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The unclear understanding of the water diffusion behavior posts a big challenge to the manipulation of water absorption properties in epoxy resins. Herein, we investigated the water diffusion behavior and its relationship with molecule structures inside an epoxy resin mainly by the nonequilibrium molecular dynamics and experiments. It is found that at the initial rapid water absorption stage, bound water and free water both contribute, while at the later slow water absorption stage, free water plays a dominant role. The observed evolution of free water and bound water cannot be explained by the traditional Langmuir model. In addition, molecule polarity, free volume, and segment mobility can all influence the water diffusion process. Hence, the epoxy resin with low polarity and high molecular segment mobility is endowed with higher diffusion coefficients. The saturated water absorption content is almost dependent on the polarity. The understanding of how water diffuses and what decides the diffusion process is critical to the rational design of molecule structures for improving the water resistance in epoxy resin.
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The covalently cross-linked network gives thermosets superior thermal, mechanical, and electrical properties, which, however, squarely makes the large residual stress that is inevitably induced during preparation hardly relieved in the glassy state. In this work, an incredible reduction in residual stress is successfully achieved in bulk thermosets in the glassy state through introducing highly dynamic thiocarbamate bonds by "click" reactions of thiols and isocyanates. Due to the excellent dynamic behaviors of thiocarbamate bonds, local network rearrangement is achieved through thermal stimulation, while the strong 3D cross-linked network is well maintained. Ultimately, a decrease by 44% in residual stress is detected by simply annealing samples at 30 °C below glass transition temperature (Tg), during which they could well maintain more than 98.4% of the storage modulus. After the annealing, more uniform residual stress distribution is also observed, showing a 32% decline in sample standard deviation. However, the residual stress of epoxy resin, a typical thermoset as a reference, changes little even after annealing at Tg. The results prove it a feasible strategy to reduce residual stress in bulk thermosets in the glassy state by introducing proper dynamic covalent bonds.
Assuntos
Vidro , Vidro/química , Temperatura de Transição , Compostos de Sulfidrila/química , Estrutura Molecular , Isocianatos/química , Estresse Mecânico , TemperaturaRESUMO
Anisotropic structures exist in almost all living organisms to endow them with superior properties and physiological functionalities. However, conventional artificial materials possess unordered isotropic structures, resulting in limited functions and applications. The development of anisotropic structures on carbohydrates is reported to have an impact on their properties and applications. In this review, various alignment strategies for carbohydrates (i.e., cellulose, chitin and alginate) from bottom-up to top-down strategies are discussed, including the rapidly developed innovative technologies such as shear-induced orientation through extrusion-based 3D/4D printing, magnetic-assisted alignment, and electric-induced alignment. The unique properties and wide applications of anisotropic carbohydrate materials across different fields, from biomedical, biosensors, smart actuators, soft conductive materials, to thermal management are also summarized. Finally, recommendations on the selection of fabrication strategies are given. The major challenge lies in the construction of long-range hierarchical alignment with high orientation degree and precise control over complicated architectures. With the future development of hierarchical alignment strategies, alignment control techniques, and alignment mechanism elucidation, the potential of anisotropic carbohydrate materials for scalable manufacture and clinical applications will be fully realized.
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Polypropylene (PP)-based composites have attracted numerous attention as a replacement of prevailing cross-linked polyethylene (XLPE) for high-voltage insulation due to their ease of processing, recyclability, and excellent electrical performance. However, the poor resistances against high-temperature creep and thermal aging are obstacles to practical applications of PP-based thermoplastic high-voltage insulation. To address these problems, in this Letter, we synthesized an impact polypropylene copolymer (IPC) containing multifold long-chain branched (LCB) structures in phases, especially the interfaces between the PP matrix and the rubber phase. The results indicated that the structural stability of LCBIPC was significantly enhanced under extreme conditions. In comparison to IPC (without LCB structures), 24.1% less creep strain and 75.2% less unrecoverable deformation are achieved in LCBIPC at 90 °C. In addition, the thermal aging experiments were performed at 135 °C for 48 and 88 days for IPC and LCBIPC, respectively. The results show that the resistance against thermal aging was also enhanced in LCBIPC, which showed a 133% longer thermal aging life compared to IPC. Further results revealed that the interfacial layer between the PP matrix and the rubber phase was constructed in LCBIPC. The two phases are tightly linked by chemical bonds in LCB structures, leading to enforced constraints of the rubber phase at the micro level and better resistance performance against creep and thermal aging at the macro level. Evidently, the reported eco-friendly LCBIPC thermoplastic insulation shows great potential for applications in high-voltage cable insulation.
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This study is the first to extract and characterize pectin from citrus physiological premature fruit drop. The extraction yield of pectin reached 4.4 % by acid hydrolysis method. The degree of methoxy-esterification (DM) of citrus physiological premature fruit drop pectin (CPDP) was 15.27 %, indicating it was low-methoxylated pectin (LMP). The monosaccharide composition and molar mass test results showed CPDP was a highly branched macromolecular polysaccharide (ß: 0.02, Mw: 2.006 × 105 g/mol) with rich rhamnogalacturonan I domain (50.40 %) and long arabinose and galactose side chain (32.02 %). Based on the fact that CPDP is LMP, Ca2+ was used to induce CPDP to form gels. Textural and rheological tests showed that the gel strength and storage modulus of CPDP were higher than commercial citrus pectin (CP) used in this paper due to the lower DM and rich neutral sugar side chains of CPDP. Scanning electron microscope (SEM) results showed CPDP had stable gel network structure.
Assuntos
Citrus , Citrus/química , Frutas/química , Pectinas/química , Géis/análiseRESUMO
In this paper, evolution of microstructures, electrical properties and defects of the double Schottky barrier during the sintering process were investigated by quenching ZnO varistor ceramics at different sintering stages. It was found that morphology of the samples changed little when the temperature was below 800 °C. Remarkable enhancement of the Schottky barrier height and electrical properties took place in the temperature range between 600 °C and 800 °C. The Bi-rich intergranular layer changed from ß phase to α phase. The interfacial relaxation at depletion/intergranular layers became detectable in the samples. Meanwhile, a distinct relaxation loss peak from electron trapping of interface states was observed instead of two dispersed ones. It indicated that the differences among the Schottky barriers in ZnO varistor ceramics became smaller with the process of sintering, which was also supported by the admittance spectra. In addition, oxygen vacancy was found more sensitive to the sintering process than zinc interstitial. The results could provide guidance for fine manipulating the Schottky barrier and its underlying defect structures by optimizing sintering process.
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Ningxia wolfberry is the only wolfberry product with medicinal value in China. However, the nutritional elements, active ingredients, and economic value of the wolfberry vary considerably among different origins in Ningxia. It is difficult to determine the origin of wolfberry by traditional methods due to the same variety, similar origins, and external characteristics. In the study, we have for the first time used a multi-task residual fully convolutional network (MRes-FCN) under Bayesian optimized architecture for imaging from visible-near-infrared (Vis-NIR, 400-1000 nm) and near-infrared (NIR-1700 nm) hyperspectral imaging (HSI) technology to establish a classification model for near geographic origin of Ningxia wolfberries (Zhongning, Guyuan, Tongxin, and Huinong). The denoising auto-encoder (DAE) was used to generate augmented data, then principal component analysis (PCA) was combined with gray level co-occurrence matrix (GLCM) to extract the texture features. Finally, three datasets (HSI, DAE, and texture) were added to the multi-task model. The reshaped data were up-sampled using transposed convolution. After data-sparse processing, the backbone network was imported to train the model. The results showed that the MRes-FCN model exhibited excellent performance, with the accuracies of the full spectrum and optimum characteristic spectrum of 95.54% and 96.43%, respectively. This study has demonstrated that the MRes-FCN model based on Bayesian optimization and DAE data augmentation strategy may be used to identify the near geographical origin of wolfberries.
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ZnO varistor ceramics with a high potential gradient, as well as a high nonlinear coefficient, were reported and analyzed in this paper. With the use of nano-sized ZnO powders, the average grain size was reduced to about 2.6 µm, which successfully raised the potential gradient to 1172 V/mm. Moreover, the nonlinear coefficient increased to 48, and the leakage current was decreased to 8.4 µA/cm2 by doping a moderate amount of MnO (0.9 mol%). This was proven to be caused by the high Schottky barrier height formed at the grain boundary, where the Mn element segregated and, consequently, led to the increased density of interface states. Therefore, this could be considered as a potential method to simultaneously enhance the potential gradient and the nonlinear coefficient of ZnO varistor ceramics.
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Thermal ageing of cross-linked polyethylene (XLPE) cable insulation is an important issue threatening the safe operation of power cables. In this paper, thermal ageing of XLPE was carried out at 160 °C in air for 240 h. The influence of oxygen diffusion on thermal ageing of XLPE was investigated by Ultraviolet-visible spectrophotometer (UV-Vis), tensile testing, and Fourier transformed infrared spectroscopy (FTIR). It was observed that the degradation degree not only depended on ageing time but also on sample positions. The thermally aged samples were more oxidized in the surface region, presented a darker color, more carbon atoms appeared in the conjugate cluster, had smaller elongation at break and tensile strength, and a larger carbonyl index. As ageing time increased, the non-uniform oxidation of the XLPE samples became more prominent. The degree of non-uniform oxidation caused by oxygen diffusion was quantitatively studied by first order oxidation kinetic. The calculated results demonstrated that carbonyl index measured by FTIR was more sensitive to non-uniform oxidation with a shape parameter in the range of 1-2. The result shown in this paper is helpful for interpreting and predicting the non-uniform ageing behavior of high voltage XLPE cables.