JP7339347B2 - Carbon nanotube product manufacturing system and manufacturing method thereof - Google Patents

Description

One embodiment of the present invention relates generally to systems and methods for manufacturing carbon nanotube products.

The production of articles from carbon nanotube molecules has found application in many technical fields. In particular, research and development in the production of carbon nanotube fibers and sheets have gone in a myriad of different directions. However, the availability of high quality carbon nanotube articles that can be produced consistently has raised concerns about the desire to exploit the properties of carbon nanotube articles.

Accordingly, there remains a need for systems for producing high quality carbon nanotube articles. Given the ever-increasing commercial competitive pressures, rising consumer expectations, and diminishing opportunities for meaningful product differentiation in the marketplace, finding answers to these problems has become increasingly important. In addition, the need to reduce costs, improve efficiency and performance, and meet competitive pressures adds even greater urgency to the critical need to find answers to these problems.

Solutions to these problems have long been sought, but previous developments have not taught or suggested solutions, and thus solutions to these problems have long been unknown to those skilled in the art.

One embodiment of the present invention is a method of making a carbon nanotube product comprising blending non-aligned carbon nanotube material with solid solvent particles and activating the nanotube solvent by liquefying the solid solvent particles. mixing a nanotube solvent and a non-aligned carbon nanotube material to form a nanotube dope solution; extruding the nanotube dope solution to form a carbon nanotube proto-product; and solidifying the carbon nanotube proto-product. and forming an aligned carbon nanotube article by doing.

One embodiment of the present invention is a method of making a carbon nanotube product by mixing a non-aligned carbon nanotube material with a solvent precursor material and reacting the solvent precursor with a solvent activator. activating the nanotube solvent; mixing the nanotube solvent and the unaligned carbon nanotube material to form a nanotube dope solution; extruding the nanotube dope solution to form a carbon nanotube proto-product; forming an aligned carbon nanotube product by solidifying the carbon nanotube proto-product.

One embodiment of the present invention is a carbon nanotube product manufacturing system comprising a solid blending unit configured to blend non-aligned carbon nanotube material with solid solvent particles; a homogenization unit configured to activate the nanotube solvent by liquefying the particles and to mix the nanotube solvent and the unaligned carbon nanotube material to produce a nanotube dope solution; A carbon nanotube product manufacturing system is provided comprising an extrusion assembly configured to extrude a nanotube proto-product and a consolidation module configured to consolidate the carbon nanotube proto-product into an aligned carbon nanotube product.

Certain embodiments of the invention have other steps or elements in addition to or in place of those described above. The steps or elements will become apparent to those skilled in the art from reading the following detailed description when used with reference to the accompanying drawings.

1 is a schematic diagram of a carbon nanotube product manufacturing system; FIG. FIG. 2 is a schematic diagram of a mixing module for the carbon nanotube product manufacturing system of FIG. 1; 2 is a schematic diagram of an extrusion module of the carbon nanotube product manufacturing system of FIG. 1; FIG. 2 is a schematic diagram of a solidification module of the carbon nanotube product manufacturing system of FIG. 1; FIG. 2 is a schematic diagram of a post-production module of the carbon nanotube product manufacturing system of FIG. 1; FIG. 2 is a flowchart of a method for manufacturing the aligned carbon nanotube product 102 of FIG. 1 by the carbon nanotube product manufacturing system of FIG. 1;

The present invention relates generally to systems, methods, and apparatus for processing misaligned carbon nanotube material. One aspect relates to a system for producing aligned carbon nanotube materials of various morphologies. Systems disclosed herein include modular units, assemblies, devices, etc. for producing aligned carbon nanotube materials.

The following embodiments are described in sufficient detail to enable those skilled in the art to make and use the invention. It is to be understood that other embodiments will be apparent based on the present disclosure and that system, process or mechanical changes may be made without departing from the scope of embodiments of the present invention.

In the following description, numerous specific details are given in order to provide a thorough understanding of the invention. It may be evident, however, that the invention may be practiced without these specific details. In order to avoid obscuring the embodiments of the present invention, some well-known circuits, system configurations and process steps have not been disclosed in detail.

The drawings showing embodiments of the system are semi-diagrammatical and not to scale and, in particular, some dimensions are shown exaggerated in the drawings for clarity of presentation. Similarly, although points of view in the figures generally show similar orientations for ease of illustration, this depiction of the figures is in most cases arbitrary. In general, the invention can operate in any orientation.

For convenience, certain terms used throughout the application are collected here. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

With respect to carbon nanotube materials, the term "substantially pure" refers to at least about 75%, preferably at least about 85%, more preferably at least about 90%, most preferably at least about 90%, carbon nanotube molecules that make up the carbon nanotube material. Refers to carbon nanotube material that is at least about 95% pure. In other words, the term "substantially pure" or "essentially purified" with respect to a carbon nanotube material means that less than about 20%, more preferably about 15%, 10%, Refers to carbon nanotube material containing less than 8%, 7%, most preferably less than about 5%, 4%, 3%, 2%, 1%, or less than 1%.

As used herein, the term "comprising" or "comprising" is used in reference to compositions, methods, and their respective components essential to the invention, whether or not they are essential. open to the inclusion of unspecified elements, regardless of As a further example, compositions containing the elements A and B also include compositions consisting of A, B and C. The term "including" means "including principally, but not solely necessary". Further, variations of the word "comprising," such as the original "including," and the singular "including," have correspondingly altered meanings. The term "consisting essentially of" means "primarily including but not necessarily at least one" and thus "selecting one or more and in any combination is intended to mean In the context of this specification, the term "comprising" means "including primarily, but not necessarily solely".

As used herein, the term "consisting essentially of" refers to those elements required for a given embodiment. This term allows for the presence of additional elements that do not materially affect the basic and novel or functional characteristics of that embodiment of the invention.

The term “consisting of” refers to the compositions, methods, and their respective components described herein, excluding any elements not described in that description of the embodiments.

As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "a method" refers to one or more methods and/or steps of the type described herein and/or steps that would be apparent to one of ordinary skill in the art upon reading this disclosure or the like. including.

It is understood that the foregoing detailed description and the following examples are illustrative only and should not be construed as limitations on the scope of the invention. Various changes and modifications to the disclosed embodiments, which will become apparent to those skilled in the art, can be made without departing from the spirit and scope of the invention.

It is to be understood that this invention is not limited to the particular methodology, protocols, and reagents, etc., described herein, as such may vary. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the claims.

Referring now to FIG. 1, a schematic diagram of a carbon nanotube product manufacturing system 100 is shown. Carbon nanotube product manufacturing system 100 can produce aligned carbon nanotube product 102 from unaligned carbon nanotube material 104 . Misaligned carbon nanotube material 104 is a structure that includes a large number of carbon nanotube molecules 106 . For example, the unaligned carbon nanotube material 104 can be a low density bulk solid fiber structure. Carbon nanotube molecules 106 are individual carbon nanotube macromolecules within unaligned carbon nanotube material 104 and aligned carbon nanotube product 102 . As an example, carbon nanotube molecules 106 can be single-walled carbon nanotube molecules, but carbon nanotube molecules 106 are of other structures, shapes, or morphologies, such as double-walled, multi-walled carbon nanotube molecules, or combinations thereof. It is understood that it is possible. In unaligned carbon nanotube material 104, carbon nanotube molecules 106 are randomly oriented and can be held together by attractive intermolecular Van der Waals forces.

Aligned carbon nanotube product 102 is a material formed by aligning carbon nanotube molecules 106 axially and longitudinally along their long axis or combination of lengths of carbon nanotube molecules 106 . In general, the aligned carbon nanotube product 102 is produced by separating each of the carbon nanotube molecules 106 from each other by overcoming the attractive intermolecular van der Waals forces and longitudinally re-establishing the attractive intermolecular forces. , which provides the basis for highly desirable mechanical properties. Aligned carbon nanotube product 102 can be produced in several different forms. For example, aligned carbon nanotube product 102 can be in the form of filaments, fibers, films, or combinations thereof, which can be other materials such as threads, yarns, sheets, fabrics, foams, or tapes or Can be built into or integrated into the structure. Aligned carbon nanotube product 102 can be combined by itself or with other types of materials.

The carbon nanotube molecules 106 selected to produce the aligned carbon nanotube product 102 have a length-to-diameter (L/D) aspect ratio and purity determined by the G-band to D-band (G/D) ratio. can be characterized by For example, the carbon nanotube molecule 106 can preferably have an aspect ratio greater than 500 and a G/D ratio greater than 4, more preferably the carbon nanotube molecule 106 has an aspect ratio greater than 1000 and a G /D ratio, most preferably the carbon nanotube molecule 106 can have an aspect ratio greater than 2000 and a G/D ratio greater than 10.

Carbon nanotube product manufacturing system 100 can include one or more processing modules for producing aligned carbon nanotube product 102 . Each of the processing modules can include one or more physical processing units such as devices, machines, mechanisms, assemblies, physical couplings, or combinations thereof for manufacturing aligned carbon nanotube products 102. . Examples of units of carbon nanotube product manufacturing system 100 can include mixing module 110, extrusion module 120, solidification module 130, post-production module 140, or combinations thereof. As a further example, extrusion module 120 can be coupled to homogenization unit 220, solidification module 130 can be coupled to extrusion module 130, and post-production module 140 can be coupled to solidification module 130. . In yet another example, a module can be an integrated in-line continuous or semi-continuous process.

Mixing module 110 is for producing a solution of extrudable carbon nanotube molecules 106 . For example, mixing module 110 can include processing units for producing nanotube dope solution 112 from unaligned carbon nanotube material 104 . Nanotube dope solution 112 is a liquid solution in which carbon nanotube molecules 106 are separated from each other in a solvent. In some embodiments, the mixing module 110 includes units for solid blending of the unaligned carbon nanotube material 104, dissolution and liquid state mixing of the unaligned carbon nanotube material 104, or combinations thereof. can be done. In some embodiments, mixing module 110 can include units for adjusting the concentration of nanotube dope solution 112 . Details of the mixing module 110 are described further below.

Extrusion module 120 is for processing nanotube dope solution 112 to form carbon nanotube proto-product 122 . For example, extrusion module 120 is for homogenizing temperature, pressure, chemical composition, or a combination thereof of nanotube dope solution 112 prior to forming carbon nanotube proto-product 122 . Carbon nanotube proto-product 122 is a material that has the initial physical form of aligned carbon nanotube product 102 prior to full alignment of carbon nanotube molecules 106 . For example, carbon nanotube proto-product 112 can be produced by extrusion module 120 and has a composition that is primarily solvent as measured by volume or weight fraction. In some embodiments, extrusion module 120 can include processing units for purifying nanotube dope solution 112, shaping nanotube dope solution 112 into various physical forms and shapes, or a combination thereof. can. Details of the extrusion module 120 are described further below.

Solidification module 130 is for producing aligned carbon nanotube product 102 from carbon nanotube proto-product 122 . In some embodiments, solidification module 130 includes a processing unit to solidify carbon nanotube proto-product 122, a processing unit to impart alignment to carbon nanotube molecules 106 within carbon nanotube proto-product 122, or a combination thereof. can contain. Details of the solidification module 130 are described further below.

Post-production module 140 is for enhancing or modifying aligned carbon nanotube product 102 . In some embodiments, post-processing module 140 performs purification of aligned carbon nanotube product 102, any modification of aligned carbon nanotube product 102, manipulation or alteration of the physical form of aligned carbon nanotube product 102, alignment of carbon nanotube product 102, Processing units for integration of the carbon nanotube product 102 into additional structures or with additional materials, or combinations thereof, may be included. Details of the post-generation module 140 are described further below.

In some embodiments, carbon nanotube product manufacturing system 100 can produce aligned carbon nanotube product 102 as carbon nanotube filaments, fibers, or films. By way of example, the aligned carbon nanotube products 102 in the form of filaments, fibers, or films produced by the carbon nanotube product manufacturing system 100 may have tensile strength, elongation, stress fatigue, porosity or void fraction, molecular alignment, purity, electrical conductivity, It can be characterized by one or more characteristics such as rate, or a combination thereof. The following are examples of aligned carbon nanotube product 102 properties achieved by carbon nanotube product manufacturing system 100 .

The tensile strength properties of the aligned carbon nanotube product 102 can exceed 3 GPa. Generally, the tensile strength of carbon nanotube molecules 106 is about 60 GPa. The carbon nanotube product manufacturing system 100 can produce an aligned carbon nanotube product 102 that converts up to 40% of the molecular scale properties to the macroscale of the aligned carbon nanotube product 102, which is a 24 GPa CNT fiber. can be generated. For comparison, Kevlar is about 3.6 GPa, but many different grades of Kevlar are available.

The elongation property of the aligned carbon nanotube article 102 can be from 0.5% to 10% elongation to failure. The carbon nanotube product manufacturing system 100 can be tuned for a trade-off between strength and elongation such that the aligned carbon nanotube product 102 can be stronger and stiffer at the expense of elongation. and vice versa.

The stress-fatigue properties of the aligned carbon nanotube article 102 withstand billions of cycles of deformation before failure at 15% deformation. The porosity or void fraction properties of the aligned carbon nanotube article 102 are determined by the Brunauer-Emmett-Teller (BET) method of nitrogen (N ₂ ) or carbon dioxide (CO ₂ ) gas absorption. If so, it may preferably have a void fraction of less than 20%, more preferably less than 10%, and most preferably less than 5%. The property of molecular alignment of the aligned carbon nanotube product 102 is preferably greater than 0.8, more preferably 0.9, and most preferably greater than 0.95 as measured by diffraction or scattering techniques such as X-ray and neutron diffraction. It can be the Hermann orientation factor. A purity characteristic of the aligned carbon nanotube product 102 may preferably be a G/D ratio of greater than 5, more preferably greater than 10, and most preferably greater than 20 as measured by Raman spectroscopy. Conductivity properties of the aligned carbon nanotube product 102 can exceed 10Λ6 S/m.

Carbon nanotube product manufacturing system 100 can include additional units or devices for producing devices and components that can be assembled with aligned carbon nanotube product 102 . For example, devices and components assembled from aligned carbon nanotube products 102 can include wire antennas, patch antennas, coil transformers, and coaxial cables. In another example, the aligned carbon nanotube product 102 is a configuration that is integrated into other structures such as ropes, yarns, fabrics, tapes or fabrics pre-impregnated with resin, foams, chopped fiber filler materials, or laminated films. can be an element.

Referring now to FIG. 2, a schematic diagram of the mixing module 110 of the carbon nanotube product manufacturing system 100 of FIG. 1 is shown. Mixing module 110 can include one or more processing units for producing nanotube dope solution 112 from misaligned carbon nanotube material 104 . For example, the mixing module 110 can include a blending unit 202, a homogenizing unit 220, a consistency adjusting unit 230, or combinations thereof.

Blending unit 202 is for solid comminution, classification, blending, or combinations thereof of materials. More specifically, the blending unit 202 can produce a free-flowing dry powder blend material that does not spontaneously separate or segregate during transport. For example, in one embodiment, the blending unit 202 can be configured to uniformly disperse the nanotube solvent 204 as solid solvent particles 206 throughout the unaligned carbon nanotube material 104 to produce a solid blend 208. . Generally, the nanotube solvent 204 is solidified in the solid solvent particles 206 so that the solid blend 208 of the solid solvent particles 206 and the unaligned carbon nanotube material 104 is a dry mixture. In another embodiment, blending unit 202 can be configured to evenly disperse solvent precursor material 240 throughout unaligned carbon nanotube material 104 to produce solid blend 202 . In further embodiments, the blending unit 202 can be configured to physically treat the unaligned carbon nanotube material 104 without adding nanotube solvent 204 .

In one example, nanotube solvent 204 is a solvent that can dissolve carbon nanotube molecules 106 into non-aligned carbon nanotube material 104 . More specifically, nanotube solvent 204 can protonate delocalized π electrons on the sp2 carbon lattice of carbon nanotube molecule 106 . As an example, the carbon nanotube solvent 204 may be chlorosulfonic acid (HSO ₃ Cl), fluorosulfonic acid, fluorosulfuric acid, hydrochloric acid, methanesulfonic acid, nitric acid, hydrofluoric acid, fluoroantimonic acid, magic acid, or any other can be acids such as carborane-based acids of the type. As another example, nanotube solvent 204 can be a supercritical fluid, which is a substance at a temperature and pressure above its critical point. Nanotube solvent 204 as a supercritical fluid provides screening of electrostatic interactions between solute molecules, in this case carbon nanotube molecules 106, to counteract surface tension effects and particle-particle interactions, and is described herein. of nanotube dope solution 112 . Once the critical point of the nanotube solvent 204 is exceeded, its temperature and pressure can be adjusted to maintain maximum solubility of the carbon nanotube molecules 106, thereby allowing the nanotube solvent 204 in its supercritical state to reach all effective can be regarded as non-thermal for some purposes. As an example, the nanotube solvent 204 as a supercritical fluid can include supercritical carbon dioxide.

Solvent precursor material 240 is a compound that alone cannot dissolve misaligned carbon nanotube material 104 . Solvent precursor material 240 is generally a solid material that can be mixed, reacted, or a combination thereof with solvent activator 242 to produce nanotube solvent 204 . An exemplary combination of solvent precursor material 240 and solvent activator 242 can be phosphorus pentachloride and sulfuric acid in powder form, respectively.

In one embodiment, the blending unit 202 can include a blending chamber 210 configured to receive and blend the misaligned carbon nanotube material 104 and solid solvent particles 206 . As an example, blending chamber 210 can be a container having a conical shape. As a particular example, blend chamber 210 may include walls having an angle of repose of 45° to 75°, most preferably 60°, to facilitate evacuation of solid blend 208 . For purposes of illustration, the blend chamber 210 is shown having a conical shape, but it is understood that the blend chamber 210 can be other shapes or configurations such as cylindrical, oval profile, or oval. be done.

Blending unit 202 may include blending elements within blending chamber 210 . For example, the blending element can be a helical screw that travels a path determined by the interior surface of blending chamber 210 .

The blending element can include a separation device to physically separate the misaligned carbon nanotube material 104. FIG. For example, the separating device can be small bristles, claws, or hooks. The separation device can be attached to the surface of the blending element or can extend from the surface of the blending element. For example, the blending elements can include separating devices along their surfaces to separate the misaligned carbon nanotube material 104 . In some embodiments, the blending elements can expose the surface of the non-aligned carbon nanotube material 104 to solid solvent particles 206 . In other embodiments, the blending element can expose the surface of the non-aligned carbon nanotube material 104 to the solvent precursor material 240 .

The blending unit 202 includes top and side filling capabilities of the blending chamber 210 . For example, the non-aligned carbon nanotube material 104 loading capability can include one or more mechanical feeder mechanisms.

In some embodiments, the filling capacity of the blending unit 202 for the nanotube solvent 204 in liquid state is determined by one or more spray nozzles, misting nozzles, atomizers, or It can include combinations thereof. As a particular example, the spray nozzle or atomizer may be configured to discharge the nanotube solvent 204 in droplet size and in liquid form to facilitate the formation of solid solvent particles 206 in the form of amorphous or crystalline particles. can be done. In another embodiment, the ability to load blending unit 202 for nanotube solvent 204 can include the ability to introduce solid solvent particles 206 or solvent precursor material 240 .

Examples of solid fill capabilities can include powder dispensers or powder coating mechanisms. Blending unit 202 may include a discharge capability for solids blend 208 through the bottom of blending unit 202 .

Blending unit 202 may include a blending recycle loop 218 . Blending recirculation loop 218 can be a closed recirculation loop around blending unit 202 . The blend recycle loop 218 allows the blend unit 202 to continuously recycle the misaligned carbon nanotube material 104 through the blend unit 202 .

Blending unit 202 may include a temperature control device. For example, the temperature control device can include a thermal barrier, a cooling system covered with liquid nitrogen or liquid helium, or a combination thereof.

Blending unit 202 can be coupled to homogenization unit 220 . Homogenization unit 220 is for producing nanotube dope solution 112 . Homogenization unit 220 can be an apparatus or device that includes mixing elements within a closed mixing chamber 224, such as a closed reciprocating kneading assembly. As an example, the homogenization unit 220 can be horizontally oriented with the mixing elements enclosed within a barrel as a single or twin screw kneading assembly. The mixing elements can provide low-to-moderate shear for mixing materials within homogenization unit 220 . Homogenization unit 220 may be configured to allow interchangeability of mixing elements and sealed mixing chamber 224 .

In some embodiments, homogenization unit 220 can include a charging capability along mixing chamber 224 . In some embodiments, mixing chamber 224 can include a spray head or nozzle for introducing solvent activator 242 into mixing chamber 224 . In other embodiments, mixing chamber 224 can include a spray head or nozzle for introducing nanotube solvent 204 into mixing chamber 224 .

The sealed mixing chamber 224 can include volatile gas removal capabilities. In particular, closed mixing chamber 224 is created during dissolution of misaligned carbon nanotube material 104 in nanotube solvent 204, reaction of solvent precursor material 240 with solvent activator 242, or combinations thereof. gases such as hydrochloric acid (HCl) gas and other volatile by-products can be vented.

Homogenization unit 220 may include temperature control capabilities for monitoring, varying, maintaining the temperature within homogenization unit 220, or a combination thereof. For example, the homogenization unit 220 can gradually or progressively increase the temperature over a given period of time. In some embodiments, the temperature control capability of homogenization unit 220 can enable controlled liquefaction of solid solvent particles 206 into nanotube solvent 204 in a liquid state. In other embodiments, the temperature control capability of homogenization unit 220 provides a gradual change in temperature to control reaction, mixing, or a combination thereof between solvent precursor material 240 and solvent activator 242. can allow ascent.

Measurement units can be included at one or more locations along the homogenization unit 220 to monitor the quality of the nanotube dope solution 112 . For example, the measurement unit can be an in-line sensor unit including a spectrometer for measuring wavelength shift due to protonation of the carbon nanotube backbone. As another example, the measurement unit can be a device for rheological evaluation of nanotube dope solution 112 . In another example, the measurement unit can be a device for optically measuring the birefringence of nanotube dope solution 112 .

Homogenization unit 220 may include a flow recirculation loop 226 to allow recirculation of nanotube dope solution 112 through homogenization unit 220 . Additional mixing hardware, such as a high shear mixer, can be included along flow recirculation loop 226 .

The mixing module 110 can optionally include a density adjustment unit 230, as indicated by the dashed outline arrow. The concentration adjustment unit 230 is for adjusting the concentration of the nanotube dope solution 112 . Concentration adjustment unit 230 is one or more pressure and temperature controlled vessels configured to remove or add a specified amount of nanotube solvent 204 from or to nanotube dope solution 112 . can include For example, concentration adjustment unit 230 can include one or more distillation columns or devices configured to evaporate nanotube solvent 204 from nanotube dope solution 112 . For purposes of illustration, concentration adjustment unit 230 is shown in a single example of a distillation apparatus, but concentration adjustment unit 230 may be used in parallel, in series, or a combination thereof to process nanotube dope solution 112 . It is understood that multiple instances of distillation apparatus coupled together may be included. In another example, concentration adjustment unit 230 can include concentration recycle loop 232 for recycling nanotube dope solution 112 through concentration adjustment unit 230 .

Concentration adjustment unit 230 can be configured to operate under various atmospheric conditions and compositions. For example, concentration adjustment unit 230 can provide an atmosphere saturated with HCl that can co-flux with nanotube solvent 204 evaporated from nanotube dope solution 112 . As another example, concentration adjustment unit 230 may be configured to operate under a range of pressures, temperatures, or combinations thereof. In general, concentration adjustment unit 230 can be configured to operate at pressures of 30-35 mmHg or 0.039-0.046 atmospheres and temperatures in the range of 85-90°C.

Concentration adjustment unit 230 may include a measurement device for monitoring the concentration of nanotube dope solution 112 . For example, the measurement device can include a rheometer for contact or non-contact evaluation of viscoelastic and liquid crystalline properties of nanotube-doped solution 112 . In another example, the measurement device can include a spectrometer for determining wavelength shifts associated with backbone protonation of carbon nanotube molecules 106 in nanotube dope solution 112 by Raman spectroscopy.

Referring now to FIG. 3, a schematic diagram of extrusion module 120 of carbon nanotube product manufacturing system 100 of FIG. 1 is shown. Extrusion module 120 can include one or more processing units for producing carbon nanotube proto-product 122 from nanotube dope solution 112 . For example, extrusion module 120 can include flow drive mechanism 312, filtration unit 302, extrusion assembly 310, extrusion flow manifold 316, or combinations thereof.

Extrusion module 120 may be coupled to mixing module 110 of FIG. For example, extrusion module 120 can be coupled to mixing module 110 by a fluid transfer path 350 such as a pipe or tube. Nanotube dope solution 112 can be transferred from mixing module 110 to extrusion module 120 via fluid transfer path 350 . In some embodiments, the fluid transfer path 350 can include a static mixing element for creating a sustained turbulent flow regime for the nanotube dope solution 112, which includes a provides mixing and controlled heat transfer from heat exchange fluid recirculation within the static mixing element, heat exchange fluid recirculation external to the static mixing element, or a combination thereof.

Extrusion module 120 can receive nanotube dope solution 112 via flow drive mechanism 312 . Flow drive mechanism 312 is for promoting the flow of nanotube dope solution 112 through extrusion module 120 and maintaining uniform properties of nanotube dope solution 112 . Flow drive mechanism 312 provides constant pressure generation, which promotes uniform flow of nanotube dope solution 112 through extrusion module 120 . As a particular example, the flow drive mechanism 312 can be a twin-screw extruder, which is capable of “starvation feeding” and provides a balance of kneading and mixing elements that allow the nanotube dope solution 112 help maintain uniform properties such as temperature, pressure, concentration, or a combination thereof.

In some embodiments, extrusion module 120 can include filtration unit 302 . A filtration unit 302 can be included to increase the purity of the nanotube dope solution 112 . For example, the filtration unit 302 can include a filtration element 304 for removing residual particles such as metal catalyst particles, amorphous carbon particles, sp3 carbon particles, or combinations thereof from the nanotube dope solution 112 . Different embodiments of filtration unit 302 can include various configurations and combinations of filtration elements 304 depending on the size of the residual particles or the purity of the misaligned carbon nanotube material 104 . For example, the filtration unit 302 may include one or more coarse filtration elements 330 such as a coarse screen pack or coarse screen changer, one or more fine filtration elements 332 such as a fine screen pack or fine screen changer, or a combination thereof. can include Filtration element 304 can be configured to be continuously or semi-continuously updated or changeable during operation of filtration unit 302 . In some embodiments, filtration unit 302 can include booster pumps and pressure sensors as needed to assist or facilitate flow of nanotube dope solution 112 through filtration element 304 .

Extrusion flow manifold 316 may be coupled to filtration unit 302 . Extrusion flow manifold 316 is for directing the flow of nanotube dope solution 112 within extrusion module 120 . More specifically, any passageway within extrusion flow manifold 316 through which nanotube dope solution 112 passes before exiting extrusion unit 120 is designed to direct nanotube dope solution 112 after exiting extrusion unit 120 to achieve desired results. can have adjustable structures to change the flow pattern or symmetry of the Extrusion flow manifold 316 can separate or combine the flow of nanotube dope solution 112 in various configurations to accommodate different flow schemes through extrusion module 120 . As an example, the extrusion flow manifold 316 may include different schemes of filtration elements 304 of the filtration unit 302 within the fractionation unit 306, such as a recycle loop (not shown) for recycling the nanotube dope solution 112 to the filtration unit 302 or placement can be provided.

Extrusion flow manifold 316 may include fractionation path 306 . The sorting path 306 is for separating the carbon nanotube molecules 106 in the nanotube dope solution 112 based on the aspect ratio of the carbon nanotube molecules 106 . For example, fractionation path 306 can include elements configured to impart shear to the flow of nanotube dope solution 112 . Under sufficiently high shear, nanotube dope solution 112 exhibits a highly crystalline phase 332 composed primarily of carbon nanotube molecules 106 with the highest aspect ratio in nanotube dope solution 112 and the lowest aspect ratio in nanotube dope solution 112 . It is expected to phase separate into a concentrated isotropic phase 330 composed primarily of carbon nanotube molecules 106 having an aspect ratio.

Extrusion flow manifold 316 can accommodate different flow schemes or arrangements for the different phases of fractionation path 306 . For example, the fractionation path 306 is a flow separation and recombination manifold configured to separate and divert the enriched isotropic phase 330 from the highly crystalline phase 332 as process waste or low grade material. can include A highly crystalline phase 332 may be advanced toward the extrusion assembly 310 . Optionally, extrusion flow manifold 316 can include pumps for driving the flow of highly crystalline phase 332 and enriched isotropic phase 330 through extrusion flow manifold 316 to extrusion assembly 310 . can.

Extrusion assembly 310 is for producing carbon nanotube proto-product 122 . Extrusion assembly 310 may include extrusion die 314 . Extrusion die 314 is for extruding nanotube dope solution 112 to form carbon nanotube proto-product 122 . For example, extrusion die 314 can be for shaping, initial alignment, or a combination thereof of carbon nanotube proto-product 122 . Extrusion assembly 310 can be configured to include one or more instances of extrusion die 314 . In general, extrusion assembly 310 can include an extrusion die 314 with die openings or apertures corresponding to the form factor of carbon nanotube proto-product 122 and eventual aligned carbon nanotube product 102 .

Extrusion dies 314 for forming, shaping, and initial alignment of carbon nanotube proto-products 122 as fibers or filaments or films can be set in one or more different configurations. When producing the carbon nanotube proto-product 122 in film form, the extrusion die 314 can be a slot die. When producing carbon nanotube proto-product 112 in the form of fibers or filaments, extrusion die 314 can be a single-hole spinneret or a multi-hole spinneret. Generally, the holes of the extrusion die 314 can have a conical cross-sectional profile terminating in a flat portion of length suitable to elongate the domains and promote alignment of the carbon nanotube molecules 106 . As another example, the spinneret housing of extrusion die 314 can be static. In a further example, the spinneret housing of extrusion die 314 can be held in a sealed bearing assembly, which allows the liquid crystal domains of nanotube dope solution 112 to twist, rotate, or a combination thereof during flow. , imparting additional strength to the carbon nanotube proto-product 122 when the domains are consolidated in a twisted, spiral, helical, or combination thereof.

Extrusion assembly 310 can optionally include a vibrating device in line with extrusion die 314 or upstream of extrusion die 314 . The vibrations generated by the vibrating device can aid in the flow of the nanotube dope solution 112 through the extrusion die 314 by disrupting the undesirable elastic turbulence just prior to the exit of the extrusion die 314, and along the flow plane. Improve flow stability by reducing undesirable friction and shear effects, or by a combination thereof.

Extrusion flow manifold 316 can accommodate inclusion of multiple instances, various types, and shapes of extrusion dies 314, such as for co-extrusion of nanotube dope solution 112. In a further example, the extrusion flow manifold 316 can accommodate different flow rates and production rates, allowing multiple upstream and downstream components to be used to increase production capacity without substantially changing the architecture of the system. to

Referring now to FIG. 4, a schematic diagram of the consolidation module 130 of the carbon nanotube product manufacturing system 100 of FIG. 1 is shown. Solidification module 130 can include one or more processing units for producing aligned carbon nanotube product 102 from carbon nanotube proto-product 122 . For example, the solidification module 130 can include an initial alignment unit 402, an irradiation solidification unit 404, an intermediate alignment unit 408, a chemical solidification unit 410, a solid alignment unit 414, or combinations thereof.

Initial alignment unit 402 is for imposing alignment on carbon nanotube molecules 106 within carbon nanotube proto-product 122 after exiting extrusion module 120 . For example, the initial alignment unit 402 can be a temperature controlled drum or godet roll assembly. The initial alignment unit 402 can be configured to stretch the carbon nanotube proto-product 122 under tension at a velocity greater than the flow velocity at the extrusion die 314 of FIG. impose and reduce the cross-sectional area of the carbon nanotube proto-product 122 .

The irradiation solidification unit 404 is for irradiation solidification of the carbon nanotube proto-product 122 . For example, the irradiation coagulation unit 404 can include a radiation source 406 such as an array of infrared (IR) radiation emitters. The irradiation coagulation unit 404 can include a radiation source 406 positioned around the proto-product in a controlled atmosphere. Radiation emitted from radiation source 406 can induce solidification of carbon nanotube proto-product 122 .

Radiation source 406 can emit radiation at a wavelength such that absorption by nanotube solvent 204 is minimized and absorption by carbon nanotube molecules 106 of carbon nanotube proto-product 122 is maximized. Radiation source 406 may be configured to pulse the radiation to prevent localized heating effects.

Irradiation coagulation unit 404 can include devices for venting volatiles and forcing a gas flow into the atmosphere surrounding carbon nanotube proto-product 122 . This provides convective heat transfer and helps control the solidification rate of the carbon nanotube proto-product 122 as well as helps transport the carbon nanotube proto-product 122 .

The intermediate alignment unit 408 is for providing alignment to the carbon nanotube molecules 106 in the partially consolidated carbon nanotube proto-product 122 . For example, intermediate alignment unit 408 can be a temperature controlled drum or godet roll assembly. Intermediate alignment unit 408 can be configured to stretch carbon nanotube proto-product 122 under tension at a velocity greater than the flow velocity at extrusion die 314 to impose alignment on carbon nanotube molecules 106 . The speed and tension at which carbon nanotube proto-product 122 is stretched by intermediate alignment unit 408 can be the same, greater than, or less than that of initial alignment unit 402 .

Chemical solidification unit 410 is for chemical solidification of carbon nanotube proto-product 122 . A chemical coagulation unit 410 can expose the carbon nanotube proto-product 122 to a chemical coagulant 412 . Chemical coagulant 412 is a compound that is a solvent for nanotube solvent 204 and a non-solvent for carbon nanotube proto-product 122 . For example, chemical coagulants 412 can include acetone, water, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), ether, chloroform, mixtures of sulfuric acid in water. As an example, the chemical coagulant 412 concentration can be less than 20% concentration, a mixture of acetic acid in water less than 40% concentration, or a combination thereof.

For purposes of illustration, the chemical coagulation unit 410 is shown with a showerhead or spray nozzle for applying the chemical coagulant 412 to the carbon nanotube proto-product 122, although the chemical coagulation unit 410 can be of different configurations. It is understood that you can. For example, carbon nanotube proto-product 122 can include a bath or immersion tank, a continuously renewed fluid film, or a combination thereof that exposes carbon nanotube proto-product 122 to chemical coagulant 412 . Chemical solidification unit 410 can be configured to provide a uniform solidification rate along the cross-section of carbon nanotube proto-product 122 . Chemical coagulation unit 410 controls convective heat transfer within chemical coagulation unit 410, such as by evacuating volatiles, forced gas flow in the atmosphere surrounding carbon nanotube proto-product 122, and helping to transport carbon nanotube proto-product 122. can include devices and mechanisms for providing

The solid alignment unit 414 is for providing alignment to the carbon nanotube molecules 106 in the solidified carbon nanotube proto-product 122 . For example, solid alignment unit 414 can be a temperature controlled drum or godet roll assembly. Intermediate alignment unit 408 can be configured to stretch carbon nanotube proto-product 122 under tension at a velocity greater than the flow velocity in the extrusion die to impose alignment on carbon nanotube molecules 106 . The final dimensions of aligned carbon nanotube product 102 can be set by solid alignment unit 414 . The speed and tension with which the carbon nanotube proto-product 122 is stretched by the solid alignment unit 414 is the same, greater than or less than that of the initial alignment unit 402, the intermediate alignment unit 408, or a combination thereof. can do. Solid alignment unit 414 can include a creel for capture and storage of aligned carbon nanotube product 102 .

Referring now to FIG. 5, a schematic diagram of the post-production module 140 of the carbon nanotube product manufacturing system 100 of FIG. 1 is shown. Post-production module 140 can include one or more processing units for modifying aligned carbon nanotube product 102 . For example, post-production module 140 can include purification unit 502, functionalization unit 512, coating unit 514, doping unit 516, product integration unit 518, or combinations thereof.

Purification unit 502 is for removing residual treatment materials from aligned carbon nanotube product 102 . For example, purification unit 502 is configured to remove residual amounts of nanotube solvent 204 of FIG. 2, chemical coagulant 412 of FIG. 4, other undesirable residual particles on aligned carbon nanotube product 102, or combinations thereof. can do. The purification unit 502 can include a solvent removal unit 504, a thermal annealing unit 506, a chemical cleaning unit 508, or combinations thereof. Purification unit 502 can be directly or indirectly coupled to extrusion module 120 to receive aligned carbon nanotube product 102 .

Solvent removal unit 504 is for removing residual traces of nanotube solvent 204 from aligned carbon nanotube product 102 . For example, solvent removal unit 504 can include an aqueous bath, showerhead, spray nozzle, or combination thereof to clean aligned carbon nanotube product 102 . Solvent removal unit 504 can be configured to deliver and maintain an aqueous wash at a temperature range of about 60°C to 80°C, for example.

Thermal annealing unit 506 is for removing residual traces of chemical coagulant 412 from aligned carbon nanotube product 102 . For example, thermal annealing unit 506 can include an oven or enclosed heating element configured to exhaust gases and volatiles from the environment surrounding aligned carbon nanotube product 102 .

Chemical cleaning unit 508 is for removing residual traces of process byproduct materials from aligned carbon nanotube product 102 . For example, chemical cleaning unit 508 can include a spray nozzle, showerhead, bath or tank, continuously renewed fluid film, or combinations thereof for exposing aligned carbon nanotube product 102 to a chemical cleaning solution. . The choice of chemical cleaning solution can depend on the choice of chemical coagulant 412 used in chemical coagulation unit 410 of FIG.

Optionally, post-production module 140 can include one or more additional units for further processing aligned carbon nanotube product 102 . For example, post-production module 140 may include any unit such as functionalization unit 512, coating unit 514, doping unit 516, product integration unit 518, or combinations thereof. Inclusion of optional units of post-production module 140 , generally indicated by dashed lines and arrows, can depend on the intended use of aligned carbon nanotube product 102 .

Functionalization unit 512 is for modifying the molecular structure of aligned carbon nanotube product 102 . For example, functionalization unit 512 can include a reaction chamber, an oven, or a combination thereof for covalent chemical functionalization of aligned carbon nanotube product 102 .

The coating unit 514 is for applying a coating substance to the aligned carbon nanotube product 102 . For example, coating unit 514 can include an apparatus for mechanical coating of aligned carbon nanotube product 102, such as a dip coater, roll-to-roll coater, slide coater, dip coater, or combinations thereof. In another example, coating unit 514 may include apparatus for electrolytic coating of aligned carbon nanotube article 102, such as an electrolytic bath or tank containing ionic compounds for water dispersion at appropriate zeta potential levels. can be done. In a further example, the coating unit 514 can include equipment capable of electrostatic coating of charged solid particles or vapor phase deposition onto the aligned carbon nanotube article 102 .

Doping unit 516 is for non-covalent chemical functionalization of aligned carbon nanotube product 102 . Doping unit 516 may include a doping chamber with doping process-based functionality and capabilities. In one example, the doping unit 516 can include a vacuum oven for vapor phase doping processes. In another example, the doping unit 516 can include a spray nozzle, showerhead, bath or tank, continuously renewed fluid film, or combinations thereof for liquid phase doping processes.

Product integration unit 518 is for integrating aligned carbon nanotube product 102 into a device, component, or structure. As an example, the product integration unit 518 may process one or more examples of aligned carbon nanotube material 102 such as ropes, yarns, fabrics, foams, resin pre-impregnated tapes or fabrics, chopped fiber filler materials, or laminated materials. It can include units or devices for integration into structures. Examples of such units can include looms, cradles, winders, presses, rollers, or laser cutters. Similarly, product integration unit 518 can include units for integrating aligned carbon nanotube product 102 into devices or components, such as wire antennas, patch antennas, coil transformers, coaxial cables, or combinations thereof. can include

Referring now to FIG. 6, a flowchart of a method 600 of manufacturing the aligned carbon nanotube product 102 of FIG. 1 by the carbon nanotube product manufacturing system 100 of FIG. 1 is shown. Method 600 can include several steps for manufacturing aligned carbon nanotube product 102 . Although the manufacturing steps below are arranged below for purposes of illustration, it is understood that the steps may be arranged in other orders or arrangements.

In one embodiment of the invention, method 600 may include material preparation step 602 . A material preparation step 602 is for preparing materials to be processed by the carbon nanotube product manufacturing system 100 . For example, in material preparation step 602 , nanotube solvent 204 can be prepared for solid state blending with unaligned carbon nanotube material 104 .

In some embodiments, the nanotube solvent 204 can be provided in a liquid state to the blending chamber 210 of the blending unit 202, both of FIG. Allows solid blending of material 104 . More specifically, sufficient cooling of the blending chamber 210 is necessary to convert the nanotube solvent 204 from a liquid state to a solid state and maintain a dry solid state for the duration of the blending process. Formation of solid solvent particles 206 in the blend can ensure that initiation of reaction between nanotube solvent 204 and misaligned carbon nanotube material 104 is prevented. For example, prior to introducing the nanotube solvent 214, the material preparation step 602 can include introducing a liquid or vapor phase chamber coolant into the blending chamber 210 until a solid blending temperature is reached. As a specific example, the solid blending temperature is preferably below 100°C. The chamber coolant is preferably a chemically inert substance such as nitrogen (N2) or helium (He). A chamber coolant can be introduced into the blending chamber 210 by a pressure differential directed along a contained path from the coolant reservoir to the blending chamber 210 to cool and maintain the interior of the blending chamber 210 at a solid blending temperature. do. Optionally, unaligned carbon nanotube material 104 can be introduced into blending unit 202 for cooling to a solid blending temperature prior to introduction of nanotube solvent 204 .

Prior to introducing nanotube solvent 204 into blending chamber 210 , nanotube solvent 204 can be stored in a compartment or reservoir of blending unit 202 . Once the blending chamber 210 is prepared, such as after cooling to the solids blending temperature*, the method 600 can proceed to a solids blending step 606 . The solids blending step 606 is for dry solid state pulverization, classification, blending, or a combination thereof of materials. More specifically, a free-flowing powder blend material can be produced that does not spontaneously separate or segregate during transport. For example, the dry solid state nanotube solvent 204 can be blended with the non-aligned carbon nanotube material 104 in a solid blending step 606 to form the solid blend 208 of FIG. 1 as a dry mixture. In a solid blending step 606 , the non-aligned carbon nanotube material 104 can be introduced into the blending chamber 210 of the blending unit 202 . As an example, misaligned carbon nanotube material 104 can be introduced into blending chamber 210 at a rate that maintains a "starvation" condition.

In one embodiment, solids blending step 606 can continue with introduction of nanotube solvent 204 or solvent precursor material 240 of FIG. 2 into blending chamber 210 . In one implementation of the solid blending step 606, for nanotube solvent 204 provided in a liquid state, the nanotube A solvent 204 can be introduced into the blending chamber 210 . Formation of solid solvent particles 206 can be accomplished by introducing nanotube solvent 204 in droplet sizes small enough to satisfy the cooling rate for freezing nanotube solvent 204 . In this implementation, the unaligned carbon nanotube material 104 can be cooled to a solid blending temperature prior to blending with the solid solvent particles 206 .

The amount of nanotube solvent 204 or solvent precursor material 240 introduced into blending chamber 210 depends on the doping concentration of nanotube dope solution 112 and the amount of unaligned carbon nanotube material 104 supplied to blending chamber 210 . Doping concentration is defined as the concentration of unaligned carbon nanotube material 104 in nanotube solvent 204 determined by the weight of unaligned carbon nanotube material 104 . For example, the target concentration can range from 2-20% by weight of the unaligned carbon nanotube material 104; however, in the mixing module 110 of FIG. 1, the concentration can vary throughout the manufacturing process. is understood. For example, the doping concentration of nanotube dope solution 112 at this stage of processing can be lower than the doping concentration of nanotube dope solution 112 during extrusion.

In another embodiment of solid blending step 606 , unaligned carbon nanotube material 104 can be processed within blending chamber 202 without the addition of solid solvent particles 206 or solvent precursor material 240 . For example, the separating element of the blending element within the blending chamber 202 separates or decomposes the misaligned carbon nanotube material 104 to increase the exposed surface area of the misaligned carbon nanotube material 104. The unaligned carbon nanotube material 104 can be processed, such as cooling the material 104, drying or venting the unaligned carbon nanotube material 104, or other processes to facilitate downstream processing.

A solid blending step 606 can allow solid solvent particles 206 or solvent precursor material 240 to penetrate exposed surfaces of the unaligned carbon nanotube material 104 . For example, a blending element separation device within the blending chamber 210 separates the non-aligned carbon nanotube material 104 to force solid solvent particles 206 or solvent precursor material 240 onto the surface of the non-aligned carbon nanotube material 104 . Blending can be facilitated. A solid blending step 606 constantly re-exposes the non-aligned carbon nanotube material 104 to the solid solvent particles 206 until uniform distribution of the solid solvent particles 206 through the non-aligned carbon nanotube material 104 is achieved. To do so, can include recycling the non-aligned carbon nanotube material 104 to the blending chamber 210 . This distribution of solid solvent particles 206 is preferably randomized in a ratio defined by the target concentration and consists of very similar solvent and solute particle shapes and sizes, preferably 10 particles of size along the longest particle dimension. % standard deviation, more preferably within 5% standard deviation of size along the longest particle dimension, and most preferably within 1% standard deviation of size along the longest particle dimension.

The solid blending step 606 provides controlled introduction of the nanotube solvent 204 into the non-aligned carbon nanotube material 104, which is highly enthalpically favorable and diffusion limited for controlling the protonation reaction. found to be important. A solid blending step 606 allows dispersion of the nanotube solvent without initiating a chemical reaction between the nanotube solvent 204 and the unaligned carbon nanotube material 104 until a uniform blend of solid solvent particles 206 is achieved. , thereby providing uniform and controlled dissolution of the misaligned carbon nanotube material 104 into the nanotube solvent 204 . This can maximize the dispersion of carbon nanotube molecules 106 and optimizes the alignment of carbon nanotube molecules 106 when producing aligned carbon nanotube product 102 .

Once the blending between solid solvent particles 206 or solvent precursor material 240 and unaligned carbon nanotube material 104 is completed in solid blending step 606 , method 600 can continue to solvent activation step 610 . Solvent activation step 610 is for activating solid solvent particles 206, solvent precursor material 240, or a combination thereof. At the solvent activation step 610, the solid blend 208 can be transferred to the homogenization unit 220 of FIG.

In one embodiment, nanotube solvent 204 can be activated by liquefying solid solvent particles 206 . For example, the cryogenic solid state nanotube solvent 204 can be activated by controlled heating from the solid blending temperature to the solution mixing temperature. Generally, solution mixing temperatures are below temperatures that cause nanotube solvent 204 to degrade. In the particular example of nanotube solvent 204 as chlorosulfonic acid, the solution mixing temperature can range from 25° C. to 80° C., but must not exceed the boiling point of 154° C. to 156° C. at atmospheric pressure, more preferably , below 80°C. In some embodiments, the solution mixing temperature can exceed the boiling point of chlorosulfonic acid when controlled under a saturated HCl atmosphere, which can prevent degradation of chlorosulfonic acid.

Liquifying the solid solvent particles 206 activates the protonation reaction between the nanotube solvent 204 and the misaligned carbon nanotube material 104 . The protonation reaction occurs when the delocalized π-electrons on the sp2 carbon lattice are protonated and the electrostatic repulsion between the protons on the molecular backbone of the carbon nanotube molecule 106 overcomes the mutual attractive van der Waals forces. , initiates the formation of a true solution, allowing the carbon nanotube molecules 106 to separate and go into solution.

In another embodiment of solvent activation step 606, nanotube solvent 204 may be activated by introducing solvent activator 242 of FIG. For example, phosphorus pentachloride solvent precursor material 240 and sulfuric acid solvent activator 242 can be reacted in sealed mixing chamber 224 at a controlled heating rate to produce nanotube solvent 204 of chlorosulfonic acid. do.

Following solvent activation step 610 , method 600 may proceed to homogenization step 614 . Homogenization step 614 is for producing nanotube dope solution 112 . In a homogenization step 614, the homogenization unit 220 may mix the non-aligned carbon nanotube material 104 with the nanotube solvent 204 in a liquid state. In one embodiment of the homogenization step 614 , the nanotube solvent 204 produced from the liquefaction of the solid solvent particles 206 or the reaction between the solvent precursor material 240 and the solvent activator 242 is transferred to the non-aligned carbon nanotube material 104 . can be mixed with In another embodiment of the homogenization step 614, a nanotube solvent 204, such as liquid chlorosulfonic acid or a supercritical fluid, is introduced into the homogenization unit 220 and aligned unblended with the solid solvent particles 206 or solvent precursor material 240. It can be shear mixed with the uncured carbon nanotube material 104 . Mixing misaligned carbon nanotube material 104 with nanotube solvent 204 can produce nanotube dope solution 112 in an optically birefringent nematic liquid crystal phase.

Generally, the nanotube dope solution 112 can be produced at concentrations ranging from 2-20% by weight of the unaligned carbon nanotube material 104, although it is understood that the nanotube dope solution 112 can be produced at different concentrations. For example, an additional amount can be introduced into the sealed mixing chamber to reduce the concentration of nanotube dope solution 112 .

During the homogenization step 614 , the nanotube dope solution 112 can be evaluated to determine the degree of protonation between the nanotube solvent 204 and the misaligned carbon nanotube material 104 . For example, the measurement device of homogenization unit 220 can monitor properties or attributes of nanotube dope solution 112, such as wavelength shift and viscosity, to determine whether adequate homogenization of nanotube dope solution 112 has been achieved. . In one particular example, the wavelength shift associated with protonation of sp2 carbon structures can be measured by a measurement device such as an in-line Raman spectrometer. In another specific example, the viscoelasticity and optical birefringence of the nanotube-doped solution 112 can be measured to determine the extent of liquid crystal formation by a measuring device such as mechanical, optical, or other non-contact rheometer. . Nanotube dope solution 112 can be recycled through homogenization unit 220 via flow recirculation loop 226 in FIG. 2 until satisfactory protonation is achieved.

Both solvent activation step 610 and homogenization step 614 can be performed in homogenization unit 220 . Homogenization unit 220 may exhaust by-products produced from the protonation reaction, such as hydrochloric acid gas, during solvent activation step 610, homogenization step 614, or a combination thereof.

The method 600 can optionally include a density adjustment step 616, as indicated by the dashed arrow and line. Concentration adjustment step 616 is for adjusting the concentration of nanotube dope solution 112 . In some embodiments, the non-aligned carbon nanotube material 104 and the nanotube solvent 204 are ratioed to target a lower concentration than the target concentration of the nanotube dope solution 112 during formation of the nanotube proto-product 122 of FIG. can fill the blending unit 202 with a reduced strain on the various units and elements within the mixing module 110 . The final target concentration of nanotube dope solution 112 can be achieved by feeding a dilute form of nanotube dope solution 112 to concentration adjustment unit 230 of FIG. 2, which evaporates nanotube solvent 204 without degradation. be able to.

In concentration adjustment step 616 , concentration adjustment unit 230 may operate under temperature and atmospheric conditions to prevent degradation of nanotube solvent 204 . For example, concentration adjustment unit 230 can be operated to provide an atmosphere enriched or saturated with HCl gas that can co-flux or co-flow with nanotube solvent 204 evaporated from nanotube dope solution 112 . Generally, concentration adjustment unit 230 can operate at pressures of 30-35 mmHg or 0.039-0.046 atmospheres and temperatures in the range of 85-90°C.

Once sufficient mixing and target concentration of nanotube dope solution 112 is achieved in homogenization step 614 , nanotube dope solution 112 can undergo passive transmixing step 618 . In a passive transfer mixing step 618, the nanotube dope solution 112 undergoes additional passive mixing through the static mixing elements of FIG. can be done. The purpose of the passive moving mixing step 618 is to create a sustained turbulent flow regime for the nanotube dope solution 112 . Turbulent flow of the nanotube dope solution 112 provides continuous mixing while also providing controlled heat transfer within the nanotube dope solution 112, such as through heat exchange fluid recirculation inside and outside static mixing elements. .

Method 600 can include a filtering step 620 to remove impurities from nanotube dope solution 112 . For example, in some cases, despite using purified unaligned carbon nanotube material 104, a plurality of undesired undispersed particles, insufficiently pure unaligned carbon nanotube material 104 Impurities such as, for example, residual catalyst particles, residual amorphous or sp3 carbon, or combinations thereof, can be present in the nanotube dope solution 112 . Impurities may be removed from nanotube dope solution 112 in filtering step 620 by passing nanotube dope solution 112 through filtering unit 302 of FIG. As an example, filtration of impurities can be accomplished by flow through filter element 304 of FIG. 3, such as coarse filter element 330, fine filter element 332, or a combination thereof. The inclusion of coarse filtering elements 330 or fine filtering elements 332 can depend on the initial purity of the non-aligned carbon nanotube material 104 .

Following filtering step 620 , process flow may continue to fractionation step 624 . A sorting step 624 is for separating the carbon nanotube molecules 106 in the nanotube dope solution 112 based on the aspect ratio of the carbon nanotube molecules 106 . In general, nanotube dope solution 112 can include a mixture of carbon nanotube molecules 106 having a wide range of aspect ratios. At fractionation step 624, nanotube dope solution 112 may be subjected to shear flow within fractionation path 306 of extrusion flow manifold 316 in both FIG. Under sufficiently high shear, nanotube dope solution 112 is composed primarily of carbon nanotube molecules 106 with the highest aspect ratios in nanotube dope solution 112 and highly crystalline phase 340 of FIG. is expected to phase separate into the enriched isotropic phase 342 of FIG.

In a fractionation step 624, the extrusion flow manifold 316 can separate and redirect the enriched isotropic phase 342 from the highly crystalline phase 340 as process waste or low grade material. The highly crystalline phase can proceed toward extrusion assembly 310 in FIG. Additional homogenization and temperature control may be provided to nanotube dope solution 112 during transfer to extrusion assembly 310 via a static mixer or assembly of static mixers in extrusion flow manifold 316 .

The process continues from fractionation step 624 to extrusion step 626 . In extrusion step 626 , nanotube dope solution 112 is processed to provide the initial morphology and alignment of aligned carbon nanotube product 102 , which is carbon nanotube proto-product 122 . For example, nanotube dope solution 112 may flow through one of various possible configurations of extrusion assembly 310 of FIG. A proto product 122 can be generated. In some embodiments, the liquid crystal domains of the nanotube-doped solution 112 can be twisted, rotated, or a combination thereof during the extrusion step 626 such that the domains are in a twisted configuration, a spiral configuration, a helical configuration, or both. provides additional strength to the carbon nanotube proto-product 122 when solidified with a combination of

The extrusion step 626 can optionally include a flow agitation step 628, as indicated by the dashed arrows and lines. A flow agitation step 628 is to facilitate the flow of the nanotube dope solution 112 through the extrusion die 314 . For example, in flow vibrating step 628 , extrusion die 314 is vibrated by a vibrating device to disrupt undesirable elastic turbulence of nanotube dope solution 112 through extrusion die 314 just prior to the exit of extrusion die 314 . It can aid flow and improve flow stability by reducing undesirable friction and shear effects along the flow surface, or a combination thereof.

Following extrusion step 626 , carbon nanotube proto-product 122 can proceed to alignment and consolidation step 630 . At this stage, carbon nanotube proto-product 112 can be produced to have a composition consisting primarily of nanotube solvent 204, as measured by volume or weight fraction. In an alignment and solidification step 630, carbon nanotube proto-product 122 is treated with a combination of stretching and alignment processes to form aligned carbon nanotube product 102. FIG. As an example, the alignment and solidification step 630 can include an initial alignment step 632, a radiation coagulation step 634, an intermediate alignment step 636, a chemical coagulation step 638, a solid alignment step 640, or combinations thereof.

An initial alignment step 632 can follow the creation of the carbon nanotube proto-product 122 to give the carbon nanotube proto-product 122 an initial alignment. For example, in initial alignment step 632, carbon nanotube proto-product 122 is stretched under tension by initial alignment unit 402 of FIG. Alignment can be achieved by operating at a draw speed that is faster than the flow rate of the carbon nanotube proto-product 122 as it exits the extrusion die 314 of FIG. As an example, the draw rate during the initial alignment step 632 is preferably at least 0.8, more preferably at least 0.9, and most preferably at least 0.95 Hermann orientation as measured by an in-line X-ray or neutron scattering technique. It can be set to generate alignments corresponding to the coefficients.

An irradiation coagulation step 634 can follow the initial alignment step 632 . An irradiation solidification step 634 is to initiate solidification by exposing carbon nanotube proto-product 122 to radiation from radiation source 406 in FIG. In an irradiation solidification step 634, carbon nanotube proto-product 122 is exposed to infrared radiation from radiation source 406 at a wavelength that minimizes absorption by nanotube solvent 204 and maximizes absorption of radiation by carbon nanotube molecules 106 of carbon nanotube proto-product 122. Exposure to radiation, such as radiation. As an example, radiation coagulation unit 404 can generate incident radiation at wavelengths in the range of 1-130 μm. The irradiation solidification step 634 can include pulsing the radiation source 406 to prevent localized heating effects within and along the carbon nanotube proto-product 122 . Irradiation solidification step 634 provides convective heat transfer, for example, by exhausting nanotube solvent 204 from irradiation solidification unit 404 , forcing gas flow in the atmosphere surrounding carbon nanotube proto-product 122 , and forcing carbon nanotube proto-product 122 to can help carry.

An intermediate alignment step 636 can follow the irradiation coagulation step 634 . An intermediate alignment step 636 is for providing alignment to the carbon nanotube proto-product 122 . At intermediate alignment step 636, carbon nanotube proto-product 122 is in a partially consolidated state and stretched under tension by intermediate alignment unit 408 of FIG. For example, the intermediate alignment unit 408 can be aligned by operating at a velocity greater than the flow velocity of the carbon nanotube proto-products 122 as they exit the extrusion die 314 . The speed and tension with which carbon nanotube proto-product 122 is stretched by intermediate alignment unit 408 can be the same, greater than, or less than that of initial alignment unit 402 in initial alignment step 632 .

A chemical coagulation step 638 can follow an intermediate alignment step 636 . In chemical solidification step 638 , carbon nanotube proto-product 122 is solidified by exposure to chemical coagulant 412 . For example, carbon nanotube proto-product 122 can be exposed to chemical coagulant 412 in chemical coagulation unit 410 of FIG. As a specific example, exposing the carbon nanotube proto-product 122 to the chemical coagulant 412 can include spraying, bath immersion, passage through a continuously renewed fluid film, or combinations thereof. Chemical solidification step 638 can provide a uniform solidification rate along the cross-section of carbon nanotube proto-product 122 . In addition, the chemical coagulation step 638 includes atmospheric control of the chemical coagulation unit 410 and convective heat transfer by exhausting volatiles and forced gas flow in the atmosphere surrounding the carbon nanotube proto-product 122 and the carbon nanotube proto-product 122 . Can include helping to carry.

Solid alignment step 640 can follow irradiation coagulation step 634, chemical coagulation step 638, or a combination thereof. Solid alignment step 640 is for solid alignment of carbon nanotube proto-product 122 . At solid alignment step 640, solidification of carbon nanotube proto-product 122 is nearly complete and is stretched under tension by solid alignment unit 414 of FIG. The alignment can be imposed to form the aligned carbon nanotube product 102, set the final dimensions of the aligned carbon nanotube product 102, or a combination thereof. As an example, solid alignment unit 414 can be operated at a velocity greater than the flow velocity of carbon nanotube proto-product 122 as it exits extrusion die 314 . Are the speed and tension at which carbon nanotube proto-product 122 is stretched by solid alignment unit 414 the same as the speed and tension of initial alignment unit 402 in initial alignment step 632, intermediate alignment unit 408 in intermediate alignment step 404, or a combination thereof? , which can be larger or smaller. The aligned carbon nanotube product 102 can be creeled for storage following the solid alignment step 640 .

Following production of aligned carbon nanotube product 102, method 600 may proceed to purification step 650. FIG. In purification step 650, aligned carbon nanotube product 102 is purified to remove residual amounts of nanotube solvent 204, residual amounts of chemical coagulant 412, other undesirable residual particles on aligned carbon nanotube product 102, or a combination thereof. can be subjected to a combination of one or more treatments of As an example, the purification step 650 can include an aqueous wash step 652, a thermal annealing step 654, a chemical wash step 656, or combinations thereof. Although purification step 650 represents one embodiment for purifying aligned carbon nanotube product 102, it is understood that additional steps and other arrangements or arrangements can be performed.

Aqueous wash step 652 is to remove residual traces of nanotube solvent from aligned carbon nanotube product 102 . In aqueous wash step 652, aligned carbon nanotube product 102 may be exposed to an aqueous solution, such as distilled or purified water, in solvent removal unit 504 of FIG. 5 to remove residual amounts of nanotube solvent 204. For example, exposing the aligned carbon nanotube product 102 to an aqueous solution can include spraying, bath immersion, passage through a continuously renewed fluid film, or combinations thereof. During the aqueous wash step 652, the aqueous solution can be maintained at a temperature in the range of 60°C to 80°C.

Thermal annealing step 654 is to remove residual traces of chemical coagulant 412 from aligned carbon nanotube product 102 . Thermal annealing step 654 can be performed within thermal annealing unit 506 of FIG. 5 in a heated and controlled environment. For example, in thermal annealing step 654 , aligned carbon nanotube product 102 may be heated to a volatilization temperature within thermal annealing unit 506 to remove residual amounts of chemical coagulant 412 . As a specific example, the volatilization temperature can range from 120°C to 250°C.

A chemical wash step 656 is to remove byproducts from the reaction between the nanotube coagulant and the nanotube solvent 204 . For example, in chemical cleaning step 656, aligned carbon nanotube product 102 can be exposed to the chemical cleaning solution of FIG. 5 in chemical cleaning unit 508 of FIG. As a specific example, exposing the aligned carbon nanotube article 102 to a chemical cleaning solution can include spraying, bath immersion, passage through a continuously renewed fluid film, or combinations thereof. The chemical cleaning solution can be a non-carbon nanotube solvent that can remove unwanted by-products of the reaction between nanotube solvent 204 and chemical coagulant 412 .

Method 600 can include one or more optional steps for modifying aligned carbon nanotube product 102 . For example, method 600 may optionally include functionalization step 660, coating step 670, doping step 680, product integration step 690, or combinations thereof.

Functionalization step 660 is to modify the molecular structure of aligned carbon nanotube product 102 . For example, functionalization step 660 can include a vulcanization process that can crosslink carbon nanotube molecules 106 in aligned carbon nanotube article 102 . As a specific example, in the vulcanization process, by doping the aligned carbon nanotube product 102 with polystyrene sulfonic acid (PEDOT), sulfur groups can be attached to the molecular backbone of the carbon nanotube molecule 106, which It can then be annealed at 800° C. in an oxygen-free atmosphere in the oven of the functionalization unit 512 of FIG. Once a set number of sulfur groups have been attached to the molecular backbone of the carbon nanotube molecule 106, standard vulcanization reactions can be performed to cross-link the sulfur groups.

Functionalization step 660 , which includes vulcanization, can improve the mechanical properties of aligned carbon nanotube product 102 , but can reduce the electrical conductivity of aligned carbon nanotube product 102 . Similarly, other forms of chemical functionalization are also possible, possibly at the expense of reduced conductivity.

A coating step 670 is for coating the surface of the aligned carbon nanotube article 102 . In a coating step 670 , a layer of coating material can be applied to the surface of the aligned carbon nanotube article 102 . In one example, the coating material is applied to the aligned carbon nanotube product through a mechanical process such as dip coating, roll-to-roll coating, slide coating, dip coating, or other available mechanical coating techniques, determined by the coating material. 102. In another example, the coating material is applied to the aligned carbon nanotubes via an electrolytic process that involves immersing the aligned carbon nanotube article 102 in an electrolytic bath containing an ionic compound in an aqueous dispersion at a suitable zeta potential level. It can be applied to product 102 . In a further example, the coating material can be applied to the aligned carbon nanotube article 102 by electrostatic coating or vapor deposition of charged solid particles.

Doping step 680 is for non-covalent chemical functionalization of aligned carbon nanotube product 102 . For example, in doping step 680, aligned carbon nanotube product 102 can undergo p-type doping with a p-type donor such as iodine or sulfuric acid. In one embodiment, doping step 680 may include vapor phase doping, such as by iodine doping. In another embodiment, the doping step 680 can include liquid phase doping, such as by acid doping. Following the doping step 680, the aligned carbon nanotube product 102 can be coated with a coating step 670 to ensure dopant stability over time.

A product integration step 690 is for integrating the aligned carbon nanotube product 102 into a device, component, or structure. For example, the aligned carbon nanotube product 102 produced after the alignment and solidification step 630, the purification step 650, the functionalization step 660, the coating step 670, the doping step 680, or combinations thereof can be processed in various in-line or semi-in-line processes. It can be integrated into a structure, device or component. Examples of structures are ropes, yarns, fabrics, foams, tapes or fabrics pre-impregnated with resin, chopped fiber filler materials, laminated films made from aligned carbon nanotube products 102, or Kevlar, fiberglass, or Combinations with other materials such as metals can be included. In a product consolidation step 690, the aligned carbon nanotube product 102 is twisted, braided, woven, pressed, rolled, bonded, laminated, coated, cut, or combinations thereof, and variously processed. structure can be formed.

Examples of integration of aligned carbon nanotube products 102 into devices or components can include wire antennas, patch antennas, coil transformers, coaxial cables. In an example of producing a wire antenna, the coated or uncoated form of the aligned carbon nanotube article 102 can be cut into lengths determined by the specific resonant frequency of single or multifilament threads, yarns, Or can be woven into a rope.

In the example of creating a patch antenna, a coated or uncoated film form cut of the aligned carbon nanotube product 102 can be cut into a specified antenna shape. The resulting morphology can be deposited onto a dielectric substrate, which can be coextruded using melt or solution processing.

In the example of creating a coil transformer, aligned carbon nanotube products 102 can be woven into threads, yards, or ropes, which can be wound around ferrite or magnetic cores to form coils. The number of windings can be determined by the inductance achieved by the coil.

In the example of producing a coaxial cable, the carbon nanotube proto-product 104 can be coextruded with a dielectric material. Once the carbon nanotube proto-product 104 is solidified, the dielectric material can be solidified as an encapsulation with the carbon nanotube product 102 aligned as an inner conductor.

As a result, these and other valuable aspects of embodiments of the present invention further advance the state of the art to at least the next level.

Although the invention has been described in relation to a specific best mode, it should be understood that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the scope of the appended claims. All matter contained in the specification or shown in the accompanying drawings is to be interpreted in an illustrative and non-limiting sense.

Claims (11)

A method of manufacturing a carbon nanotube product, comprising:
The method comprises
blending a non-aligned carbon nanotube material comprising carbon nanotube molecules with solid solvent particles;
activating the nanotube solvent by liquefying the solid solvent particles, wherein activating the nanotube solvent optionally comprises heating the solid solvent particles;
forming a nanotube dope solution by mixing the nanotube solvent and the unaligned carbon nanotube material;
forming a carbon nanotube proto-product by extruding said nanotube dope solution, wherein said nanotube dope solution is optionally extruded as nanotube filaments or nanotube films;
forming an aligned carbon nanotube product;
including
forming the aligned carbon nanotube article exposing the carbon nanotube proto-article to an infrared radiation source at a wavelength in the range of 1-130 μm, wherein the infrared radiation is optionally pulsed;
Alignment of carbon nanotube molecules in said carbon nanotube proto-product is provided prior to and/or after said exposing, wherein providing alignment of carbon nanotube molecules is optionally provided in said carbon nanotube proto-product and exposing the carbon nanotube proto-product to a chemical coagulant, wherein the chemical coagulant is a solvent for the nanotube solvent and a non-solvent for the carbon nanotube proto-product ,
Method. 2. The method of claim 1, further comprising cryo-freezing the nanotube solvent to form the solid solvent particles prior to blending with the non-aligned carbon nanotube material. further comprising adding the nanotube solvent in a liquid state to the unaligned carbon nanotube material;
2. The method of claim 1, wherein forming the nanotube dope solution comprises shear mixing the nanotube solvent in a liquid state into the non-aligned carbon nanotube material. 2. The method of claim 1, further comprising removing the nanotube solvent by evaporation under co-current flow with gaseous hydrochloric acid to prevent degradation of the nanotube solvent. 2. The method of claim 1, further comprising fractionating the nanotube dope solution to remove the lowest aspect ratio carbon nanotube molecules in the nanotube dope solution. 2. The method of claim 1, further comprising doping the aligned carbon nanotube product, coating a surface of the aligned carbon nanotube product, or a combination thereof. Integrating the aligned carbon nanotube product with additional examples of the aligned carbon nanotube product, other materials, or combinations thereof to produce (i) yarns, threads, fabrics, laminated films, tapes, foams, composites creating an integrated structure selected from pre-impregnated material and discrete lengths of chopped fiber material; or (ii) creating components selected from wire antennas, patch antennas, coil transformers, and coaxial cables; 2. The method of claim 1, further comprising: A method of manufacturing a carbon nanotube product, comprising:
The method comprises
mixing a non-aligned carbon nanotube material with a solvent precursor material;
activating the nanotube solvent by reacting the solvent precursor with a solvent activator;
forming a nanotube dope solution by mixing the nanotube solvent and the unaligned carbon nanotube material;
forming a carbon nanotube proto-product by extruding the nanotube dope solution;
forming an aligned carbon nanotube product;
including
forming the aligned carbon nanotube article comprises exposing the carbon nanotube proto-article to an infrared radiation source at a wavelength in the range of 1-130 μm;
Alignment of carbon nanotube molecules in said carbon nanotube proto-product is provided prior to and/or after said exposing, wherein providing alignment of carbon nanotube molecules is optionally provided in said carbon nanotube proto-product and exposing the carbon nanotube proto-product to a chemical coagulant, wherein the chemical coagulant is a solvent for the nanotube solvent and a non-solvent for the carbon nanotube proto-product ,
Method. A carbon nanotube product manufacturing system,
a blending unit configured to blend the misaligned carbon nanotube material with solid solvent particles;
a homogenization unit,
a homogenization unit configured to activate the nanotube solvent by liquefying the solid solvent particles and to mix the nanotube solvent and the unaligned carbon nanotube material to produce a nanotube dope solution;
an extrusion assembly configured to extrude the nanotube dope solution as a carbon nanotube proto-product;
a consolidation module configured to consolidate the carbon nanotube proto-product as an aligned carbon nanotube product, wherein the infrared radiation source is arranged to expose the carbon nanotube proto-product to radiation at a wavelength in the range of 1-130 μm. a solidification module containing the assembly,
A carbon nanotube product manufacturing system comprising: 2. The method of claim 1, further comprising removing the chemical coagulant from the aligned carbon nanotube product by thermally annealing the aligned carbon nanotube product. 3. The method of claim 1, wherein exposing the carbon nanotube proto-product to a chemical coagulant comprises exposing to a continuously renewed fluid film comprising the chemical coagulant .