11 Search Results

Many structure/property relationships of hydrolyzed poly(ester urethane) (PEU) – a thermoplastic – have been reported. Examples include changes in molecular weight vs. elongation at break and crosslink density vs. mechanical strength. However, the effect of molecular weight (or molar mass) reduction on some physical, thermal, and chemical properties of hydrolyzed PEU have not been reported. Therefore, a large set of hydrolyzed PEU (Estane®5703) samples were obtained from two aging experiments: 1) accelerated aging conducted under various environments (air, nitrogen, moisture) and at 64 °C and below for almost three years, and 2) natural aging conducted under ambient conditions for moremore » than three decades. The hydrolyzed samples were characterized via multi-detection gel permeation chromatography (GPC), thermogravimetric analysis (TGA), modulated differential scanning calorimetry (mDSC), UV–vis spectroscopy, nuclear magnetic resonance (NMR), and Fourier-transform infrared (FTIR) spectroscopy techniques. Hydrolysis of ester linkages in the soft-segments decreases both the molecular weight (M_w) and the melting point (T_m) of Estane (from ~55 °C to 39 °C). Aging above this T_m, increased mobility of polymer chains and water diffusivity in the PEU matrix alter the PEU degradation pathway from those expected at aging temperatures below this T_m and have significant bearing on the critical molecular weight (M_C) at which the physical, chemical, thermal, and mechanical properties of Estane change abruptly. While a M_C value of 20 kDa is found for PEU hydrolysis at mild temperatures (e.g., as low as 39 °C), the value of M_C increases with increasing aging temperatures. To complement the existing structure/property relationships reported in the literature, more correlations are obtained, which include the effect of M_w on polydispersity, intrinsic viscosity (Mark-Houwink equation), UV extinction coefficient, and dn/dc (GPC analysis) values. Furthermore, we seek to bolster previously reported aging models for PEU by developing a practical model with which the extent of degradation and material performance can be predicted based on aging under different temperature ranges both above and below the melting point of Estane.« less

In hybrid perovskite solar cells (PSCs), the reaction of hydrogens (H) located in the amino group of the organic A-site cations with their neighboring halides plays a central role in degradation. Inspired by the retarded biological activities of cells in heavy water, we replaced the light H atom with its abundant, twice-as-heavy, nonradioactive isotope, deuterium (D) to hamper the motion of H. This D substitution retarded the formation kinetics of the detrimental H halides in Pb-based PSCs, as well as the H bond-mediated oxidation of Sn²⁺ in Sn–Pb-based narrow-bandgap PSCs, evidenced by accelerated stability studies. A computational study indicated thatmore » the zero point energy of D-based formamidinium (FA) is lower than that of pristine FA. In addition, the smaller increase in entropy in D-based FA than in pristine FA accounts for the increased formation free energy of the Sn²⁺ vacancies, which leads to the retarded oxidation kinetics of Sn²⁺. In this study, we show that substituting active H with D in organic cations is an effective way to enhance the stability of PSCs without sacrificing photovoltaic (PV) performance. This approach is also adaptable to other stabilizing methods.« less

We report the octadentate hydroxypyridinone ligand 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO) has been identified as a promising candidate for both chelation and f-element separation technologies, two applications that require optimal performance in radiation environments. However, the radiation robustness of HOPO is currently unknown. Here, we employ a combination of time-resolved (electron pulse) and steady-state (alpha self-radiolysis) irradiation techniques to elucidate the basic chemistry of HOPO and its f-element complexes in aqueous radiation environments. Chemical kinetics were measured for the reaction of HOPO and its Nd(III) ion complex ([Nd^III(HOPO)]^-) with key aqueous radiation-induced radical transients (eaq^-, H^· atom, and ^·OH and NO₃^·more » radicals). The reaction of HOPO with eaq^- is believed to proceed via reduction of the hydroxypyridinone moiety, while transient adduct spectra indicate that reactions with the H^· atom and ^·OH and NO₃^· radicals proceeded by addition to HOPO's hydroxypyridinone rings, potentially allowing for the generation of an extensive suite of addition products. Complementary steady-state ²⁴¹Am(III)-HOPO complex ([²⁴¹Am^III(HOPO)]^-) irradiations showed the gradual release of ²⁴¹Am(III) ions with increasing alpha dose up to 100 kGy, although complete ligand destruction was not observed.« less

Chlorophyll pigments are used by photosynthetic organisms to facilitate light capture and mediate the conversion of sunlight into chemical energy. Due to the indispensable nature of this pigment and its propensity to form reactive oxygen species, organisms heavily invest in its biosynthesis, recycling, and degradation. One key enzyme implicated in these processes is chlorophyllase, an α/β hydrolase that hydrolyzes the phytol tail of chlorophyll pigments to produce chlorophyllide molecules. This enzyme was discovered a century ago, but despite its importance to diverse photosynthetic organisms, there are still many missing biochemical details regarding how chlorophyllase functions. Here, we present the 4.46-Åmore » resolution crystal structure of chlorophyllase from Triticum aestivum. This structure reveals the dimeric architecture of chlorophyllase, the arrangement of catalytic residues, an unexpected divalent metal ion–binding site, and a substrate-binding site that can accommodate a diverse range of pigments. Further, this structure exhibits the existence of both intermolecular and intramolecular disulfide bonds. We investigated the importance of these architectural features using enzyme kinetics, mass spectrometry, and thermal shift assays. Through this work, we demonstrated that the oxidation state of the Cys residues is imperative to the activity and stability of chlorophyllase, illuminating a biochemical trigger for responding to environmental stress. Additional bioinformatics analysis of the chlorophyllase enzyme family reveals widespread conservation of key catalytic residues and the identified “redox switch” among other plant chlorophyllase homologs, thus revealing key details regarding the structure-function relationships in chlorophyllase.« less

Solid oxide fuel cells (SOFC) have attracted attention as clean and efficient energy conversion devices with low emissions. However, several degradation mechanisms limit the electrochemical performance of current SOFCs, with cathode degradation due to Cr-poisoning from metal interconnects particularly problematic. The acidity/basicity of binary additives has been found to be a sensitive descriptor of the oxygen exchange kinetics, indicating that acidic Cr-species/basic Ca-species can be expected to deactivate/activate the cathode surface, respectively. Inspired by recent advances, the feasibility of relative acidity as a tool for reviving degraded SOFCs is demonstrated by neutralizing Cr-poisoned SOFCs by subsequent serial infiltration of Ca-species.more » Furthermore, a model mixed ionic and electronic conducting oxide, Pr_0.1Ce_0.9O_2-δ (PCO), is selected as the cathode material. Area-specific resistances (ASR) of symmetric cells obtained by electrochemical impedance spectroscopy show that Cr-infiltration results in a seven-fold increase in ASR, while subsequent infiltration of Ca-species leads to complete recovery. Performance degradation and recovery are attributed to depressed/enhanced redox properties at the PCO surface, as supported by XPS analysis. Experiments using anode-supported fuel cells show a reduction in peak power density by 26% upon Cr-infiltration, reversed following Ca-infiltration, after which no degradation is observed during subsequent operation for 100 h.« less

Metal oxides are an important class of functional materials, and for many applications, ranging from solid oxide fuel/electrolysis cells, oxygen permeation membranes, and oxygen storage materials to gas sensors (semiconducting and electrolytic) and catalysts, the interaction between the surface and oxygen in the gas phase is central. Ubiquitous Si-impurities are known to impede this interaction, commonly attributed to the formation of glassy blocking layers on the surface. Here, the surface oxygen exchange coefficient (k_chem) is examined for Pr_0.1Ce_0.9O_2-δ (PCO), a model mixed ionic electronic conductor, via electrical conductivity relaxation measurements, and the area-specific resistance (ASR) by electrochemical impedance spectroscopy. Itmore » is demonstrated that even low silica levels, introduced by infiltration, depress k_chem by a factor 4000, while the ASR increases 40-fold and we attribute this to its acidity relative to that of PCO. The ability to fully regenerate the poisoned surface by the subsequent addition of basic Ca- or Li-species is further shown. Furthermore, this ability to not only recover Si-poisoned surfaces by tuning the relative surface acidity of an oxide surface, but subsequently outperform the pre-poisoned response, promises to extend the operating life of materials and devices for which the catalytic oxygen/solid interface reaction is central.« less

Everybody knows TNT, the most widely used explosive material and a universal measure of the destructiveness of explosions. A long history of use and extensive manufacture of toxic TNT leads to the accumulation of these materials in soil and groundwater, which is a significant concern for environmental safety and sustainability. Reliable and cost-efficient technologies for removing or detoxifying TNT from the environment are lacking. Despite the extreme urgency, this remains an outstanding challenge that often goes unnoticed. We report here that highly controlled energy release from explosive molecules can be accomplished rather easily by preparing TNT–perovskite mixtures with a tailoredmore » perovskite surface morphology at ambient conditions. These results offer new insight into understanding the sensitivity of high explosives to detonation initiation and enable many novel applications, such as new concepts in harvesting and converting chemical energy, the design of new, improved energetics with tunable characteristics, the development of powerful fuels and miniaturized detonators, and new ways for eliminating toxins from land and water.« less

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study theirmore » effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T_d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T_d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T_g for P20 to about 225 °C while CE had T_g >350 °C.« less

Here, hybrid poplar from the clone DN34 was studied to determine the rate of production of bio-oil species with respect to time during the fast pyrolysis process. 300–660 ug samples were pyrolyzed using a micropyrolzer at 500 °C at very high heating rates and very short vapor residence times. Individual poplar samples were run in triplicate at discrete time points ranging from 1 to 20 s in the micropyrolzer. Several bio-oil compounds from each individual sample were analyzed using GC/MS. Select bio-oil compounds, derived from the hemicellulose, cellulose, and lignin fractions of the wood, were used to determine their ratesmore » of production from thermal degradation of the biomass. These rates were quantified using standards to determine the weight percent relative to the original raw biomass with respect to time. Pyrolysis kinetic reaction models were fit to this experimental data in order to determine suitability of each model. A first order exponential decay model for degradation of the solid biomass was fit against the data along with a six-step consecutive degradation model previously developed by our group. The experimental data suggests that compounds derived from the hemicellulose are produced at faster rates than that of the lignin or cellulose fractions of the wood, consistent with prior data from thermogravimetric analysis (TGA). When applying the first order exponential decay model, the reaction rates calculated did prove that holocellulose compounds reaction rates were approximately twice that of the lignin compounds reaction rate but did not provide the best fit. The six-step degradation model provided a better fit to all of the biooil compounds and char data, and the stoichiometric parameters derived from the model fit showed that the first three reactions involved mostly the hemicellulose derived compounds while reaction steps 4–6 released cellulose- and lignin-derived compounds.« less

Several conversion pathways of lignocellulosic biomass to advanced biofuels require or benefit from using concentrated sugar syrups of 600 g/L or greater. And while concentration may seem straightforward, thermal sugar degradation and energy efficiency remain major concerns. This study evaluated the trade-offs in product recovery, energy consumption, and economics between evaporative and membrane-based concentration methods. The degradation kinetics of xylose and glucose were characterized and applied to an evaporator process simulation. Though significant sugar loss was predicted for certain scenarios due to the Maillard reaction, industrially common falling-film plate evaporators offer short residence times (<5 min) and are expected tomore » limit sugar losses. Membrane concentration experiments characterized flux and sugar rejection, but diminished flux occurred at >100 g/L. A second step using evaporation is necessary to achieve target concentrations. Techno-economic process model simulations evaluated the overall economics of concentrating a 35 g/L sugar stream to 600 g/L in a full-scale biorefinery. A two-step approach of preconcentrating using membranes and finishing with an evaporator consumed less energy than evaporation alone but was more expensive because of high capital expenses of the membrane units.« less