Solvent effect in polymer analysis by MALDI-TOF mass spectrometry

Solvent effect is one of the important factors in sample preparation which may affect matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra of synthetic polymers. MALDI imaging, a useful imaging tool for discovering biomarkers in tissues, is applied here for better comprehension of solvent effect in polymer analysis by MALDI-TOF mass spectrometry. Nylon-6 was chosen as a model polymer for the study of solvent effect. Its MALDI mass spectra in different solvents were performed. MALDI imaging analysis was performed for studying the incorporation of analytes into matrix crystals in different solvent combinations. Specifically, the colocalization of matrix and analyte was obtained through Pearson’s correlation (PC) coefficient analysis of their MALDI images. The results demonstrated that satisfactory spectra were obtained in higher PC value conditions. PC decreased along with an increase in the ratio of poor solvent, which suggested that we should minimize the poor solvent ratio to obtain better MALDI spectra.     

基于甲基三苯乙炔基硅烷的新型聚三唑树脂的制备与性能

首先采用格氏试剂法合成了甲基三苯乙炔基硅烷(MTPES),通过傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)对其结构进行了表征。然后以MTPES和4,4’-二叠氮甲基联苯(BAMBP)为原料制备了新型聚三唑树脂(MPTA)。利用FT-IR和差示扫描量热(DSC)研究了MPTA树脂的固化行为,通过动态力学热分析(DMA)和热重分析(TG)研究了炔基与叠氮基配比对树脂热性能的影响,并通过测试凝胶时间随贮存时间的变化研究了树脂及其四氢呋喃(THF)溶液的贮存稳定性。结果表明,固化后的树脂玻璃化转变温度(Tg)达到236℃,在氮气中的5%热失重温度(T_(d5))在320℃左右。MPTA树脂在35℃和25℃下分别贮存7d和20d后,100℃下树脂的凝胶时间分别为40min和25min,MPTA树脂的THF溶液在同样条件下贮存28d后,凝胶时间分别为54min和61min,具有比现有聚三唑树脂更好的贮存稳定性。单向T700碳纤维-MPTA复合材料常温下的弯曲强度为1 660 MPa,弯曲模量为129 GPa,150℃下的弯曲强度保留率为70%。     

Rheological and thermal behavior of PLA modified by chemical crosslinking in the presence of ethoxylated bisphenol A dimethacrylates

Crosslinking structures can be partly introduced into PLA by melt mixing in a twin screw extruder with dicumyl peroxide (DCP) and ethoxylated bisphenol A dimethacrylates (Bis‐EMAs) as a crosslinking coagent. The study of DCP and Bis‐EMA contents on the melt rheology, thermal properties, dynamic mechanical properties and morphology of the reactive extruded pellets is presented. The results show that PLA with a DCP content higher than 3 phr exhibits increases in both the melt modulus and complex viscosity as compared with PLA. The introduction of DCP into PLA improved the thermal stability of the PLA. PLAs with various Bis‐EMA contents showed the optimum storage modulus and complex viscosity to occur at 5 phr Bis‐EMAs. Moreover, the glass transition, cold crystallization and melting temperature of PLAs decreased with increasing Bis‐EMA content. The crystallinity of the partly crosslinked PLAs was lower than that of PLA. Similar to the rheological results, the thermo‐mechanical properties showed that the storage modulus and loss modulus of the partly crosslinked PLAs increased with increasing Bis‐EMA contents up to 5 phr. In addition, these partly crosslinked PLAs showed rough surface or sea island‐like structure. Copyright © 2016 John Wiley & Sons, Ltd.     

A novel method to prepare microcellular poly(vinyl alcohol) foam based on thermal processing and supercritical fluid

Combining the thermal processing and supercritical fluid technology develops a novel preparation method of microcellular poly(vinyl alcohol) (PVA). Water, as the plasticizer in system, can form the hydrogen bonding with pendant hydroxyl of PVA and weaken its strong intermolecular and intramolecular forces to realize the thermal processing. Supercritical carbon dioxide (sc‐CO₂) can easily dissolve into water‐plasticized PVA (WPVA) because of the destruction of crystal region caused by water, and the enhanced sc‐CO₂ solubility can greatly improve the foamability of WPVA. The porous structure generates through the saturation of sc‐CO₂ in WPVA sample and followed by pressure drop‐induced phase separation. The foaming behavior of WPVA was studied as a function of saturation pressure, foaming temperature, and saturation time. The cell density, cell size, and distribution of the obtained foam can be controlled by tuning processing conditions. The results revealed that the cell size decreased, and its distribution narrowed with saturation pressure increasing, or decrease of foaming temperature. But excessively increasing the saturation time generated a negative effect on the foaming behavior owing to the deteriorated plasticization effect resulted from the loss of water. Copyright © 2016 John Wiley & Sons, Ltd.     

Efficient removal of hexavalent chromium and lead from aqueous solutions by s‐triazine containing nanoporous polyamide

s‐Triazine containing dicarboxylic acid was synthesized. Then, it was reacted with 1,3‐phenylenediamine in molten tetrabutylammonium bromide to formed soluble aromatic polyamide with good yield and moderate inherent viscosity of 0.35 dL g^?1. The solubility and flexibility of polyamides are low. So, we used ether group such as di(4‐aminephenyl) ether in building polyamide. The structure of monomer and polymer was confirmed by Fourier transform infrared spectroscopy, elemental analysis, and proton nuclear magnetic resonance techniques. Thermogravimetric analysis was used to evaluate the thermal properties of synthesized polyamide, and their results show that this polymer had a good thermal stability. The surface morphology of s‐triazine containing polyamide was studied by field emission‐scanning electron microscopy and transmission electron microscopy, and the results show that it has a porous morphology and moderate Brunauer–Emmett–Teller specific surface (367 m² g^?1). It was further investigated for Pb (II) and Cr(VI) ion removal by optimizing the parameters including pH and contact time. The maximum uptakes of Pb(II) and Cr(VI) at pH 5.0 and pH 4.0 are 57% and 76%, respectively. Also, sorption kinetics of this polymer was investigated. Copyright © 2017 John Wiley & Sons, Ltd.     

A parametric investigation of the friction performance of PC‐ABS parts processed by FDM additive manufacturing process

The friction performance is an important factor of parts processed by fused deposition modeling (FDM) for various engineering applications. It is one type of failure made of surface contact. The proper use of FDM process parameters can bring a significant reduction in friction and the amount of wear, thereby leading to a reduction in the material waste. To date, very little studies have been performed in this area. This paper investigates the effect of FDM manufacturing parameters on the friction performance of polycarbonate‐acrylonitrile butadiene styrene prototypes processed by FDM using definitive screening design and partial least squares method. The observation of surface morphology was obtained by the scanning electron microscopy to examine the effect of process parameters on the microstructure. The experimental results have shown that layer thickness, air gap, raster angle, and build orientation are the most influential factors affecting the friction performance of FDM manufactured parts. The proposed approach presented in this study provides an impetus to develop analytical modeling and functional relationships between FDM manufacturing parameters and friction performance. Copyright © 2017 John Wiley & Sons, Ltd.     

Zr的添加对提高NH3选择性催化还原NOx整体式催化剂热稳定性的影响

采用共沉淀的方法制备了CeTiO_x和CeZrTiO_x两种用于NH₃选择性催化还原NO_x的催化剂.两种催化剂在不同的高温条件下进行热老化以考察Zr的添加对CeTiO_x催化剂热稳定性的影响.NH₃-SCR活性数据显示,经过650、750和850 ℃的高温老化处理,Zr改性后的催化剂较CeTiO_x催化剂具有更好的催化活性和N₂选择性.XRD、Raman和H₂-TPR结果表明添加Zr可以阻止Ce物种的烧结并且抑制金红石相TiO₂的生成.催化剂的SEM图像显示Zr的添加可以抑制颗粒随着焙烧温度升高而产生的聚集长大.XPS的Ce3d光谱表明,随着老化温度的提升,CeTiO_x催化剂表面的Ce³⁺/Ce⁴⁺比相对于CeZrTiO_x催化剂下降更加明显.这意味着随着Zr的添加,更多的晶格缺陷和氧空缺出现在Zr改性催化剂的表面,这有利于催化性能的提升.另外,NH₃-TPD结果表明经过相同的高温老化,改性的催化剂保持了更多的Brönsted酸性位,提高了催化活性并抑制了氨的氧化.因此,Zr的添加提高了催化剂的热稳定性能.     

ChemInform Abstract: Electronic Structure,Elastic Anisotropy,Thermal Conductivity and Optical Properties of Calcium Apatite Ca5(PO4)3X (X: F,Cl or Br).

The structural properties, phase stability, electronic structure, elastic properties, and optical properties of Ca₅(PO₃)₄F (FA), Ca₅(PO₃)₄Cl (ClA) and Ca₅(PO₃)₄Br (BrA) are studied by DFT calculations with the generalized gradient approximation.     

Lattice Boltzmann method for the fractional sub‐diffusion equation

A lattice Boltzmann model for the fractional sub‐diffusion equation is presented. By using the Chapman–Enskog expansion and the multiscale time expansion, several higher‐order moments of equilibrium distribution functions and a series of partial differential equations in different time scales are obtained. Furthermore, the modified partial differential equation of the fractional sub‐diffusion equation with the second‐order truncation error is obtained. In the numerical simulations, comparisons between numerical results of the lattice Boltzmann models and exact solutions are given. The numerical results agree well with the classical ones. Copyright © 2015 John Wiley & Sons, Ltd.     

Design of robust differential microphone arrays with the Jacobi–Anger expansion

Due to their small size, differential microphone arrays (DMAs) are very attractive. Moreover, they have been effective in combating noise and reverberation. Recently, a new class of DMAs of different orders have been developed with the MacLaurin’s series and the frequency-independent patterns. However, the MacLaurin’s series does not approximate well the exponential function, which appears in the general definition of the beampattern, when the intersensor spacing is not small enough. To circumvent this problem, we propose in this paper to approximate the exponential function with the Jacobi–Anger expansion. Based on this approximation and the frequency-independent Chebyshev patterns, we derive first-, second-, and third-order DMAs. Furthermore, in order to improve the robustness of DMAs against white noise amplification, we propose to use more microphones combined with minimum-norm filters. It is also shown that the Jacobi–Anger expansion is optimal from a mean-squared error perspective. Simulations are carried out to evaluate the performance of the proposed DMAs.