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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4

Development of a weatherable acrylic elastomer for solar cell encapsulation

Poly-n-butylacrylate (PnBA) will be discussed as a potential candidate to be used in solar cell encapsulation. A new process has been developed in which PnBA can be readily cross-linked from a solvent-free syrup by a thermal process to give a highly flexible transparent film which does not creep significantly at temperature of up to 90 C. This process can be automated without the use of high cost capital equipment. Photodegradation of PnBA has also been modeled as a function of wavelengths and intensities. Its photostability will be discussed.

Liang, R.↗

Advanced double layer capacitors

There is a need for large amounts of power to be delivered rapidly in a number of airborne and space systems. Conventional, portable power sources, such as batteries, are not suited to delivering high peak power pulses. The charge stored at the electrode-electrolyte double layer is, however, much more assessible on a short time scale. Devices exploiting this concept were fabricated using carbon and metal oxides (Pinnacle Research) as the electrodes and sulfuric acid as the electrolyte. The approach reported, replaces the liquid sulfuric acid electrolyte with a solid ionomer electrolyte. The challenge is to form a solid electrode-solid ionomer electrolyte composite which has a high capacitance per geometric area. The approach to maximize contact between the electrode particles and the ionomer was to impregnate the electrode particles using a liquid ionomer solution and to bond the solvent-free structure to a solid ionomer membrane. Ruthenium dioxide is the electrode material used. Three strategies are being pursued to provide for a high area electrode-ionomer contact: mixing of the RuOx with a small volume of ionomer solution followed by filtration to remove the solvent, and impregnation of the ionomer into an already formed RuOx electrode. RuOx powder and electrodes were examined by non-electrochemical techniques. X-ray diffraction has shown that the material is almost pure RuO2. The electrode structure depends on the processing technique used to introduce the Nafion. Impregnated electrodes have Nafion concentrated near the surface. Electrodes prepared by the evaporation method show large aggregates of crystals surrounded by Nafion.

Sarangapani, S.↗

Polyimide Foams

A fully imidized, solvent-free polyimide foam having excellent mechanical, acoustic, thermal, and flame resistant properties is produced. A first solution is provided, which includes one or more aromatic dianhydrides or derivatives of aromatic dianhydrides, and may include one or more aromatic diamines, dissolved in one or more polar solvents, along with an effective amount of one or more blowing agents. This first solution may also advantageously include effective amounts respectively of one or mores catalysts, one or more surfactants, and one or more fire retardants. A second solution is also provided which includes one or more isocyanates. The first and second solutions are rapidly and thoroughly mixed to produce an admixture, which is allowed to foam-in an open container, or in a closed mold-under ambient conditions to completion produce a foamed product. This foamed product is then cured by high frequency electromagnetic radiation, thermal energy, or a combination thereof. Alternatively, the process is adapted for spraying or extrusion.

Juan M Vazquez↗

Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

Chuang, CHun-Hua↗

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Meador, Mary Ann B.↗

Polyimide foams

A fully imidized, solvent-free polyimide foam having excellent mechanical, acoustic, thermal, and flame resistant properties is produced. A first solution is provided, which includes one or more aromatic dianhydrides or derivatives of aromatic dianhydrides, and may include one or more aromatic diamines, dissolved in one or more polar solvents, along with an effective amount of one or more blowing agents. This first solution may also advantageously include effective amounts respectively of one or mores catalysts, one or more surfactants, and one or more fire retardants. A second solution is also provided which includes one or more isocyanates. The first and second solutions are rapidly and thoroughly mixed to produce an admixture, which is allowed to foam?in an open container, or in a closed mold?under ambient conditions to completion produce a foamed product. This foamed product is then cured by high frequency electromagnetic radiation, thermal energy, or a combination thereof. Alternatively, the process is adapted for spraying or extrusion.

Vazquez, Juan M.↗

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Baldwin, Richard S.↗

Low Viscosity Imides Based on Asymmetric Oxydiphthalic Anhydride

A series of low-melt viscosity imide resins were prepared from asymmetric oxydiphthalic dianhydride (a-ODPA) and 4-phenylethynylphthalic anhydride as the endcap, along with 3,4' - oxydianiline (3,4' -ODA), 3,4' -methylenedianiline (3,4' -MDA), 3,3' -methylenedianiline (3,3' - MDA) and 3,3'-diaminobenzophenone (3,3'-DABP), using a solvent-free melt process. These imide oligomers displays low-melt viscosities (2-15 poise) at 260-280 C, which made them amenable to low-cost resin transfer molding (RTM) process. The a-ODPA based RTM resins exhibits glass transition temperatures (Tg's) in the range of 265-330 C after postcure at 343 C. The mechanical properties of these polyimide/carbon fiber composites fabricated by RTM will be discussed.

Chuang, Kathy C.↗

Polyimide Composites Based on Asymmetric Dianhydrides (a-ODPA vs a-BPDA)

Two series of low-melt viscosity imide resins (2-15 poise at 260-280 C) were formulated from either asymmetric oxydiphthalic anhydride (a-ODPA) or asymmetric biphenyl dianhydride (a- BPDA) with 4-phenylethynyl endcap (PEPA), along with 3,4'-oxydianiline, 3,4 - methylenedianiline, 3,3 -methylenedianiline or 3,3 -diaminobenzophenone, using a solvent-free melt process. These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fabric composites by resin transfer molding (RTM). Composites from a-ODPA based resins display better open-hole compression strength and short beam shear strength from room temperature to 288 C than that of the corresponding a-BPDA based resins. However, due to the lower Tg s of a-ODPA based resins (265-330 C), their corresponding composites do not possess 315 C use capability while the a-BPDA based composites do. In essence, RTM 370 (T g = 370 C), derived from a-BPDA and 3,4 -ODA and PEPA, exhibits the best overall property performance at 315 C (600 F).

Chuang, Kathy C.↗

Polyimide foams

A fully imidized, solvent-free polyimide foam having excellent mechanical, acoustic, thermal, and flame resistant properties is produced. A first solution is provided, which includes one or more aromatic dianhydrides or derivatives of aromatic dianhydrides, and may include one or more aromatic diamines, dissolved in one or more polar solvents, along with an effective amount of one or more blowing agents. This first solution may also advantageously include effective amounts respectively of one or mores catalysts, one or more surfactants, and one or more fire retardants. A second solution is also provided which includes one or more isocyanates. The first and second solutions are rapidly and thoroughly mixed to produce an admixture, which is allowed to foam--in an open container, or in a closed mold--under ambient conditions to completion produce a foamed product. This foamed product is then cured by high frequency electromagnetic radiation, thermal energy, or a combination thereof. Alternatively, the process is adapted for spraying or extrusion.

Vazquez, Juan M.↗

Highly Efficient Multilayer Thermoelectric Devices

Multilayer thermoelectric devices now at the prototype stage of development exhibit a combination of desirable characteristics, including high figures of merit and high performance/cost ratios. These devices are capable of producing temperature differences of the order of 50 K in operation at or near room temperature. A solvent-free batch process for mass production of these state-of-the-art thermoelectric devices has also been developed. Like prior thermoelectric devices, the present ones have commercial potential mainly by virtue of their utility as means of controlled cooling (and/or, in some cases, heating) of sensors, integrated circuits, and temperature-critical components of scientific instruments. The advantages of thermoelectric devices for such uses include no need for circulating working fluids through or within the devices, generation of little if any noise, and high reliability. The disadvantages of prior thermoelectric devices include high power consumption and relatively low coefficients of performance. The present development program was undertaken in the hope of reducing the magnitudes of the aforementioned disadvantages and, especially, obtaining higher figures of merit for operation at and near room temperature. Accomplishments of the program thus far include development of an algorithm to estimate the heat extracted by, and the maximum temperature drop produced by, a thermoelectric device; solution of the problem of exchange of heat between a thermoelectric cooler and a water-cooled copper block; retrofitting of a vacuum chamber for depositing materials by sputtering; design of masks; and fabrication of multilayer thermoelectric devices of two different designs, denoted I and II. For both the I and II designs, the thicknesses of layers are of the order of nanometers. In devices of design I, nonconsecutive semiconductor layers are electrically connected in series. Devices of design II contain superlattices comprising alternating electron-acceptor (p)-doped and electron-donor (n)-doped, nanometer- thick semiconductor layers.

Boufelfel, Ali↗

Polyimides Based on Asymmetric Dianhydrides (II) (a-BPDA vs a-BTDA) for Resin Transfer Molding (RTM)

A new series of low-melt viscosity imide resins (10-20 poise at 280 C) were formulated from asymmetric 2,3,3',4' -benzophenone dianhydride (a-BTDA) and 4-phenylethynylphthalic endcaps, along with 3,4' -oxydianiline, 3,3' -methylenedianiline and 3,3'- diaminobenzophenone, using a solvent-free melt process. a-BTDA RTM resins exhibited higher glass transition temperatures (Tg's = 330-400 C) compared to those prepared by asymmetric 2,3,3',4' -biphenyl dianhydride, (a-BPDA, Tg's = 320-370 C). These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fiber composites by a RTM process. Composites properties of a-BTDA resins, such as open-hole compression and short-beam shear strength, are compared to those of composites made from a-BPDA based resin at room temperature, 288 C and 315 C. These novel, high temperature RTM imide resins exhibit outstanding properties beyond the performance of conventional RTM resins, such as epoxy and BMI resins which have use-temperatures around 177 C and 232 C for aerospace applications.

Chuang, Kathy C.↗

Bulk Preparation of Holey Graphene via Controlled Catalytic Oxidation

A scalable method allows preparation of bulk quantities of holey carbon allotropes with holes ranging from a few to over 100 nm in diameter. Carbon oxidation catalyst nanoparticles are first deposited onto a carbon allotrope surface in a facile, controllable, and solvent-free process. The catalyst-loaded carbons are then subjected to thermal treatment in air. The carbons in contact with the carbon oxidation catalyst nanoparticles are selectively oxidized into gaseous byproducts such as CO or CO.sub.2, leaving the surface with holes. The catalyst is then removed via refluxing in diluted nitric acid to obtain the final holey carbon allotropes. The average size of the holes correlates strongly with the size of the catalyst nanoparticles and is controlled by adjusting the catalyst precursor concentration. The temperature and time of the air oxidation step, and the catalyst removal treatment conditions, strongly affect the morphology of the holes.

Watson, Kent↗

Plasma Cleaning

NASA's Kennedy Space Center has developed two solvent-free precision cleaning techniques: plasma cleaning and supercritical carbon dioxide (SCCO2), that has equal performance, cost parity, and no environmental liability, as compared to existing solvent cleaning methods.

supercritical fluid cleaning↗

Ultrahigh Mass Loading Batteries with Holey Graphene-Enabled Dry-Pressed Cathode Architectures

Holey graphene is a structural derivative of graphene with arrays of nanometer-sized, through-thickness holes across the lateral surface of the atomically thin nanosheet. It has been widely acknowledged that the presence of holes improves ion transport through the graphene planes, making holey graphene an ideal electrode material for electrochemical energy storage. We recently discovered another unique attribute of holey graphene in that it can be directly compressed from powder into electrode in a single step without the use of solvent or binder. In addition to neat holey graphene electrodes, composite electrodes with holey graphene as an ultralightweight scaffold host filled with various active materials can also be readily prepared in a similar solvent-free and binder-free fashion. The active materials can be metal-containing catalysts for lithium-oxygen batteries, lithium-ion battery electrode materials, or high energy density components such as sulfur. Compared to the conventional slurry-based process, the dry-press method is comparably much more suitable toward the facile and scalable preparation of ultrahigh mass loading electrodes with ultrahigh areal capacities.

holey graphene, cathode scaffold, lithium metal, h↗

Layered Electrode Architectures Enabled by Holey Graphene Hosts

Battery electrodes are typically prepared using a slurry-based method, where high boiling point organic solvents are typically used with a polymer binder to disperse active electrode materials and conductive carbon additives followed by casting into current collector sheets. In this process, the use of organic solvents are environmentally hazardous, energy intensive, and time-consuming, while polymeric binders add weight and can undergo parasitic reactions during battery cycling. Here we discuss the use of a unique conductive carbon nanomaterial, namely holey graphene, as a multifunctional host that can be processed via a facile, solvent-free, binder-free, cold pressing method to prepare electrodes with unique architectures. This approach can accommodate a broad range of battery chemistries, such as lithium oxygen/carbon dioxide (Li-O2/CO2), lithium sulfur/selenium (Li-S/Se), and various lithium ion chemistries. The successful use of dry, cold compression allows the convenient modification of electrode mass loading with unique architectures containing active materials randomly mixed or layered with single or multiple layers of one or more active materials. In the conventional slurry-based electrode fabrication method, it is difficult, if not impossible, to achieve such layered architectures. In particular, the layered electrode architectures from the dry, cold press approach are easy to fabricate without significantly sacrificing device performance, and are amenable to continuous roll-to-roll dry processing. In addition, these architectures offer unprecedented perspectives on the battery material loading vs. utilization efficiency, as well as enabling unique characterization opportunities to advance mechanistic understanding of various battery chemistries. Potential applications of this unique electrode fabrication approach for solid-state batteries will also be discussed.

holey graphene, batteries, electrode architecture,↗

One Step Plasma Passivation and Precision Cleaning

Over the past several years, Kennedy Space Center (KSC) researchers developed two solvent-free techniques for precision cleaning of ground support equipment (GSE) that possess low commodity requirements and produce small or no waste streams. During testing of low-pressure air plasma as one of these cleaning techniques, physical changes in the surface of stainless steel test pieces were observed; cursory testing revealed that the test part had developed a thick oxide layer on the surface compared to untreated parts. This result indicated that the plasma process might not only serve as a green technology for precision cleaning of parts, but it may also passivate the surface at the same time. Current methodology in use at KSC’s Components Refurbishment & Chemical Analysis (CRCA) Facility for passivation of corrosion-resistant steels for aerospace applications follows an SAE International Standard, AMS2700, where parts are submerged in either a nitric acid or nitric acid/sodium dichromate bath at predetermined temperatures and contact times. These baths require constant testing to ensure effective treatment, use corrosive and carcinogenic chemicals, and produce hazardous waste. The passivation bath is one of the multiple steps employed at the facility, while cleaning with multiple environmentally-unfriendly solvents comprise several more steps before parts are recertified to a specific cleanliness level in their clean room. Based on the behavior of the stainless steel surface during cleaning optimization studies, it was believed that the plasma technology could be extended to passivation, combining what is currently many steps into a single, solvent- and waste-free system.

Paul Hintze↗

Zinc‐Imidazolate Films as an All‐Dry Resist Technology

Here, motivated by the drawbacks of solution phase processing, an all‐dry resist formation process is presented that utilizes amorphous zinc‐imidazolate (aZnMIm) films deposited by atomic/molecular layer deposition (ALD/MLD), patterned with electron beam lithography (EBL), and developed by novel low temperature (120 °C) gas phase etching using 1,1,1,5,5,5‐hexafluoroacetylacetone (hfacH) to achieve well‐resolved 22 nm lines with a pitch of 30 nm. The effects of electron beam irradiation on the chemical structure and hfacH etch resistance of aZnMIm films are investigated, and it is found that electron irradiation degrades the 2‐methylimidazolate ligands and transforms aZnMIm into a more dense material that is resistant to etching by hfacH and has a C:N:Zn ratio effectively identical to that of unmodified aZnMIm. These findings showcase the potential for aZnMIm films to function in a dry resist technology. Sensitivity, contrast, and critical dimensions of the patterns are determined to be 37 mC cm −2 , 0.87, and 29 nm, respectively, for aZnMIm deposited on silicon substrates and patterned at 30 keV. This work introduces a new direction for solvent‐free resist processing, offering the prospect of scalable, high‐resolution patterning techniques for advanced semiconductor fabrication processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗