 7, pp. 1210-1212; Aug. 12, 2002.
Xiao et al., “High-Mobility Thin-Film Transistors Based on Aligned Carbon Nanotubes,” Applied Physics Letters, 83(1), pp. 150-152 (Jul. 2003).
Zhang, et al.; “Multifunctional Carbon Nanotube Yarns by Downsizing an Ancient Technology”; Science; vol. 306; pp. 1358-1361; Nov. 19, 2004.
Zhu et al., “Direct Synthesis of Long Single-Walled Carbon Nanotube Strands,” Science, 296, pp. 884-886 (May 2002).
Australian Examiner's Report cited in AU Serial No. 2006249601 dated Jun. 24, 2010.
Australian Examiner's Report cited in AU Serial No. 2006350110 dated Feb. 9, 2010.
Canadian Search Report for Canadian Patent Application No. 2,609,712 dated Jul. 30, 2012.
Communication pursuant to Artide 94(3) EPC based on EP06849762.7 dated Sep. 16, 2010.
European Search Report based on EP 06849762.7 dated Jan. 14, 2010.
European Search Report based on EP 09816625.9 dated Sep. 7, 2011.
European Search Report based on EP 11168621.8 dated Jul. 8, 2011.
European Search Report for European Patent Application No. 08726128.5 dated Aug. 10, 2012.
European Search Report for European Patent Application No. 101600989 dated Mar. 9, 2012.
European Search Report for European Patent Application No. 12160856.6 dated May 10, 2012.
Final Office Action in U.S. Appl. No. 11/415,927 dated Mar. 10, 2011.
Final Office Action in U.S. Appl. No. 11/488,387 dated Jan. 21, 2011.
Final Office Action in U.S. Appl. No. 12/038,408 dated Apr. 13, 2011.
Final Office Action in U.S. Appl. No. 12/140,263 dated Mar. 9, 2011.
Final Office Action in U.S. Appl. No. 12/187,278 dated Feb. 25, 2011.
Final Office Action in U.S. Appl. No. 12/191,765 dated Oct. 28, 2010.
Final Office Action in U.S. Appl. No. 12/390,906 dated Jan. 24, 2011.
Related Publications (1)
Number Date Country
20150176163 A1 Jun 2015 US
Provisional Applications (1)
Number Date Country
60703328 Jul 2005 US
Divisions (2)
Number Date Country
Parent 13191109 Jul 2011 US
Child 14633765 US
Parent 11488387 Jul 2006 US
Child 13191109 US