Phosphorus‐containing polyaryloxydiphenylsilanes with high flame retardance arising from a phosphorus–silicon synergistic effect

Polyaryloxydiphenylsilanes were prepared from phosphorus‐containing diols and diphenydichlorolsilane through solution polymerization. With a stoichiometric imbalance in feed monomers, the resulting polymers exhibited moderate melting points and good processing properties. The polymers prepared showed initial decomposition temperatures above 340 °C, excellent thermal stability, high char yields at 850 °C and very high limited oxygen index values of 56–59. The polymers' char yields and their (P + Si) contents showed linear relationships. © 2003 Society of Chemical Industry     

Development of a Continuous Segmented Flow Tubular Reactor and the “Scale‐out” Concept – In Search of Perfect Powders

The synthesis of powders with controlled shape and narrow particle size distributions is still a major challenge for many industries. A continuous Segmented Flow Tubular Reactor (SFTR) has been developed to overcome homogeneity and scale‐up problems encountered when using batch reactors. Supersaturation is created by mixing the co‐reactants in a micromixer inducing precipitation; the suspension is then segmented into identical micro‐volumes by a non‐miscible fluid and sent through a tube. These micro‐volumes are more homogeneous when compared to large batch reactors leading to narrower size distributions, better particle morphology, polymorph selectivity and stoichiometry. All these features have been demonstrated on single tube SFTR for different chemical systems. To increase productivity for commercial application the SFTR is being “scaled‐out” by multiplying the number of tubes running in parallel instead of scaling‐up by increasing their size. The versatility of the multi‐tube unit will allow changes in type of precipitate with a minimum of new investment as new chemistry can be researched, developed and optimised in a single tube SFTR and then transferred to the multi‐tube unit for powder production.     

Advanced disturbance observer design for mechanical positioning systems

Disturbance-observer (DOB)-based controller design is one of the most popular methods in the field of motion control. In this paper, the generalized disturbance compensation framework, named the robust internal-loop compensator (RIC) is introduced and an advanced design method of a DOB is proposed based on the RIC. The mixed sensitivity optimization problem, which is the main issue of DOB design, is also solved through the parametrization of the DOB in the RIC framework. Differently from conventional methods, the Q-filter is separated from the mixed sensitivity optimization problem and a systematic design law for the DOB is proposed. This guarantees the robustness and optimality of the DOB and enables the design for unstable plants.     

合成己二腈反应技术研究——(Ⅴ)己二腈工业反应过程模拟与反应器改造

对己二腈工业反应器提出了两釜串联带回流的模型,通过模拟计算得出模型的级间返混系数 f=6的结论。该模型能较好地预测工业反应器中物料组分浓度变化和气、液两相的流动特性;指出了现工业反应器的鼓泡中和段体积偏小是造成己二酸浓度偏高的关键;提出了可以通过增加串连一个鼓泡预反应段的改造方案,能有效地降低己二酸的浓度,从7%降至4%左右,从而能较好地减缓腐蚀和结焦。     

NO emission characteristics in counterflow diffusion flame of blended fuel of H2/CO2/Ar

Flame structure and NO emission characteristics in counterflow diffusion flame of blended fuel of H₂/CO₂/Ar have been numerically simulated with detailed chemistry. The combination of H₂, CO₂ and Ar as fuel is selected to clearly display the contribution of hydrocarbon products to flame structure and NO emission characteristics due to the breakdown of CO₂. A radiative heat loss term is involved to correctly describe the flame dynamics especially at low strain rates. The detailed chemistry adopts the reaction mechanism of GRI 2.11, which consists of 49 species and 279 elementary reactions. All mechanisms including thermal, NO₂, N₂O and Fenimore are taken into account to separately evaluate the effects of CO₂ addition on NO emission characteristics. The increase of added CO₂ quantity causes flame temperature to fall since at high strain rates a diluent effect is prevailing and at low strain rates the breakdown of CO₂ produces relatively populous hydrocarbon products and thus the existence of hydrocarbon products inhibits chain branching. It is also found that the contribution of NO production by N₂O and NO₂ mechanisms are negligible and that thermal mechanism is concentrated on only the reaction zone. As strain rate and CO₂ quantity increase, NO production is remarkably augmented. Copyright © 2002 John Wiley & Sons, Ltd.     

An EM‐based adaptive multiple target tracking filter

Tracking targets of interest is one of the major research areas in radar surveillance systems. We formulate the problem as incomplete data estimation and apply EM to the MAP estimate. The resulting filter has a recursive structure analogous to the Kalman filter. The advantage is that the measurement‐update deals with multiple measurements in parallel and the parameter‐update estimates the system parameters on the fly. Experiments tracking separate targets in parallel show that tracking maintenance ratio of the proposed system is better than that of NNF and RMS position error is smaller than that of PDAF. Also, the system parameters are correctly obtained even from incorrect initial values. Copyright © 2001 John Wiley & Sons, Ltd.     

Improvement in hydrolytic procedure for GLC determination of non-indolyl glucosinolates in rapeseed as isothiocyanates

Some methods determine the non-indolyl glucosinolates content in rapeseed as their hydrolysates: the isothiocyanates and the oxazolidinethiones. These methods in their present form underestimate the amount of the glucosinolates content. In this investigation, a modified method was developed to give a better quantitative estimate, indicating a glucosinolate level five times that obtained by a typical existing method.     

A new efficient method for one‐pot conversions of aryl carboxylic acids into nitriles without solvent

A new efficient method for synthesising nitriles, important organic reagents, is reported in this paper. In an environmentally benign solvent‐free system, aryl carboxylic acids were converted into the corresponding nitriles via one‐pot reactions, by amidation with ethyl carbamate followed by dehydration with thionyl chloride, in excellent yields. The results showed that the method has the advantages of lower cost, higher yield, less pollution and greater ease of work‐up. Copyright © 2008 Society of Chemical Industry     

Cooling and Solidification of Melted Drops in an Immiscible Cooling Medium

The cooling and solidification of melted drops during their movement in an immiscible cooling medium is widely employed for granulation in the chemical industry, and a study of these processes to provides a basis for the design of the granulation tower height and the temperature of the cooling medium is reported. A physical model of the cooling and solidification of the drop is established and the numerical calculation is performed. The influences of the key factors in the solidification, i.e., Bi number, drop diameter, temperature of the cooling medium, etc. are presented. The cooling and solidification during wax granulation in a water‐cooling tower and during urea granulation in an air‐cooling tower (spraying tower) are described in detail. Characteristics of the solidification and temperature distribution within the particle at different times are shown. The model and calculations can be used for structure design of the granulation tower and optimization of the operation parameters.     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry