# US 2015/0147573 A1 · Nanofiber ribbons and sheets and fabrication and application thereof

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- Number: US 2015/0147573 A1
- Document ID: US20150147573A1
- Status: Published application
- Kind: A1
- Application number: 14/581,092
- Filed: 2014-12-23
- Published: 2015-05-28
- Earliest claimed: 2004-11-09
- Assignees: Board of Regents, The University of Texas System
- Applicants: Board of Regents, The University of Texas System
- Inventors: Mei Zhang; Shaoli Fang; Ray H. Baughman; Anvar A. Zakhidov; Kenneth Ross Atkinson; Ali E. Aliev; Sergey Li; Chris Williams
- Web page: https://patentgrep.com/patent/US20150147573A1

## CPC

- B01L 3/502707: {characterised by the manufacture of the container or its components}
- B29C 48/0019: {combined with shaping by flattening, folding or bending}
- B32B 5/02: characterised by structural features of a {fibrous or filamentary} layer {(layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02)}
- B32B 5/12: characterised by the relative arrangement of fibres or filaments of {different layers, e.g. the fibres or filaments being parallel or perpendicular to each other}
- B32B 18/00: Layered products essentially comprising ceramics, e.g. refractory products
- B32B 37/12: characterised by using adhesives
- B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
- C01B 32/15: Nano-sized carbon materials
- C01B 32/154: Preparation
- C01B 32/158: Carbon nanotubes
- C01B 32/16: Preparation
- C01B 32/164: involving continuous processes
- C01B 32/168: After-treatment
- C01B 32/17: Purification
- C01B 32/18: Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
- C01B 32/36: Reactivation or regeneration
- C04B 35/62231: {based on oxide ceramics}
- C04B 35/62272: {based on non-oxide ceramics (carbon nanotubes C01B32/15; carbon fibers D01F9/12)}
- C04B 35/62281: {based on silicon carbide (C04B35/571 takes precedence)}
- C04B 35/62855: {Refractory metal oxides}
- C04B 35/62892: {with a coating layer consisting of particles}
- C04B 35/62897: {Coatings characterised by their thickness}
- C04B 35/80: Fibres, filaments, whiskers, platelets, or the like
- C23C 16/44: characterised by the method of coating (C23C16/04 takes precedence)
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- D01F 9/08: of inorganic material (working or processing of metal wire B21F; from softened glass, minerals or slags C03B37/00)
- D01F 9/12: Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F 9/127: by thermal decomposition of hydrocarbon gases or vapours {or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols}
- D01F 9/1273: {Alkenes, alkynes}
- D01F 9/1275: {Acetylene}
- D02G 3/16: Yarns or threads made from mineral substances
- D02G 3/28: Doubled, plied, or cabled threads {(D02G3/32, D02G3/36 take precedence; effect yarns D02G3/34; details of spindles, e.g. bearings D01H7/86)}
- D02G 3/44: Yarns or threads characterised by the purpose for which they are designed {(protective gloves A41D19/00; protective clothing A62B17/00; ropes D07B1/02)}
- D04H 3/002: Inorganic yarns or filaments
- D06B 15/00: Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
- D06M 15/256: containing fluorine
- D06M 15/333: of vinyl acetate; Polyvinylalcohol
- G01L 1/2287: {constructional details of the strain gauges (adjustable resistors H01C10/00)}
- G02F 1/133308: {Support structures for LCD panels, e.g. frames or bezels}
- H01B 1/24: the conductive material comprising carbon-silicon compounds, carbon or silicon
- H01B 5/08: Several wires or the like stranded in the form of a rope
- H01G 11/36: Nanostructures, e.g. nanofibres, nanotubes or fullerenes
- H01M 4/926: {on carbon or graphite}
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H05K 9/0081: {Electromagnetic shielding materials, e.g. EMI, RFI shielding (H05K9/0003 takes precedence)}
- H10K 30/821: {comprising carbon nanotubes}
- H10K 59/8051: {Anodes}
- H10K 85/221: {Carbon nanotubes}
- B32B 2262/106: Carbon fibres, e.g. graphite fibres
- B32B 2307/202: Conductive
- B32B 2310/00: Treatment by energy or chemical effects
- B32B 2313/04: Carbon
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01B 2202/06: Multi-walled nanotubes
- C01B 2202/08: Aligned nanotubes
- C04B 2235/422: Carbon
- C04B 2235/5248: Carbon, e.g. graphite
- C04B 2235/526: characterised by the length of the fibers
- C04B 2235/5264: characterised by the diameter of the fibers
- C04B 2235/616: Liquid infiltration of green bodies or pre-forms
- D10B 2101/122: Nanocarbons
- G02F 1/133334: {Electromagnetic shields}
- G02F 1/15165: {Polymers}
- H01M 4/8605: {Porous electrodes}
- H10K 50/30: Organic light-emitting transistors
- H10K 59/80524: {Transparent cathodes, e.g. comprising thin metal layers}
- Y02E 10/549: Organic PV cells
- Y02E 60/10: Energy storage using batteries
- Y02E 60/13: Energy storage using capacitors
- Y02E 60/50: Fuel cells
- Y02P 20/133: Renewable energy sources, e.g. sunlight
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y10S 977/742: Carbon nanotubes, CNTs
- Y10S 977/745: having a modified surface
- Y10S 977/746: Modified with biological, organic, or hydrocarbon material
- Y10S 977/752: Multi-walled
- Y10S 977/843: Gas phase catalytic growth, i.e. chemical vapor deposition
- Y10S 977/844: Growth by vaporization or dissociation of carbon source using a high-energy heat source, e.g. electric arc, laser, plasma, e-beam
- Y10S 977/847: Surface modifications, e.g. functionalization, coating
- Y10S 977/848: Tube end modifications, e.g. capping, joining, splicing
- Y10S 977/932: for electronic or optoelectronic application
- Y10S 977/948: Energy storage/generating using nanostructure, e.g. fuel cell, battery
- Y10S 977/961: for textile or fabric treatment
- Y10T 428/30: Self-sustaining carbon mass or layer with impregnant or other layer
- B01L: CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D02G: CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D04H: MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL (weaving D03; knitting D04B; braiding D04C; net-making D04G; sewing D05B; tufting D05C; finishing non-woven fabrics D06); FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING {; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION}(non-woven fabrics having an intermediate or external layer of a different kind, e.g. of woven fabric, B32B)
- D06B: TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS (mechanical treatment of natural fibrous or filamentary material to obtain fibres or filaments D01B)
- D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- G01L: MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE (weighing G01G)
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- D10B: INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention is directed to nanofiber yarns, ribbons, and sheets; to methods of making said yarns, ribbons, and sheets; and to applications of said yarns, ribbons, and sheets. In some embodiments, the nanotube yarns, ribbons, and sheets comprise carbon nanotubes. Particularly, such carbon nanotube yarns of the present invention provide unique properties and property combinations such as extreme toughness, resistance to failure at knots, high electrical and thermal conductivities, high absorption of energy that occurs reversibly, up to 13% strain-to-failure compared with the few percent strain-to-failure of other fibers with similar toughness, very high resistance to creep, retention of strength even when heated in air at 450° C. for one hour, and very high radiation and UV resistance, even when irradiated in air. Furthermore these nanotube yarns can be spun as one micron diameter yarns and plied at will to make two-fold, four-fold, and higher fold yarns. Additional embodiments provide for the spinning of nanofiber sheets having arbitrarily large widths. In still additional embodiments, the present invention is directed to applications and devices that utilize and/or comprise the nanofiber yarns, ribbons, and sheets of the present invention.

## Claims

### Claim at position 1

1-469. (canceled)

### Claim 470

A process of producing ribbons or sheets comprising nanofibers, the process comprising:
(a) providing a pre-primary assembly comprising a substantially parallel array of nanofibers oriented in a direction; and
(b) drawing the nanofibers from the array of nanofibers to form a ribbon or sheet having an alignment direction, wherein the alignment direction of the ribbon or sheet is at an angle to the direction of the array of nanofibers at no more than 90°.

### Claim 471 (depends on 470)

The process of claim 470, wherein the nanofibers comprise carbon nanotubes.

### Claim 472 (depends on 470)

The process of claim 470, wherein the nanofibers comprise carbon nanotubes that have an interior that are, at least partially, filled with a material.

### Claim 473 (depends on 470)

The process of claim 470, further comprising infiltrating the ribbon or sheet with a liquid and subsequently evaporating the liquid from the ribbon or sheet wherein the infiltration and evaporation at least partially densifies the ribbon or sheet and forms a densified carbon nanotube ribbon or sheet.

### Claim 474 (depends on 470)

The process of claim 470, wherein said infiltration with the liquid comprises a method selected from the group consisting of vapor condensation, imbibing a liquid, exposure to an aerosol of a liquid, and combinations thereof.

### Claim 475 (depends on 473)

The process of claim 473, wherein the liquid comprises a substance selected from the group consisting of acetone, ethanol, methanol, isopropyl alcohol, toluene, chloroform, chlorobenzene, liquids having similar cohesive energy densities, and combinations thereof.

### Claim 476 (depends on 470)

The process of claim 470, wherein at least the drawing is conducted at an elevated temperature using a heating means selected from the group consisting of
(a) resistive heating of the nanofibers by conducting current along the ribbons or sheets;
(b) the absorption by the nanofibers of electromagnetic radiation from a region selected from the group consisting of visible, ultraviolet, infrared, radio frequency, microwave frequency, and combinations thereof; and
(c) combinations thereof.

### Claim 477 (depends on 470)

The process of claim 470, wherein the pre-primary assembly is formed by growing a nanofiber forest on a substrate using a catalyst.

### Claim 478 (depends on 477)

The process of claim 477, wherein the direction of the nanofibers in pre-primary assembly is approximately orthogonal to the substrate.

### Claim 479 (depends on 477)

The process of claim 477, wherein the substrate has a first side and a second side, and wherein forests of nanofibers are grown on both the first side and the second side.

### Claim 480 (depends on 470)

The process of claim 470, wherein the nanofiber array comprises a forest of nanofibers, and wherein the forest of nanofibers is stripped from a growth substrate for the forest and produced into the ribbon or sheet while not attached to said growth substrate.

### Claim 481 (depends on 480)

The process of claim 480, wherein more than one forest of nanofibers is stripped from growth substrates for the forests of nanofibers and stacked upon each other to provide an array of nanofiber forest layers from which the ribbon or sheet is produced.

### Claim 482 (depends on 477)

The process of claim 477, further comprising connecting an attachment to a sidewall of the nanofiber forest or near the sidewall.

### Claim 483 (depends on 482)

The process of claim 482, wherein the attachment is selected from the group consisting of adhesives, arrays of pins, or a combination thereof.

### Claim 484 (depends on 470)

The process of claim 470, wherein the nanofibers are drawn without substantially twisting the ribbon or sheet.

### Claim 485 (depends on 470)

The process of claim 470, further comprising applying an enhancing agent to the ribbon or sheet, wherein the enhancing agent comprises a polymer selected from the group consisting of polyvinyl alcohol, a polyvinyl alcohol copolymer, and combinations thereof.

### Claim 486 (depends on 485)

The process of claim 485, wherein the enhancing agent is applied to the ribbon or sheet while the ribbon or sheet is subjected to tensile strain.

### Claim 487 (depends on 470)

The process of claim 470, wherein electrical conductivity of the ribbon or sheet is increased by incorporating an electrically conducting material with the ribbon or sheet, and wherein the electrically conducting material is selected from the group consisting of conducting polymers, metals, metal alloys, and combinations thereof.

### Claim 488 (depends on 470)

The process of claim 470, further comprising coating the pre-primary assembly with a hydrophobic material.

### Claim 489 (depends on 488)

The process of claim 488, wherein the hydrophobic material comprises a fluorocarbon polymer.

### Claim 490 (depends on 470)

The process of claim 470, further comprising infiltrating the ribbon or sheet with a catalyst and growing the nanofibers within the sheet or ribbon by chemical vapor deposition.

### Claim 491 (depends on 470)

The process of claim 470, wherein the nanofibers are synthesized as a forest in a furnace growth region on a substrate the continuously moves from a furnace growth region into a region where the nanofibers in the forest are drawn.

### Claim 492 (depends on 491)

The process of claim 491, wherein the substrate is selected from the group consisting of a belt, a substrate attached to a belt, a drum, a substrate attached to a drum, and combinations thereof.

### Claim 493 (depends on 470)

The process of claim 470, further comprising subjecting the ribbon or sheet to radiation selected from the group consisting of electron beam, ion beam, microwave, radio frequency and combinations thereof.

### Claim 494 (depends on 470)

The process of claim 470, wherein the drawing of the nanofibers forms a ribbon and the ribbon is laminated to form a sheet.

### Claim 495 (depends on 494)

The method of claim 494, wherein the laminating involves the use of at least one of a chemical binding agent, an organic polymer, an electron beam, thermal treatment, an ion beam, radio frequency, irradiation, microwave irradiation, and combinations thereof.

### Claim 496

A nanofiber ribbon or sheet made by the process of
(a) providing a pre-primary assembly comprising a substantially parallel array of nanofibers oriented in a direction, and
(b) drawing the nanofibers from the array of nanofibers to form a ribbon or sheet having an alignment direction, wherein the alignment direction of the ribbon or sheet is at an angle to the direction of the array of nanofibers at no more than 90°,
wherein the nanofiber ribbon or sheet is attached to a substrate.

### Claim 497 (depends on 496)

The nanofiber ribbon or sheet of claim 496, wherein said substrate comprises a material selected from the group consisting of plastics, adhesive coated tapes, glass, metal, paper, and combinations thereof.

### Claim 498

Plied layers comprising nanofiber ribbons or sheets made by the process of
(a) providing a pre-primary assembly comprising a substantially parallel array of nanofibers oriented in a direction, and
(b) drawing the nanofibers from the array of nanofibers to form a ribbon or sheet having an alignment direction, wherein the alignment direction of the ribbon or sheet is at an angle to the direction of the array of nanofibers at no more than 90°,
wherein the nanofiber ribbons and sheets are each oriented but do not have the same preferential direction of alignment of the carbon nanotubes.