# US 8,784,937 B2 · Glass substrates having carbon nanotubes grown thereon and methods for production thereof

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- Number: US 8,784,937 B2
- Document ID: US8784937B2
- Status: Granted
- Kind: B2
- Application number: 13/230,751
- Filed: 2011-09-12
- Published: 2012-03-15
- Granted: 2014-07-22
- Earliest claimed: 2010-09-14
- Assignees: Applied Nanostructured Solutions, LLC
- Applicants: Brandon K. Malet; Tushar K. Shah
- Inventors: Brandon K. Malet; Tushar K. Shah
- Web page: https://patentgrep.com/patent/US8784937B2

## CPC

- B05D 3/10: by other chemical means
- B01J 21/185: {Carbon nanotubes (carbon nanotubes per se C01B32/15)}
- B01J 23/75: Cobalt
- B01J 35/58: Fabrics or filaments
- B01J 37/0213: {Preparation of the impregnating solution}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01B 32/162: characterised by catalysts
- C01B 32/164: involving continuous processes
- C03C 17/28: with organic material (C03C17/34, C03C17/44 take precedence)
- C03C 25/1095: to obtain coated fabrics
- C03C 25/223: by chemical vapour deposition or pyrolysis
- C03C 25/24: Coatings containing organic materials
- C03C 25/44: Carbon, e.g. graphite
- C23C 16/26: Deposition of carbon only
- C23C 16/458: characterised by the method used for supporting substrates in the reaction chamber
- C23C 16/545: {for coating elongated substrates}
- 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}
- B05D 2203/35: Glass
- B05D 2256/00: Wires or fibres
- C01B 2202/34: Length
- Y10S 977/843: Gas phase catalytic growth, i.e. chemical vapor deposition
- Y10S 977/891: Vapor phase deposition
- Y10T 428/25: Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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}
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Methods for growing carbon nanotubes on glass substrates, particularly glass fiber substrates, are described herein. The methods can include depositing a catalytic material or a catalyst precursor on a glass substrate; depositing a non-catalytic material on the glass substrate prior to, after, or concurrently with the catalytic material or catalyst precursor; and exposing the glass substrate to carbon nanotube growth conditions so as to grow carbon nanotubes thereon. The glass substrate, particularly a glass fiber substrate, can be transported while the carbon nanotubes are being grown thereon. Catalyst precursors can be converted into a catalyst when exposed to carbon nanotube growth conditions. The catalytic material or catalyst precursor and the non-catalytic material can be deposited from a solution containing water as a solvent. Illustrative deposition techniques include, for example, spray coating and dip coating.

## Claims

### Claim 1

A carbon nanotube growth process comprising:
depositing a catalyst precursor on a glass substrate, the catalyst precursor being deposited from a solution comprising water as a solvent;
wherein the catalyst precursor is formed from a reaction between at least one transition metal salt and hydrogen peroxide in the solution from which the catalyst precursor is deposited; and
after depositing the catalyst precursor, exposing the glass substrate to carbon nanotube growth conditions so as to grow carbon nanotubes thereon;
wherein the catalyst precursor is converted into a catalyst that is operable for forming carbon nanotubes when exposed to the carbon nanotube growth conditions.

### Claim 2 (depends on 1)

The carbon nanotube growth process of claim 1, further comprising:
transporting the glass substrate while the carbon nanotubes are being grown thereon.

### Claim 3 (depends on 1)

The carbon nanotube growth process of claim 1, wherein the catalyst precursor comprises a transition metal salt selected from the group consisting of a transition metal nitrate, a transition metal acetate, a transition metal citrate, a transition metal chloride, hydrates thereof, and combinations thereof.

### Claim 4 (depends on 3)

The carbon nanotube growth process of claim 3, wherein the transition metal salt is selected from the group consisting of iron (II) nitrate, iron (III) nitrate, cobalt (II) nitrate, nickel (II) nitrate, copper (II) nitrate, iron (II) acetate, iron (III) acetate, cobalt (II) acetate, nickel (II) acetate, copper (II) acetate, iron (II) citrate, iron (III) citrate, iron (III) ammonium citrate, cobalt (II) citrate, nickel (II) citrate, copper (II) citrate, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, nickel (II) chloride, copper (II) chloride, hydrates thereof, and combinations thereof.

### Claim 5 (depends on 1)

The carbon nanotube growth process of claim 1, wherein the at least one transition metal salt comprises an iron (II) salt or a hydrate thereof and a cobalt (II) salt or a hydrate thereof.

### Claim 6

A carbon nanotube growth process comprising:
depositing a catalyst precursor on a glass fiber substrate, the catalyst precursor being deposited from a solution comprising water as a solvent;
wherein the catalyst precursor is formed from a reaction between at least one transition metal salt and hydrogen peroxide in the solution from which the catalyst precursor is deposited;
converting the catalyst precursor into a catalyst that is operable for forming carbon nanotubes when exposed to carbon nanotube growth conditions; and
exposing the glass fiber substrate to carbon nanotube growth conditions while the glass fiber substrate is being transported so as to grow carbon nanotubes thereon.

### Claim 7 (depends on 6)

The carbon nanotube growth process of claim 6, wherein the at least one transition metal salt comprises iron (II) acetate or a hydrate thereof and cobalt (II) acetate or a hydrate thereof.

### Claim 8 (depends on 6)

The carbon nanotube growth process of claim 6, wherein the catalyst precursor comprises a transition metal salt selected from the group consisting of a transition metal nitrate, a transition metal acetate, a transition metal citrate, a transition metal chloride, hydrates thereof, and combinations thereof.

### Claim 9 (depends on 8)

The carbon nanotube growth process of claim 8, wherein the transition metal salt is selected from the group consisting of iron (II) nitrate, iron (III) nitrate, cobalt (II) nitrate, nickel (II) nitrate, copper (II) nitrate, iron (II) acetate, iron (III) acetate, cobalt (II) acetate, nickel (II) acetate, copper (II) acetate, iron (II) citrate, iron (III) citrate, iron (III) ammonium citrate, cobalt (II) citrate, nickel (II) citrate, copper (II) citrate, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, nickel (II) chloride, copper (II) chloride, hydrates thereof, and combinations thereof.

### Claim 10

A carbon nanotube growth process comprising:
allowing a solution comprising water, hydrogen peroxide, an iron (II) salt or a hydrate thereof, and a cobalt (II) salt or a hydrate thereof to form a catalyst precursor in the solution, the solution comprising water as a solvent;
depositing the solution with the catalyst precursor therein onto a glass fiber substrate;
converting the catalyst precursor into a catalyst that is operable for forming carbon nanotubes upon exposure to carbon nanotube growth conditions; and
exposing the glass fiber substrate to carbon nanotube growth conditions so as to grow carbon nanotubes thereon.

### Claim 11 (depends on 10)

The carbon nanotube growth process of claim 10, further comprising:
transporting the glass fiber substrate while the carbon nanotubes are being grown thereon.

### Claim 12 (depends on 10)

The carbon nanotube growth process of claim 10, wherein the iron (II) salt comprises iron (II) acetate or a hydrate thereof and the cobalt (II) salt comprises cobalt (II) acetate or a hydrate thereof.

### Claim 13 (depends on 10)

The carbon nanotube growth process of claim 10, wherein the catalyst comprises at least an iron-cobalt alloy.

### Claim 14 (depends on 10)

The carbon nanotube growth process of claim 10, wherein converting comprises heating the catalyst precursor to form an intermediate catalyst state and exposing the intermediate catalyst state to the carbon nanotube growth conditions to form the catalyst.

### Claim 15 (depends on 10)

The carbon nanotube growth process of claim 10, wherein a molar ratio of iron to cobalt ranges from about 5:1 to about 6:1.