An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg12-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.

Non-isothermal crystallization kinetics of reactive microgel/nylon 6 blends

The non-isothermal crystallization kinetics of reactive microgel/nylon 6 blends was investigated by differential scanning calorimetry(DSC). The Mo equation was employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. The results show that the crystallization onset temperature(T onset) and crystallization peak temperature(T p) decrease with the increase of the content of reactive microgel, while ΔT(T onset–T p), the crystallization half-time(t1/2) and the crystallization enthalpy(ΔH c) increase. The required cooling rates of blends are higher than that of neat nylon6 in order to achieve the same relative crystallinity in a unit of time. The crystallization activation energies of the reactive microgel/nylon 6 blends are greater than those of the neat nylon 6. When the content of reactive microgel is 30%, the relative crystallinity(X t) reaches the maximum.

Kinetic Study of Thermal Polymerization Reactions between Diazide and Different Diynes

The reaction kinetics between diazide（4,4＇-biphenyl dibenzyl azide） and different diynes（dipropargyl bisphenol A and 1,3-diethynylbenzene） were studied by means of differential scanning calorimetry（DSC） and nuclear magnetic resonance spectroscopy（~1H-NMR）.DSC was adopted to analyze the reactions under bulk polymerization condition,while ~1H-NMR for solution reaction polymerization was conducted.The apparent activation energies（E_α） calculated by Kissinger＇s method were 77.96,81.24 k J/mol,which were confirmed by Friedman＇s method,and 65.45,69.36 k J/mol by ~1H-NMR for dispropargyl bisphenol A/4,4＇-biphenyl dibenzyl azide and 1,3-diethynylbenzene/4,4＇-biphenyl dibenzyl azide,respectively.The polymerizations between the diazide and diynes were first-order reactions based on calculation from both DSC and ~1H-NMR.The results showed that the reaction between dipropargyl bisphenol A and 4,4＇-biphenyl dibenzyl azide was easier than that between 1,3-diethynylbenzene and 4,4＇-biphenyl dibenzyl azide,verifying that the reactivity of aliphatic alkyne was higher than that of aromatic alkyne.

Kinetic Characteristics in Pyrolysis of RPF with Additives

PVC（polyvinyl chloride） was isolated from waste plastic before manufacturing RPF（refuse paper ＆ plastic fuel）, and the characteristics of manufactured RPF including properties, calorific value, pyrolysis, chlorine content and kinetics analysis were analyzed. Based on the result of TGA（Thermogravimetric analysis）, the kinetics characteristics was analyzed by using Kissinger method and Ozawa method which are the most common methods for obtaining activation energy, and the experimental conditions of TGA were set as follows： in a nitrogen atmosphere, with gas flow rate of 20mL/min, heating rate of 5-50 ℃/min, and maximum temperature of 800 ℃. In conclusion, the activation energy showed a tendency to gradually increase by a rise of reaction rate. Although the activation energy with pyrolysis of RPF was irregularly scattered, it was shown that the activation energy was stabilized by co-pyrolysis of RPF and additives（rice bran and sawdust）.

Microstructure and Growth Kinetics of Silicide Coatings for TiAl Alloy

In order to improve the oxidation resistance of Ti Al alloy, silicide coatings were prepared by pack cementation method at 1273, 1323, and 1373 K for 1-3 hours. Scanning electron microscopy（SEM）, energy dispersive spectrometry（EDS） and X-ray diffraction（XRD） were employed to investigate the microstructures and phase constitutions of the coatings. The experimental results show that all silicon deposition coatings have multi-layer structure. The microstructure and composition of silicide coatings strongly depend on siliconizing temperatures. In order to investigate the rate controlling step of pack siliconizing on Ti Al alloy, coating growth kinetics was analyzed by measuring the mass gains per unit area of silicided samples as a function of time and temperature. The results showed that the rate controlling step was gas-phase diffusion step and the growth rate constant（k） ranged from 1.53 mg^2/（cm^4·h^2） to 2.3 mg^2/（cm^4·h^2）. Activation energy（Q） for the process was calculated as 109 k J/mol, determined by Arrhenius＇ equation： k = k0 exp[–Q/（RT）].

Morphology of Oxide Scale and Oxidation Kinetics of Low Carbon Steel

The oxidation kinetics and composition of oxide scales on low carbon steel （SPHC） were studied during i- sothermal oxidation. Thermogravimetric analyzer （TGA） was used to simulate isothermal oxidation process of SPHC for 240 min under air condition, and the temperature range was from 500 to 900 ℃. Scanning electron microscope （SEM） was used to observe cross-sectional scale morphology and analyze composition distribution of oxide scales. The morphology of oxide scale was classical three-layer structure. Fe2 03 developed as whiskers at the outermost lay- er, and interlayer was perforated-plate Fe3 04 while innermost layer was pyramidal FeO. From the oxidation curves, the oxidation mass gain per unit area with time was of parabolic relation and oxidation rate slowed down. On the ba- sis of experimental data, the isothermal oxidation kinetics model was derived and oxidation activation energy of SPHC steel was 127. 416 kJ/mol calculated from kinetics data.

Coarsening Kinetics of γ' Precipitates in Dendritic Regions of a Ni_3 Al Base Alloy

Coarsening behavior of γ＇ precipitates in the dendritic regions of a Ni 3 Al base alloy containing chromium,molybdenum,zirconium and boron was investigated.Annealing treatment was performed up to 50 h at 900,1000 and 1100℃.The alloy was produced by vacuum-arc remelting technique.Results show that coarsening of the γ＇ precipitates in this complex alloy containing high volume fractions of γ＇ phase follows Lifshitz-Slyozov-Wagner（LSW） theory.Coarsening activation energy of the γ＇ precipitates was evaluated to be about 253.5 kJ.mol-1 which shows that the growth phenomenon is controlled by volume diffusion of aluminum.With an innovative approach,diffusion coefficient of the solute element（s） and the interfacial energy between γ＇ precipitates and γ＇（matrix） were estimated at 900,1000 and 1100℃.Accordingly,the interfacial energies at 900,1000 and 1100℃ are 4.49±1.48,2.08±0.69 and 0.98±0.32 mJ.m-2,respectively.Also the diffusivities of solute element（s） at these temperatures are 3.41±1.08,30±9.5 and 145.15±45.85（10-15 m-2.s-1）,respectively.

Effects of tantalum on austenitic transformation kinetics of RAFM steel

The RAFM（reduced activation ferritic/martensitic）steels containing different tantalum contents（0wt.%,0.027wt.%,0.073wt.%）were designed and cast.Differential scanning calorimetry and optical microscopy were employed to explore the influence of tantalum content on the austenitic transformation of RAFM steels.The austenitic transformation kinetics was described by aphase-transformation model.The model,involving site saturation nucleation,diffusion-controlled growth and impingement correction,was established based on the classical Johnson-Mehl-Avrami-Kolmogorov model.The phase-transformation kinetics parameters,including D_0（pre-exponential factor for diffusion）and Q_d（activation energy for diffusion）,were calculated by fitting the experimental data and the kinetic model.The results indicated that the average grain size is decreased with the increase of tantalum.The values of A_（c1） and A_（c3） （onset and finish temperature of austenitic transformation,respectively）are increased by increasing the tantalum content.The increase of tantalum caused the decrease of D_0.However,Q_d is increased with the increase of tantalum.In addition,as a carbides forming element,tantalum would reduce the carbon diffusion coefficient and slow down the austenitic transformation rate.

Hydrogen Storage Kinetics of Nanocrystalline and Amorphous LaMg_(12)-Type Alloy–Ni Composites Synthesized by Mechanical Milling

The nanocrystalline and amorphous LaMg11Ni ＋ x wt% Ni （x = 100, 200） composites were synthesized by the mechanical milling, and their gaseous and electrochemical hydrogen storage kinetics performance were systematically investigated, The results indicate that the as-milled composites exhibit excellent hydrogen storage kinetic performances, and increasing Ni content significantly facilitates the improvement of the hydrogen storage kinetics properties of the composites. The gaseous and electrochemical hydrogen storage kinetics of the composites reaches a maximum value with the variation of milling time. Increasing Ni content and milling time both make the hydrogen desorption activation energy lower, which are responsible for the enhancement in the hydrogen storage kinetics properties of the composites. The diffusion coefficient of hydrogen atom and activation enthalpy of charge transfer on the surface of the as-milled composites were also calculated, which are considered to be the dominated factors for the electrochemical high rate discharge ability.

Hydrogen Storage Thermodynamics and Dynamics of Nd–Mg–NiBased Nd Mg_(12^-)Type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous Nd Mg_（12^-）type Nd Mg_（11）Ni＋ x wt% Ni（x=100, 200） hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The gaseous hydrogen absorption and desorption properties were investigated by Sieverts apparatus and differential scanning calorimeter connected with a H_2 detector. Results show that increasing Ni content significantly improves hydrogen absorption and desorption kinetics of the alloys. Furthermore,varying milling time has an obvious effect on the hydrogen storage properties of the alloys. Hydrogen absorption saturation ratio（R^a_（10）; a ratio of the hydrogen absorption capacity in 10 min to the saturated hydrogen absorption capacity） of the alloys obtains the maximum value with varying milling time. Hydrogen desorption ratio（R^d_（20）, a ratio of the hydrogen desorption capacity in 20 min to the saturated hydrogen absorption capacity） of the alloys always increases with extending milling time. The improved hydrogen desorption kinetics of the alloys are considered to be ascribed to the decreased hydrogen desorption activation energy caused by increasing Ni content and milling time.

The determination of thermal junction potential difference

A novel method has been designed and exploited to determine the thermal junction potential difference(TJPD) between two acids or alkalies of the same composition but with different temperature. The absolute value of measured TJPD between two strong acids(or alkalies) maintained at different temperatures increases with increasing of the temperature difference between the two electrolytes over the range from 0 to 40 °C. In strong acids, the hot end always has the lower potential while in strong alkalies, the cold end has the lower potential. This is because the ions of fast diffusion rate contribute most to the TJPD. Our results demonstrate the importance of the correction for TJPD in deriving the kinetic parameters when studying the temperature effect on reaction kinetics.