# US 11,305,998 B2 · Methods for manufacturing carbon nanotube (CNT) hybrid sheet and yarn by gas phase assembly, and CNT-hybrid materials

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- Number: US 11,305,998 B2
- Document ID: US11305998B2
- Status: Granted
- Kind: B2
- Application number: 16/488,379
- Filed: 2018-02-23
- Published: 2020-08-06
- Granted: 2022-04-19
- Earliest claimed: 2017-02-24
- Assignees: University of Cincinnati; North Carolina Agricultural & Technical State Univ
- Applicants: University of Cincinnati
- Inventors: Mark Schulz; Guangfeng Hou; Vianessa Ng
- Web page: https://patentgrep.com/patent/US11305998B2

## CPC

- B01J 4/002: {Nozzle-type elements (nozzle-type reactors B01J19/26)}
- C01B 32/164: involving continuous processes
- B01D 39/06: Inorganic material, e.g. asbestos fibres, glass beads or fibres
- B01J 8/003: {in a downward flow}
- B01J 8/0035: {Periodical feeding or evacuation}
- B01J 8/025: {in a cylindrical shaped bed}
- B01J 19/26: Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
- C01B 32/162: characterised by catalysts
- C02F 1/001: {Processes for the treatment of water whereby the filtration technique is of importance (C02F1/44 takes precedence; construction of filters in general B01D24/00 - B01D41/00)}
- D01F 9/12: Carbon filaments; Apparatus specially adapted for the manufacture thereof
- H01B 1/04: mainly consisting of carbon-silicon compounds, carbon or silicon
- H10N 30/852: {Composite materials, e.g. having 1-3 or 2-2 type connectivity}
- B01D 2239/0258: comprising nanoparticles
- B01D 2239/1208: Porosity
- B01J 10/007: {in the presence of catalytically active bodies, e.g. porous plates}
- B01J 2204/005: the outlet side being of particular interest
- B01J 2208/00769: Details of feeding or discharging
- B01J 2208/02: with stationary particles
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01B 2202/22: Electronic properties
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/02: obtained by optical microscopy
- C01P 2004/03: obtained by SEM
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)
- D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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})
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

Systems and methods for the gas-phase production of carbon nanotube (CNT)-nanoparticle (NP) hybrid materials in a flow-through pyrolytic reactor specially adapted to integrate nanoparticles (NP) into CNT material at the nanoscale level, and the second generation CNT-NP hybrid materials produced thereby.

## Claims

### Claim 1

A gas-phase method for the production of carbon nanotube (CNT)-hybrid yarn and sheets using a pyrolytic reactor tube comprising an inlet port, an inlet zone, a furnace zone, an exit zone, and an exit port, the method comprising:
delivering an atomized fuel flow to the furnace zone at a point proximate the inlet port at a fuel flow rate, said fuel flow comprising a carrier gas and at least one source of carbon;
delivering a particle flow to the furnace zone at a point in the inlet zone at or beyond the delivery point of the fuel flow at a particle flow rate, said particle flow comprising carrier gas and at least one particle selected from ceramic, polymer, metal, a carbon source, and combinations thereof;
independently controlling the fuel flow rate and the particle flow rate to achieve a production time sufficient to continuously form a CNT-hybrid sock at a furnace zone temperature of between 1200° C. and 1600° C.;
and
collecting the emerging CNT-hybrid sock in a harvest box;
wherein the collected CNT-hybrid sock comprises carbon nanotube bundles integrated with the injected particles.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the furnace zone temperature is maintained at about 1400° C. across the production time.

### Claim 3 (depends on 1)

The method according to claim 1, further comprising twisting the emerging CNT-hybrid sock into yarn or rolling the emerging CNT-hybrid sock into sheets.

### Claim 4 (depends on 3)

The method according to claim 3, wherein the twisting and/or rolling is accompanied by one or more of water densification and electric charging.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the emerging CNT-hybrid sock is wound onto a rolling drum partially submerged in a water bath.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the CNT-hybrid sock is rolled with a backing sheet, tape or fiber.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the backing sheet comprises
polytetrafluoroethylene.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the fuel flow and/or the particle flow comprises at least one catalyst.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the catalyst comprises ferrocene.

### Claim 10 (depends on 8)

The method according to claim 8, wherein the fuel flow further comprises thiophene.

### Claim 11 (depends on 8)

The method according to claim 8, wherein the fuel flow further comprises xylene.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the fuel flow carbon source comprises a C1-6 hydrocarbon, optionally as an alcohol.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the fuel flow comprises a carbon source and the particle flow comprises particles selected from the group consisting of Li, Na, K, Mg, Ca, Ba, Ti, Zr, Nb, Cr, Ni, Pd, Cu, Al, Ag-coated Cu, Si, granulated activated carbon, granulated activated carbon and ferrocene, powder CNT, boron nitride nanotubes, C-60, nitinol, Cu—Ni alloy, Fe, and gaseous C13.

### Claim 14 (depends on 1)

The method according to claim 1, wherein the particles comprise a nanopowder.

### Claim 15 (depends on 14)

The method according to claim 14, wherein the particles comprise a functional group selected from the group consisting of —OH, —COOH, —CHO, —X (F, Cl, Br, I), N2, epoxide, and a combination of two or more thereof.

### Claim 16 (depends on 1)

The method according to claim 1, wherein the carrier gas comprises Argon.

### Claim 17 (depends on 1)

The method according to claim 1, wherein there is no independent fuel flow and particles comprising a high aspect ratio carbon are injected from a particle injector.

### Claim 18 (depends on 17)

The method according to claim 17, wherein the high aspect ratio carbon particles are selected from the group consisting of carbon nanotubes, carbon nanofibers, carbon microfibers, and C-60.

### Claim 19 (depends on 18)

The method according to claim 18, wherein one or more non-carbon particles are mixed with the high aspect ratio carbon particles in a particle injector, or delivered into the reactor inlet by different particle injectors.

### Claim 20 (depends on 1)

The method according to claim 1, wherein to achieve continuous product the fuel flow rate is adjusted to between 10 ml/hr and 60 ml/hr, and the particle delivery rate is roughly adjusted to between 1 g/hr and 100 g/hr for a 2 inch outer diameter reactor tube.

### Claim 21 (depends on 1)

The method according to claim 1, wherein hydrogen exhaust gas generated in the furnace is vented through one or more openings in the exit port to a hood at least partially surrounding the exit port, and through a conduit in communication with a first bubbler located exterior to the harvest box.

### Claim 22 (depends on 21)

The method according to claim 21, wherein hydrogen gas present in the harvest box is vented via a conduit from the harvest box to a second bubbler situated exterior to the harvest box.

### Claim 23 (depends on 1)

The method according to claim 1, further comprising delivering a dilution gas flow into the harvest box at a dilution gas flow rate of from about 2 SLM to about 15 SLM.

### Claim 24 (depends on 1)

The method according to claim 1 wherein hydrogen exhaust gas generated in the furnace is vented through one or more openings in the exit port to a hood at least partially surrounding the exit port, and through a conduit in communication with a first bubbler located exterior to the harvest box, hydrogen gas present in the harvest box is vented via a conduit from the harvest box to a second bubbler situated exterior to the harvest box, said first bubbler at a pressure of about 0.5 inches of water, said second bubbler at a pressure of about 1.0 inches of water and further comprising a dilution gas flow into the harvest box at a dilution gas flow rate of from about 2 SLM to about 15 SLM.

### Claim 25 (depends on 1)

The method according to claim 1, wherein delivering a particle flow comprises injecting particles via at least one particle injector selected from the group consisting of a flow type injector, a venturi eductor, and combinations thereof, wherein prior to delivering the particle flow, the particles are mixed with the carrier gas in the at least one injector.

### Claim 26 (depends on 25)

The method according to claim 25, wherein particles are delivered from at least two different particle injectors, each particle injector comprising a different particle.

### Claim 27 (depends on 1)

The method according to claim 1, wherein delivering an atomized fuel flow and delivering a particle flow are effectuated via a dual injection device comprising a first nozzle and a second nozzle that meet at a merged injection outlet, the first nozzle providing carrier gas and particles at a first flow rate, the second nozzle providing fuel at a second flow rate via a positive displacement pump, whereby the first flow rate and the second flow rate are independently controlled.

### Claim 28 (depends on 27)

The method according to claim 27, wherein the positive displacement pump comprises a syringe.

### Claim 29 (depends on 27)

The method of claim 27, wherein a voltage between about −20 kV and +3 kV is applied to the duel injection device during a production time.

### Claim 30 (depends on 1)

The method according to claim 1, further comprising applying an electromagnetic field to the reactor during the production time.

### Claim 31

A carbon nanotube (CNT)-NP hybrid material having NPs integrated into the material at a nanoscale level, wherein the CNT-NP hybrid material is formed from a continuous CNT-NP hybrid sock.

### Claim 32

A filter comprising a CNT-NP hybrid material having NPs integrated into the material at a nanoscale, the filter comprising a porosity defined by pore size and pore density, the CNT-NP hybrid material comprising CNT bundles integrated with one or more of the NPs, the NPs being selected from granulated activated carbon and iron, wherein the CNT-NP hybrid material is formed from a continuous CNT-NP hybrid sock.

### Claim 33 (depends on 32)

The filter according to claim 32, wherein the filter pore size and density are uniform.

### Claim 34 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising a CNT-Cu wire.

### Claim 35 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising CNT-Al sheet.

### Claim 36 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising CNT-(Ag-coated-Cu) sheet.

### Claim 37 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising CNT-Si sheet.

### Claim 38 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising a magnetic CNT-Fe material.

### Claim 39 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising CNT-nitinol sheet.

### Claim 40 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising CNT-Y—X, wherein Y is selected from carbon nanofiber (CNF) and carbon microfiber (CMF), and X is selected from the group consisting of Li, Na, K, Mg, Ca, Ba, Ti, Zr, Nb, Cr, Ni, Pd, Cu, Al, Ag-coated Cu, Si, granulated activated carbon, granulated activated carbon and ferrocene, powder CNT, boron nitride nanotubes, C-60, nitinol, Cu—Ni alloy, Fe, and gaseous C13.

### Claim 41 (depends on 31)

The CNT-NP hybrid material according to claim 31 comprising a CNT-X material, wherein X is selected from the group consisting of Li, Na, K, Mg, Ca, Ba, Ti, Zr, Nb, Cr, Ni, Pd, Cu, Al, Ag-coated Cu, Si, granulated activated carbon, granulated activated carbon and ferrocene, powder CNT, boron nitride nanotubes, C-60, nitinol, Cu—Ni alloy, Fe, gaseous C13, rubidium, cesium, and francium.

### Claim 42 (depends on 41)

The CNT-NP hybrid material according to claim 41, wherein X is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, and a combination of two or more thereof, and, prior to removal from the harvest box, the CNT-X material is coated with a dielectric coating.

### Claim 43 (depends on 31)

The CNT-NP hybrid material according to claim 31, wherein the CNT-NP hybrid material comprises a plurality of nano-voids between adjacent CNT, at least one of the plurality of nano-voids containing at least one NP.