Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

红外背景干扰研究

根据从许多地区收集来的录象磁带上的图象数据和大量红外图象数据，对红外背景图象内的干扰进行了研究。图象内的噪声是以象元电平为单位的均方根形成计算。图象经过空间滤波处理，对其内的干扰再进行计算。为获得关于红外背景图象的空间频率构成的信息，在滤波和非滤波两种状态下计算了图象的光谱密度，把计算出的干扰值输入数据库取出多组数据并绘图，确定参数量（如天气、背景类型和测量条件等）对干扰电平的影响。     

Experimental densities for compressed R134a

This paper reports densities of compressed R134a (1,1,1,2-tetrafluoroethane) determined by using a contiuously weighed pycnometer at 20 K intervals between 180 and 380 K at pressures from slightly greater than the vapour pressure to 70 MPa. The results are accurate to within ±0.1%. Saturated liquid densities derived by extrapolation from the experimental values agree with other reported values to within ±0.3%.     

Extracting Electron Densities in N-Type GaAs From Raman Spectra: Theory

In this paper, we present the theory for calculating Raman line shapes as functions of the Fermi energy and finite temperatures in zinc blende, n-type GaAs for donor densities between 10¹⁶ cm⁻³ and 10¹⁹ cm⁻³. Compared to other theories, this theory is unique in two respects: 1) the many-body effects are treated self-consistently and 2) the theory is valid at room temperature for arbitrary values of the ratio R = (Q²/α), where Q is the magnitude of the normalized wave vector and α is the normalized frequency used in the Raman measurements. These calculations solve the charge neutrality equation self-consistently for a two-band model of GaAs at 300 K that includes the effects of high carrier concentrations and dopant densities on the perturbed densities of states used to calculate the Fermi energy as a function of temperature. The results are then applied to obtain the carrier concentrations from Fermi energies in the context of line shapes in Raman spectra due to the coupling between longitudinal optical phonons and plasmons. Raman measurements have been proposed as a non-destructive method for wafer acceptance tests of carrier density in semiconductor epilayers. The interpretation of Raman spectra to determine the majority electron density in n-type semiconductors requires an interdisciplinary effort involving experiments, theory, and computer-based simulations and visualizations of the theoretical calculations.     

Thermophysical Properties of Binary Mixtures of Methyl Methacrylate+Di-Ethers (Ethyl, Isopropyl, and Butyl) at 298.15 and 308.15 K

Experimental data for the densities, dynamic viscosities, sound speeds, and relative permittivities and for three binary systems of methyl methacrylate (MMA)+di-ethers (ethyl, isopropyl, and butyl) at 298.15 and 308.15 K and at atmospheric pressure are reported. The mixture viscosities are correlated by Grunberg–Nissan, McAllister, and Auslander equations over the complete composition range. The sound speeds for the mixtures are also calculated by using free length and collision factor theories, and Nomoto and Junjie equations. From the measured primary properties, deviation functions such as deviations in viscosities, sound speeds, relative permittivities, molar polarizations, excess isentropic compressibilities, and molar electrical susceptibilities were calculated, and the compositional dependence of each of the functions was expressed with a Redlich–Kister type equation. The variation of the Kirkwood correlation factor was determined over the complete composition range.     

长期不同施肥对玉米田间杂草生物多样性的影响

通过田间小区试验,研究了长期不同施肥对田间杂草总密度、优势杂草组成及生物多样性的影响。结果表明:综合施用N、P、K肥,不仅降低了田间杂草的总密度,降低了优势杂草在群落中的比重,而且有利于维持田间杂草的生物多样性;不施用N或P肥,田间杂草的总密度增大,优势杂草的比重也明显增强,但不利于维持田间杂草的生物多样性。所以,平衡施用N、P、K肥,有利于维持农田生态系统中的生物多样性,并能更好地进行杂草控制。     

Study of the coupling reactions between electrochemically generated aromatic radical anions and methyl, alkyl and benzyl radicals

Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×10⁹ M⁻¹ s⁻¹. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an S_N2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such S_N2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 10⁹ M⁻¹ s⁻¹.     

Glyoxal Ozonation Process in Aqueous Solution

The process of ozonation of glyoxal in aqueous solution has been studied by following its chemical and kinetic evolution. Results show that the oxidative process leads to formation of carboxylic functions and carbon dioxide according to a constant selectivity ratio at varying conversion degree.. Comparison between the oxygen amounts of reaction products and the corresponding ozone consumptions reveals that molecular oxygen takes part in the reaction process. System behavior is explained on the basis of radical reaction mechanism.     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part III. The importance of the interactions between volatiles and char at high temperature

A novel two-stage fluidised-bed/fixed-bed reactor was designed to investigate the effects of volatile-char interactions on the volatilisation of alkali and alkaline earth metallic (AAEM) species during the pyrolysis of Victorian brown coal at 900 °C. With the two-stage reactor configuration, the AAEM-free volatiles generated from the pyrolysis of the H-form coal in the fluidised bed came into direct contact with the char from NaCl-loaded or Na-form coals in the fixed bed. The results indicated that the interactions between the volatiles, especially free radicals in the volatiles, and the char particles enhanced the volatilisation of Na from the char drastically. However, such radical-char interactions resulted in little volatilisation of Mg and Ca, indicating the importance of valence of the AAEM species. The degree of the volatile-char interactions was also related to the ageing of the char and the chemical form of AAEM species in the coal substrate. The volatiles interacted more strongly with the nascent char than the aged char, indicating that the AAEM species existed in the aged char in more stable forms than in the nascent char.