Pore formation during the pyrolysis of C-Nb2O5 and C-Ta2O5 xerogels

Binary organic-inorganic gels have been prepared by mixing a carbonaceous hydrosol and a Nb₂O₅ or Ta₂O₅ sol derived by hydrolysis of the alkoxides. The gels are pyrolyzed under an inert atmosphere into precursors in which carbon and the metal oxides are mixed very intimately. High temperature treatment converts the precursors into the cubic face centered carbides. The precursors as well as the carbides have been shown to be micro- and mesoporous materials. Measurements of nitrogen adsorption reveal a characteristic change of the shapes of the isotherms (Type I Type IV) and of the hysteresis loops (H4H2H1) during the thermal processes. Pore widening has been observed with rising temperature. The phenomena of crystallization, carbothermal reduction and sintering were found to control the pore shape and size. The results of the adsorption measurement correlate well with those of the thermoanalytical and X-ray diffraction studies.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Spatial relaxation of electrons in nonisothermal plasmas

The spatial relaxation of electrons to homogeneous states under the action of space-independent electric fields is investigated in helium, krypton, and N₂ plasmas for various electric field strengths. These investigations are based on a new method recently developed for solving the one-dimensional inhomogeneous electron Boltzmann equation in weakly ionized, collision-dominated plasmas. Elastic as well as conservative inelastic collisions of electrons with gas atoms have been included in the kinetic treatment. The spatial relaxation is caused by an imposed direct disturbance in the velocity distribution of the electrons on a spatial boundary. A pronounced dependence of the relaxation structure and the resultant relaxation length on the atomic data of the electron collision processes in different gases has been found. Furthermore the relaxation process sensitively depends on the electric field strength in the region of medium field values.     

Analysis of semiconducting materials by high-resolution radiofrequency glow discharge mass spectrometry

The analytical capabilities of a high-resolution mass spectrometer in combination with a 13.56 MHz glow discharge ion source for the analysis of semiconducting materials (silicon carbide and gallium arsenide) were studied. It was shown that single positively charged ions of sample material have about 10 eV higher average energy than the ions of the discharge and residual gas. Therefore effective energy separation of the ions of analyte from the ions of the discharge and residual gas was achieved by adjusting the ion transfer optics (breadth and position of energy slit), which improves the analytical capabilities of the developed method.Some analytical applications are presented to illustrate the performance of r.f. GDMS for the bulk analysis of semiconducting materials. The results of the trace element analysis of gallium arsenide and silicon carbide samples are compared with data of independent methods (LIMS, ICP-AES, SIMS).Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthdayOn leave from the Institute of Inorganic Chemistry, 630090 Novosibirsk, Russia     

Crosslinking network structure governing particle shape and size distribution by one-step emulsion polymerization in the presence of particle coagulation

In this study, sub-200?nm, crosslinked latex particles with a narrow particle size distribution were prepared by one-step emulsion polymerization in the presence of particle coagulation. The relationship between the particle shape and particle coagulation was investigated by varying the time of crosslinking network structure formation and particle coagulation. Particles with irregular shapes such as doublet, triplet, and ellipsoid were obtained using divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDMA) as the crosslinking agents, because the crosslinking network structure of particles was formed before the particle coagulation. In contrast, latex particles with a uniform spherical shape were also prepared using triallyl isocyanurate (TAIC) or dihydrodicyclopentadienyl acrylate (DCPA) as the crosslinking agents by delaying the time of crosslinking network structure formation. Alternatively, uniform spherical latex particles were prepared by bringing forward the particle coagulation time using cationic initiator, 2, 2′-azobis (2-methylpropionamidine) dihydrochloride (AAPH). This study presents a new idea that would further broaden the application of particle coagulation in emulsion polymerization.     

The oblique chiral nematic phase in calamitic bimesogens

ABSTRACT

The discovery of the oblique chiral (or, the twist-bend, N_TB) nematic phase predicted for bent-core mesogens has engendered much interest due to its unique structure and physical properties, and the possibility of use in the next generation of fast electro-optic technology. Bimesogenic calamitic as well as bent-core mesogens are found to form the N_TB phase. Here, we report direct measurements of the temperature dependence of the conical tilt and the evidence of volcano-like orientational distribution of molecules in the N_TB phase. Optical and x-ray scattering investigations of two single-component calamitic bimesogens and their mixtures show that, while the Maier–Saupe orientational distribution function (ODF) is valid for the higher temperature nematic phase, a generalised expansion in terms of even Legendre functions is needed for the N_TB phase. Temperature dependence of the ODFs and the order parameters 〈P₂(cosβ)〉, 〈P₄(cosβ)〉, and 〈P₆(cosβ)〉 has been measured in both phases. The parameters 〈P₂(cosβ)〉 and 〈P₄(cosβ)〉 increase/decrease in the N/N_TB phase with decreasing temperature, while 〈P₆(cosβ)〉 remains vanishingly small for all samples. The value of 〈P₄(cosβ)〉 becomes negative in the N_TB phase confirming a conical distribution of molecules as they follow a helical trajectory keeping the local director tilted at an angle α wrt the macroscopic director. The heliconical tilt calculated from ODFs, exhibits a power law behaviour with temperature, vanishing at the transition to the N phase.     

Absorption,transportation and distribution of imidacloprid in maize

The neonicotinoid imidacloprid is a very important insecticide in maize cultivation in China. A laboratory experiment was conducted to investigate its absorption, transportation and distribution in maize plants. Plants were exposed to an aqueous solution of imidacloprid at five concentrations (10, 20, 50, 100 and 200 μg/mL). The residues of imidacloprid in different plant parts were determined by using a quick and effective method of high-performance liquid chromatography. Results showed that the average recoveries ranged from 85.16% to 102.23%, with relative standard deviations of 1.82–4.40% at three different spiking levels in each different matrix. The half-lives of imidacloprid in hydroponic maize water were from 5.33 to 11.55 days. The concentrations in roots, stems and leaves were from 5.61 to 7.48, 1.03 to 4.03 and 0 to 30.57 μg/mL after 6 h–7 days exposed in 10 μg/mL imidacloprid aqueous solutions, respectively. Our study showed that imidacloprid was strongly absorbed by roots and mainly accumulated in leaves. Quantity ratio and bioconcentration factors (BCFs) were also used to estimate the distribution and accumulation in maize. The values of quantity ratios were the highest in the leaves while lowest in the root after 7 days treatments, with the ranking of leaves > stem > root. The BCFs were 0.63–1.66, 0.52–0.92 and 3.20–6.78 in root, stem and leaves, respectively. These results demonstrated that the exposed time and imidacloprid application concentrations were also the main factors influencing the absorption. This study enhances our understandings of the uptake and distribution of imidacloprid in maize plants.     

A Safety Strategy for Producing Poly(Acrylic Acid) of Low Molar Mass

The synthesis of poly(acrylic acid) (PAA) of low molar mass under safe conditions is difficult due to the high polymerization rate of acrylic acid (AA) and the fast heat generation. The aqueous‐solution “semibatch” polymerization of non‐ionized AA in almost starved conditions involves high initiator loads when low molar masses are required. This article proposes the simultaneous feeding of AA and nonconventional chain transfer agents (CTA) as a strategy aimed at controlling both the molar masses and the generated heat rate. Three CTAs are investigated: 2‐mercaptoethanol, thioglycolic acid, and isopropyl alcohol. Even when PAA of relatively low molar mass can be produced by adequately selecting the flow rates and concentrations of both AA and CTA, it is found that the nature of CTA can have a significant effect on the polymerizations kinetics. The mechanisms responsible for these effects are discussed with the help of a representative mathematical model.

     

Reactivity Ratios and Sequence Distribution Characterization by Quantitative 13C NMR for RAFT Synthesis of Styrene‐Acrylonitrile Copolymers

The kinetics and reactivity ratios of styrene‐acrylonitrile (SA) copolymerization have been studied extensively in bulk and in a variety of solution media using conventional free radical polymerizations (FRPs). Due to the significant difference in the two reactivity ratios for this monomer pair, at certain feed ratios the copolymers display composition drift with conversion due to monomer depletion. In this study, the kinetics of SA copolymerization using Reversible Addition‐Fragmentation Chain Transfer (RAFT) has been studied in bulk at 80 °C. The reactivity ratios for the terminal model were calculated from the comonomer sequence distributions for the RAFT process at low conversion for nine different compositions and found to be in the same range as those reported for conventional FRP of SA. The changes in the composition and sequence distribution with conversion were studied for three feed compositions. The copolymers show compositional drift with conversion, except at the azeotropic composition, and match the predictions from the reactivity ratios obtained at low conversion. From quantitative ¹³C NMR the triad distributions of these copolymers were estimated and found to match the predicted triad distributions as conversion increased. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 919–927     

胰岛素反相制备色谱的方法开发

以胰岛素反相制备色谱方法的开发和优化为目标,通过考察色谱保留参数、峰展宽及样品流出曲线的浓度分布等色谱参数,对流动相梯度、色谱填料、载样量等色谱条件进行了优化,并建立了胰岛素制备色谱峰参数的描述方法。结果表明,所建立的方法可快速筛选出最适于胰岛素分离的色谱条件(包括流动相梯度及分离填料),即流动相中的强洗脱溶剂(有机相)需采取缓梯度窄区间的变化条件,筛选出的分离填料需具备峰向两侧展宽且展宽程度较小、样品最高浓度居中分布的特点。将方法用于实际胰岛素粗品的纯化制备,获得了杂质去除效果好、胰岛素纯度高的产品。该法为胰岛素反相色谱纯化制备方法的快速建立提供了指导,具有较强的实用价值,同时为发展大分子化合物的制备色谱方法提供了参考。     

Large impact in electrical properties of polypropylene by improving the filler-matrix interface effect in PP/PS blends

Inorganic nanoparticles are widely used to improve space charge behavior, DC breakdown strength and other electrical properties of polymer insulating materials, but the uniform distribution of inorganic nanofillers in matrix is difficult due to their agglomeration and bad compatibility with the polymeric matrix. In this paper, polypropylene (PP)/polystyrene (PS) blends were prepared to suppress space charge accumulation and improve DC breakdown strength. Polypropylene-g-polystyrene (PP-g-PS) graft copolymer was used as compatibilizer to improve the compatibility of PP matrix and PS filler. The evolution of microstructure of PP/PS blends were investigated by scanning electron microscope (SEM), the space charge distributions were measured by a pulsed electro-acoustic (PEA) system, and DC breakdown strength was also tested. The morphologies show that the size of PS particles reduced to 310 nm when the content of PP-g-PS graft copolymer increased to 24 wt%, and the interaction between PP matrix and PS particles enhanced. The presence of PS particles in all PP/PS blends suppressed the space charge accumulation compared to neat PP, but the DC breakdown strength in uncompatibilized blend was lower than neat PP. The increasing of content of PP-g-PS improved the DC breakdown strength with the maximum value of 408.9 kV/mm was obtained. This may attribute to excellent interface structure formed between PP matrix and PS particles.