Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.     

Influence of the mesophase structure on the β-relaxation in liquid crystalline poly(meth)acrylates

The dependence of the rotation of the mesogenic unit around its long axis (β-relaxation) on the actual mesophase in liqid crystalline polymethacrylates and polyacrylates was studied by dielectric spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and in a temperature range from 170 K to 430 K. As mesogenic units derivatives of (p-alkoxy-phenyl)-benzoate were used where different mesophases were achieved by small variation of the mesogenic structure, the spacer length and the tail group of the mesogenic unit. For all samples the temperature dependence of the relaxation rate of the β-relaxation can be described by an Arrhenius equation where both the pre-exponential factor and the activation energy increase significantly with the order of the mesophase. To characterize the structure X-ray measurements were also carried out. The mean lateral mesogenic distance was correlated directly with relaxational quantities.     

Natural Polymers-Based Materials: A Contribution to a Greener Future

Natural polymers have emerged as promising candidates for the sustainable development of materials in areas ranging from food packaging and biomedicine to energy storage and electronics. In tandem, there is a growing interest in the design of advanced materials devised from naturally abundant and renewable feedstocks, in alignment with the principles of Green Chemistry and the 2030 Agenda for Sustainable Development. This review aims to highlight some examples of the research efforts conducted at the Research Team BioPol4fun, Innovation in BioPolymer-based Functional Materials and Bioactive Compounds, from the Portuguese Associate Laboratory CICECO–Aveiro Institute of Materials at the University of Aveiro, regarding the exploitation of natural polymers (and derivatives thereof) for the development of distinct sustainable biobased materials. In particular, focus will be given to the use of polysaccharides (cellulose, chitosan, pullulan, hyaluronic acid, fucoidan, alginate, and agar) and proteins (lysozyme and gelatin) for the assembly of composites, coatings, films, membranes, patches, nanosystems, and microneedles using environmentally friendly strategies, and to address their main domains of application.     

Dielectric Properties of Colossal-Dielectric-Constant Na1/2La1/2Cu3Ti4O12 Ceramics Prepared by Spark Plasma Sintering

In the current study, we report on the dielectric behavior of colossal-dielectric-constant Na_1/2La_1/2Cu₃Ti₄O₁₂ (NLCTO) ceramics prepared by mechanochemical synthesis and spark plasma sintering (SPS) at 850 °C, 900 °C, and 925 °C for 10 min. X-ray powder diffraction analysis showed that all the ceramics have a cubic phase. Scanning electron microscope observations revealed an increase in the average grain size from 175 to 300 nm with an increase in the sintering temperature. SPS NLCTO ceramics showed a room-temperature colossal dielectric constant (>10³) and a comparatively high dielectric loss (>0.1) over most of the studied frequency range (1 Hz–40 MHz). Two relaxation peaks were observed in the spectra of the electrical modulus and attributed to the response of grain and grain boundary. According to the Nyquist plots of complex impedance, the SPS NLCTO ceramics have semiconductor grains surrounded by electrically resistive grain boundaries. The colossal dielectric constant of SPS NLCTO ceramics was attributed to the internal barrier layer capacitance (IBLC) effect. The high dielectric loss is thought to be due to the low resistivity of the grain boundary of SPS NLCTO.     

交变电场作用下骨表面温升的实验研究

骨具有力电性质,这一性质可促进骨组织生长。骨既是生理器官又是介电材料,在交变电场作用下,其表现行为可能有生理作用。为此,本文测量了骨悬臂梁试样在交变电场下的表面温升与顶端挠度。发现在电压70V,频率为10~70kHz的交流电场下,最大表面温升达到2~4℃,最大挠度变化为9.0~78.7μm;在频率10kHz,电压为70~175V的交流电场下,最大表面温升达到4~6℃,最大挠度变化为13.0~114.3μm。同时测量了两种经典介电材料有机玻璃和聚乙烯在交变电场下的温升与顶端挠度,最大温升低于0.5℃,但是挠度与骨试样相当,所以相对高温升是骨特有的性质。将交流电压有效值替换成相同幅值的直流电压时,最大温升也低于0.5℃,基本没有挠度变化,所以相对的高温升反映了骨的交流性质。分析后认为,骨在交变电场作用下的温升由胶原的介电损耗引起。实验数据显示,骨在交变电场下,表面温度变化与加载电压的平方成正比,且在实验加载的10~70kHz频段内,骨的介电常数随频率的变化明显。     

石墨基液流电池复合双极板

液流电池是一种安全性高、使用寿命长、可扩展的大规模储能系统,可以协助电网调峰储能,提高能源利用率,发展前景广阔。双极板是液流电池的重要组成部分。功能上起到了分隔、串联电池、传导电流、为电堆提供结构支撑等作用。从成本构成角度看,双极板的价格占电堆成本的比重也较大。开发高性能、低成本的双极板对加快液流电池的商业化应用具有重要意义,也是目前业界的迫切需求。虽然文献上报道了许多针对液流电池双极板开发的工作,但是目前高性能、低成本的液流电池双极板产品仍无法充分满足市场需求。本文着重介绍了石墨基复合双极板的研究现状,介绍了材料选择、工艺流程对关键性能的影响,对相关工作进行了评述,并为液流电池双极板的开发提出了建议。     

介孔铁铝/蒙脱土复合材料：解离柱撑制备、结构及催化羟基化性能

利用极稀悬浮液中蒙脱土的解离作用并结合柱化技术过程，制备了介孔结构的铝铁/蒙脱土复合材料(Fe-Al/mmt)；并采用粉末X射线衍射、氮等温吸脱附、傅立叶红外光谱、紫外可见光漫反射光谱及苯酚催化羟基化反应表征了其结构和性能。结果显示，铁铝聚合前驱液中铁/铝比影响复合材料中蒙脱土的解离程度，且仅当低铁/铝比时(即Fe/(Fe+Al)物质的量的比介于0.05～0.3)，嵌入解离的蒙脱土片层间的混合铁铝物种呈现能耐温350 ℃的热稳定性；氮等温吸脱附分析反映出这种解离的蒙脱土堆积结构呈现介孔特征，孔径分布窄，介于2.0～2.3 nm；红外分析表明材料表面具有L酸和B酸位，并且L酸位量与嵌入解离的蒙脱土结构中的混合铁铝物种相关；由于结构中混合铁铝物种的存在及相应的Si-O → Fe、Al-O → Fe间的电子跃迁，Fe-Al/mmt材料在紫外区呈现宽泛的能量吸收特征。这些结果说明，由于混合铁铝物种嵌入于解离的蒙脱土片层堆积结构中，形成了“卡片屋”式介孔结构。实验条件下，Fe/(Fe+Al)物质的量的比为0.3的Fe-Al/mmt呈现较佳的催化羟基化性能，苯酚转化率为36.7%，二酚产物选择性32.3%；并且初步表明铝掺杂后，通过铁铝比和表面酸性的调整，材料的部分选择氧化性能可以得到改善。     

有机凹凸棒粘土的制备及复合高吸水性树脂的性能

有机凹凸棒粘土的制备及复合高吸水性树脂的性能;凹凸棒粘土;有机改性;高吸水性树脂     

Measurement of moisture in grains at extreme temperatures

Summary This research has demonstrated that the dielectric method can be used successfully for grain moisture measurements for diverse grain types over wide ranges of temperatures if the grain moisture content is below certain (grain-specific) threshold values. These high-moisture limits were estimated. Optimum temperature correction coefficients for 149 MHz moisture measurements were determined for grain samples at different moisture levels. This information should be very helpful for grain moisture meter manufacturers and for moisture meter users who need to determine grain moisture contents at temperature extremes to be able to market grain more efficiently.     

Role of Bipolar Pulsed DBD on the Growth of <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis> in Three-Phase Discharge Plasma Reactor

Algae in drinking water supplies often bring about impact on the water treatment. In this study, a bipolar pulsed dielectric barrier discharge system in three-phase discharge plasma reactor was constructed for investigating its ability to control excessive growth of cyanobacteria, Microcystis aeruginosa. Experimental results show there was almost no change in optical density immediately after the interruption of electrical discharge, but the decreasing trend of optical density, cell density and chlorophyll-a content was obvious during the incubation period, indicating a significant residual effect of electrical discharge process on the algal growth inhibition. Scanning electron microscopy investigation of algae revealed surface damage, apparent leakage of intracellular contents and pores formed after electrical discharge process, which showed that algal cells had no potential to survive and grow. Compared with the control sample, it was observed that electrical discharge on the algal extracellular products has almost no residual effect and the growth rate of algae slightly decreased before three days storage. Hydrogen peroxide was produced by electrical discharge in the μM level and showed a first-order decay. But at such level, the external addition of hydrogen peroxide alone is not likely to cause the residual effect. These results implicated that the growth inhibition of M. aeruginosa was mainly caused by electrical discharge process, and it made the algal cells lose ability to survive, demonstrating the considerable potential of such an alternative process for efficient water purification.