William Marsh Rice University

Efh, Inc.

Houston Advanced Research Center

John L Margrave

Robert H Hauge

Valery Khabashesku

Richard E Smalley

Peter James Boul

Daniel T Colbert

Jie Liu

Ken A Smith

Mary Lou Margrave, Legal Representative

Chad Huffman

Edward T Mickelson

Haiqing Peng

James W Campbell

Enrique V Barrera

Zhenning Gu

Jiang Zhu

Wilbur Edward Billups

Donald E Patterson

Yunming Ying

C Judith Chu

Lei Zhang

Yu Liu

Charles A Rey

George Phillip Hansen

Jong Dae Kim

Valery Aleksandrovich Davydov

Aleksandra Viktorovna Rakhmanina

Lyudmile Stepanovna Kashevarova

John L Zimmerman

Shankar Krishnan

Valery N Khabashesku

Enrique Barrera

The present invention is directed to methods of integrating carbon nanotubes into epoxy polymer composites via chemical functionalization of carbon nanotubes, and to the carbon nanotube-epoxy polymer composites produced by such methods. Integration is enhanced through improved dispersion and/or covalent bonding with the epoxy matrix during the curing process. In general, such methods involve the attachment of chemical moieties (i.e., functional groups) to the sidewall and/or end-cap of carbon nanotubes such that the chemical moieties react with either the epoxy precursor(s) or the curing agent(s) (or both) during the curing process. Additionally, in some embodiments, these or additional chemical moieties can function to facilitate dispersion of the carbon nanotubes by decreasing the van der Waals attractive forces between the nanotubes.

Fiber-reinforced polymer composites containing functionalized carbon nanotubes

The present invention is directed toward compositions comprising carbon nanotubes (CNTs) that are sidewall-functionalized with amino acid groups, and to amino acid compositions comprising carbon nanotubes. The present invention is also directed to simple and relatively inexpensive methods for the preparation of such compositions. Such compositions are expected to greatly extend the bio-medical applications of CNTs.

Nanotube-amino acids and methods for preparing same

A method for functionalizing the wall of single-wall or multi-wall carbon nanotubes involves the use of acyl peroxides to generate carbon-centered free radicals. The method allows for the chemical attachment of a variety of functional groups to the wall or end cap of carbon nanotubes through covalent carbon bonds without destroying the wall or endcap structure of the nanotube. Carbon-centered radicals generated from acyl peroxides can have terminal functional groups that provide sites for further reaction with other compounds. Organic groups with terminal carboxylic acid functionality can be converted to an acyl chloride and further reacted with an amine to form an amide or with a diamine to form an amide with terminal amine. The reactive functional groups attached to the nanotubes provide improved solvent dispersibility and provide reaction sites for monomers for incorporation in polymer structures. The nanotubes can also be functionalized by generating free radicals from organic sulfoxides.

Method for functionalizating carbon naontubes utilizing peroxides

The present invention is directed to functionalized nanoscale diamond powders, methods for making such powders, applications for using such powders, and articles of manufacture comprising such powders. Methods for making such functionalized nanodiamond powders generally comprise a fluorination of nanodiamond powder. In some embodiments, such methods comprise reacting fluorinated nanodiamond powder with a subsequent derivatization agent, such as a strong nucleophile.

Functionalization of nanodiamond powder through fluorination and subsequent derivatization reactions

This invention is directed to chemical derivatives of carbon nanotubes wherein the carbon nanotubes have a diameter up to 3 nm. In one embodiment, this invention also provides a method for preparing carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single-wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents are dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium.

Sidewall derivatized carbon nanotubes

Method for functionalizing carbon nanotubes utilizing peroxides

The present invention is directed to methods of forming sidewall-functionalized carbon nanotubes, wherein such functionalized carbon nanotubes have hydroxyl-terminated moieties covalently attached to their sidewalls. Generally, such methods involve chemistry on carbon nanotubes that have first been fluorinated. In some embodiments, fluorinated carbon nanotubes ('fluoronanotubes') are reacted with mono-metal salts of a dialcohol, MO&#x2014;R&#x2014;OH, where M is a metal and R is hydrocarbon or other organic chain and/or ring structural unit. In such embodiments, &#x2014;O&#x2014;R&#x2014;OH displaces &#x2014;F on the nanotube, the fluorine leaving as MF. Generally, such mono-metal salts are formed in situ by the addition of MOH to one or more dialcohols in which the fluoronanotubes have been dispersed. In some embodiments, fluoronanotubes are reacted with amino alcohols, such as being of the type HN&#x2014;R&#x2014;OH, wherein &#x2014;N(H)&#x2014;R&#x2014;OH displaces &#x2014;F on the nanotube, the fluorine leaving as HF.

Sidewall functionalization of nanotubes with hydroxyl terminated moieties

Fabrication of carbon nanotube reinforced epoxy polymer composites using functionalized carbon nanotubes

This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.

Functionalized single-wall carbon nanotubes

The present invention is directed towards the fluorination of polymeric Cand towards the chemical and physical modifications of polymeric Cthat can be accomplished through fluorination.

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A method for cutting single-wall carbon nanotubes involves partially fluorinating single-wall carbon nanotubes and pyrolyzing the partially fluorinated nanotubes in an inert atmosphere or vacuum up to about 1000&#xb0; C. The nanotubes are optionally purified before cutting. The partial fluorination involves fluorinating the nanotubes to a carbon-fluorine stoichiometry of CF, where x is up to about 0.3. The invention also relates to the derivatization of fluorinated and cut single-wall carbon nanotubes. The single-wall carbon nanotubes can be cut to any length depending on the fluorination and pyrolysis conditions. Short nanotubes are useful in various applications, such as field emitters for flat panel displays and as 'seeds' for further nanotube growth.

Method for cutting single-wall carbon nanotubes through fluorination

Chemically modifying single wall carbon nanotubes to facilitate dispersal in solvents

Methods of chemically derivatizing single-wall carbon nanotubes

Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof, and use of derivatized nanotubes

Dispersions and solutions of fluorinated single-wall carbon nanotubes

Growing community of inventors

Bellaire, TX, United States of America

John L Margrave