Carbon nanofiber electrodes without commercial polymer precursors deliver superior electrochemical performance
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Cincotta, Robert E. F.↗
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Electron spin resonance and optical spectroscopic studies of the conducting polymer precursor - Poly(3,4-diisopropylidene cyclobutene)
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Kim, Soon Sam↗
Organoborosilane Polymers And Ceramic Products
Process developed to make polyorganoborosilane polymers. Precursor polymers prepared by using alkali metal to couple boron halide with organohalosilane. In representative application, polymer drawn into fibers, then pyrolyzed to produce ceramic cloth. Ceramics exhibit high thermo-oxidative stability.
Riccitiello, Salvatore R.↗
Biocatalytic microcapsules for catalyzing gas conversion
According to one embodiment, a microcapsule for selective catalysis of gases, the microcapsule comprising: a polymeric shell permeable to one or more target gases; and at least one biocatalyst disposed in an interior of the polymeric shell. In more embodiments, methods of forming such microcapsules include: emulsifying at least one biocatalyst in a polymer precursor mixture; emulsifying the polymer precursor mixture in an aqueous carrier solution; crosslinking one or more polymer precursors of the polymer precursor mixture to form a plurality of microcapsules each independently comprising: a polymeric shell permeable to one or more target gases; and at least one biocatalyst disposed in an interior of the polymeric shell. In further embodiments, corresponding methods of using the inventive microcapsules for catalyzing one or more target gases using include: exposing a plurality of the biocatalytic microcapsules to the one or more target gases.
36 MATERIALS SCIENCE↗
Ceramic silicon-boron-carbon fibers from organic silicon-boron-polymers
Novel high strength ceramic fibers derived from boron, silicon, and carbon organic precursor polymers are discussed. The ceramic fibers are thermally stable up to and beyond 1200 C in air. The method of preparation of the boron-silicon-carbon fibers from a low oxygen content organosilicon boron precursor polymer of the general formula Si(R2)BR(sup 1) includes melt-spinning, crosslinking, and pyrolysis. Specifically, the crosslinked (or cured) precursor organic polymer fibers do not melt or deform during pyrolysis to form the silicon-boron-carbon ceramic fiber. These novel silicon-boron-carbon ceramic fibers are useful in high temperature applications because they retain tensile and other properties up to 1200 C, from 1200 to 1300 C, and in some cases higher than 1300 C.
Riccitiello, Salvatore R.↗
Composite components and methods of manufacturing composite components using magnetic forces at fiber preform seams
A method of manufacturing a composite component according to various aspects of the present disclosure includes disposing a fiber preform in a mold. The fiber preform includes a first portion having a first edge and a second portion having a second edge. The first edge and the second edge cooperate to at least partially define a gap. One of the first portion or the second portion includes a first ferromagnetic material and the other of the first portion or the second portion includes a first magnetic or magnetizable component. The method further includes closing the gap by generating a magnetic field from the first magnetic or magnetizable component. The method further includes injecting a polymer precursor into the mold. The method further includes forming the composite component by solidifying the polymer precursor to form a polymer. The composite component includes the fiber preform and the polymer.
Aitharaju, Venkateshwar R.↗
Advanced Algal Biofoundries for the Production of Polyurethane Precursors [Abstract]
The collaboration between PNNL, LBNL, and UCSD will develop novel algae bioproduction platforms for the generation of polymer precursors. To achieve this, we will design and construct genetic tools for enhanced production of target chemicals. Biosensors will be developed to detect target chemical production. We will expand our knowledge of metabolic and regulatory systems that control or inhibit biosynthesis of the target molecules, and use this knowledge base to optimize production titers. Finally, we will integrate the knowledge gained from each activity to produce a set of the most promising production strains used to demonstrate the economic viability of producing polymer precursors in algal bioproduction platforms at scale under either heterotrophic or photosynthetic growth.
60 APPLIED LIFE SCIENCES↗
Surface modified aerogel monoliths
This invention comprises reinforced aerogel monoliths such as silica aerogels having a polymer coating on its outer geometric surface boundary, and to the method of preparing said aerogel monoliths. The polymer coatings on the aerogel monoliths are derived from polymer precursors selected from the group consisting of isocyanates as a precursor, precursors of epoxies, and precursors of polyimides. The coated aerogel monoliths can be modified further by encapsulating the aerogel with the polymer precursor reinforced with fibers such as carbon or glass fibers to obtain mechanically reinforced composite encapsulated aerogel monoliths.
Leventis, Nicholas↗
Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme
A document discusses a new, simplified method for cross-linking silica and other oxide aerogels, with a polymeric material to increase strength of such materials without adversely affecting porosity or low density. This innovation introduces the polymer precursor into the sol before gelation either as an agent, which co-reacts with the oxide gel, or as soluble polymer precursors, which do not interact with the oxide gel in any way. Subsequent exposure to heat, light, catalyst or other method of promoting polymerization causes cross-linking without any additional infiltration steps.
Meador, Ann B.↗
Forcespun Polymers as Precursors to Boron Nitride Fibers
The need for multifunctional materials in aerospace technologies is currently driving the development of new novel composite materials. Specifically, insulation materials with high thermal conductivity, high electrical resistivity, and are chemically inert are needed for high voltage power applications. Boron nitride (BN) nanomaterials fit these criteria and can be incorporated into composites for further material design. The synthesis of boron nitride through a polymer derived ceramic route allows for the morphology of the resulting BN to be tailored. This is especially beneficial since the polymers can be shaped or spun into fibers prior to the ceramic conversion. This project utilizes the Forcespinning technique to produce boron-containing polymer fibers that are converted to boron nitride through a heat treatment. The chemical compositions and fiber morphologies were studied and reported here.
Boron nitride, Fibers, Forcespinning↗
Template-free fabrication of fractal porous Y 2 O 3 monolithic foam and its functional modification by Ni-doping
Fractal structures which display nearly the same character at every scale exist widely in nature, however, it is still a great challenge to fabricate a fractal nanostructure. Herein, a Y 2 O 3 monolith with unique hierarchically fractal porous structure was fabricated via calcination of a fractal porous coordination polymer precursor. The monolith exhibits porous feature with the pore-size ranging from micrometers to nanometers. Interestingly, each level of the pore-wall is composed of secondary porous structures, whose pore-wall is composed of sub-level self-similar porous feature. Moreover, by Ni-doping in the coordination polymer precursor, fractal porous Ni@Y 2 O 3 was prepared, and exhibited enhanced activity in ethanol steam reforming compared with that of a common supported NiO catalyst.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Self-Assembling, Flexible, Pre-Ceramic Composite Preforms
In this innovation, light weight, high temperature, compact aerospace structures with increased design options are made possible by using self-assembling, flexible, pre-ceramic composite materials. These materials are comprised of either ceramic or carbon fiber performs, which are infiltrated with polymer precursors that convert to ceramics upon thermal exposure. The preform architecture can vary from chopped fibers formed into blankets or felt, to continuous fibers formed into a variety of 2D or 3D weaves or braids. The matrix material can also vary considerably. For demonstration purposes, a 2D carbon weave was infiltrated with a SiC polymer precursor. The green or unfired material is fabricated into its final shape while it is still pliable. It is then folded or rolled into a much more compact shape, which will occupy a smaller space. With this approach, the part remains as one continuous piece, rather than being fabricated as multiple sections, which would require numerous seals for eventual component use. The infiltrated preform can then be deployed in-situ. The component can be assembled into its final shape by taking advantage of the elasticity of the material, which permits the structure to unfold and spring into its final form under its own stored energy. The pre-ceramic composites are converted to ceramics and rigidized immediately after deployment. The final ceramic composite yields a high-temperature, high-strength material suitable for a variety of aerospace structures. The flexibility of the material, combined with its high-temperature structural capacity after rigidization, leads to a less complex component design with an increased temperature range. The collapsibility of these structures allows for larger components to be designed and used, and also offers the potential for increased vehicle performance. For the case of collapsible nozzle extensions, a larger nozzle, and thus a larger nozzle exit plane, is possible because interference with surrounding structures can be avoided in the collapsed state. The larger exit plane leads to an increase in expansion area ratio, which has the potential to increase thrust and overall rocket performance. In general, the use of advanced ceramic materials can lead to improved engine and vehicle performance. The ceramics can run hotter, so less cooling is required. Fuel to coolant ratios can be balanced more readily to reduce weight. Engine efficiency can also be increased with hotter combustion and exhaust temperatures. In addition, the ceramic composites themselves can reduce the component weight by as much as 50 percent, which can translate into greater payload for the vehicle
Jaskowiak, Martha H.↗
Additive manufacturing of hierarchical three- dimensional micro-architected aerogels
Disclosed here is a method for making a three-dimensional micro-architected aerogel, comprising: (a) curing a reaction mixture comprising a co-sol-gel material (e.g., graphene oxide (GO)) and at least one catalyst to obtain a crosslinked co-sol-gel (e.g., GO hydrogel); (b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel (e.g., GO hydrogel); (c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure; (d) drying the wet gel to produce a dry gel; and (e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel (e.g., graphene aerogel). Also disclosed is a photoresin for projection microstereolithography, comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of a crosslinked co-sol-gel.
Worsley, Marcus A.↗
Investigations of Polymethacrylate Tribochemical Films Using X-Ray Spectroscopy and Optical Profilometry
This study investigates the elemental composition and surface morphology of solid tribochemical films formed on steel surfaces. The reversible addition-fragmentation chain transfer (RAFT) method was used to synthesize nine different metal-free polymers, which were blended into commercial base oils. The polymers were either homopolymers of dodecyl methacrylate and ethylhexyl methacrylate or were co-polymers of these monomers with six polar monomers. After tribological testing at 100 degrees C using the ball-on-flat geometry, the resulting tribochemical films were imaged using scanning electron microscopy (SEM) and optical microscopy. The resulting tribochemical films have thicknesses around 50-100 nm. Two of the films corresponding to small (P1-imidazole-containing copolymer) and large (P3-less polar homopolymer) wear were cross-sectioned using focused ion beam (FIB) and analyzed for elemental composition using energy-dispersive X-Ray (EDX) mapping. Oxygen and nitrogen enrichment was observed, consistent with the relative chemical composition of the precursor polymers. Transmission electron microscopy (TEM) evidence suggests that at the worn surface, some organic elements penetrate or are mixed into the steel substrate giving an interlocking appearance. The two samples examined with TEM showed that P1 tribofilm is diffused or mixed with the steel substrate more so than P3, suggesting a stronger affinity and contact during tribofilm formation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High efficiency environmental sampling with rapidly cured peelable coatings
A rapidly curable liquid gel for collecting an analyte from a sampling surface includes a polymer precursor mixture including a monomer and/or an oligomer; and an additive to enhance extraction of the analyte from the sampling surface. A kit for collecting an analyte from a sampling surface may include the rapidly curable liquid gel and a portable device for rapidly curing the gel. The rapidly curable liquid gel is cured to thereby form a peelable sampling film, and the sampling film is removed from the sampling surface, thereby collecting the analyte. In one embodiment, the rapidly curable liquid gel is UV-curable, the polymer precursor mixture further includes a photoinitiator compound, and the portable device includes a UV light source configured to emit UV light of a wavelength range absorbed by the photoinitiator compound.
Henzl, Vladimir↗
Integration of proteomics and metabolomics into the Design, Build, Test, Learn cycle to improve 3-hydroxypropionic acid production in Aspergillus pseudoterreus
Biological engineering of microorganisms to produce value-added chemicals is a promising route to sustainable manufacturing. However, overproduction of metabolic intermediates at high titer, rate, and yield from inexpensive substrates is challenging in non-model systems where limited information is available regarding metabolic flux and its control in production conditions. Integrated multi-omic analyses of engineered strains offers an in-depth look at metabolites and proteins directly involved in growth and production of target and non-target bioproducts. Here we applied multi-omic analyses to overproduction of the polymer precursor 3-hydroxypropionic acid (3HP) in the filamentous fungus Aspergillus pseudoterreus. A synthetic pathway consisting of aspartate decarboxylase, beta-alanine pyruvate transaminase, and 3HP dehydrogenase was designed and built for A. pseudoterreus. Strains with single- and multi-copy integration events were isolated and multi-omics analysis consisting of intracellular and extracellular metabolomics and targeted and global proteomics was used to interrogate the strains in shake-flask and bioreactor conditions. Production of a variety of co-products (organic acids and glycerol) and oxidative degradation of 3HP were identified as metabolic pathways competing with 3HP production. Intracellular accumulation of nitrogen as 2,4-diaminobutanoate was identified as an off-target nitrogen sink that may also limit flux through the engineered 3HP pathway. Elimination of the high-expression oxidative 3HP degradation pathway by deletion of a putative malonate semialdehyde dehydrogenase improved the yield of 3HP by 3.4× after 10 days in shake-flask culture. This is the first report of 3HP production in a filamentous fungus amenable to industrial scale biomanufacturing of organic acids at high titer and low pH.
Pomraning, Kyle R.↗
Method of producing carbon fibers from multipurpose commercial fibers
A method of producing carbon fibers includes the step of providing polyacrylonitrile precursor polymer fiber filaments. The polyacrylonitrile precursor filaments include from 87-97 mole % acrylonitrile, and less than 0.5 mole % of accelerant functional groups. The filaments are no more than 3 deniers per filament. The polyacrylonitrile precursor fiber filaments can be arranged into tows of at least 150,000 deniers per inch width. The arranged polyacrylonitrile precursor fiber tows are stabilized by heating the tows in at least one oxidation zone containing oxygen gas and maintained at a first temperature T1 while stretching the tows at least 10% to yield a stabilized precursor fiber tow. The stabilized precursor fiber tows are carbonized by passing the stabilized precursor fiber tows through a carbonization zone. Carbon fibers produced by the process are also disclosed.
Naskar, Amit K.↗
Approaches to polymer-derived CMC matrices
The use of polymeric precursors to ceramics permits the fabrication of large, complex-shaped ceramic matrix composites (CMC's) at temperatures which do not degrade the fiber. Processing equipment and techniques readily available in the resin matrix composite industry can be adapted for CMC fabrication using this approach. Criteria which influence the choice of candidate precursor polymers, the use of fillers, and the role of fiber architecture and ply layup are discussed. Three polymer systems, polycarbosilanes, polysilazanes, and polysilsesquioxanes, are compared as candidate ceramic matrix precursors.
Hurwitz, Frances I.↗