Oxidation behavior of FeV_(2)O_(4)and FeCr_(2)O_(4)particles in the air:Nonisothermal kinetic and reaction mechanism

High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium vanadium slag.Herein,the nonisothermal oxidation behavior of FeV_(2)O_(4)and FeCr_(2)O_(4)prepared by high-temperature solid-state reaction was examined by thermogravimetry and X-ray diffraction(XRD)at heating rates of 5,10,and 15 K/min.The apparent activation energy was determined by the Kissinger-Akahira-Sunose(KAS)method,whereas the mechanism function was elucidated by the Malek method.Moreover,in-situ XRD was conducted to deduce the phase transformation of the oxidation mechanism for FeV_(2)O_(4)and FeCr_(2)O_(4).The results reveal a gradual increase in the overall apparent activation energies for FeV_(2)O_(4)and FeCr_(2)O_(4)during oxidation.Four stages of the oxidation process are observed based on the oxidation conversion rate of each compound.The oxidation mechanisms of FeV_(2)O_(4)and FeCr_(2)O_(4)are complex and have distinct mechanisms.In particular,the chemical reaction controls the entire oxidation process for FeV_(2)O_(4),whereas that for FeCr_(2)O_(4)transitions from a three-dimensional diffusion model to a chemical reaction model.According to the in-situ XRD results,numerous intermediate products are observed during the oxidation process of both compounds,eventually resulting in the final products FeVO_(4)and V2O_(5)for FeV_(2)O_(4)and Fe_(2)O_(3)and Cr_(2)O_(3)for FeCr_(2)O_(4),respectively.

Nonisothermal Kinetics of Dehydration Process of [Sm(m-ClBA)_3phen]_2·2H_2O and [Sm(p-ClBA)_3phen]_2·2H_2O

Compounds [Sm（m-CIBA）3phen]2.2H20 and [Sm（p-CIBA）3phen]2·2H20（m-CIBA=m-chlorobenzoate, pClBA=p-chlorobenzoate, phen=l,10-phenanthroline） were prepared. The dehydration processes and kinetics of these compounds were studied from the analysis of the DSC curves using a method of processing the data of thermal analysis kinetics. The Arrhenius equation for the dehydration process can be expressed as lnk=-38.65-243.90×l0^3/RT for [Sm（m-CIBA）3phen]2·2H2O, and lnk=38.70-172.22×103/RT for [Sm（p-CIBA）3phen]2·2H2O. The values of △H^1, △G^1, and △S^1 of dehydration reaction for the title comnonnds are determined respectively.

Thermal Behavior,Nonisothermal Decomposition Reaction Kinetics of Mixed Ester Double-base Gun Propellants

The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by thermogravimetry（TG） and differential thermogravimetry（DTG）, and differential scanning calorimetry（DSC） under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates and decomposes in the first stage, and nitrocellulose and centralite II（C2） decompose in the second stage. The mass loss, the DTG peak points, and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG. There is only one obvious exothermic peak in the DSC curves under the different pressures. With the increase in the furnace pressure, the peak temperature decreases, and the decomposition heat increases. With the increase in the content of TEGDN, the decomposition heat decreases at 0.1 MPa and rises at high pressure. The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures. The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as： dα/dt=1021.59（1-α）3e-2.60×104/T. The reaction mechanism of the process can be classified as chemical reaction. The critical temperatures of the thermal explosion（Tbe and Tbp） obtained from the onset temperature（Te） and the peak temperature（Tp） are 456.46 and 473.40 K, respectively. ΔS≠, ΔH≠, and ΔG≠ of the decomposition reaction are 163.57 J·mol^-1·K^-1, 209.54 kJ·mol^-1, and 133.55 kJ·mol^-1, respectively.

Nonisothermal Crystallization Kinetics of Poly(butylene adipate-co-terephthalate) Copolyester

Nonisothermal crystallization behavior of poly(butylene adipate-co-terephthalate)(PBAT) synthesized via direct esterification and polycondensation reactions was investigated by the differential scanning calorimetry(DSC).The Avrami equation modified by Jeziorny and the Z.S.Mo equation were employed to describe the non-isothermal crystallization kinetics of copolyester samples.The test results showed that the Avrami equation was successful in describing nonisothermal crystallization process of PBAT copolyesters.PBAT copolyester could give birth to secondary crystallization.The crystallization parameter(Zc) increased with an increasing cooling rate and the Avrami exponent(n) was around 2.3.For a given cooling rate,the value of Zc demonstrated a sagging trend with an increase in adipic acid(AA) content.The equation proposed by Z.S.Mo was successful in describing the nonisothermal crystallization kinetics of PBAT copolyesters.

Thermal Decomposition Kinetics of Ni(Ⅱ)Complex with Norfloxacin

The thermal decomposition of the 2H2O (NFA=C16H18FN3O3, norfloxacin) and its kinetics were studied under the nonisothermal condition in nitrogen by TGDTG and DTA methods. The intermediate and residue for each decomposition were identified from TG curve. The Achar method and the MadhusudananKrishnanNinan (MKN) method were used to analyze the nonisothermal kinetic data. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the third stage and the mathematical expressions for the kinetic compensation effects of the third stage were obtained.

Non-isothermal kinetics and characteristics of calcium carbide nitridation reaction with calcium-based additives

The nitridation reaction of calcium carbide and N_(2) at high temperatures is the key step in the production of lime-nitrogen.However,the challenges faced by this process,such as high energy consumption and poor product quality,are mainly attributed to the lack of profound understanding of the reaction.This study aimed to improve this process by investigating the non-isothermal kinetics and reaction characteristics of calcium carbide nitridation reaction at different heating rates(10,15,20,and 30℃·min^(-1))using thermogravimetric analysis.The kinetic equation for the nitridation reaction of additive-free calcium carbide sample was obtained by combining model-free methods and model-fitting method.The effect of different calcium-based additives(CaCl_(2) and CaF_(2))on the reaction was also investigated.The results showed that the calcium-based additives significantly reduced reaction temperature and activation energy E_(a) by about 40% with CaF_(2) and by 55%-60% with CaCl_(2).The reaction model f(α)was also changed from contracting volume(R3)to 3-D diffusion models with D3 for CaCl_(2) and D4 for CaF_(2).This study provides valuable information on the mechanism and kinetics of calcium carbide nitridation reaction and new insights into the improvement of the lime-nitrogen process using calcium-based additives.

Investigation on the thermal decomposition of aged La_2O_3

The thermal decomposition process of air-aged La203 in argon atmosphere was studied using nonisothermal TG-DSC. X-ray diffraction and TG-DSC analysis showed that the aged powder was composed of La（OH）3 with small amounts of oxycarbonate. The decomposition process of air-aged La2O3 involves the two-step decomposition of La（OH）3 and the decomposition of oxycarbonate. The kinetic analysis of the two-step decomposition of La（OH）3 was carried out using Coats-Redfern and isoconversion （Ozawa） methods. The kinetics of the two-step decomposition can be described in terms of the nucleation and growth model A （m=1.5, m is the model parameter） and A （m=2.5）, respectively. The apparent activation energy for the first step is 136-144 （Coats-Redfern） and 137-164 kJ/mol （isoconversion）. The apparent activation energy for the second step is 191-194 （Coats-Redfern） and 186-213 kJ/mol （isoconversion）.

Direct Synthesis, Crystal Structure and Thermal Kinetics of Supramolecular Complex [Co（H2O）6]·（Hnip）2·（H2nip）2·（DMA）2·（H2O）8 （nip=5-nitroisophthalate, DMA=CH3NHCH3）

The crystal of [Co（H2O）6]·（Hnip）2·（H2nip）2·（OMA）2·（H2O）8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012（1） nm, b=1.1378（2） nm, c=1.6612（3） nm, α= 84.92（3）°, β=85.19（3）°, γ=85.91（3）°, V= 1.3128（5） nm^3, Z=1, Dc= 1.573 g·cm^-3. Final R indices [1〉2σ（I）] are： R1 =0.0279, wR2=0.0765 while R indices for all data are： R1 =0.0327, wR2=0.0806. The Co coordination octahadra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods.