Non-isothermal kinetic analysis of thermal dehydration of La_2(CO_3)_3·3.4H_2O in air

The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characterized by XRD, FTIR and DTA-TG. The kinetics of dehydration of La2（CO3）3·3.4H2O in the temperature range of 30-366 °C was investigated under non-isothermal conditions. Flynn-Wall-Ozawa and Friedman isoconversion methods were used to calculate the activation energy and analyze the reaction steps; multivariate non-linear regression program was applied to determine the most probable mechanism and the kinetic parameters. The results show that the thermal dehydration of La2（CO3）3·3.4H2O is a kind of three-step competitive reaction, and controlled by an n-order initial reaction followed by n-order competitive reaction（FnFnFn model）. The activation energy matching with the most probable model is close to value obtained by Friedman method. The fitting curves match the original TG-DTG curves very well.

Non-Isothermal Kinetic Analysis of Thermal Decomposition of the Ca-Bentonite from Santai, China

The thermal decompositions of Ca-bentonites (CaB) from Santai ,Shichuan Province, China over the temperature rage of 30-1100℃ were investigated by simultaneous thermal analyzer. Non-isothermal Kinetic analysis were employed to study the thermal decomposition mechanism by using Netzsch Thermokinetics software. The dependence of the activation energy on conversion degree were evaluated by isoconversional methods. The probably mechanism and the corresponding kinetic parameters were determined by multivariate non-linear regression program.

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.

Thermal Degradation and Decomposition Kinetics of Freeze Dried Cow and Camel Milk as well as Their Constituents

A study was conducted to evaluate thermal properties and degradation kinetic parameters of FD cow milk and camel milk powder. FT-IR was used to confirm the fat removal from the whole milk powder. Differential Scanning Calorimetry （DSC） was used to study the thermal transitions. DSC thermograms of WMP showed a two-step endotherm, the former at lower temperatures （cow milk 16-35 ℃, camel milk 25-60 ℃） and the later at higher temperatures （cow milk 75-125 ℃, camel milk 90-160 ℃）. The main difference observed between cow and camel milk was peak maximum temperature for fat melting, AH and other decomposition temperatures. The enthalpy of fat melting was 2.314 J/g and 3.397 J/g for cow and camel milk respectively. Thermogravimetric Analysis （TGA）/derivative thermogravimetric analysis （DTG） also showed two steps degradation. The first step involves lactose degradation and second step corresponds to combined degradation of protein and fat. Hence logβ vs 1000/T was plotted separately for individual components to determine cumulative value of activation energy using Flynn-Wall-Osawa method.

Thermal Analysis of Composite Cements

The hydration of cement compounds gives hydrated compounds, which allow linking together, the different particles and aggregate of cement, and gives the concrete the required qualities. The dynamics of hydration reactions will depend on many factors, such as the fineness of cement, the ratio w/c during hydration, temperature, mixing technique, and the presence of additives in blended cement, as pozzolan, tuff and slag from blast furnaces. We studied the thermal and kinetic reactions of Portland cement hydration, and its variants with different additions using a differential scanning calorimetric analysis. The parameters from these models of curves allow us to evaluate the enthalpies, and the degree of progression of this blended cement, and finally determine their activation energies. We can say that the hydration of Portland cement is due to a series of reactions as （ C3S,C2S,C3A and C4AF reactions with water） and each of them, has its own kinetic, the experimental measurement of the heat of hydration, allows us to represent the overall kinetics of these reactions values of activation energy, they are therefore apparent and global energy. In our experiments, significant differences in these physicochemical parameters were observed, depending on the additive used.

Evaluation on the Thermal Stability and Hazards Behaviors of ADVN Using Green Thermal Analysis Approach

ADVN （2,2＇-Azobis （2,4-dimethyl） valeronitrile）, a free radical initiator, is widely applied for the polymerization reaction of polymers in the chemical industries. When ADVN releases free radical during the decomposition process, it can accompany abundant heat and huge pressure to increase the possibility of thermal runaway and hazard, causing unacceptable thermal explosion or fire accidents. To develop an inherently safer process for ADVN, the thermal stability parameters of ADVN were obtained to investigate thermal decomposition characteristics using a DSC （differential scanning calorimetry） and TG （thermogravimetry）. We used various kinetic models to completely depict the kinetic behavior and determine the thermal safety parameters for ADVN. The green thermal analysis approach could be used to substitute for complicated procedures and large-scale experiments of traditional thermal analysis methods, avoiding environmental pollution and energy depletion.

Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices

This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis(STA) and differential scanning calorimetry(DSC) to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis(TGA) indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn—Wall—Ozawa(FWO) and Kissinger-Akahira-Sunose(KAS)methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.

Pyrolysis Characteristics and Thermal Kinetics of Degradable Films

Developing degradable films is an important means for resolving the problem of film pollution; however, in recent years, there have been only few studies related to the thermal analysis of degradable plastic films. This research detailed the composition and pyrolysis of one kind of ordinary and three kinds of degradable plastic films using the differential thermal analysis （DTA） technique. The results showed that degradable films and ordinary film had similar DTA curves, which reflected their similar compositions; however, small differences were measured, which were due to the added constituents of the degradable films. The pyrolysis reaction orders of each film were about 0.93. The pyrolysis activation energies and pre-exponential factors followed the order of ordinary film 〉 photodegradable film 〉 photodegradable calcium carbonate film 〉 biodegradable film. The results of this research laid the foundation for new theories for harnessing soil pollution caused by plastic films.

Isoconversional kinetic analysis of decomposition of bastnaesite concentrates with calcium hydroxide

Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.

THERMAL DEGRADATION OF POLY(ARYLENE SULFIDE SULFONE)/NMETHYLPYRROLIDONE CRYSTAL SOLVATE

The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.

Thermal Stability and Decomposition Kinetics of Polysuccinimide

The thermal stability and decomposition kinetics of polysuccinimide (PSI) were investigated using analyzer DTG-60 under high purity nitrogen atmosphere at different heating rates (3, 6, 9, 12 K/min). The thermal decomposition mechanism of PSI was determined by Coats-Redfern method. The kinetic parameters such as activation energy (E), pre-exponential factor (A) and reaction order (n) were calculated by Flynn-Wall-Ozawa and Kissinger methods. The results show that the thermal decomposition of PSI under nitrogen atmosphere mainly occurs in the temperature range of 619.15-693.15 K, the reaction order (n) was , the activation energy (E) and pre-exponential factor (A) were obtained to be 106.585 kJ/mol and 4.644 × 109 min-1, the integral and differential forms of the thermal decomposition mechanism of PSI were found to be and , respectively. The results play an important role in understanding the thermodynamic properties of polysuccinimide.

Thermal Dehydration Kinetics of Gypsum and Borogypsum under Non-isothermal Conditions

Thermal dehydration of gypsum and borogypsum was investigated under nonisothermal conditions in air by using simultaneous thermogravimetric-differential thermal analyzer. Nonisothermal experiments were carried out at various linear heating rates. Kinetics of dehydration in the temperature range of 373-503 K were evaluated from the DTA (differential thermal analysis)-TGA (thermogravimetric analysis) data by means of Coats-Redfern,Kissinger and Doyle Equations. Values of the activation energy and the pre-exponential factor of the dehydration were calculated. The results of thermal experiments and kinetic parameters indicated that borogypsum is similar to gypsum from dehydration mechanism point of view although it consists of boron and small amount of alkali metal oxides.

Thermal Degradation Studies of Some Strongly Acidic Cation Exchange Resins

The thermal degradation of some sulfonic cationites namely Amberlite IR-120, Indion-223 and In-dion-225 was investigated using instrumental techniques like thermal analysis (TG) and Scanning Electron Microscopy (SEM). Fourier Transform Infrared Spectroscopy (FTIR) was used to characterize the resins degradation steps. The sulfonic cationites undergo degradation through dehydration, followed by decomposition of sulfonic acid functional groups liberating SO2. The thermogravimetric analysis of above cationites at higher temperature up to 520oC, show mass loss of 61.61% and 25.43% respectively for Indion-223 and Indion-225, while Amberlite IR-120 cationite get burned off completely.

Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

The kinetics of removal of loss on ignition(LOI) by thermal decomposition of hydrated minerals present in natural iron ores(i.e.,kaolinite,gibbsite,and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor(FBR) using isothermal methods of kinetic analysis.Experiments in the FBR in batch processes were carried out at different temperatures(300 to 1200°C) and residence time(1 to 30 min) for four different iron ore samples with various LOIs(2.34wt% to 9.83wt%).The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity(Umf).We observed that,below a certain critical temperature,the FBR did not effectively reduce the LOI to a desired level even with increased residence time.The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100°C.The kinetics for low-LOI samples(<6wt%) indicates two different reaction mechanisms in two temperature regimes.At lower temperatures(300 to 700°C),the kinetics is characterized by a lower activation energy(diffusion-controlled physical moisture removal),followed by a higher activation energy(chemically controlled removal of LOI).In the case of high-LOI samples,three different kinetics mechanisms prevail at different temperature regimes.At temperature up to 450°C,diffusion kinetics prevails(removal of physical moisture);at temperature from 450 to 650°C,chemical kinetics dominates during removal of matrix moisture.At temperatures greater than 650°C,nucleation and growth begins to influence the rate of removal of LOI.

THERMAL DEGRADATION OF THERMOTROPIC LIQUID CRYSTALLINE TERPOLYESTERS BASED ON VANILLIC ACID, p-HYDROXYBENZOIC ACID AND POLY(ETHYLENE TEREPHTHALATE )

Nine thermotropic liquid crystalline terpolyesters based on vaniUic acid(V), p-hydroxybenzoic acid(H) and poly(ethylene terephthalate)(E) were investigated by thermogravimetry to ascertain their thermostability and the kinetic parameters for thermal degradation. Overall activation energy data of the degradation had been calculated over the range 5 ～ 70% weight loss. The temperatures and the activation energy of the degradation lie in the ranges of 384 ～ 394 ℃ at a heating rate of 1℃/min and 176 ～ 205 KJ/mol at the weight loss of 5%, respectively, which suggests that the terpolyesters have good thermostability.

Thermal Decomposition and Kinetics of Rigid Polyurethane Foams Derived from Sugarcane Bagasse

Rigid polyurethane foams were fabricated with five kinds of liquefied sugarcane bagasse polyols （LBP）. The foams derived from sugarcane bagasse were investigated by thermogravimetric analysis （TGA）, and the thermal degradation data were analyzed using the Coast-Redfern method and Ozawa method to obtain the reaction order and activation energy. The results indicate that the sugarcane bagasse-foams exhibit an excellent heat-resistant property, whereas their pyrolysis procedures are quite complicated. The reaction as first order only takes place from 250 to 400 ℃, and the pyrolysis activation energies vary from 20 to 140 kJ/mol during the whole pyrolysis process.

Thermal Decomposition Kinetics of Ursodeoxycholic Acid Drug Crystal

The crystallization of ursodeoxycholic acid drug crystals in gel by reduction of solubility method is the first of its kind to be reported in literature. Monoclinic crystalline form of the structure was confirmed using single crystal X-ray diffraction analysis. This report deals with the kinetic analysis made from the thermogravimetric analysis/differential thermal analysis (TGA/DTA) data using Coats-Redfern (CR) relation. Thermodynamic parameters were also determined. Arrhenius equation for ursodeoxycholic acid was derived as k = 3.10 × 1010 e&minus;172581/RT mol&minus;1&bull;s&minus;1.

Thermal oxidation of two aviation synthetic lubricant base oils

The thermal degradation of two synthetic lubricants base oils, poly-a-olefins （PAO） and di-esters （DE）, was investigated under oxidative pyrolysis condition and their properties were characterized in simulated ＂areo-engine＂ by comparing the thermal stability and identifying the products of thermal decomposition as a function of exposure temperature. The characterization of the products were performed by means of Fourier transform infrared spectrometry （FTIR）, gas chromatography/mass spectrometry （GC/MS） and viscosity experiments. The results show that PAO has the lower thermal stability, being degraded at 200℃ different from 300 ℃ for DE. Several by-products are identified during the thermal degradation of two lubricant base oils. The majority of PAO products consist of alkenes and olefins, while more oxygen-contained organic compounds are detected in DE samples based on GC/MS analysis. The related reaction mechanisms are discussed based on the experimental results.

DSC ANALYSIS OF A CuZnAl TWO WAY SHAPE MEMORY ALLOY DURING AGEING

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Isochronal and isothermal crystallization in Zr_(55)Cu_(30)Ni_5Al_(10) bulk metallic glass

Non-isothermal crystallization transformation kinetics and isothermal crystallization kinetics in super-cooled liquid region（SLR） in Zr55Cu30Ni5Al10 bulk metallic glasses were studied by differential scanning calorimetry（DSC） and X-ray diffraction（XRD）.In isochronal mode,the average values of activation energy in Zr55Cu30Ni5Al10 bulk metallic glass determined by different models（Kissinger method,Flynn-Wall-Ozawa method and Augis-Bennett method） are in good agreement with each other.In addition,the isothermal transformation kinetics in Zr55Cu30Ni5Al10 bulk metallic glasses was described by the Johnson-Mehl-Avrami（JMA） model.For Zr55Cu30Ni5Al10 bulk metallic glass,the Avrami exponent n ranges from 2.2 to 2.9,indicating that crystallization mechanism in the bulk metallic glass was mainly diffusion-controlled;crystal growth is controlled by long range ordering diffusion in three-dimensional growth during isothermal crystallization process.The average value of activation energy in Zr55Cu30Ni5Al10 bulk metallic glass is 469 kJ/mol in isothermal transformation process.