Ultrahigh molecular mass polyethylene (UHMMPE) is filled with carbon nano-tubes (CNTs) by solution in the presence of maleic
anhydride grafted styrene-(ethylene-co-butylene)-styrene copolymer (MA-SEBS) as a compatibilizer. The UHMMPE/CNT composites
crystallized from melt were prepared at a cooling rate of 20C min-1. The melting and crystallization behaviors of UHMMPE/ CNT composites were investigated by differential scanning calorimetry.
The results showed that onset melting temperature (Tm) and degree of crystallinity (Xc) of UHMMPE/CNT composites crystallized from solution are higher than those from melt due to the larger crystalline lamellar
thickness. The onset crystallization temperature (Tc) of UHMMPE/CNT composites tends to shift to higher temperature region with increasing CNT content in the composites. Tm and
Tc of UHMMPE phase in UHMMPE/CNT composites decrease with the addition of MA-SEBS. Moreover, the crystallization rate of UHMMPE
phase in UHMMPE/CNT composite is increased due to the introduction of CNTs. MA-SEBS acts as compatilizer, enhances the dispersion
of CNTs in the UHMMPE matrix. Thereby, the crystallization rate of UHMMPE phase in UHMMPE/CNT composite is further increased
with the addition of MA-SEBS.
Authors:Y. Chen, H. Wang, X. Meng, X. Zeng, and J. Xie
A novel thermokinetic research method for determination of the rate constant of a reaction taking place in a batch conduction
calorimeter under isothermal conditions is proposed: the double-thermoanalytical curve method. The method needs only the characteristic
time parameter tm, the peak height Δm at time tm and the peak area a*m after time tm for two thermoanalytical curves measured with different initial concentrations of the reactants: it conveniently calculates
the rate constants. The thermokinetics of four reaction systems were studied with this method, and its validity was verified
by the experimental results.
Authors:X. Zeng, Y. Chen, S. Cheng, X. Meng, and Q. Wang
A novel method for the determination of rate constants of reactions, the time-variable method, is proposed in this paper. The method needs only three time points (t), peak heights () and pre-peak areas (), obtained from the measured thermoanalytical curve. It does not require the thermokinetic reaction to be completed. It utilizes data-processing on a computer to give the rate constants. Four reaction systems, including a first-order reaction, second-order reactions (with equal concentrations and with unequal concentrations) and a third-order reaction, were studied with this method. The method was validated and its theoretical basis was verified by the experimental results.
Authors:D. Shen, X. Fan, X. Su, J. Zeng, and Y. Dong
The sorption behavior of technetium on pyrrhotine was studied with batch experiments and diluted sulfuric acid (less than 2.88 mol/l) was used to dissolve the technetium adsorbed on pyrrhotine. A significant sorption of technetium on pyrrhotine was observed under aerobic and anaerobic conditions, and the sorption on the mineral was supposed to be due to the reduction of TcO4- to insoluble TcO2.nH2O. Sorbed technetium on the mineral could be desorbed by diluted sulfuric acid. The maximum desorption ratio under aerobic conditions was much higher than that of under anaerobic conditions, meanwhile, the desorption rates under anaerobic conditions were higher than that of under aerobic conditions in the initial stage of the experiments.
A novel thermokinetic research method for determination of rate constants of simple-order reaction in batch conduction calorimeter
under isothermal condition, the characteristic parameter method, is proposed in this paper. Only needing the characteristic
time parameter tm obtained from the measured thermoanalytical curve, the kinetic parameters of reactions studied can be calculated
conveniently with this method. The saponifications of ethyl propionate and ethyl acetate in aqueous ethanol solvent, the polymerization
of acrylamide in aqueous solution, the ring opening reaction of epichlorohydrin with hydrobromic acid have been studied. The
experimental results indicate that the characteristic parameter method for simple-order reaction is correct.
The transformation equation for the thermokinetics of consecutive first-order reactions has been deduced, and a thermokinetic
research method of irreversible consecutive first-order reactions, which can be used to determine the rate constants of two
steps simultaneously, is proposed. The method was validated and its theoretical basis was verified by the experimental results.
According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of opposing reactions have been derived, and a novel thermokinetic research method, the characteristic parameter method for opposing reactions which taking place in a batch conduction calorimeter under isothermal condition, has been proposed in this paper. Only needing the characteristic thermoanalytical data corresponding to tm and 2tm from the same curve, the rate constants of forward and backward reactions and equilibrium constant can be calculated simultaneously with this method. In order to test the validity of this method, the proton-transfer reactions of nitroethane with ammonia at 15 and 25°C, and with trihydroxymethyl aminomethane (Tris) at 15 and 30°C have been studied, respectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in the literature. Therefore, the characteristic parameter method for opposing reaction is believed to be correct.
In order to enrich the thermokinetic research methods and enlarge the applicable range of the thermokinetic time-parameter
method, the integral and differential thermokinetic equations of consecutive first-order reaction have been deduced, and the
mathematical models of the time-parameter method for consecutive first-order reactions have been proposed in this paper. The
rate constants of two steps can be calculated from the same thermoanalytical curve measured in a batch conduction calorimeter
simultaneously with this method. The thermokinetics of saponifications of diester in aqueoushanol solvent has been studied.
The experimental results indicate that the time-parameter method for the consecutive first-order reaction is correct.
This paper presents calorimeter measurement for the thermal decomposition of n-propyl nitrate (NPN), isopropyl nitrate (IPN) and 2-ethylhexyl nitrate (EHN). Similar experimental results of triethylene
glycol dinitrate (tri-EGDN) and tetraethylene glycol dinitrate (tetra-EGDN) are included for comparison. The potential energy
surfaces (PESs) along O-NO2 bond stretch are investigated using the DFT (B3P86, B3PW91 and B3LYP), ab initio Hartree-Fock and PM3 methods. The good coincidence
of experimental with theoretical results indicates that initial stage in the thermal decomposition of five nitrates is only
unimolecular homolytical dissociation of the O-NO2 bonds and the activation energies of thermolysis by DSC correspond to the energies of O-NO2 bond scission of nitrates.
Authors:Y.-Q. Zhang, X.-C. Zeng, Y. Chen, X.-G. Meng, and A.-M. Tian
On the basis of the theory of thermokinetics proposed in the literature, a novel thermokinetic method for determination of the reaction rate, the characteristic parameter method, is proposed in this paper. Mathematical models were established to determine the kinetic parameters and rate constants. In order to test the validity of this method, the saponifications of ethyl benzoate, ethyl acetate and ethyl propionate, and the formation of hexamethylenetetramine were studied with this method. The rate constants calculated with this method are in agreement with those in the literature, and the characteristic parameter method is therefore believed to be correct.In the light of the characteristic parameter method, we have developed further two thermo-kinetic methods, the thermoanalytical single and multi-curve methods, which are convenient for simultaneous determination of the reaction order and the rate constant. The reaction orders and rate constants of the saponifications of ethyl acetate and ethyl butyrate and the ring-opening reaction of epichlorohydrin with hydrobromic acid were determined with these methods, and their validity was verified by the experimental results.