利用Taguchi法以高岭土为原料制备高硅NaY分子筛

采用Taguchi试验方法优化出了以高岭土为原料制备高硅NaY分子筛的最佳合成参数,考察了硅溶胶的加入量、反应体系的碱度、加水量以及晶化时间对NaY分子筛硅铝比和结晶度的影响。结果表明,高硅NaY分子筛的最佳合成条件是：反应体系各组分的物质的量比为7.5SiO₂∶1.0Al₂O₃∶2.2Na₂O∶120H₂O,晶化时间为16 h。同时发现,对合成样品性能的影响最为显著的因素是硅溶胶的加入量和碱度。采用X射线衍射、N₂静态容量吸附法和扫描电镜对利用最佳条件所合成样品的硅铝比、比表面积、孔分布以及表观形貌进行了表征。结果显示,以高岭土原料制备的NaY分子筛比参考样品拥有更高的硅铝比和更大的比表面积。     

Comparison of T-piece and concentric mixing systems for continuous flow synthesis of anatase nanoparticles in supercritical isopropanol/water

T-piece and concentric counter-flow mixing systems are compared in continuous flow supercritical solvothermal synthesis of TiO₂ at identical system parameters. The phase pure anatase nanoparticle products were characterized with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS), and the particle size, size distribution and absolute crystallinity mapped as a function of temperature, precursor concentration, flow rate and pressure for the two different continuous flow reactors. The particles synthesized with the T-piece geometry are smaller with a narrower size distribution, possibly indicating a more effective mixing, than particles synthesized at the same conditions with concentric counter-flow geometry. In general, an increased synthesis temperature leads to an increase in absolute crystallinity. For the particles synthesized with the concentric reactor geometry crossing of the critical point of the solvent causes a decrease in the particle size and size distribution, and conditions just above the critical temperature are demonstrated to be optimal for continuous solvothermal synthesis of anatase.     

Modified Vonk's Method to Determine Crystallinity and Crystal Distortion in Polymers

Using a modified method developed from Vonk's method, detailed values of crystallinity and crystal disorder were obtained by wide angle X-ray diffraction (WAXD). In Vonk's method, the crystallinity (w) is determined by extrapolation of the WAXD experimental curve back to zero scattering angle, while the distortion factor (k) is determined by the inclination of the experimental curve at zero scattering angle. In our new method, both w and k are determined at the same time by using the least squares method. In order to show the efficiency of our method, the new fitting procedure was applied to the experimental values of polyethylene and polyethylene terephthalate as measured by Vonk, and the values of w and k determined by our new method were compared with those found by Vonk's method. The new fitting method has the advantage that it uses the whole experimental curve. Moreover, our modified Vonk's method enables us to discuss crystal distortions as arising from first-kind (thermal) disorder and second-kind (paracrystalline) disorder.     

钴铁氧体亚微米球吸波性能与成分的关系研究

用溶剂热方法制备CoxFe3-xO4 (0≤x≤1)亚微米球, 可看作不同比例Fe3O4和CoFe2O4的混合物.实验发现:当原料中钴铁原子比为1∶1、1∶2、1∶4和0时,反应得到的球分别为CoFe2O4、Co0.9Fe2.1O4、Co0.73Fe2.27O4和Fe3O4.Fe3O4与石蜡混合物(质量分数75wt;)厚度为5.5 mm时,反射率最低为-38 dB,对应频率为4 GHz;Co0.9Fe2.1O4与石蜡混合物在3~14 GHz频率范围内介电损耗大于磁损耗,计算出来的反射率分贝值(-41.1 dB,12.08 GHz,2 mm)低于相关报道.比较四种成分的钴铁氧体球可以看出:当x值不同时,由于成分Fe3O4和CoFe2O4的自然共振频率不同,引起磁性能随微波频率发生变化,而且由于二价铁离子被钴离子取代,结晶性也发生改变,进而改变了材料的介电和吸波性能.     

Synthesis and Properties of Novel Aromatic Azo Compounds from Hydroxyazobenzene and Cyanuric Chloride

A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p‐hydroxyazobenzene, 4,4′‐dihydroxyazobenzene and cyanuric chloride under very mild conditions. Their solubility, crystallinity, thermostability, UV‐vis absorption properties and photoisomerization behaviors were carefully examined. When the number of azobenzene unit grew, the solubility of the synthesized compounds basically decreased, the crystallinity of the synthesized compounds firstly rose then dropped, while the thermostability and UV‐vis absorption ability of the synthesized compounds greatly improved. All the aromatic azo compounds exhibited typical reversible photoisomerization behaviors and were expected to be applied in photosensitive material areas.     

Effects of ion exchange and calcinations on the structure and photocatalytic activity of hydrothermally prepared titanate nanotubes

Titanate nanotubes (TiNTs) were prepared by alkaline hydrothermal processing. The TiNTs are thermodynamically unstable and easily transformed to the titania phase by heat or acid treatment. These phase transformations are affected by the preparation conditions. In this study, we investigated the effects of using the washing process to modify the sodium content of the TiNTs. After an alkaline hydrothermal process was used to prepare the TiNTs, the resulting suspensions were washed with weak acid solution and distilled water until the pH value of the wash solution reached approximately 1 or 7, and the products were identified as H‐TiNTs or Na‐TiNTs, respectively. The characteristics and photocatalytic activities of the H‐TiNTs and Na‐TiNTs were compared for various calcination temperatures. The H‐TiNTs were transformed completely to anatase‐type TiO₂ by dehydration during calcination, while the crystallinity of the Na‐TiNTs increased with calcination temperature. However, the photocatalytic H₂ production rates on calcined H‐TiNTs were much higher than on Na‐TiNTs, which could be attributed to the crystalline anatase phase.     

Extraction and Characterization of Cellulose Nanowhiskers from Balsa Wood

Summary: In this study cellulose nanowhiskers were obtained from balsa wood. For this purpose, fibers of balsa wood were exposed to hydrolysis reactions for lignin and hemicellulose digestion and acquisition of nano-scale cellulose. Transmission electron microscopy (TEM) results demonstrated that the obtained cellulose nanocrystals had average length and thickness of 176 (±68 nm) and 7.5 (±2.9 nm), respectively. Infrared spectroscopy (FTIR) and wide angle x-ray diffraction (WAXD) showed that the process for extracting the nanowhiskers digested nearly all the lignin and hemicellulose from the balsa fiber and still preserved the aspect ratio and crystallinity satisfactory enough for future application as nanofillers in polymer nanocomposites. The thermogravimetric analysis (TGA) showed that the onset temperature of thermal degradation of the cellulose nanocrystals (226 °C) was higher than the onset temperature of the balsa fiber (215 °C), allowing its use in molding processes with polymers melts.     

用广角X光衍射测定不同晶型间规聚苯乙烯结晶度

多晶型;用广角X光衍射测定不同晶型间规聚苯乙烯结晶度     

Synthesis and characterization of fully aromatic thermotropic liquid‐crystalline copolyesters containing m‐hydroxybenzoic acid units

A series of fully aromatic copolyesters based on p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA), and m‐acetoxybenzoic acid (m‐ABA) were prepared by a modified melt‐polycondensation reaction. The copolyesters were characterized by DSC, thermogravimetric analysis, ¹H NMR, polarized optical microscopy, X‐ray diffraction, and intrinsic viscosity measurements. The copolyesters exhibited nematic liquid‐crystalline phases in a broad temperature range of about 150 °C, when the content of linear (p‐ABA, HQDA, and TPA) units was over 67 mol %. DSC analysis of the anisotropic copolyesters revealed broad endotherms associated with the nematic phases, and the melting or flow temperatures were found to be in the processable region. The flow temperatures and crystal‐to‐nematic and nematic‐to‐isotropic transitions depend on the type of linear monomer units, and these transitions increased as the content of the p‐ABA units increased, as compared to the HQDA/TPA units. When the content of the p‐ABA units increased, as compared to other linear units (HQDA and TPA), the intrinsic viscosity and degree of crystallinity of the copolyesters also increased, implying a higher reactivity for p‐ABA in the p‐ABA/HQDA/TPA/m‐ABA polymer system. The aromatic region in the ¹H NMR spectra of the copolyesters containing equal molar compositions of p‐ABA, HQDA, and TPA units were sensitive to the sequence distribution of aromatic rings. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3263–3277, 2001