Standard-state entropies and their impact on the potential-dependent apparent activation energy in electrocatalysis

The apparent activation energy,Eapp,is a common measure in thermal catalysis to discuss the activity and limiting steps of catalytic processes on solid-state materials.Recently,the electrocatalysis community adopted the concept of Eappand combined it with the Butler-Volmer theory.Certain observations though,such as potential-dependent fluctuations of Eapp,are yet surprising because they conflict with the proposed linear decrease in Eappwith increasing overpotential.The most common explanation for this finding refers to coverage changes upon alterations in the temperature or the applied electrode potential.In the present contribution,it is demonstrated that the modulation of surface coverages cannot entirely explain potential-dependent oscillations of Eapp,and rather the impact of entropic contributions of the transition states has been overlooked so far.In the case of a nearly constant surface coverage,these entropic contributions can be extracted by a dedicated combination of Tafel plots and temperature-dependent experiments.

Determination of the Apparent Activation Energy of Concrete Carbonation

Accelerated carbonation experiments about the development of carbonation rates of ordinary Portland cement concrete under different artificial climates were carried out. Six water cement ratios and six climate condition combinations of temperature and relative humidity were used. Results indicate that changes of concrete carbonation rate with environmental temperature agree the Arrhenius law well, which suggests concrete carbonation rate has obvious dependence on temperature. The higher the temperature is, the more quickly the concrete carbonates, and at the same time it is also affected by environmental relative humidity. Thereafter, the apparent activation energy Ea of concrete carbonation reaction was obtained, ranging from 16.8 to 20.6 kJ/mol corresponding 0.35-0.74 water cement ratio, and lower water cement ratio will cause the apparent activation energy increase. Concrete carbonation rates will increase 1.1-1.69 times as temperature increase every 10 ℃ at the temperature range of 10 to 60 ℃.

Apparent Activation Energy of Concrete in Early Age Determined by Adiabatic Test

The apparent activation energy of concrete in early age was determined by adiabatic temperature rise test with different initial temperatures. The influence of mineral admixtures such as fly ash, slag and silica fume on the apparent activation energy of concrete was investigated. The equivalent age that expresses the maturity of concrete was calculated to evaluate the cracking risk of concrete in structures. The results reveal that a substitution of 20% fly ash for Portland cement obviously decreases the apparent activation energy of concrete, however, a substitution of 10% silica fume for Portland cement increases the apparent activation. Finite element method analysis of a simulating concrete wall shows that the concrete containing 20% fly ash has the lowest cracking risk.

Characteristics of Hydrogen Storage Alloy Mg_2Ni Produced by Hydriding Combustion Synthesis

A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.

SUPERPLASTICITY IN SiC_w/ZK60 COMPOSITE

The superplastic deformation behavior of SiCw/ZK60 composite was investigated at temperatures ranging from 573K to 723K and at initial strain rates ranging from 8.3x10-4s-1 to 8.3x10-2s-1. A maximum elongation of 200% with a m-value of 0.35 was obtained at 613K and a initial strain rate of 1.67x 10-2s-1. The apparent activation energy (98kJ/mol) approximates that for grain boundary diffusion (92kJ/mol) in magnesium. It is proposed that the dominant mechanism of superplastic deformation in the present composite is grain boundary sliding accommodated by diffusional transport, besides, interfacial sliding plays an important role in the superplastic deformation.

Hydration Characteristics of Sodium Sulfate Slag Cement System

The hydration characteristics by thermal analysis (DTA) were determined, and an isothermal calorimeter (IC) was used to study the pastes. The experimental results indicate: (1) The main hydration products of SSC are C-S-H (I) gel with a low Ca/Si ratio, crystalline Thomsonite-type and AFt-type phases containing certain alkali cations; (2) No phases of the AFm-type and high alkaline Ca (OH)(2) in SSC system could benefit the hydrated cements to improve its strength and durability; (3) Crystalline Thomsonite-type and AFt-type phases containing Na+ will greatly reduce free alkali and alleviate the harmness of alkali aggregate reaction (AAR) in SSC system; (4) Similar to ordinary Portland cement (OPC), the hydration process of SSC could be classified into five stage: initial, induction, acceleration, deceleration and decay; (5) Regardless of the activator used, the apparent activation energy is higher with the increased slag in cement system, and the rising temperature could promote the hydration of SSC.

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite（TTM） ironsand, which contains 11.41wt% TiO_2 and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence： Fe O ＋ FeTiO_3 → Fe_2 TiO_4 → FeTiO_3 → FeTi_2O_5 → TiO_2. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 k J·mol^（-1）.

Glass transition kinetics of La_(55)Al_(25)Ni_(10)Cu_(10) bulk metallic glass by electrical resistivity measurement

The glass transition behavior of La55A125-Ni10CU10 bulk metallic glass was investigated using elec-trical resistivity and differential-scanning calorimetry measurements. There are good agreements of the onset temperature （Tg-onset） and the end temperature （Tg-end） of the glass transition between the DSC curve and tempera-ture dependent electrical resistivity （TER） curve in the same heating rate. Kinetics of the glass transition is studied with the electrical resistivity data. The apparent activation energy of the glass transition （△Eg） is found to be 306.4 kJ.mol^-1. Fragility parameter D^＊ and VFT temper-ature To are 9.8 and 324.9 K, respectively.

Effect of trace calcium on melting behavior of Ag-Cu-Zn brazing alloy by thermal analysis kinetics

The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry （ DSC ） , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF2–CaO–SiO2-based slags

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO–SiO2–MgO–FeO–MnO–Al2O3–TiO2–CaF2 was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step（RCS） for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide（MnO）, the apparent activation energy of the demanganization reaction was estimated to be 189.46 kJ·mol^–1 in the current study, which indicated that the mass transfer of MnO in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the ＂specific reaction interface＂（SRI） value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.

Effect of Al2O3 on the viscosity of CaO-SiO2-Al2O3-MgO-Cr2O3 slags

We investigated the effect of Al2O3 content on the viscosity of CaO-SiO2-Al2O3-8wt%MgO-1wt%Cr2O3(mass ratio of CaO/SiO2 is 1.0,and Al2O3 content is 17wt%-29wt%)slags.The results show that the viscosity of the slag increases gradually with increases in the Al2O3 content in the range of 17wt%to 29wt%due to the role of Al2O3 as a network former in the polymerization of the aluminosilicate structure of the slag.With increases in the Al2O3 content from 17wt%to 29wt%,the apparent activation energy of the slags also increases from 180.85 to 210.23 kJ/mol,which is consistent with the variation in the critical temperature.The Fourier-transform infrared spectra indicate that the degree of polymerization of this slag is increased by the addition of Al2O3.The application of Iida’s model for predicting the slag viscosity in the presence of Cr2O3 indicates that the calculated viscosity values fit well with the measured values when both the temperature and Al2O3 content are at relatively low levels,i.e.,the temperature range of 1673 to 1803 K and the Al2O3 content range of 17wt%-29wt%in CaO-SiO2-Al2O3-8wt%MgO-1wt%Cr2O3 slag.

Influence of Sugar Filter Mud on Formation of Portland Cement Clinker

To explore the mechanisms of filter mud （FM） in the portland cement clinker formation, and to make effective use of FM in the cement production as lime-based raw materials, the influences of FM on the apparent activation energy of calcium carbonate decomposition, liquid phase amount, crystalline phase and tricalcium silicate polymorphism were investigated by TA, SEM and XRD. The experimental results show that FM can reduce apparent activation energy of calcium carbonate decomposition, and increase liquid phase amount. Appropriate FM replacement ratios are useful to promoting the C3S formation and heightening the C3S content. New phases of ct-C2S and C2S-0.5Ca3 （PO4）2 can be found in the clinkers while the ratios are above 15%. In addition, impurities in FM can induce the C3S polymorpb to transform. Key words： filter mud; apparent activation energy; liquid phase; mineral phase; tricalcium silicate polymorphism

Decomposition mechanisms and non-isothermal kinetics of LiHC_2O_4·H_2O

The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non-isothermal thermal decomposition of LiHC2O4?H2O; finally, the kinetic parameters of each reaction were also calculated herein.

STUDY OF RECOVERY IN DEFORMED Ni-Cr-Co SUPERALLOYS USING POSITRON ANNIHILATION

The recovery recrystallization of 3 deformed Ni-Cr-Co superalloys with different Co con- tents has been studied using positron annihilation technique and TEM.The alloys with low Co content have more defects occurred than ones with high Co content,and the former may be faster in dislocation recovery than the latter.Thus,the apparent activation energy of recrystallization increases with the increase of their Co content in alloys.The relationship be- tween apparent activation energy and stacking fault energy together with their effect on re- covery were also discussed.

Effect of melt cooling rate on glass transition kinetics and structural relaxation of Vit1 metallic glass

The thin ribbons and the bulk cylindrical rods with diameters of 2 mm and 10 mm of the Vit1 metallic glass(MG)were prepared by the single roller melt spinning method and the copper mold injection casting method,respectively.The cooling rates of the samples during melt solidification were evaluated.The glass transition behaviors of three groups of MG samples with different solidification cooling rates were studied by differential scanning calorimetry(DSC)at different heating rates.The effects of melt cooling rate on the glass transition kinetic parameters such as apparent activation energy(E)and fragility parameter(m)of the Vit1 MG were studied using the Kissinger and the Vogel-Fulcher-Tammann(VFT)equations.Additionally,the structural relaxation enthalpy(ΔHrel)of three groups of MG samples was quantitatively analyzed by DSC through multi-step temperature rise and fall measurements.Results show that the melt cooling rate(R)has a significant effect on the glass transition kinetics and the structural relaxation of the Vit1 MG.As R decreases in the order of magnitude,the glass transition temperature(Tg),E,m,andΔHrel of the Vit1 MG gradually decreases.Furthermore,in the range of the experimental cooling rates,E,m,andΔHrel all have an approximately linear relationship with lgR.

Thermal Analysis of Precipitate Dissolution in Binary Al-Li Alloy

In this paper,the activation energy for precipi- tate dissolution in binary AI-Li alloy has been in- vestigated by considering precipitate dissolution in Al-Li alloy,continuously heated as a thermally ac- tivated process.The proposed calculation was car- ried out by changing the scanning rate in DSC measurement.The results show that the formation of GP zone is easy because the activation energy for its dissolution is smaller than that for Li atom diffu- sion in the matrix.The δ′dissolution consists of two steps:the first step needs larger thermal activation to break down the superlattice structure,and the second is much easier like GP zone dissolution.The phase is the most stable,which needs much larger thermal activation to disappear.

Effects of Sequence Distribution and Physical Aging on Physical Properties of PES/PEES Random, Block, and Alternative Copolymers

The random, block, and alternative copolymers of poly ether sulfone（PES） and poly ether ether sulfone（PEES） were synthesized v/a three kinds of methods. The chemical structures of the three kinds of copolymers were characterized by ^13C NMR. Three kinds of PES/PEES copolymers（ Tg =215 ℃ ）, which were almost identical in composition but different in sequence distribution, were used. Their physical aging process was studied by differential scanning calorimetry（DSC） at three aging temperatures ranging between Tg -15 ℃ and Tg -25℃. The experimental results reveal that the alternative copolymer shows a lower enthalpy relaxation time 〈T〉 and apparent activation energy when compared with the random and block copolymers. The result of the electron-microscopy investigation of the three copolymers that were treated at 200 ℃ for 96 h indicates that the molecular aggregation of the copolymers changed from a randomly coiled amorphous phase to an ordered phase, and the ordered structure of the alternative copolymer was more distinct than that of the random phase. The experimental results of this study suggest that the motion of the sagments is affected by the different molecular-chain sequence distribution.

Kinetics of Autoclave Curing Process on Autoclaved Aerated Concrete with Magnetite Tailings

Lightweight and energy saving autoclaved aerated concrete(AAC) acting as a newbuilding material were prepared by using magnetite tailings from iron ore as main rawmaterials,and the purpose of comprehensive utilization of tailings resources was to improve their utilization efficiency.The effects of curing system on AAC product performance were discussed.The autoclave curing reaction kinetics was studied as well as the generated amount of hydration product trends over autoclave curing temperature and time were analyzed.The results indicated that the properties of AAC was in accordance with Chinese national standard the A3.5 B06 class of GB/T11968-2006 by prepared from magnetite tailing as the main rawmaterials.Meanwhile,autoclave curing process was controlled by the diffusion velocity through the products ' layers of reactants,and the apparent activation energy of autoclave curing process was 19.269 k J/mol.Compressive strength of aerated concrete is improved by mutual cementation between the appropriate amount of calcium silicate hydrate and tobermorite crystal.

Crystal Structure and Thermal Decomposition Kinetics of 3-Nitro-4-diazo-5-oxygenpyrazole

A novel compound 3-nitro-4-diazo-5-oxypyrazole was synthesized by the nitration of 4-amino-3,5-dinitropyrazole using nitrification agents of fuming nitric acid and trifluoroacetic anhydride. The compound was purified by column chromatography and characterized by IR, NMR, MS and elemental analysis. Two different single crystals obtained by culturing with ethyl acetate as a solvent were measured by X-ray single-crystal diffractometer. The molecular weight of C3HN5O3 is 155.09 and the two crystals belong to monoclinic system, space groups P21/n and P21/c. For 1： a = 5.5007（2）, b = 9.0691（4）, c = 11.4158（4） A, β = 92.710°, V = 568.85 A3, Z = 4, Dc = 1.811 g/cm3, μ = 0.162 mm-1, F（000） = 312 and the final deviation factor is 0.0213. Crystals 1 and 2 have similar unit cell parameters, except that a = 10.1828（12）, b = 5.5925（6）, c = 10.5574（10） A and β = 108.330（4）° in crystal 2. The thermal behavior of the compound was studied by TG-DSC and melting endothermic peak and decomposition exothermic peak are at 425.7 and 534.5 K in DSC curve. The activation energy and pre-exponential factor of the exothermic decomposition reaction of the title compound obtained by Kissinger method and Flynn-Wall-Ozawa method are 50.38 k J/mol, 4.59 × 1022 s^（-1） and 55.89 k J/mol.

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.