木质素化学降解及其在聚合物材料中应用的研究进展

木质素是自然界储量丰富的可再生天然酚类高分子，可替代传统化石资源应用于聚合物材料合成。木质素分子结构中的大分子刚性骨架可赋予材料独特的力学性能和热稳定性。但木质素化学组成和分子结构复杂、反应活性低，限制了在聚合物材料领域的应用。化学降解是一种高效、高选择性且应用广泛的降解方法，经化学降解处理得到的木质素低聚物具有活性官能团多、反应活性高、溶解性好等优点，有利于拓展木质素在聚合物材料领域的高附加值应用。重点综述了近年来国内外有关木质素化学降解及其降解产物应用于聚合物材料的研究进展。     

含氟无皂乳液P(CTFE-IBVE-SUA)的合成及性能研究

通过无皂乳液聚合法制备得到聚(三氟氯乙烯-乙烯基异丁基醚-十一烯酸钠)[P(CTFE-IBVE-SUA)]含氟乳液。考察了单体配比对聚合反应的影响,研究了SUA用量对乳液及聚合物性能的影响,并对聚合物的结构及乳胶粒的形貌进行了测定。结果表明:含氟无皂乳液P(CTFE-IBVE-SUA)的稳定性好、粒径分布均匀;改变单体配比中IBVE和CTFE的比例可以得到不同结构的含氟聚合物乳液;SUA用量对乳液的稳定性、乳胶粒的粒径大小及粒径分布、聚合物膜与水的接触角都有很大的影响;制得的乳液具有明显的核壳结构。     

One‐shot radical polymerization of vinyl monomers with different reactivity accompanying spontaneous delay of polymerization for the synthesis of double‐network hydrogels

Double‐network hydrogels were conveniently synthesized by the one‐shot radical polymerization of an ionic monomer for the first network and a non‐ionic monomer for the second network in the presence of crosslinkers by simultaneous addition of the monomers, that is, one‐shot and spontaneous two‐step polymerization accompanying the delay of polymerization of a second network monomer. We analyzed the polymerization process based on the conversion of each monomer during the reaction in the absence of crosslinkers. Then we fabricated the double‐network hydrogels using several polymerization systems consisting of a conjugated monomer and a non‐conjugated monomer in the presence of the dual crosslinkers. We analyzed the swelling, mechanical and viscoelastic properties of hydrogels synthesized by one‐shot radical polymerization to confirm the production mechanism and the network structure of the hydrogels. © 2020 Society of Chemical Industry     

Novel high-energy ionic molecules deriving from new monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties

ABSTRACT

In recent years, the exploration of a practical strategy for novel energetic molecules with high energy and low sensitivity is very desirable but highly challenging. Novel ionic energetic molecules have attracted much attention in this area due to their prominent advantages including low sensitivities, high thermal stability, and excellent energy performances. Herein, five different ionic energetic molecules based on new monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties with enhanced oxygen balance have been synthesized, characterized and evaluated as potential high-energy materials. Thermal stability, sensitivities and energy output test were measured and studied in detail. The heats of formation and energetic parameters were calculated by using Gaussian 09 suite of programs and EXPLO 5 code. The results suggest that all as-prepared new molecules exhibit good thermal stability with high decomposition temperature (3, 231°C; 5, 160°C; 6, 185°C; 7, 180°C; 8, 213°C), and relative low sensitivity (IS > 20 J, FS = 324 N). Inheriting the significant oxygen content of monovalent and divalent 4-oxyl-3,5-dinitropyrazolate moieties, they also possess good energy properties (v _D = 8238 ~ 9208 m s^?1, P = 26.8 ~ 36.7 GPa, V _o = 481.8 ~ 959.4 L kg^?1), which make them competitive high-energy materials.     

Suppressing Ion Migration across Perovskite Grain Boundaries by Polymer Additives

Passivation of organometal halide perovskites with polar molecules has been recently demonstrated to improve the photovoltaic device efficiency and stability. However, the mechanism is still elusive. Here, it is found that both polymers with large and small dipole moment of 3.7 D and 0.6 D have negligible defect passivation effect on the MAPbI₃ perovskite films as evidenced by photothermal deflection spectroscopy. The photovoltaic devices with and without the polymer additives also have comparable power conversion efficiencies around 19%. However, devices with the additives have noticeable improvement in stability under continuous light irradiation. It is found that although the initial mobile ion concentrations are comparable in both devices with and without the additives, the additives can strongly suppress the ion migration during the device operation. This contributes to the significantly enhanced electrical-field stress tolerance of the perovskite solar cells (PVSCs). The PVSCs with polymer additives can operate up to −2 V reverse voltage bias which is much larger than the breakdown voltage of −0.5 V that has been commonly observed. This study provides insight into the role of additives in perovskites and the corresponding device degradation mechanism.     

Silicene Nanoribbons on an Insulating Thin Film

Silicene, a new 2D material has attracted intense research because of the ubiquitous use of silicon in modern technology. However, producing free-standing silicene has proved to be a huge challenge. Until now, silicene could be synthesized only on metal surfaces where it naturally forms strong interactions with the metal substrate that modify its electronic properties. Here, the authors report the first experimental evidence of silicene nanoribbons on an insulating NaCl thin film. This work represents a major breakthrough, for the study of the intrinsic properties of silicene, and by extension to other 2D materials that have so far only been grown on metal surfaces.     

Effect of sintering conditions on structural and morphological properties of Y- and Co-doped BaZrO3 proton conductors

BaZrO₃-based materials doped with a trivalent cation have excellent chemical stability and relatively high proton conductivity which makes them potential proton conducting oxide materials for various electrochemical device applications such as hydrogen processing, high-temperature electrolysis, and solid electrolyte in fuel cells. However, BaZrO₃ showed poor sinterability, requiring high sintering temperatures (1700–2100 °C) with longtime sintering (20–100 h) to achieve the desired microstructure and grain growth. This sintering problem can be solved by slightly doping BaZrO₃ with a sintering aid element. Therefore, in this study, two different zirconate proton conductors: BaZr_0·9Y_0·1O_3-α (BZY) and BaZr_0·955Y_0·03Co_0·015O_3-α (BZYC) were sintered in an air atmosphere and an oxygen atmosphere for 20 h in the temperature range of 1500–1640 °C. The sinterability was evaluated by analyzing the XRD diffraction patterns, lattice constant, lattice strain, crystallite size, relative density, open porosity, closed porosity, surface morphology, grain size, and grain boundary distribution, using the XRD, SEM, EDX, and Archimedes density measurement methods. It is concluded that in an oxygen atmosphere, sintering aid Co not only improves the relative density but also produces highly dense fine particles with clear grain boundaries which are promising for electrochemical hydrogen device applications.     

Synthesis and Characterization Superabsorbent Polymers Made of Starch,Acrylic Acid,Acrylamide, Poly(Vinyl Alcohol), 2-Hydroxyethyl Methacrylate, 2-Acrylamido-2-methylpropane Sulfonic Acid

Three polymers with excellent absorption properties were synthesized by graft polymerization: soluble starch-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate), poly(vinyl alcohol)/potato starch-g-poly(acrylic acid-co-acrylamide), poly(vinyl alcohol)/potato starch-g-poly(acrylic acid-co-acrylamide-co-2-acrylamido-2-methylpropane sulfonic acid). Ammonium persulfate and potassium persulfate were used as initiators, while N,N′-methylenebisacrylamide was used as the crosslinking agent. The molecular structure of potato and soluble starch grafted by synthetic polymers was characterized by means of Fourier Transform Infrared Spectroscopy (FTIR). The morphology of the resulting materials was studied using a scanning electron microscope (SEM). Thermal stability was tested by thermogravimetric measurements. The absorption properties of the obtained biopolymers were tested in deionized water, sodium chroma solutions of various concentrations and in buffer solutions of various pH.     

Thermodynamic modeling of gas solubility in aqueous sodium chloride solution

An electrolyte Equation of State is presented by combining the Cubic Plus Association Equation of State,Mean Spherical Approximation and the Born equation.This new model uses experimental relative static permittivity,intend to predict well the activity coefficients of individual ions (ACI) and liquid densities of aqueous solutions.This new model is applied to model water + NaCl binary system and water + gas +NaCl ternary systems.The cation/anion-water interaction parameters of are obtained by fitting the exper-imental data of ACI,mean ionic activity coefficients (MIAC) and liquid densities of water + NaCl binary system.The cation/anion-gas interaction parameters are obtained by fitting the experimental data of gas solubilities in aqueous NaCl solutions.The modeling results show that this new model can correlate well with the phase equilibrium and volumetric properties.Without gas,predictions for ACI,MIAC,and liquid densities present relative average deviations of 1.3％,3.6％ and 1.4％ compared to experimental ref-erence values.For most gas-containing systems,predictions for gas solubilities present relative average deviations lower than 7.0％.Further,the contributions of ACI,and salting effects of NaCl on gases are ana-lyzed and discussed.     

Influence of anode current density on carbon parasitic reactions during electrolysis

In the electro-deoxidation process, carbon parasitic reaction (CO₃^2- + 4e^-=C + 3O^2-) usually occurs when using carbon materials as the anode, which leads to increase of the carbon content in the final metal and decrease of the current efficiency of the process. The aim of this work is to reduce the negative effect of carbon parasitic reaction on the electrolysis process by adjusting anode current density. The results indicate that lower graphite anode area can achieve higher current density, which is helpful to increase the nucleation site of CO₂ bubbles. Most of CO₂ would be released from the anode instead of dissolution in the molten CaCl₂ and reacting with O^2- to form CO₃^2-, thus decreasing the carbon parasitic reaction of the process. Furthermore, the results of the compared experiments show that when the anode area decreases from 172.78 to 4.99 cm², CO₂ concentration in the released gases increases significantly, the carbon mass content in the final metal product decreased from 1.09% to 0.13%, and the current efficiency increased from 6.65% to 36.50%. This study determined a suitable anode current density range for reducing carbon parasitic reaction and provides a valuable reference for the selection of the anode in the electrolysis process.