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...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.展开更多
The classical crystallization theories proposed by Avrami, Evans, and Mandelkern wereextended to the nonisothermal situation. The expressions derived from the classical equations canbe expressed in either the differen...The classical crystallization theories proposed by Avrami, Evans, and Mandelkern wereextended to the nonisothermal situation. The expressions derived from the classical equations canbe expressed in either the differential form or the integral form. A method was provided so as toobtain the parameters characterizing the crystallization rate and mechanism from DSC curves withseveral constant heating or cooling rates. The rate constants of crystallization obtained from bothisothermal and nonisothermal curves of poly(ethylene terephthalate)were compared.展开更多
Biodegradable poly（butylene succinate） （PBS） and layered double hydroxide （LDH） nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within ...Biodegradable poly（butylene succinate） （PBS） and layered double hydroxide （LDH） nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy （TEM）, which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry （DSC） technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoeonversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.展开更多
A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibr...A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.展开更多
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 compou...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.展开更多
Considering both the effect of the nonisothermal nature of the interface as well as the effect of forced convection,an extended free dendritic growth model for binary alloys was proposed.Comparative analysis indicates...Considering both the effect of the nonisothermal nature of the interface as well as the effect of forced convection,an extended free dendritic growth model for binary alloys was proposed.Comparative analysis indicates that the effect of convection on solute diffusion is more remarkable compared with the ignorable effect of convection on thermal diffusion at low bath undercooling,due to the fact that solute diffusion coefficient is usually three orders of magnitude less than thermal diffusion coefficient.At high bath undercooling,the effect of convection on the dendritic growth is very slight.Furthermore,a satisfying agreement between the model predictions with the available experiment data for the Cu70Ni30 alloy was obtained,especially at low bath undercoolings,profiting from the higher values of interfacial migration velocity predicted by the present model with nonideal fluid case than that predicted by the one ignoring the effect of convection.展开更多
Nonisothermal crystallization behavior of poly(butylene adipate-co-terephthalate)(PBAT) synthesized via direct esterification and polycondensation reactions was investigated by the differential scanning calorimetry(DS...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.展开更多
A thermal via has been used to enhance the heat transfer through the printed circuit board (PCB). Because the thermal conductivity of a dielectric material is very low, the array of metal vias is placed to make therma...A thermal via has been used to enhance the heat transfer through the printed circuit board (PCB). Because the thermal conductivity of a dielectric material is very low, the array of metal vias is placed to make thermal paths in the PCB. This paper describes the numerical analysis of the PCB having metal vias and focuses on the heat transfer characteristics under the nonisothermal boundary conditions. The mathematical model of the PCB has the metal vias between two metal sheets. Under 2nd and 3rd kinds of boundary conditions, the temperature distribution is obtained numerically by changing the design parameters. The discussion is also made on the effective thermal conductivity of the PCB. In industry, the use of effective thermal conductivity is convenient for thermal engineers because it simplifies the calculation process, that is, the composite board can be modeled as a homogeneous medium. From the numerical results, it is confirmed that the placement of metal sheets and the population of metal vias are important factors to dominate the heat transfer characteristics of the PCB. It is also shown that although the nonisothermal boundary conditions are applied at the boundary surface, the temperature difference between the heated and the cooled section is almost uniform when the metal vias are populated densely with the metal sheets. In this case, the effective thermal conductivity of the PCB is found to be the same irrespective of the boundary conditions, that is, whether the isothermal or the nonisothermal boundary conditions are applied.展开更多
Binary alloy samples consisting of poly（phenylene sulfide） （PPS）/poly（ethylene terephthalate-co-cyclohexane 1,4-dimethanol terephthalate） （PETG） blend were prepared by the melt blending technology using a twin...Binary alloy samples consisting of poly（phenylene sulfide） （PPS）/poly（ethylene terephthalate-co-cyclohexane 1,4-dimethanol terephthalate） （PETG） blend were prepared by the melt blending technology using a twin-screw extruder. The nonisothermal crystallization kinetics of binary alloys made of poly（phenylene sulfide） （PPS） and poly（ethyleneco-cyclohexane 1,4-dimethanol terephthalate） （PETG） was studied by the differential scanning calorimetry （DSC） at different cooling rates. The test results revealed that the addition of PETG could shift the crystallization temperature of PPS toward the high-temperature direction. The nonisothermal crystallization kinetic parameters of the PPS/PETG alloy samples were calculated by the methods proposed by Avrami and Mo. Test results demonstrated that the PPS/PETG alloy could give birth to apparent secondary crystallization. The value of Avrami exponent was lower relatively, while Mo＇s method was more suited to the nonisothermal crystallization process of the PPS/PETG alloy.展开更多
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 va...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.展开更多
The kinetics of nonisothermal and isothermal crystallization of metallocene catalyzed and conventional polyethylenes has been studied by differential scanning calorimetry. Using Avrami equation, Ozawa theory and Mo Zh...The kinetics of nonisothermal and isothermal crystallization of metallocene catalyzed and conventional polyethylenes has been studied by differential scanning calorimetry. Using Avrami equation, Ozawa theory and Mo Zhishen method, the experimental data have been analyzed. It is shown that metallocene polyethylene possesses a higher rate of crystallization due to a higher stereoregularity of its molecular chains. Moreover, they have different nonisothermal crystallization mechanisms and identical isothermal crystallization mechanisms.展开更多
The nonisothermal effectiveness fcator for reaction with kinetics r=kc^m/(l+Kc)~a can be improved bycatalysts with nonuniform activity distribution.The optimal distribution function in one-dimensional modelwith which ...The nonisothermal effectiveness fcator for reaction with kinetics r=kc^m/(l+Kc)~a can be improved bycatalysts with nonuniform activity distribution.The optimal distribution function in one-dimensional modelwith which the effectiveness factor can be maximized is a δ-function which means that the activity of thecatalyst should be concentrated on a layer with negligible thickness in a precise locationfrom the centerof pellets.The general equations for predicting the value ofand maximum effectiveness factor as a functionof thermodynamic,kinetic and transport parameters are derived and they can be given explicitly in the case ofa=O,m=a or isothermal reaction.An active layer with definite thickness and a deviation from the optimal locationboth decrease thevalue of the effectiveness factor.It has been shown numerically that the effectiveness factor decreases slightlywith an active layer at the inner side of x but seriously at outer side.展开更多
Based on two preconditions, the local thermal equilibrium is satisfied and emissivities donot change with temperature, the concept of component effective emissivity of nonisothermal mixed pixel has been put forward an...Based on two preconditions, the local thermal equilibrium is satisfied and emissivities donot change with temperature, the concept of component effective emissivity of nonisothermal mixed pixel has been put forward and then the radiant directionality model of nonisothermal mixed pixel constructed from it. Our study shows that the component effective emissivity is associated with geometric structure, optical properties of target, and viewing angle, but does not depend on the component temepratures. The component temperatures can only change the ratio of component radiance to the total radiance of the mixed-pixel. The total effective emissivity of this pixel is the complement of its directional-hemisphere reflectance. After the simulation of component effective emissivity of the discrete cones and continuous vegetation canopy (winter wheat) by the Monte Carlo method, our model of radiant directionality of nonisothermal mixed pixel have been proved by lab and field measurements.展开更多
In this paper we consider mixed finite element methods for second order elliptic problems. In the case of the lowest order Brezzi-Douglas-Marini elements （if d = 2） or Brezzi- Douglas-Duran-Fortin elements （if d = ...In this paper we consider mixed finite element methods for second order elliptic problems. In the case of the lowest order Brezzi-Douglas-Marini elements （if d = 2） or Brezzi- Douglas-Duran-Fortin elements （if d = 3） on rectangular parallelepipeds, we show that the mixed method system, by incorporating certain quadrature rules, can be written as a simple, cell-centered finite difference method. This leads to the solution of a sparse, positive semidefinite linear system for the scalar unknown. For a diagonal tensor coefficient, the sparsity pattern for the scalar unknown is a five point stencil if d = 2, and seven if d = 3. For a general tensor coefficient, it is a nine point stencil, and nineteen, respectively. Applications of the mixed method implementation as finite differences to nonisothermal multiphase, multicomponent flow in porous media are presented.展开更多
A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction...A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction of SnO2 are large, and suggest CH4 :SnO2 = 2:1 as the feasible reduction condition for achieving high purities of syngas and avoiding vaporization of produced Sn. Subsequently, the amount of H2 and energetic upgrade factors under different oxidation conditions are compared, in which excess water vapor is found beneficial for hydrogen production and fuel energetic upgradation. Moreover, the effect of incom plete recovery of SnO2 on the subsequent cycle is underscored and explained. After accounting for factors such as isothermal operation and cycle stability, CH4 :SnO2 = 2:1 and H2O:Sn = 4:1 are suggested for highest solar-to-fuel efficiency of 46.1% at nonisothermal condition, where the reduction and oxidation temperature are 1400 and 600 K, respectively.展开更多
In order to better understand the thermodynamic properties of magnesium oxysulfate(MOS)cement,pure reagent was analyzed to prepare magnesium sulfide cement,non-isothermal kinetics calculation of the main hydration pro...In order to better understand the thermodynamic properties of magnesium oxysulfate(MOS)cement,pure reagent was analyzed to prepare magnesium sulfide cement,non-isothermal kinetics calculation of the main hydration products was also carried out,and the conversion process of magnesium sulfide cement 517 phase at different temperatures was investigated.Composition of magnesium sulfide cement prepared was measured by XRD technique,and decomposed by a comprehensive thermal analyzer,and DSC curves of magnesium sulfide cement under different temperature rising rates were processed by Kinssinger method and Dolye-Ozawa method.According to the TG-DSC curves of magnesium sulfide cement,the thermal decomposition reaction process can be divided into five stages under normal conditions.The DSC curve was processed by Kinssinger method and Dolye-Ozawa method,and the kinetic analysis was carried out to calculate the 517 phase activation energy of magnesium sulfide cement.The three stages correspond to different activation energies.Therefore,flame retardant mechanism and thermal decomposition mechanism of magnesium sulfide cement based materials are deduced.展开更多
The influence of Ultrafine Full-Vulcanized Acrylate Powdered Rubber(UFAPR) on the isothermal crystallization kinetics and nonisothermal crystallization behavior of PA6 has been studied by means of DSC. The results sho...The influence of Ultrafine Full-Vulcanized Acrylate Powdered Rubber(UFAPR) on the isothermal crystallization kinetics and nonisothermal crystallization behavior of PA6 has been studied by means of DSC. The results show that with the introduction of a small amount of UFAPR, the crystallization rate of PA6 can be increased obviously, and the crystallization temperature range can be augmented and the crystallite size distribution of the crystal can be narrowed down. The change of free energy perpendicular to the crystal nucleus, which has been calculated according to the Hoffman theory, is consistent with the result of Avrami′s equation. The unit surface free energy of the radial-developing crystal spherulite decreases while the crystallization rate of PA6 increases with the introduction of UFAPR. Meanwhile, it is shown by means of the polarizing microscope(PLM) that the crystal size drops down and the number of the crystal grains augments with the addition of UFAPR, which shows that UFAPR can function as a nucleating agent.展开更多
Effects of branches on the crystallization kinetics of polypropylene-g-polystyrene （PP-g-PS） and polypropylene-g- poly（n-butyl acrylate） （PP-g-PnBA） graft copolymers with well-defined molecular structures were s...Effects of branches on the crystallization kinetics of polypropylene-g-polystyrene （PP-g-PS） and polypropylene-g- poly（n-butyl acrylate） （PP-g-PnBA） graft copolymers with well-defined molecular structures were systematically investigated by DSC. The Avrami equation was used to analyze the isothermal crystallization process, while the analysis of nonisothermal crystallization process was based on the Jeziorny-modified Avrami model and Mo model. The kinetics results of isothermal and nonisothermal crystallization verified the peculiar effects of branches on the crystallization process of PP backbones in PP-g-PS and PP-g-PnBA graft copolymers： on one hand, the interaction between branches （n-n interaction between PS branches, or dipole-dipole interaction between PnBA branches） restrained the mobility and reptation ability of the PP backbones, which hindered the crystallization process; on the other hand, the heterogeneous nucleation effect resulting from the branched structure and fluctuation-assisted nucleation mechanism （caused by microphase separation between the PS or PnBA rich phase and the PP rich phase） became more pronounced with increasing branch length, which facilitated the crystallization process.展开更多
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 decompo...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.展开更多
基金the National Natural Science Foundation of China(No.20573098)the Foundation of Key Laboratory of Science and Technology for National Defence of Propellant and Explosive of China(No.9140C3503020605).
文摘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.
基金This work was supported by the Tianjin Youth Science Foundation for the 21th Century,Tianjin,China.
文摘The classical crystallization theories proposed by Avrami, Evans, and Mandelkern wereextended to the nonisothermal situation. The expressions derived from the classical equations canbe expressed in either the differential form or the integral form. A method was provided so as toobtain the parameters characterizing the crystallization rate and mechanism from DSC curves withseveral constant heating or cooling rates. The rate constants of crystallization obtained from bothisothermal and nonisothermal curves of poly(ethylene terephthalate)were compared.
基金supported by the National High Technology Research and Development Program of China (863 Program No. 2009AA03Z319)the National Natural Science Foundation of China (Nos. 30870633, 31000427)the Fundamental Research Funds for the Central Universities (DUT12JB09)
文摘Biodegradable poly（butylene succinate） （PBS） and layered double hydroxide （LDH） nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy （TEM）, which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry （DSC） technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoeonversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.
基金Supported by the National Science Funds for Distinguished Young Scholars(No.5 0 12 5 312 ) Special Funds for MajorState Basic Research Project of China(No.G19990 6 4 80 0 ) and Key Program of the National Natural Science Foundation ofChina(No.5 0 1
文摘A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.
基金Supported by the National Natural Science Foundation of China(No20773034)the Natural Science Foundation of Hebei Province, China(NoB2007000237)+2 种基金Hebei Science and Technology Department(No07215120)Hebei Normal University (NosL2006Z06 and L2005Y12)Handan College(No2006004)
文摘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.
基金the financial supports from the National Natural Science Foundation of China(No.51671075)the Heilongjiang Postdoctoral Fund for Scientific Research Initiation(No.LBH-Q16118)the Fundamental Research Foundation for Universities of Heilongjiang Province,China(No.LGYC2018-JC004).
文摘Considering both the effect of the nonisothermal nature of the interface as well as the effect of forced convection,an extended free dendritic growth model for binary alloys was proposed.Comparative analysis indicates that the effect of convection on solute diffusion is more remarkable compared with the ignorable effect of convection on thermal diffusion at low bath undercooling,due to the fact that solute diffusion coefficient is usually three orders of magnitude less than thermal diffusion coefficient.At high bath undercooling,the effect of convection on the dendritic growth is very slight.Furthermore,a satisfying agreement between the model predictions with the available experiment data for the Cu70Ni30 alloy was obtained,especially at low bath undercoolings,profiting from the higher values of interfacial migration velocity predicted by the present model with nonideal fluid case than that predicted by the one ignoring the effect of convection.
文摘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.
文摘A thermal via has been used to enhance the heat transfer through the printed circuit board (PCB). Because the thermal conductivity of a dielectric material is very low, the array of metal vias is placed to make thermal paths in the PCB. This paper describes the numerical analysis of the PCB having metal vias and focuses on the heat transfer characteristics under the nonisothermal boundary conditions. The mathematical model of the PCB has the metal vias between two metal sheets. Under 2nd and 3rd kinds of boundary conditions, the temperature distribution is obtained numerically by changing the design parameters. The discussion is also made on the effective thermal conductivity of the PCB. In industry, the use of effective thermal conductivity is convenient for thermal engineers because it simplifies the calculation process, that is, the composite board can be modeled as a homogeneous medium. From the numerical results, it is confirmed that the placement of metal sheets and the population of metal vias are important factors to dominate the heat transfer characteristics of the PCB. It is also shown that although the nonisothermal boundary conditions are applied at the boundary surface, the temperature difference between the heated and the cooled section is almost uniform when the metal vias are populated densely with the metal sheets. In this case, the effective thermal conductivity of the PCB is found to be the same irrespective of the boundary conditions, that is, whether the isothermal or the nonisothermal boundary conditions are applied.
文摘Binary alloy samples consisting of poly（phenylene sulfide） （PPS）/poly（ethylene terephthalate-co-cyclohexane 1,4-dimethanol terephthalate） （PETG） blend were prepared by the melt blending technology using a twin-screw extruder. The nonisothermal crystallization kinetics of binary alloys made of poly（phenylene sulfide） （PPS） and poly（ethyleneco-cyclohexane 1,4-dimethanol terephthalate） （PETG） was studied by the differential scanning calorimetry （DSC） at different cooling rates. The test results revealed that the addition of PETG could shift the crystallization temperature of PPS toward the high-temperature direction. The nonisothermal crystallization kinetic parameters of the PPS/PETG alloy samples were calculated by the methods proposed by Avrami and Mo. Test results demonstrated that the PPS/PETG alloy could give birth to apparent secondary crystallization. The value of Avrami exponent was lower relatively, while Mo＇s method was more suited to the nonisothermal crystallization process of the PPS/PETG alloy.
基金This work was supported by the National Natural Science Foundation of China(No.52004044)the Natural Science Foundation of Chongqing,China(Nos.cstb2022nscqmsx0801 and cstc2021jcyj-msxmx0882)+2 种基金the Foundation of Chongqing University of Science and Technology(No.ckrc2022030)the Graduate Research Innovation Project of Chongqing University of Science and Technology(No.YKJCX2220216)the National Undergraduate Training Program for Innovation and Entrepreneurship(No.202311551007).
文摘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.
文摘The kinetics of nonisothermal and isothermal crystallization of metallocene catalyzed and conventional polyethylenes has been studied by differential scanning calorimetry. Using Avrami equation, Ozawa theory and Mo Zhishen method, the experimental data have been analyzed. It is shown that metallocene polyethylene possesses a higher rate of crystallization due to a higher stereoregularity of its molecular chains. Moreover, they have different nonisothermal crystallization mechanisms and identical isothermal crystallization mechanisms.
文摘The nonisothermal effectiveness fcator for reaction with kinetics r=kc^m/(l+Kc)~a can be improved bycatalysts with nonuniform activity distribution.The optimal distribution function in one-dimensional modelwith which the effectiveness factor can be maximized is a δ-function which means that the activity of thecatalyst should be concentrated on a layer with negligible thickness in a precise locationfrom the centerof pellets.The general equations for predicting the value ofand maximum effectiveness factor as a functionof thermodynamic,kinetic and transport parameters are derived and they can be given explicitly in the case ofa=O,m=a or isothermal reaction.An active layer with definite thickness and a deviation from the optimal locationboth decrease thevalue of the effectiveness factor.It has been shown numerically that the effectiveness factor decreases slightlywith an active layer at the inner side of x but seriously at outer side.
文摘Based on two preconditions, the local thermal equilibrium is satisfied and emissivities donot change with temperature, the concept of component effective emissivity of nonisothermal mixed pixel has been put forward and then the radiant directionality model of nonisothermal mixed pixel constructed from it. Our study shows that the component effective emissivity is associated with geometric structure, optical properties of target, and viewing angle, but does not depend on the component temepratures. The component temperatures can only change the ratio of component radiance to the total radiance of the mixed-pixel. The total effective emissivity of this pixel is the complement of its directional-hemisphere reflectance. After the simulation of component effective emissivity of the discrete cones and continuous vegetation canopy (winter wheat) by the Monte Carlo method, our model of radiant directionality of nonisothermal mixed pixel have been proved by lab and field measurements.
文摘In this paper we consider mixed finite element methods for second order elliptic problems. In the case of the lowest order Brezzi-Douglas-Marini elements （if d = 2） or Brezzi- Douglas-Duran-Fortin elements （if d = 3） on rectangular parallelepipeds, we show that the mixed method system, by incorporating certain quadrature rules, can be written as a simple, cell-centered finite difference method. This leads to the solution of a sparse, positive semidefinite linear system for the scalar unknown. For a diagonal tensor coefficient, the sparsity pattern for the scalar unknown is a five point stencil if d = 2, and seven if d = 3. For a general tensor coefficient, it is a nine point stencil, and nineteen, respectively. Applications of the mixed method implementation as finite differences to nonisothermal multiphase, multicomponent flow in porous media are presented.
基金supported by the National Key R&D Program of China (Grant no. 2018YFB1502005)the National Natural Science Foundation of China (Grant nos. 51476163 , 51806209 and 81801768)Institute of Electrical Engineering, Chinese Academy of Sciences (No.Y770111CSC)
文摘A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction of SnO2 are large, and suggest CH4 :SnO2 = 2:1 as the feasible reduction condition for achieving high purities of syngas and avoiding vaporization of produced Sn. Subsequently, the amount of H2 and energetic upgrade factors under different oxidation conditions are compared, in which excess water vapor is found beneficial for hydrogen production and fuel energetic upgradation. Moreover, the effect of incom plete recovery of SnO2 on the subsequent cycle is underscored and explained. After accounting for factors such as isothermal operation and cycle stability, CH4 :SnO2 = 2:1 and H2O:Sn = 4:1 are suggested for highest solar-to-fuel efficiency of 46.1% at nonisothermal condition, where the reduction and oxidation temperature are 1400 and 600 K, respectively.
基金Fund by the National Natural Science Foundation of China (No.51778101)the General Program (Key Program,Major Research Plan)of National Natural Science Foundation of China+2 种基金the National Key R&D Program (No.2020YFC1909304)the National Program on Key Basic Research Project of Chinathe Joint Fund Project of National Natural Fund of China (U1908227)。
文摘In order to better understand the thermodynamic properties of magnesium oxysulfate(MOS)cement,pure reagent was analyzed to prepare magnesium sulfide cement,non-isothermal kinetics calculation of the main hydration products was also carried out,and the conversion process of magnesium sulfide cement 517 phase at different temperatures was investigated.Composition of magnesium sulfide cement prepared was measured by XRD technique,and decomposed by a comprehensive thermal analyzer,and DSC curves of magnesium sulfide cement under different temperature rising rates were processed by Kinssinger method and Dolye-Ozawa method.According to the TG-DSC curves of magnesium sulfide cement,the thermal decomposition reaction process can be divided into five stages under normal conditions.The DSC curve was processed by Kinssinger method and Dolye-Ozawa method,and the kinetic analysis was carried out to calculate the 517 phase activation energy of magnesium sulfide cement.The three stages correspond to different activation energies.Therefore,flame retardant mechanism and thermal decomposition mechanism of magnesium sulfide cement based materials are deduced.
基金Supported by the National Natural Science Foundation of China( No.5 99730 0 3)
文摘The influence of Ultrafine Full-Vulcanized Acrylate Powdered Rubber(UFAPR) on the isothermal crystallization kinetics and nonisothermal crystallization behavior of PA6 has been studied by means of DSC. The results show that with the introduction of a small amount of UFAPR, the crystallization rate of PA6 can be increased obviously, and the crystallization temperature range can be augmented and the crystallite size distribution of the crystal can be narrowed down. The change of free energy perpendicular to the crystal nucleus, which has been calculated according to the Hoffman theory, is consistent with the result of Avrami′s equation. The unit surface free energy of the radial-developing crystal spherulite decreases while the crystallization rate of PA6 increases with the introduction of UFAPR. Meanwhile, it is shown by means of the polarizing microscope(PLM) that the crystal size drops down and the number of the crystal grains augments with the addition of UFAPR, which shows that UFAPR can function as a nucleating agent.
基金financially supported by the National Natural Science Foundation of China for the projects(Nos.51233005 and 51073149)
文摘Effects of branches on the crystallization kinetics of polypropylene-g-polystyrene （PP-g-PS） and polypropylene-g- poly（n-butyl acrylate） （PP-g-PnBA） graft copolymers with well-defined molecular structures were systematically investigated by DSC. The Avrami equation was used to analyze the isothermal crystallization process, while the analysis of nonisothermal crystallization process was based on the Jeziorny-modified Avrami model and Mo model. The kinetics results of isothermal and nonisothermal crystallization verified the peculiar effects of branches on the crystallization process of PP backbones in PP-g-PS and PP-g-PnBA graft copolymers： on one hand, the interaction between branches （n-n interaction between PS branches, or dipole-dipole interaction between PnBA branches） restrained the mobility and reptation ability of the PP backbones, which hindered the crystallization process; on the other hand, the heterogeneous nucleation effect resulting from the branched structure and fluctuation-assisted nucleation mechanism （caused by microphase separation between the PS or PnBA rich phase and the PP rich phase） became more pronounced with increasing branch length, which facilitated the crystallization process.
文摘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.
