Cure kinetics and shrinkage model for epoxy-amine systems

Manufacture of most of epoxy resins implies that cure needs to be carried out under pressure. Due to the significance of knowing the influence of the pressure factor in cure kinetics, cure shrinkage of a stoichiometric epoxy-amine system was measured using a pressure-volume-temperature (PVT) analyzer. Recording the specific volume change in the range of temperature from 100 to 180 °C and a pressure of 200 bar we could model the cure kinetics. The Runge-Kutta method was applied to obtain the kinetic constants of the cure reaction. In addition, using the differential scanning calorimeter (DSC) for measurements of 1 bar and the PVT analyzer for pressures of 200, 400, and 600 bar, we also model the kinetic constants as a function of pressure. The results obtained show that the effect of the temperature on the kinetic constants is higher than the effect of pressure. Therefore, both PVT and DSC are complementary techniques to describe the full range of cure kinetic process of epoxy mixtures.     

Bulk free radical polymerizations of methyl methacrylateunder non-isothermal conditions and with intermediate additionof initiator: Experiments and modeling

Experimental data on the monomer conversion, x_m, and the weight average molecular weight, M_w, have been generated under several isothermal and non-isothermal conditions for the polymerization of methyl methacrylate in a rheometer-reactor assembly. The non-isothermal results, in particular, can be used to provide more stringent tests of kinetic models than isothermal data alone. A simple empirical model has been used to describe this system that accounts for the gel (Trommsdorff) and glass effects. The model involves only x_m and the temperature, and is quite general. The model parameters are tuned using only three sets of isothermal data. Good agreement is found between the experimental results and model predictions for a whole variety of experimental conditions, including non-isothermal operation and with intermediate addition of initiator. Because of its generality, this model is quite suitable for use for on-line optimizing control as well as for describing industrial reactors.     

Fluorescent Brightener 28 Removal by Ozonation or Advanced Oxidation Processes (O3/H2O2)

The aim of this work is to study the reaction of ozone and combined ozone/hydrogen peroxide mixtures with the fluorescent brightener 28 in dilute aqueous solution using controlled experimental conditions. The kinetics were also evaluated under various experimental conditions. The main ozonation by-products have been identified by High Pressure Anionic Exchange Chromatography (HPAEC) and Gas Chromatography coupled with Mass Spectrometry (GC-MS) techniques and a reaction pathway is proposed. In order to confirm this mechanism, melamine and s-triazine have been treated under the same reaction conditions and their decomposition pathways were studied.     

环己烷液相无催化剂的氧化动力学研究

采用搅拌釜反应器,在确认已排除传质因素对反应速率影响的情况下,研究了环己烷液相无催化剂的氧化反应动力学。应用自由基理论及最优化计算技术,从导出的8个候选动力学模型中,确定了最佳的动力学模型,它能满意地描述环已烷氧化过程。该动力学可为环己烷氧化工业生产操作条件的优化、反应器的选型及工业设计提供依据。     

枯草杆菌碱性磷酸酶制备的最佳工艺条件及酶促反应动力学性质的研究

以枯草杆菌为菌种液体培养制备碱性磷酸酶，研究确定了培养的最佳工艺条件，并对碱性磷酸酶的酶促反应动力学性质进行了初步探讨。结果表明，枯草杆菌制备碱性磷酸酶的最佳工艺条件为：40℃，pH值7．4振荡培养10h，酶活最高。对碱性磷酸酶的动力学性质研究表明，该酶催化底物磷酸苯二钠水解反应的最适pH值8．8，最适温度52℃，米氏常数Km值为2．94mmol／L。     

Investigation of kinetics of agglomerate growth in oil agglomeration process

In this study, the kinetics of agglomerate growth in a batch oil agglomeration process has been studied using bituminous coal. The effect of operating variables such as kerosene concentration, pulp density and speed of agitation on the agglomeration process was investigated. It has been found that the second-order kinetic equation describes the growth of agglomerates adequately. The growth of the agglomerates in the oil agglomeration process shows a self-preserving growth. Using this, a characteristic curve has been developed. For the prediction of the size distribution of the agglomerates, the d₅₀ values of the agglomerates must be known. Therefore, a model has been developed by using the kinetic equation for estimation of d₅₀ values of agglomerates for this coal. It was shown that the size distribution of the agglomerates for any levels of the process variables studied can be predicted using the equation of characteristic curve and d₅₀ values. Knowledge obtained from this study will be helpful for technological advancement of this kind of study.     

HEC influence on cement hydration measured by conductometry

Cellulose ethers are of universal use in factory-made mortars, though their influences on mortar properties at a molecular scale are poorly understood. Recent studies dealt with the influence of hydroxyethylmethyl cellulose (HEMC) and hydroxypropylmethyl cellulose (HPMC) molecular parameters on cement hydration. It was concluded that the degree of substitution is the most relevant factor on cement hydration kinetics, contrary to the molecular weight. Nevertheless, the major role played by the substitution degree has not been verified for other types of cellulose ethers such as hydroxyethyl cellulose (HEC), which generally possesses a higher hydration retarding capacity compared to HPMC and HEMC. In this frame, a study of the impact of HEC molecular parameters on cement hydration was performed. A negligible influence of the molecular weight was observed. Moreover, the results emphasize that the hydroxyethyl group content mainly determines the delay of cement hydration.     

Self-propagating high-temperature synthesis of advanced ceramics MoSi2–HfB2–MoB

This study focuses on the investigation of the macrokinetic features of SHS (combustion synthesis) of elemental mixtures Mo–Hf–Si–B, in particular the mechanisms of structure and phase formation in the combustion front as well as the structure and properties of consolidated ceramics. Two routes for the fabrication of the composite SHS powder in system MoSi₂–HfB₂–MoB were used: (1) synthesis using Mo–Si–B and Hf–B mixtures followed by mixing of the combustion products and (2) synthesis using the four-component Mo–Hf–Si–B mixture. Dense ceramic samples with a homogeneous structure and low residual porosity (0.8–3.6%) were prepared by hot pressing of SHS powders. Although the particles size distribution and phase composition of SHS powders are similar for both synthesis routes, the structure and properties of both the composite SHS powders and hot-pressed ceramics differ considerably. Synthesis using the four-component Mo–Hf–Si–B mixture allows one to produce hierarchically ordered nanocomposite material with improved mechanical properties: hardness up to 17.6?GPa and fracture toughness up to 7.16?MPa?m^1/2.     

Kinetics for benzoylation of sodium 4-acetylphenoxide via third-liquid phase in the phase-transfer catalysis

In this research, the kinetics for synthesizing 4-acetylphenyl benzoate (R^*COOR) from benzoylation of sodium 4-acetylphenoxide via third-liquid phase-transfer catalysis was investigated. The reaction rate was observed to be strongly dependent on agitation speeds in the third-phase catalytic reaction. By forming the third-liquid phase, the observed reaction can be greatly enhanced to give a product yield of 100% in a duration of 3 min at 20 °C and 200 rpm. If a third-liquid phase was not formed in the liquid–liquid system, the reaction rate is very slow and the product yield is only 2% in 3 min at 20 °C. The reaction conducted in third-liquid phase-transfer catalytic system is faster than that in LLPTC system by 25–28 times. The amount of catalytic intermediate (QOR) in the third-liquid phase was about 50% of the catalyst initially added and kept about 30% of it remained after 1 min, and only small amounts of a catalytic intermediate residing in the organic phase were observed during the reaction using methyl t-butyl ether as the solvent. The concentration of catalytic intermediate slightly decreased with increasing reaction time, while the molar ratio of QOR to benzyl tri-n-butylammonium cation in the third-liquid phase remained almost constant after 1 min and increased with increasing agitation speeds. The experimental results were well described by the pseudo-first-order kinetics. The present work shows an effective method to synthesize 4-acetylphenyl benzoate.     

The role of calcium ions and lignosulphonate plasticiser in the hydration of cement

Experiments involving equilibrium dialysis, conductivity, X-ray diffraction analysis (XRD), differential thermal analysis (DTA) and isothermal titration calorimetry (ITC) have been carried out to investigate the role of calcium ions and polymeric plasticisers in cement/admixture hydration. Results from a study of lignosulphonic acid, sodium salt, acetate as a plasticiser shows that a plasticiser has dual role; one mainly as a kinetic inhibitor (poison) in cement hydration mechanism and the other as a dispersant. Evidence of a weak Ca²⁺ binding to lignosulphonate sulphonic moieties was found at low ionic strengths of 0.1 M using ITC. No evidence of formal Ca²⁺ binding to lignosulphonate sulphonic acid moieties was found using equilibrium dialysis at higher ionic strength of 1 M (ionic strengths of 0.4 M are typically found in Portland cement pore solution), as is often suggested in cement/admixture literature.