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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Biodegradation of Poly(Aspartic Acid-Itaconic Acid) Copolymers by Miscellaneous Microbes from Natural Water

Poly(aspartic acid-itaconic acid) copolymers (PAI) is a new scale inhibitor for water treatment. Thus, it is necessary to investigate its biodegradability. The biodegradability of PAI was investigated through CO{sub 2} evolution tests under different conditions based on determination of carbon dioxide production. The investigation results showed that the degradation rate of PAI on day 10 and day 28 were respectively 38.7 and 79.5%, indicating that PAI was one kind of easily biodegradable scale inhibitors. With the increase in the content of itaconic acid in copolymerization process, the biodegradability of PAI was significantly reduced. In addition, the high biodegradability might be attributed to the existence of C–N bone-structure and more –COO–. Finally, Cu{sup 2+} could decrease the degradation percentage and the enzyme inhibition effect of Cu{sup 2+} was not the linear effect, but the “low-dosage effect”.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Exploration of the Effect of Chitosan and Crosslinking Agent Concentration on the Properties of Dual Responsive Chitosan-g-Poly (N-Isopropylacrylamide) Co-polymeric Particles

The objective of the present study was to synthesize and evaluate the effect of change in concentration of chitosan (CS) and N,N-methylenebisacrylamide (MBA)- a cross linking agent, on various properties such as lower critical solution temperature (LCST), zeta potential, particle size and poly dispersity index (PDI) of the synthesized co-polymer. Nine different formulations of chitosan-g-poly (N-isopropylacrylamide) (CS-g-PNIPAAm) co-polymer with varying CS and MBA concentrations were synthesized by a surfactant free dispersion copolymerization method. The synthesized co-polymer was further characterized and confirmed for its structure, morphology, particle size, zeta-potential, thermo and pH responsive properties, in-vitro cyto-compatability and stability studies using various analytical tools. The data confirms the successful synthesis of co-polymer. The increase in the concentrations of CS and MBA during the polymerization of co-polymer, resulted in proportional increase of LCST and zeta potential with decrease in particle size of co-polymeric nanoparticles. pH responsive studies showed that as the pH of the medium increases particle size and zeta potential decreases with increase in LCST of co-polymeric nanoparticles. From the results, it can be inferred that the synthesized co-polymeric nanoparticles exerted thermo and pH responsive properties with biocompatibility. By varying the CS and MBA concentrations in the co-polymer, desired LCST, particle size and zeta potential for co-polymeric nanoparticles can be obtained and thus the synthesized co-polymer may have great potential to be used as a drug carrier (nanoform) with both thermo and pH responsiveness.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dual Function of Cellulose Triacetate–Graft–Polymethacrylic Acid Films for Dyes Removal and for High-Dose Radiation Dosimetry

Graft copolymerization of methacrylic acid (MAc) onto cellulose triacetate (CTA) films was conducted by gamma rays. The grafting conditions were optimized. The structure of grafted CTA films was characterized by Fourier transform infra red–attenuated total reflection, scanning electron microscopy, thermal gravimetric analysis, CHNS/O microanalyzer and, surface area and porosity analyzer. The grafted CTA films were exploited in adsorption of ethyl violet (EV) and phenol red (PR) dyes. The adsorption capacity of the grafted CTA films was investigated at various variables. The adsorption isotherms and kinetic study were examined. Further, the dyed grafted CTA films were used in measurements of high dose radiation. The results indicate that the useful dose range extents up to 440 and 300 kGy for EV and PR, respectively. The effects of relative humidity during irradiation, shelf-life, pre- and post-irradiation storage in dark and indirect daylight conditions on dosimeters performance were investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Poly(N,N-dimethylacrylamide-co-acrylamide) Grafted Hydroxyethyl Cellulose Hydrogel: A Useful Congo Red Dye Remover

Composite hydrogel was prepared by cross-link copolymerization of a mixture of acrylamide, and N,N-dimethylacrylamide using N,N′-methylene-bis-acrylamide as a cross-linking agent onto hydroxyethyl cellulose backbone. Several hydrogels (H{sub 1}–H{sub 5}) were prepared by varying the amount of acrylamide and N,N-dimethylacrylamide. Swelling characteristics in water of all the hydrogels were evaluated to identify the hydrogel having highest water swelling property. The hydrogel showing highest water swelling performance (H{sub 3}) was characterized by FTIR spectroscopy, XRD and SEM studies. Swelling and deswelling kinetic studies of the hydrogel (H{sub 3}) were also carried out. The hydrogel (H{sub 3}) was used for the removal of congo red (CR), a toxic azo dye from its aqueous solution. Adsorption dynamics, kinetics and isotherms were also evaluated. The adsorption follows a pseudo second order kinetics, and the sorption data were well fitted with Langmuir adsorption isotherm. The hydrogel (H{sub 3}) showed a high monolayer adsorption capacity (Q{sub m} = 102.4 mg g{sup −1}) for the CR dye adsorption. Graphical Abstract: .

36 MATERIALS SCIENCE↗
DOE OSTI2019

Adsorption of Methylene Blue, Brilliant Green and Rhodamine B from Aqueous Solution Using Collagen-g-p(AA-co-NVP)/Fe{sub 3}O{sub 4}@SiO{sub 2} Nanocomposite Hydrogel

In this study, the collagen-g-poly(acrylic acid-co-N-vinylpyrrolidone)/Fe{sub 3}O{sub 4}@SiO{sub 2} (collagen-g-p(AA-co-NVP)/Fe{sub 3}O{sub 4}@SiO{sub 2}) as magnetic nanocomposite hydrogel was synthesized by graft copolymerization of acrylic acid (AA) and N-vinylpyrrolidone (NVP) onto collagen in the presence of the Fe{sub 3}O{sub 4}@SiO{sub 2} using ammonium persulfate as a free radical initiator and bis[2-(methacryloyloxy)ethyl] phosphate as a crosslinker under ultrasound-assisted condition. The blank collagen-g-p(AA-co-NVP) hydrogel and its composite with the Fe{sub 3}O{sub 4}@SiO{sub 2} nanoparticles were characterized by means of FTIR, SEM-EDS, XRD, VSM and TGA methods. The effects of different parameters such as pH, dose of adsorbent and time on swelling behavior were examined. The swelling ratio of the collagen-g-p(AA-co-NVP) hydrogel increased in the presence of the Fe{sub 3}O{sub 4}@SiO{sub 2} nanoparticles. Adsorption behavior of magnetic nanocomposite hydrogel was investigated for the adsorption of dyes and it was found to remove about 93% for methylene blue, 96% for brilliant green and 89% for rhodamine B in 50 mg/L of dyes solutions at pH 7. Kinetic study revealed the applicability of pseudo-first-order and pseudo-second-order models for the adsorption of mentioned dyes. The adsorption isotherm was studied in 25, 35, 45 and 55 °C using Langmuir, Freundlich, Temkin and Sips models and the adsorption data were well described by Langmuir isotherm model. Negative values of ΔG{sup º} for all three dyes suggested the feasibility of dyes removal and support for spontaneous adsorption of mentioned dyes on magnetic nanocomposite hydrogel. Desorption of dyes from the dye loaded nanocomposite hydrogel was simply done in ethanol. The results indicate that the prepared magnetic nanocomposite hydrogel is an efficient adsorbent with high adsorption capacity for the aforementioned dyes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Novel Biocide Based on Cationic Derivative of Psyllium: Surface Modification and Antibacterial Activity

To circumvent the problems (such as volatilization, photolytic decomposition, chemical instability, easy permeability through the skin) associated with low molecular weight antimicrobial agents, our strategy employed graft copolymerization of cationic monomer with the polymeric substrate viz. psyllium husk. The surface graft concentration of quaternary ammonium ion on psyllium was optimized by measuring the extent of grafting in the microwave-induced process. The surface modification of graft copolymers was evident by different physico–chemical techniques like {sup 13}C nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray diffractometer (XRD), differential scanning calorimetry (DSC), Thermo gravimeteric analysis (TGA), and viscometric study. The synthesized water soluble product resulted good antibacterial activity against Gram positive Staphylococcus aureus and Bacillus anthracis but failed to produce any antibacterial activity against Gram negative Salmonella typhi and Escherichia coli. The reason to failure has been explained on the basis of differences in the electrokinetic property between Gram-positive and Gram-negative bacteria. Optimum minimum inhibitory concentration (MIC) for the polymeric grade which showed good biocidal effect evaluated by both zone of inhibition and absorbance is found at 1000 µg/ml.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Fabrication and Testing of Soy-Based Polyurethane Foam for Insulation and Structural Applications

This study is focused on the fabrication and evaluation of polyurethane (PU) foam fabricated using soy-based polyol that can potentially replace conventional petroleum-based PU foam for thermal applications. Rigid soy-based PU foam samples investigated in this study were produced by copolymerization of diisocyanate with soy-based polyol in presence of Xiameter X0193 surfactant, dibutyltin dilaurate (DBTL) as a catalyst, and water as a blowing agent. Different formulations with varying amounts of blowing agent and catalyst were investigated to optimize the mechanical and thermal properties of soy-based PU foam when compared to commercial petroleum-based foam as a control sample. The prepared samples were tested for density, compressive strength, thermal conductivity, tensile strength, dimensional stability, and thermal stability using the ASTM standards. The cellular structure of the fabricated foam samples was investigated using scanning electron microscopy. It was observed that an increase in density leads to a decrease in insulation. Overall, soy-based foams exhibited similar thermal conductivity as compared to petroleum-based foams.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Photolytic synthesis and hydrophobization of plates of porous polymer material based on dimethacrylate oligomer MDP-2

Plates of poly-MDP-2 porous material with a characteristic size of inhomogeneities of 0.3, 0.7, 2.5, 10, and 20 µm were synthesized by the photopolymerization technique. The conditions for the photolytic modification of the hydrophilic/hydrophobic properties of poly-MDP-2 by the graft copolymerization method under visible light irradiation were selected using 9,10-phenanthrenequinone as a photoinitiator and isodecyl methacrylate as a modifying monomer. It is shown on the samples with an inhomogeneity size of 10 µm that the stable hydrophobization effect (contact angle of water droplet θ = 135°) is achieved at a photoinitiator concentration of 2.4 · 10{sup −3} mol L{sup −1} and an irradiation time of the sample in the modifying solution of 1 h. The effect of photolytic hydrophobization increases with an increase in the size of inhomogeneities in the porous polymer material and reaches θ = 140° for inhomogeneities ∼20 µm in size.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Highly porous organic polymers bearing tertiary amine group and their exceptionally high CO{sub 2} uptake capacities

We report a very simple and unique strategy for synthesis of a tertiary amine functionalized high surface area porous organic polymer (POP) PDVTA-1 through the co-polymerization of monomers divinylbenzene (DVB) and triallylamine (TAA) under solvothermal reaction conditions. Two different PDVTA-1 samples have been synthesized by varying the molar ratio of the monomers. The porous polymeric materials have been thoroughly characterized by solid state {sup 13}C CP MAS-NMR, FT-IR and UV–vis spectroscopy, N{sub 2} sorption, HR TEM and FE SEM to understand its chemical environment, nanostructure, bonding, morphology and related surface properties. PDVTA-1 with higher amine content (DVB/TAA=4.0) showed exceptionally high CO{sub 2} uptake capacity of 85.8 wt% (19.5 mmol g{sup −1}) at 273 K and 43.69 wt% (9.93 mmol g{sup −1}) at 298 K under 3 bar pressure, whereas relatively low amine loaded material (DVB/TAA=7.0) shows uptake capacity of 59.2 wt% (13.45 mmol g{sup −1}) at 273 K and 34.36 wt% (7.81 mmol g{sup −1}) at 298 K. Highly porous nanostructure together with very high surface area and basicity at the surface due to the presence of abundant basic tertiary amine N-sites in the framework of PDVTA-1 could be responsible for very high CO{sub 2} adsorption. - Graphical abstract: Exceptionally high CO2 uptake (85.8 wt % at 273 K) has been observed over a high surface area porous organic polymer PDVTA-1 synthesized through copolymerization of divinylbenzene and triallyl amine. - Highlights: • Designing the synthesis of a new N-rich cross-linked porous organic polymer PDVTA-1. • PDVTA-1 showed mesoporosity with very high surface area of 903 m{sup 2} g{sup −1}. • High surface area and presence of basic sites facilitates the CO{sub 2} uptake. • PDVTA-1 showed exceptionally high CO{sub 2} adsorption capacity of 85.8 wt% at 273 K, 3 bar pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Carbonylative Co- and Terpolymerizations of 10-Undecen-1-ol: A Route to Polyketoesters with Tunable Compositions

A strategy to synthesize branched polyketoesters from the carbonylative polymerization of bifunctional α,ω-alkenols such as 10-undecen-1-ol is presented. This strategy hinges on the competitive application of two related catalytic manifolds, alternating alkene/CO copolymerization, and alkene hydroesterification, which share a common metal acyl intermediate. Small molecule model studies of cationic Pd-catalyzed alkene carbonylation in the presence of alcohols demonstrate that the relative rates of ketone formation (through alternating alkene/CO insertion) and ester formation (through metal acyl alcoholysis) can be tuned across a wide range through judicious bis(phosphine) ligand design. Carbonylative polymerization of 10-undecen-1-ol with a (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 catalyst (dppp(3,5-CF 3 ) 4 = 1,3-bis[bis[3,5-bis(trifluoromethyl)phenyl]-phosphino]propane) led to the formation of high molecular weight polyketoesters with intermediate dispersity (M n > 20,000 g/mol, D- = 2.6) and a ketone/ester microstructure ratio of approximately 1:2. In these polymerization reactions, deploying electron-deficient bis(phosphines) to suppress deleterious alkene isomerization was the key to accessing the high molecular weight polymer. Further, terpolymerization reactions of 1-hexene/10-undecen-1-ol/CO or 1-fluoro-10-undecene/10-undecen-1-ol/CO by (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 were also successful. Furthermore, this proof of concept polymerization unlocks access to tunable polymer microstructures without extensive postpolymerization treatment.

10-undecen-1-ol↗
DOE OSTI2022

Poly(cyclosilane) Connectivity Tunes Optical Absorbance

We report herein the influence of skeletal connectivity on the conformation-dependent optical properties of cyclosilane homo- and copolymers. 1,3-Linked cyclosilanes were bathochromically shifted by 20 nm in solution relative to 1,4-linked cyclosilanes, an effect reproduced by quantum chemical calculations on oligomeric model systems. Polysilane optical properties are conformation-dependent, and 1,3-linked cyclosilanes were hypothesized to adopt a favorable conformation unavailable to 1,4-linked cyclosilanes constrained to an endocyclic gauche conformation. Copolymerization of the isomeric cyclosilanes 1,3Si 6 and 1,4Si 6 afforded linear statistical copolymers, as characterized by 1 H and 29 Si NMR spectroscopies. The distinct connectivity of each comonomer was found to give rise to tunable absorption spectra, where the position of the absorption band systematically increased with the increased corporation of 1,3Si 6 . Computational studies pointed to conformation-dependent changes in orbital symmetry in shifting the most intense transition from the low-energy highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) transition to a higher-energy HOMO → LUMO + n transition. Here, the results of these studies demonstrate for the first time the role of silicon skeletal connectivity in controlling conformation and optoelectronic properties and provide new insight into the structure-based design of solution-processable silicon-based polymeric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mapping Composition Evolution through Synthesis, Purification, and Depolymerization of Random Heteropolymers

Random heteropolymers (RHPs) consisting of three or more comonomers have been routinely used to synthesize functional materials. While increasing the monomer variety diversifies the side-chain chemistry, this substantially expands the sequence space and leads to ensemble-level sequence heterogeneity. Most studies have relied on monomer composition and simulated sequences to design RHPs, but the questions remain unanswered regarding heterogeneities within each RHP ensemble and how closely these simulated sequences reflect the experimental outcomes. Here, we quantitatively mapped out the evolution of monomer compositions in four-monomer-based RHPs throughout a design-synthesis-purification-depolymerization process. By adopting a Jaacks method, we first determined 12 reactivity ratios directly from quaternary methacrylate RAFT copolymerization experiments to account for the influences of competitive monomer addition and the reversible activation/deactivation equilibria. The reliability of in silico analysis was affirmed by a quantitative agreement (<4% difference) between the simulated RHP compositions and the experimental results. Furthermore, we mapped out the conformation distribution within each ensemble in different solvents as a function of monomer chemistry, composition, and segmental characteristics via high-throughput computation based on self-consistent field theory (SCFT). These comprehensive studies confirmed monomer composition as a viable design parameter to engineer RHP-based functional materials as long as the reactivity ratios are accurately determined and the livingness of RHP synthesis is ensured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Polyalkenamers as Drop-In Additives for Ring-Opening Metathesis Polymerization: A Promising Upcycling Paradigm

Here we report a distinct strategy to upcycle waste polyalkenamers such as polybutadiene into new, performance-advantaged materials by using them as drop-in additives for ring-opening metathesis polymerization (ROMP). The polyalkenamers serve as competent chain-transfer agents in ROMPs of common classes of cyclic olefin monomers, facilitating good molecular weight control, allowing low Ru catalyst loadings, and enabling efficient incorporation of the polyalkenamer into the synthesized polymeric material. We successfully demonstrate ROMP using model polyalkenamers and translate these learnings to leverage commercial polybutadiene and acrylonitrile butadiene styrene (ABS) as chain transfer agents for ROMP copolymerizations. Critically, our strategy is shown to be highly efficient and operationally simple, quantitatively incorporating the polyalkenamer and inheriting aspects of its thermomechanical performance. Our results highlight a promising pathway for the upcycling of polyalkenamers and provide an alternative to existing deconstruction and functional upcycling strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Optoelectronic properties and charge transfer in donor-acceptor all-conjugated diblock copolymers.

All-conjugated block copolymers, which can self-assemble into well-ordered morphologies, provide exciting opportunities to rationally design and control the nanoscale organization of electron-donor and electron-acceptor moieties in optoelectronic active layers. Here we report on the steady-state and time-resolved optical characterization of block copolymer films and solutions containing poly(3-hexylthiophene) as the donor block and poly(9,9-dioctylfluorene) with and without copolymerization with benzothiadiazole as the acceptor block. Transient absorption measurements suggest rapid charge transfer occurs in both systems, with higher efficiency observed in the latter composition. These results indicate that this class of materials has promise in preparing highly ordered bulk heterojunction all-polymer organic photovoltaic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Reactive triblock polymers from tandem ring-opening polymerization for nanostructured vinyl thermosets

Multiply functional hydroxyl telechelic poly(cyclooctene-s-5-norbornene-2-methylene methacrylate) was synthesized by ring opening metathesis (co)polymerization of cis-cyclooctene and 5-norbornene-2-methylene methacrylate using the second generation Grubbs catalyst in combination with a symmetric chain transfer agent bearing hydroxyl functionality. The resulting hydroxyl-telechelic polymer was used as a macroinitiator for the ring opening transesterification polymerization of d,l-lactide to form reactive poly(lactide)-b-poly(cyclooctene-s-5-norbornene-2-methylene methacrylate)-b-poly(lactide) triblock polymers. Subsequently, the triblocks were crosslinked by free radical copolymerization with several vinyl monomers including styrene, divinylbenzene, methyl methacrylate, and ethyleneglycol dimethacrylate. Certain conditions led to optically transparent thermosets with mesoscale phase separation as evidenced by small angle X-ray scattering, differential scanning calorimetry and transmission electron microscopy. Disordered, bicontinuous structures with nanoscopic domains were generated in several cases, rendering the samples attractive for size-selective membrane applications.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Cationic quaternization of cellulose with methacryloyloxy ethyl trimethyl ammonium chloride via ATRP method

The synthesis of a cationic cellulose copolymer from cellulose macro-initiator (MCC-BiB) and quaternary compound monomer (METMA) via atom transfer radical polymerization (ATRP) was studied. By using dimethylformamide (DMF), the optimum condition for successful synthesis was at the mole ratio of MCC-BIB:Catalyst:METMA = 1:1:26. The highest copolymer recovery was 93.2 % for 6 h and at 40°C. The copolymer was insoluble in weak polar solvents such as THF and DMF but soluble in methanol and water. The chemistry of cellulose copolymer was confirmed by the FTIR and TGA in which the METMA monomer was used as a reference. The absence of C C bond in the CiB-g-METMA spectrum indicated that graft copolymerization occurred.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Self-oscillating AB diblock copolymer developed by post modification strategy

We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy){sub 3}), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy){sub 3} was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy){sub 3} vinyl monomer and (ii) post modification (PM) of Ru(bpy){sub 3} with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔT{sub m}), where the block copolymer self-assembles into micelle at reduced Ru(bpy){sub 3}{sup 2+} state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy){sub 3}{sup 3+} state, monotonically extends as the composition of the Ru(bpy){sub 3} increases. The ΔT{sub m} of the block copolymer prepared by PM is larger than that by DP. The difference in ΔT{sub m} is rationalized from the statistical analysis of the arrangement of the Ru(bpy){sub 3} moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔT{sub m} (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2011

Poly(cyclohexadiene)-Based Polymer Electrolyte Membranes for Fuel Cell Applications

The goal of this research project was to create and develop fuel cell membranes having high proton conductivity at high temperatures and high chemical and mechanical durability. Poly(1,3-cyclohexadiene) (PCHD) is of interest as an alternative polymer electrolyte membrane (PEM) material due to its ring-like structure which is expected to impart superior mechanical and thermal properties, and due to the fact that PCHD can readily be incorporated into a range of homopolymer and copolymer structures. PCHD can be aromatized, sulfonated, or fluorinated, allowing for tuning of key performance structure and properties. These factors include good proton transport, hydrophilicity, permeability (including fuel gas impermeability), good mechanical properties, morphology, thermal stability, crystallinity, and cost. The basic building block, 1,3-cyclohexadiene, is a hydrocarbon monomer that could be inexpensively produced on a commercial scale (pricing typical of other hydrocarbon monomers). Optimal material properties will result in novel low cost PEM membranes engineered for high conductivity at elevated temperatures and low relative humidities, as well as good performance and durability. The primary objectives of this project were: (1) To design, synthesize and characterize new non-Nafion PEM materials that conduct protons at low (25-50%) RH and at temperatures ranging from room temperature to 120 C; and (2) To achieve these objectives, a range of homopolymer and copolymer materials incorporating poly(cyclohexadiene) (PCHD) will be synthesized, derivatized, and characterized. These two objectives have been achieved. Sulfonated and crosslinked PCHD homopolymer membranes exhibit proton conductivities similar to Nafion in the mid-RH range, are superior to Nafion at higher RH, but are poorer than Nafion at RH < 50%. Thus to further improve proton conductivity, particularly at low RH, poly(ethylene glycol) (PEG) was incorporated into the membrane by blending and by copolymerization. Conductivity measurements at 120 C over RH ranging from 20 to 100% using the BekkTech protocol showed much improved proton conductivities. Conductivities for the best of these new membranes exceed the DOE Year 3 milestone of 100 mS/cm at 50% RH at 120 C. Further optimization of these very promising low cost membranes could be pursued in the future.

08 HYDROGEN↗