2017
TRIARYLMETHANE DIO-OXIMATE COMPOUNDS

Dr. W. Wallace Ellis, III, Dr. Brian J. Elliott

U.S. Patent No. 9,714,346 B1

July 25, 2017

A triarylmethane dye-oximate compound derived from 2,3-butanedione monoxime reacted with a triarylmethane dye. Particular embodiments include a triarylmethane dye selected from methyl violet, crystal violet, fuchsine, pararosaniline, new fuchsine, fuchsine acid, phenol red, malachite green, brilliant green, brilliant blue, Victoria blue B Victoria blue FBR, Victoria blue BO, Victoria blue FGA, Victoria blue 4 R, Victoria blue R or methyl blue. The dye-oximate compound is suitable for use as both a reactive decontaminating compound and a color indicating compound for organophosphates.
COOLING GARMENT

Dr. Robert J. Copeland, Dr. Girish Srinivas, Mr. John D. Wright, Dr. Steven C. Gebhard

U.S. Patent No. 9,635,889

May 2, 2017

The present invention relates to a cooling garment, comprising: a moisture-wicking under layer; and an impermeable outer layer, wherein the impermeable outer layer is attached to the moisture-wicking under layer forming at least one channel within the garment having a wetted perimeter of at most 5 inches; and an above ambient pressure gas supply operably attached to the channel. The present invention also relates to the cooling shirt or vest garment, comprising: a moisture-wicking under layer and an impermeable outer layer, wherein the outer layer is attached to the under layer forming a plurality of channels.
BREATHING APPARATUS, AND METHOD FOR CONTROLLING TEMPERATURE FLUCTUATIONS

Mr. John D. Wright, Dr. Robert J. Copeland, Dr. Girish Srinivas, Dr. Steven C. Gebhard, Mr. Michael E. Karpuk

U.S. Patent No. 9,597,532

March 21, 2017

A wearable breathing apparatus includes a thermal capacitor that a user inhales and exhales through. Inhaled air is cooled as it passes through the thermal capacitor, and exhaled air cools the material of the thermal capacitor for the next breathing cycle. The breathing apparatus may be used by a firefighter, for example, as a lightweight apparatus to enable the firefighter to safely breathe dangerously heated air, for example while in a fire shelter, that may otherwise cause injury to the user. The breathing apparatus advantageously does not require external power for cooling. The thermal capacitor may also be used as a part of a rebreather that uses a scrubber that removes carbon dioxide from exhaled air, for rebreathing. Further, the thermal capacitor may be used for other purposes, such as in recirculation of building air.
2016
CONTINUOUS FIBER-POLYOLEFIN COMPOSITES AND METHODS OF MAKING

Dr. Michael D. Diener

U.S. Patent No. 9,518,171

December 13, 2016

The present invention relates to polyolefin matrix composites reinforced with continuous carbon fibers, and a process for making them. The polymer-fiber composite material comprises a plurality of continuous fibers; and a polyolefin matrix, wherein, the polyolefin matrix comprises polyolefin polymer chains with a number average molecular weight of at least 1.times.10.sup.6 amu, and wherein, the polymer-fiber composite has a notched impact strength greater than the notched impact strength of a neat polyolefin, wherein the neat polyolefin has an equivalent chemical composition and number average molecular weight as the polyolefin of the polyolefin matrix in the polymer-fiber composite material. The present invention also relates to articles of manufacture made substantially from polyolefin matrix composites reinforced with continuous carbon fibers as well as orthopedic implant devices having a wear surface, or bearing comprising a polyolefin matrix composite reinforced with continuous carbon fibers.
NON-DESTRUCTIVE EVALUATION OF FUNCTIONAL FABRICS

Dr. C. Brian France, Dr. W. Wallace Ellis, Dr. Brady Clapsaddle, Dr. William L. Bell, Dr. Ronald L. Cook

U.S. Patent No. 9,476,159

October 25, 2016

The present invention provides a method for determining the functionality remaining in a functional fabric, the method comprising the steps of: providing a used functional fabric having a known original functionality, a current wear, and a current unknown functionality, providing a light source, providing a detector, optically measuring the current wear using the light source and the detector, and evaluating the current unknown functionality using a correlation that expresses the current unknown functionality as a function of the current wear, optionally the detector further comprises a digital camera, and wherein the method further comprises the step of: obtaining a magnified image of the functional fabric and quantifying the fractal dimension using a box-method fractal analysis on the image. The method may be applied the insecticide treated fabrics.
MERCURY REMOVAL SORBENTS

Dr. Gokhan Alptekin

U.S. Patent No. 9,295,984

March 29, 2016

Sorbents and methods of using them for removing mercury from flue gases over a wide range of temperatures are disclosed. Sorbent materials of this invention comprise oxy- or hydroxyl-halogen (chlorides and bromides) of manganese, copper and calcium as the active phase for Hg0 oxidation, and are dispersed on a high surface porous supports. In addition to the powder activated carbons (PACs), this support material can be comprised of commercial ceramic supports such as silica (SiO2), alumina (Al2O3), zeolites and clays. The support material may also comprise of oxides of various metals such as iron, manganese, and calcium. The non-carbon sorbents of the invention can be easily injected into the flue gas and recovered in the Particulate Control Device (PCD) along with the fly ash without altering the properties of the by-product fly ash enabling its use as a cement additive. Sorbent materials of this invention effectively remove both elemental and oxidized forms of mercury from flue gases and can be used at elevated temperatures. The sorbent combines an oxidation catalyst and a sorbent in the same particle to both oxidize the mercury and then immobilize it.
SURFACTANT COMPOSITION AND METHOD FOR DECONTAMINATION

Dr. Allen David Willey, Dr. Valerie Jean Bradford, Dr. Claire Rebecca Yates, Dr. Jacob Robert Adams, Dr. Ronak V. Rughhani, Dr. C. Brian France

U.S. Patent No. 9,295,865

March 29, 2016

Non-corroding cleaning compositions for cleaning exterior surfaces of a vehicle are disclosed. The cleaning compositions include an alkyl dimethylamine oxide surfactant with a first chemical structure, an alkyl dimethylamine oxide surfactant with a second chemical structure, a C8-18 alkyl polyethylene glycol sorbitan fatty ester surfactant, a C12-14 secondary alcohol ethoxylate surfactant, a sodium nitrite corrosion inhibitor, and sodium metasilicate are disclosed.
POLYTHIOL CURING AGENTS WITH LOW ODOR

Dr. Silvia D. Luebben

U.S. Patent No. 9,290,462

March 22, 2016

This invention relates to the composition of matter of polythiols having a chemical structure in FIG. 1. In certain embodiments this invention provides a polythiol with low or no odor and which is a liquid, a waxy solid or a semi-solid at 22° C. In another embodiment the polythiols have a viscosity lower than 100,000 cP at 50° C. In other embodiments, the invention provides a mixture of thiol compounds or a mixture of thiol and amine compounds.
2015
HIGH CAPACITY CARBON DIOXIDE SORBENT

Dr. Steven D. Dietz, Dr. Gokhan Alptekin, Dr. Ambalavanan Jayaraman

U.S. Patent No. 9,120,079

September 1, 2015

The present invention provides a sorbent for the removal of carbon dioxide from gas streams, comprising: a CO2 capacity of at least 9 weight percent when measured at 22° C. and 1 atmosphere; an H2O capacity of at most 15 weight percent when measured at 25° C. and 1 atmosphere; and an isosteric heat of adsorption of from 5 to 8.5 kilocalories per mole of CO2. The invention also provides a carbon sorbent in a powder, a granular or a pellet form for the removal of carbon dioxide from gas streams, comprising: a carbon content of at least 90 weight percent; a nitrogen content of at least 1 weight percent; an oxygen content of at most 3 weight percent; a BET surface area from 50 to 2600 m2/g; and a DFT micropore volume from 0.04 to 0.8 cc/g.
METHOD OF ENCAPSULATING WASTE

Dr. C. Brian France

U.S. Patent No. 9,044,793

June 2, 2015

A method of encapsulating and safely transporting hazardous waste is disclosed. The method comprises the steps of: first, providing a waste object at a first location; second. covering the waste object with a closed cell polymer foam; third, allowing a sufficient time for the closed cell polymer foam to cure; and fourth, transporting the covered waste object to a second location. In another embodiment the method com­prises the steps of: first, providing a waste object at a first location; second. treating the waste object to decontaminate or neutralize the hazardous waste; third, covering the waste object with a closed cell polymer foam; fourth, allowing a sufficient time for the closed cell polymer foam to cure; and fifth, transporting the covered waste object to a second loca­tion.

RENEWABLE POLYMER AND METHOD OF MAKING

Dr. Silvia D. Luebben, Dr. James W. Raebiger, Dr. Aaron Skaggs

U.S. Patent No. 9,040,635

May 26, 2015

A polymer, optionally made from renewable sources, comprising a specific chemical structure that is a result of the polymerization of α-hydroxycarbonyl compounds (alpha-hydroxycarbonyl compounds), particularly α-hydroxyaldehydes (alpha-hydroxyaldehydes) and α-hydroxyketones (alpha-hydroxyketones), or glycolaldehyde. A method of polymerization, the method comprising the step of reacting trimethylsilyl trifluoromethanesulfonate with the cyclic dimer of one or more α-hydroxycarbonyl compounds. A method of making said polymer, the method comprising dehydrating a cyclic dimer of one or more α-hydroxycarbonyl compounds. An end-capped polymer made from one or more α-hydroxycarbonyl compounds and terminal end-cap groups.
2014
LOW TEMPERATURE SULFUR DIOXIDE OXIDATION CATALYST FOR SULFURIC ACID MANUFACTURE

Dr. Girish Srinivas, Dr. Steven C. Gebhard

U.S. Patent No. 8,758,718

June 24, 2014

Improved catalysts for oxidation of sulfur dioxide which are alkali metal-promoted vanadium catalysts which are further promoted by gold. Improved methods employing such catalyst for oxidation of sulfur dioxide and for manufacture of sulfuric acid. Improved methods for multiple step oxidation of sulfur dioxide in which the last oxidation step is carried out employing improved catalysts of this invention at temperatures lower than 400° C.
2012
HIGH TEMPERATURE GAS DESULFURIZATION SORBENTS

Dr. Gokhan Alptekin, Ms. Margarita Dubovik, Dr. Ambalavanan Jayaraman

U.S. Patent No. 8,308,848

November 13, 2012

Gas desulfurization sorbents and methods using them for removal of sulfur from gas streams, particularly at high temperatures ranging from 500 to 1000° C. The sorbents and methods are of particular application to produce a sulfur-clean feed from reformate gas generated from readily available transportation fuels containing sulfur. Sorbents of the invention can reduce the sulfur concentration in reformate gas to parts per billion on volume basis (ppbv) levels over a large range of temperatures. Sorbent materials of this invention comprise a nickel phase dispersed on a particulate support or a monolith support. The support can be a high surface area support with surface area of 100 m2/g or higher. The invention also provides systems for desulfurizing reformate gas and systems for providing a desulfurized gas to a fuel cell, particularly a solid oxide fuel cell.
NANOPOROUS POLYMER ELECTROLYTE

Dr. Brian Elliott, Mr. Vinh Nguyen

U.S. Patent No. 8,163,204

April 24, 2012

A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0×10−6 S/cm at 25° C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

PI-CONJUGATED ORGANOBORON POLYMERS IN THIN-FILM ELECTRONIC DEVICES

Dr. Silvia D. Luebben, Dr. Shawn A. Sapp

U.S. Patent No. 8,097,348

January 17, 2012

Pi-conjugated organoboron polymers for use in thin-film organic polymer electronic devices. The polymers contain aromatic and or unsaturated repeat units and boron atoms. Pi-conjugated organoboron polymers which are end capped, derivatized with solubilizing groups or both exhibit improved solubility and handling properties beneficial for the formation of thin films useful for device fabrication. The vacant p-orbital of the boron atoms conjugate with the pi-conjugated orbital system of the aromatic or unsaturated monomer units extending the pi-conjugation length of the polymer across the boron atoms. The pi-conjugated organoboron polymers are electron-deficient and, therefore, exhibit n-type semiconducting properties, photoluminescence, and electroluminescence. The invention provides thin-film organic polymer electronic devices, such as organic photovoltaic cells (OPVs), organic diodes, organic photodiodes, organic thin-film transistors (TFTs), organic field-effect transistors (OFETs), printable or flexible electronics, such as radio-frequency identification (RFID) tags, electronic papers, and printed circuit elements, organic light-emitting diodes (OLEDs), polymer light-emitting diodes (PLEDs), and energy storage devices employing the pi-conjugated organoboron polymers. In OLED and PLED applications these materials are used as the electron transport layer (ETL) to improve device efficiency. The polymers which exhibit photo- and electroluminescence are also useful as light-emitting material in PLEDs.
2010
DERIVATIZATION AND SOLUBILIZATION OF FULLERENES FOR USE IN THERAPEUTIC AND DIAGNOSTIC APPLICATIONS

Dr. Robert D. Bolskar, Dr. J. Michael Alford

U.S. Patent No. 7,812,190

October 12, 2010

The invention provides improved therapeutic and diagnostic fullerenes and endohedral fullerenes. The fullerenes and endohedral fullerenes of the invention are derivatized with at least two charged functional groups (and preferably more than two charged functional groups) to provide for water-solubility and improved in vivo biodistribution. Improved derivatized fullerenes and endohedral fullerenes carry a plurality of functional groups at least two of which are charged. Preferably at least about ⅙ of the possible derivations sites on the fullerene caged carry derivatives and preferably at least about ½ of the functional groups on the fullerene cage are charged groups. The invention also provides water-soluble endohedral metallofullerene with improved biodistribution which are useful as in vivo imaging agents, including MRI contrast agents.
METHODS OF MAKING ALKYL ESTERS

Dr. Brian Elliott

U.S. Patent No. 7,767,837

August 3, 2010

A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.
METHODS OF PRODUCTION, PURIFICATION, AND PROCESSING OF POLY(HETEROAROMATIC) BLOCK COPOLYMERS WITH IMPROVED SOLUBILITY OR DISPERSABILITY

Dr. Silvia D. Luebben, Dr. Shawn A. Sapp

U.S. Patent No. 7,687,582

March 30, 2010

This invention relates to improved methods for the preparation, purification, and processing of poly(heteroaromatic) block copolymers, as well as compositions prepared by these methods. Methods relate to preparation of multiblock and triblock copolymers of intrinsically conducting polymers (ICPs) containing at least one block of a poly(heteroaromatic) polymer and at least two blocks of a non-conducting polymer. This invention provides polymer solutions or dispersions of improved stability and better film-forming properties. The poly(heteroaromatic) block copolymers are obtained in their conducting or doped form, and are retained in a solvated, wet form throughout the production and purification processes. Stable solutions or dispersions of the purified copolymers in organic solvents, water, or mixtures thereof are provided. Stable solutions or dispersions of ICPs are useful in the preparation of semiconducting and conducting films, blends, and coatings on a variety of substrates using standard processing and coating techniques.

DERIVATIZATION AND SOLUBILIZATION OF INSOLUBLE CLASSES OF FULLERENES

Dr. Robert D. Bolskar, Dr. J. Michael Alford

U.S. Patent No. 7,671,230

March 7, 2010

This invention provides improved methods for the derivatization and solubilization of fullerenes, which are particularly useful for those fullerenes that are normally insoluble and which are specifically applied, among others, to endohedral fullerenes, including endohedral metallofullerenes; empty fullerenes, including small-bandgap fullerenes and other insoluble fullerenes and to very high molecular weight fullerenic materials generated in fullerenic soot, including giant fullerenes, fullerenic polymers, carbon nanotubes and metal-carbon nanoencapsulates. More specifically the invention relates to improved methods for cyclopropanation of fullerenes. Specific reaction conditions are provided which allow for cyclopropanation reactions to be successfully performed for the first time on insoluble classes of fullerenes. Also provided is a method for purification of one or more fullerenes from a fullerenic material containing the one or more fullerenes in addition to non-fullerenic carbonaceous material, particularly amorphous carbonaceous material, by derivatizing one or more fullerenes using the methods of the invention and separating soluble derivatizes fullerenes from insoluble materials.
2009
POROUS CARBONS FROM CARBOHYDRATES

Dr. Steven D. Dietz, Mr. Dean Recla

U.S. Patent No. 7,541,312

June 2, 2009

A porous carbon characterized by a volumetric pore size distribution having two peaks, a first of said peaks being between 0.5 and 1.0 nm and a second of said peaks being between 1.0 and 5.0 nm. The porous carbon may have a volumetric capacitance in an organic electrolyte of at least 40 F/cm3, an average pore diameter between about 2 nm and about 30 nm, a surface area of at least 900 m2/g, and/or a density of at least 0.4 g/cm3. A method for making such a carbon includes a) curing a mixture comprising a carbohydrate, a dehydrating component, and a nonmetallic cationic pore-forming agent and b) carbonizing the cured carbon under conditions effective to provide a porous carbon having a surface area between about 100 m2/g and about 3000 m2/g. The the dehydrating component and nonmetallic cationic component may comprise two moieties of one compound.
2008
OXIDATION CATALYSTS COMPRISING METAL EXCHANGED HEXAALUMINATE WHEREIN THE METAL IS SR, PD, LA AND/OR MN

U.S. Patent No. 7,442,669

October 28, 2008

The present invention provides metal-exchanged hexaaluminate catalysts that exhibit good catalytic activity and/or stability at high temperatures for extended periods with retention of activity as combustion catalysts, and more generally as oxidation catalysts, that make them eminently suitable for use in methane combustion, particularly for use in natural gas fired gas turbines. The hexaaluminate catalysts of this invention are of particular interest for methane combustion processes for minimization of the generation of undesired levels (less than about 10 ppm) of NOx species. Metal exchanged hexaaluminate oxidation catalysts are also useful for oxidation of volatile organic compounds (VOC), particularly hydrocarbons. Metal exchanged hexaaluminate oxidation catalysts are further useful for partial oxidation, particularly at high temperatures, of reduced species, particularly hydrocarbons (alkanes and alkenes).

ELECTRICALLY CONDUCTING MATERIALS FROM BRANCHED END-CAPPING INTERMEDIATES

Dr. Brian J. Elliott, Dr. William W. Ellis, Dr. Silvia D. Luebben, Dr. Shawn A. Sapp, Dr. Chieh-Hui Chang, Ms. Rachelle A. D’Sa

U.S. Patent No. 7,361,728

April 22, 2008

The present invention relates to a class of conducting oligomers and polymers and to a method for the preparation of the same. The conducting oligomers and polymers contain an end-capping group, which is non-electrically conductive and contains at least one branch point. The branched end-capping groups are made by a method that first substitutes the branched group on the heteroaromatic monomer, particularly at the “2” position on these monomers. In a second step, the end-capping intermediate is co-polymerized with one or more additional heteroaromatic monomers to form capped conducting oligomers and polymers.

2007
POLY(HETEROAROMATIC) BLOCK COPOLYMERS WITH ELECTRICAL CONDUCTIVITY

Dr. Silvia D. Luebben, Dr. Brian J. Elliott, Ms. Carolina Wilson

U.S. Patent No. 7,279,534

October 9, 2007

The present invention provides block copolymers containing at least one block of a poly(heteroaromatic) polymer and at least two blocks of a non-conjugated polymer. The chemically different blocks of the copolymer are covalently bonded to each other in an alternating fashion through an appropriate linkage group. The poly(heteroaromatic) block may exist in its neutral or oxidized form, and when in the oxidized form, it associates with organic or inorganic counter-anions to balance the charge. The poly(heteroaromatic) polymer is an intrinsically conducting polymer (ICP), and when in the oxidized form it is electrically conducting. When the ICP block or blocks of the block copolymer are in the doped form, the block copolymer is electrically conducting. Preferably the conducting block copolymers have conductivities in the range 10−6-103 S/cm. Block copolymers of this invention are soluble or dispersible in water, one or more organic solvents, or in a mixture thereof at a level of at least about 0.1 g/liter.
BURNERS AND COMBUSTION APPARATUS FOR CARBON NANOMATERIAL PRODUCTION

Dr. J. Michael Alford, Dr. Michael D. Diener, Dr. James Nabity, Mr. Michael Karpuk

U.S. Patent No. 7,279,137

Japanese Patent No. 3984956

October 9, 2007

The invention provides improved burners, combustion apparatus, and methods for carbon nanomaterial production. The burners of the invention provide sooting flames of fuel and oxidizing gases. The condensable products of combustion produced by the burners of this invention produce carbon nanomaterials including without limitation, soot, fullerenic soot, and fullerenes. The burners of the invention do not require premixing of the fuel and oxidizing gases and are suitable for use with low vapor pressure fuels such as those containing substantial amounts of polyaromatic hydrocarbons. The burners of the invention can operate with a hot (e.g., uncooled) burner surface and require little, if any, cooling or other forms of heat sinking. The burners of the invention comprise one or more refractory elements forming the outlet of the burner at which a flame can be established. The burners of the invention provide for improved flame stability, can be employed with a wider range of fuel/oxidizer (e.g., air) ratios and a wider range of gas velocities, and are generally more efficient than burners using water-cooled metal burner plates. The burners of the invention can also be operated to reduce the formation of undesirable soot deposits on the burner and on surfaces downstream of the burner.
NANOPARTICLES MODIFIED WITH MULTIPLE ORGANIC ACIDS

Dr. Ronald L. Cook, Dr. Silvia D. Luebben, Dr. Andrew W. Myers, Dr. Bryan M. Smith, Dr. Brian J. Elliott, Mr. Cory Kreutzer, Ms. Carolina Wilson, Mr. Manfred Meiser

U.S. Patent No. 7,244,498

July 17, 2007

Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.
PURIFICATION OF ENDOHEDRAL AND OTHER FULLERENES BY CHEMICAL METHODS

Dr. Robert D. Bolskar, Dr. J. Michael Alford

U.S. Patent No. 7,208,132

Japanese Patent 3926331

April 24, 2007

The invention provides a method of separating a first and a second set of fullerenes in a fullerene mixture. In the method of the invention, a stable fullerene cation is formed of one of the first or the second set of fullerenes. The fullerene cation is then separated from the other set of fullerenes. Optionally, the fullerene cation may be returned to its neutral state. The method of the invention is particularly useful for the purification and separation of endohedral fullerenes from empty fullerenes. However, the method may be applied to the purification of a broad range of endohedral and empty fullerene materials.
MESOPOROUS CARBONS AND POLYMERS FROM HYDROXYLATED BENZENES

Dr. Steven D. Dietz, Mr. Vinh Nguyen

U.S. Patent No. 7,167,354

January 23, 2007

A mesoporous polymer and method of preparing a mesoporous polymer whose polymerization kinetics are dependent upon pH and whose pore size is controlled by pH and solvent concentration are disclosed. The polymer is optionally pyrolyzed to form a primarily carbonaceous solid. The material has an average pore size in the mesopore range and is suitable for use in liquid-phase surface limited applications including chromatographic, sorbent, catalytic, and electrical applications.
COMBUSTION PROCESS FOR SYNTHESIS OF CARBON NANOMATERIALS FROM LIQUID HYDROCARBON

Dr. J. Michael Alford, Dr. Michael D. Diener, Dr. James Nabity, Dr. Bradley D. Hitch

U.S. Patent No. 7,157,066

Japanese Patent No. 3926333

January 2, 2007

The present invention provides a combustion apparatus for the production of carbon nanomaterials including fullerenes and fullerenic soot. Most generally the combustion apparatus comprises one or more inlets for introducing an oxygen-containing gas and a hydrocarbon fuel gas in the combustion system such that a flame can be established from the mixed gases, a droplet delivery apparatus for introducing droplets of a liquid hydrocarbon feedstock into the flame, and a collector apparatus for collecting condensable products containing carbon nanomaterials that are generated in the combustion system. The combustion system optionally has a reaction zone downstream of the flame. If this reaction zone is present the hydrocarbon feedstock can be introduced into the flame, the reaction zone or both.

2006
POLYNUCLEAR AROMATIC HYDROCARBONS FOR FULLERENE SYNTHESIS IN FLAMES

Dr. J. Michael Alford, Dr. Michael D. Diener

U.S. Patent No. 7,150,863

Chinese Patent No. ZL 02 8 16866.6

Japanese Patent No. 3889399

Russian Patent No. 229950

December 19, 2006

This invention provides improved methods for combustion synthesis of carbon nanomaterials, including fullerenes, employing multiple-ring aromatic hydrocarbon fuels selected for high carbon conversion to extractable fullerenes. The multiple-ring aromatic hydrocarbon fuels include those that contain polynuclear aromatic hydrocarbons. More specifically, multiple-ring aromatic hydrocarbon fuels contain a substantial amount of indene, methylnapthalenes or mixtures thereof. Coal tar and petroleum distillate fractions provide low cost hydrocarbon fuels containing polynuclear aromatic hydrocarbons, including without limitation, indene, methylnapthalenes or mixtures thereof.
NANOPOROUS COMPOSITES OF POLYMERIZED LYTROPIC LIQUID-CRYSTALLINE MONOMERS, AND HYDROPHOBIC POLYMERS

Dr. Brian Elliott

U.S. Patent No. 7,090,788

August 15, 2006

This invention provides composite materials that combine the material properties of hydrophobic polymers with internal structure and order provided by polymerization of lyotropic liquid crystals (LLCs). Composites, particularly nanocomposites, are made by forming a LLC assembly that has hydrophobic regions and hydrophilic regions, combining hydrophobic polymer in the assembly and polymerizing the polymerizable LLC monomers in the assembly. The hydrophobic polymer, polymerized LLC assembly or both can be crosslinked in the composite. Nanoporous composites, particularly those with uniform-sized pores and/or with uniform pores distribution can be prepared in this way. In addition, complex polymers in which a second polymeric material, which may be organic or inorganic, can be introduced into the pores or other structural features of the composite can be prepared. Adding flexible hydrophobic polymers to the LLC assembly increases the flexibility and toughness of the resultant polymerized composite material to provide improved composite materials for use as membranes and in other applications. Hydrophobic polymer addition can also increase the diffusion resistance in the organic phase of the composite. Of particular interest are composites in which the hydrophobic polymer is butyl rubber or related synthetic rubber.
PROCESS FOR THE SIMULTANEOUS REMOVAL OF SULFUR AND MERCURY

Dr. Girish Srinivas, Dr. Robert J. Copeland

U.S. Patent No. 7,060,233

June 13, 2006

A process for removing hydrogen sulfide, other sulfur-containing compounds and/or sulfur and mercury from a gas stream contaminated with mercury, hydrogen sulfide or both. The method comprises the step of selective oxidation of hydrogen sulfide (H2S) in a gas stream containing one or more oxidizable components other than H2S to generate elemental sulfur (S) or a mixture of sulfur and sulfur dioxide (SO2). The sulfur generated in the gas stream reacts with mercury in the gas stream to generate mercuric sulfide and sulfur and mercuric sulfide are removed from the gas stream by co-condensation.
SURFACE MODIFIED PARTICLES BY MULTI-STEP ADDITION AND PROCESS FOR THE PREPARATION THEREOF

Dr. Ronald L. Cook, Dr. Brian Elliott, Dr. Silvia D. Luebben, Dr. Andrew Myers, Dr. Bryan M. Smith

U.S. Patent No. 6,986,943

January 17, 2006

The present invention relates to a new class of surface modified particles and to a multi-step surface modification process for the preparation of the same. The multi-step surface functionalization process involves two or more reactions to produce particles that are compatible with various host systems and/or to provide the particles with particular chemical reactivities. The initial step comprises the attachment of a small organic compound to the surface of the inorganic particle. The subsequent steps attach additional compounds to the previously attached organic compounds through organic linking groups.
2005
RELEASABLE CORROSION INHIBITOR COMPOSITIONS

Dr. Ronald L. Cook

U.S. Patent No. 6,933,046

August 23, 2005

A new class of releasable corrosion inhibiting materials for protective coatings, methods of making the same, methods of using the same, and coatings containing the same are provided. The materials comprise one or more corrosion inhibitors that are chemically anchored to the surface of a particle having an aluminum oxyhydroxide surface through a carboxylate bond. The carboxylate/aluminum-oxyhydroxide-surface bond breaks under corrosion-causing conditions (for example the presence of high levels of hydroxide ions generated by the cathodic oxygen reduction reaction on metals such as iron and aluminum) thereby allowing the corrosion inhibitors to detach from the particle surface when corrosion is present.
PROCESS FOR THE REMOVAL OF IMPURITIES FROM COMBUSTION FULLERENES

Dr. J. Michael Alford, Dr. Robert D. Bolskar

U.S. Patent No. 6,923,915

Japanese Patent No. 3984957

August 2, 2005

The invention generally relates to purification of carbon nanomaterials, particularly fullerenes, by removal of PAHs and other hydrocarbon impurities. The inventive process involves extracting a sample containing carbon nanomaterials with a solvent in which the PAHs are substantially soluble but in which the carbon nanomaterials are not substantially soluble. The sample can be repeatedly or continuously extracted with one or more solvents to remove a greater amount of impurities. Preferred solvents include ethanol, diethyl ether, and acetone. The invention also provides a process for efficiently separating solvent extractable fullerenes from samples containing fullerenes and PAHs wherein the sample is extracted with a solvent in which both fullerenes and PAHs are substantially soluble and the sample extract then undergoes selective extraction to remove PAHs. Suitable solvents in which both fullerenes and PAHs are soluble include o-xylene, toluene, and o-dichlorobenzene. The purification process is capable of treating quantities of combustion soot in excess of one kilogram and can produce fullerenes or fullerenic soot of suitable purity for many applications.
SURFACE MODIFIED PARTICLES BY MULTI-STEP MICHAEL-TYPE ADDITION AND PROCESS FOR THE PREPARATION THEREOF

Dr. Ronald L. Cook, Dr. Brian J. Elliott, Dr. Silvia D. Luebben, Dr. Andrew Myers, Dr. Bryan M. Smith

U.S. Patent No. 6,887,517

May 3, 2005

A new class of surface modified particles and a multi-step Michael-type addition surface modification process for the preparation of the same is provided. The multi-step Michael-type addition surface modification process involves two or more reactions to compatibilize particles with various host systems and/or to provide the particles with particular chemical reactivities. The initial step comprises the attachment of a small organic compound to the surface of the inorganic particle. The subsequent steps attach additional compounds to the previously attached organic compounds through reactive organic linking groups. Specifically, these reactive groups are activated carbon—carbon pi bonds and carbon and non-carbon nucleophiles that react via Michael or Michael-type additions.
FILTER DEVICES AND METHODS FOR CARBON NANOMATERIAL COLLECTION

Dr. J. Michael Alford, Dr. Michael D. Diener

U.S. Patent No. 6,887,291

Japanese Patent No. 3926329

May 3, 2005

Filter devices and methods for collection of carbon nanomaterials, including fullerenes, produced in gas phase reactors are provided. The filter devices provide for in situ cleaning of filters to release captured product for collection. Product can be released and removed from the reactor without disrupting continuous synthesis of carbon nanomaterials. The filter devices facilitate increased reactor operation and larger scale production of carbon nanomaterials. The filters are cleaned by application of a motive force and/or a gas flow to the filter. In a specific embodiment filters are cleaned by a reverse flow of gas pulses to the filter provided. The invention also provides reactor systems for gas phase synthesis of carbon nanomaterials that can be operated continuously employing the filter device of this invention. Preferred reactor systems are those which synthesize carbon nanomaterials by combustion. Methods for continuous production of carbon nanomaterials using the filtering devices and methods of this invention are also provided.
2004
MESOPOROUS CARBONS AND POLYMERS

Dr. William L. Bell, Dr. Steven D. Dietz

U.S. Patent No. 6,737,445

May 18, 2004

A polymer is prepared by polymerizing a polymerizable component from a mixture containing the polymerizable component and a surfactant, the surfactant and the polymerizable component being present in the mixture in a molar ratio of at least 0.2:1, having an average pore size greater than 4 nm and a density greater than 0.1 g/cc. The polymerizable component can comprise a resorcinol/formaldehyde system and the mixture can comprise an aqueous solution or the polymerizable component can comprise a divinylbenzene/styrene system and the mixture can comprise an organic solution. Alternatively, the polymerizable component can comprise vinylidene chloride or a vinylidene chloride/divinylbenzene system. The polymer may be monolithic, have a BET surface area of at least about 50 m2/g., include a quantity of at least one metal powder, or have an electrical conductivity greater than 10 Scm−1.
2003
ISOLATION OF SMALL-BANDGAP FULLERENES AND ENDOHEDRAL METALLOFULLERENES

Dr. Michael D. Diener, Dr. J. Michael Alford

U.S. Patent No. 6,517,799

February 11, 2003

A method for recovering small bandgap fullerenes, including metallofullerenes, from soot by passivating individual fullerenes and/or metallofullerenes to an anionic configuration. The addition of extra electrons to a metallofullerene or small bandgap fullerene breaks the interfullerene bonding in the solid material, and the resulting anions are soluble in organic electrochemical solvents. Once dissolved, the small bandgap fullerenes can be plated out or precipitated by returning them to a neutral state.
2002
METHODS OF SUPPRESSION OF FILAMENTOUS COKE FORMATION

Dr. David T. Wickham, Mr. Jeffrey Engel, Mr. Michael E. Karpuk

U.S. Patent No. 6,482,311

November 19, 2002

Materials and methods for inhibiting the formation of filamentous coke on heated metal surfaces. Organoselenium compounds, including diarylselenides, diaryldiselenides, alkylarylselenides, and alkylaryldiselenides, are employed as hydrocarbon feedstock additives or as hydrocarbon fuel additives to inhibit filamentous coke formation on hydrocarbon processing systems, including reactors, furnaces, engines and parts thereof and in particular to inhibit filamentous coke formation on heat-exchangers in such systems.
PULSE THERMAL LOOP

Dr. Mark M. Weislogel

U.S. Patent No. 6,435,274

August 20, 2002

A pulse thermal loop heat transfer system includes a means to use pressure rises in a pair of evaporators to circulate a heat transfer fluid. The system includes one or more valves that iteratively, alternately couple the outlets the evaporators to the condenser. While flow proceeds from one of the evaporators to the condenser, heating creates a pressure rise in the other evaporator, which has its outlet blocked to prevent fluid from exiting the other evaporator. When the flow path is reconfigured to allow flow from the other evaporator to the condenser, the pressure in the other evaporator is used to circulate a pulse of fluid through the system. The reconfiguring of the flow path, by actuating or otherwise changing the configuration of the one or more valves, may be triggered when a predetermined pressure difference between the evaporators is reached.
METHODS AND MATERIALS FOR FABRICATION OF ALUMOXANE POLYMERS

Dr. Ronald L. Cook, Dr. Andrew R. Barron, Dr. Kevin J. Gleason, Dr. D. Brent MacQueen, Dr. Georgette L. Siparksy, Dr. Yoshihiro Koide, Dr. Cullen T. Vogelson

U.S. Patent No. 6,369,183

April 9, 2002

A composition of matter, comprising: a chemically functionalized carboxylate-alumoxane that is functionalized with a chemically reactive substituent, and a reactive compound, wherein the chemically reactive substituent reacts with the reactive compound so as to link the carboxylate-alumoxane to the reactive compound and form a polymer matrix. The functional groups on the carboxylate-alumoxane can vary depending on the desired properties of the matrix. Also, the composition of matter may comprise a cross-linked matrix in which the cross-linked components consist of functionalized alumoxanes.
FULLERENE CONTRAST AGENT FOR MAGNETIC RESONANCE IMAGING AND SPECTROSCOPY

Dr. J. Michael Alford, Dr. Lon J. Wilson

U.S. Patent No. 6,355,225

March 12, 2002

A non-toxic contrast agent for enhancing contrast in in vivo magnetic resonance measurements, comprised of a water-soluble, stable paramagnetic fullerene that is free of paramagnetic metal species. A preferred contrast agent is a fullerol having at least one unpaired electron.
2001
ISOLATION OF SMALL-BANDGAP FULLERENES AND ENDOHEDRAL METALLOFULLERENES

Dr. Michael D. Diener, Dr. J. Michael Alford

U.S. Patent No. 6,303,016

October 16, 2001

A method for recovering small bandgap fullerenes, including metallofullerenes, from soot by passivating individual fullerenes and/or metallofullerenes to an anionic configuration. Thc addition of extra electrons to a metallofullerene or small bandgap fullerene breaks the interfullerene bonding in the solid material, and the resulting anions are soluble in organic electrochemical solvents. Once dissolved, the small bandgap fullerenes can be plated out or precipitated by returning them to a neutral state.
MESOPOROUS CARBONS AND POLYMERS

Dr. William L. Bell, Dr. Steven D. Dietz

U.S. Patent No. 6,297,293

October 2, 2001

A mesoporous material prepared by polymerizing a resorcinol/formaldehyde system from an aqueous solution containing resorcinol, formaldehyde and a surfactant and optionally pyrolyzing the polymer to form a primarily carbonaceous solid. The material has an average pore size between 4 and 75 nm and is suitable for use in liquid-phase surface limited applications, including sorbent, catalytic, and electrical applications.
SELF-HEATING FLEXIBLE PACKAGE

Dr. William L. Bell, Dr. Robert J. Copeland, Dr. Jianhan Yu, Mr. James Dippo

U.S. Patent No. 6,289,889

September 18, 2001

Improved heaters and self-heating packages that function without application of external energy. Heat is generated by contact of a heat-producing composition, such as calcium oxide, and an activating solution which is typically water. The heater contains multi-compartments containing heat-producing composition and activating solution. The heater is activated by application of hand pressure to rupture a frangible seal which allows the heater components to mix. The heater compartments are at least in part formed from flexible walls. The self-heating package has one or more products or product containers in thermal contact with one or more heaters. In preferred packaging embodiments, the heating package has one or more product containers or pouches in thermal contact with one or more heaters. In a specific embodiment, the product container is integrally formed with the heater. Preferred self-heating packages are constructed entirely of flexible packaging materials.
PORTABLE HEAT SOURCE CONTINUATION

Dr. William L. Bell, Dr. Robert J. Copeland, Dr. Jianhan Yu, Mr. James L. Dippo

U.S. Patent No. 6,248,257

European Patent No. A47J36/28, B65D81/34S, C09K5/18

Korean Patent No. 10-05-76185

June 19, 2001

A portable heat source that may be used to warm food, beverage or other supplies. The heater contains a heat-producing composition that is a solid that may be stored for long periods of time, and activated by addition of water or an aqueous solution. Heat-producing compositions contain an acidic anhydride, an acidic salt, a basic anhydride or a basic salt. Preferred heat-producing compositions contain a mixture of an acidic anhydride or salt together with a basic anhydride or salt, such that addition of water to both acidic and basic anhydrides produces heat as well as acid and base respectively; subsequent reaction of the acid and base produces additional heat, as well as a safe, neutral product that is easily disposed. The invention further consists of means and methods for regulating the rate of heat production in heaters by the addition of inert additives to heat-producing compositions and the application of processing methods that regulate access of water to heat-producing compounds. Addition of inert materials and shaping, agglomerating, pelleting and like processing of heat-producing materials are applied to produced heat at a rate compatible with the rate at which the food or other materials can absorb the heat. The invention further consists of devices incorporating the materials to be heated in an advantageous arrangement with the heater composition.
METAL EXCHANGE CARBOXYLATO-ALUMOXANES

Dr. Aivaras Kareiva, Dr. Chuansheng Bai, Dr. Charles J. Harlan, Dr. D. Brent MacQueen, Dr. Andrew R. Barron, Dr. Ronald L. Cook

U.S. Patent No. 6,207,130

March 27, 2001

A method has been developed for the solution-based metal exchange of carboxylato-alumoxanes [Al(O)x(OH)y(O2CR)z]n with a wide range of metal cations. Metal-exchanged carboxylato-alumoxanes are new, particularly those in which about 10% to about 50% or more of the Al ions are exchanged for other metal ions. Additionally, the carboxylic acid ligands can be stripped from the boehmite core of metal-exchanged carboxylato-alumoxanes at low temperature leading to the formation of metal-exchanged boebmite particles. These new material phases can be used as intermediates for preparation of mixed metal aluminum oxide materials. Thermolysis of the metal-exchanged carboxylato-alumoxanes or metal-exchanged boehmite particles results in doped aluminas (M/Al2O3), binary (MAlOx), ternary (MM′AlOx) and even more complex metal aluminum oxide compounds, where M and M′ are metal ions other than those of aluminum and are preferably those of Lanthanide metals or transition metals. The method allows preparation of pure phase materials as well as the preparation of metastable metal aluminum oxide phases. The carboxylato-alumoxanes are prepared by the reaction of boehmite (or pseudoboehmite) with carboxylic acids in a suitable solvent. Up to at least half of the aluminum cations in the boehmite lattice of the carboxylato-alumoxanes can be replaced by the reaction of metal acetylacetonates with the carboxylato-alumoxane in a suitable solvent. The metal exchange reaction can also be carried out by reaction with soluble metal salts. Reactions of boehmite with the metal acetylacetonates (or soluble metal salts) do not lead to the metal exchange reaction observed for the carboxylato-alumoxanes.
2000
CATALYSTS FOR THE SELECTIVE OXIDATION OF HYDROGEN SULFIDE TO SULFUR

Dr. Girish Srinivas, Dr. Chuansheng Bai

U.S. Patent No. 6,099,819

August 8, 2000

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.
1999
PORTABLE HEAT SOURCE

Dr. William L. Bell, Dr. Robert J. Copeland, Dr. Jianhan Yu

U.S. Patent No. 5,935,486

August 10, 1999

This invention is a portable heat source that may be used to warm food, beverage or other supplies. The heater material is a solid that may be stored for long periods of time, and activated by addition of water or an aqueous solution. The heater consists of an acidic anhydride or salt together with a basic anhydride or salt, such that addition of water to both acidic and basic anhydrides produces heat as well as acid and base respectively; subsequent reaction of the acid and base produces additional heat, as well as a safe, neutral product that is easily disposed. The invention further consists of means to regulate the rate of heat production by the use of additives and processing methods, so that heat is produced at a rate compatible with the rate at which the food or other materials can absorb the heat. The invention further consists of devices incorporating the materials to be heated in an advantageous arrangement with the heater composition.
1993
HIGH TEMPERATURE REGENERABLE HYDROGEN SULFIDE REMOVAL AGENTS

Dr. Robert J. Copeland

U.S. Patent No. 5,271,907

December 21, 1993

A system for high temperature desulfurization of coal-derived gases using regenerable sorbents. One sorbent is stannic oxide (tin oxide, SnO2), the other sorbent is a metal oxide or mixed metal oxide such as zinc ferrite (ZnFe2 O4). Certain otherwise undesirable by-products, including hydrogen sulfide (H2 S) and sulfur dioxide (SO2) are reused by the system, and elemental sulfur is produced in the regeneration reaction. A system for refabricating the sorbent pellets is also described.
1989
ENHANCED PERFORMANCE OF ALCOHOL FUELED ENGINE DURING COLD CONDITIONS

Mr. Michael E. Karpuk, Dr. Scott W. Cowley

U.S. Patent No. 4,876,989

October 31, 1989

Apparatus and method are described for enhancing performance of an alcohol fueled engine during cold conditions, with such enhancement being particularly effected by generation of ether to assist cold operation including starting and/or to achieve reduced emissions during cold running. Dimethyl ether is generated by catalytic dehydration of vaporized methanol using a catalyst, preferably fluorinated alumina. Apparatus is disclosed for generating dimethyl ether on board as needed for immediate mixing with combustion air and methanol and/or for storage to enable later mixing of the dimethyl ether with combustion air and methanol to effect subsequent cold starts and/or cold running operations.