共查询到20条相似文献,搜索用时 31 毫秒
1.
The basic kinetic parameters of thermal polymerization of hexafluoropropylene, namely, general rate constants, degree of polymerization,
and their temperature and pressure dependences in the range of 230–290 °C and 2–12 kbar (200–1200 MPa) were determined. The
activation energy (E
act = 132±4 kJ mol−1) and activation volume (ΔV
0
≠ = −27±1 cm3 mol−1) were calculated. The activation energy of thermal initiation of polymerization was estimated. The reaction scheme based
on the assumption about a biradical mechanism of polymerization initiation was proposed. 相似文献
2.
S. -X. Wang Z. -C. Tan Y. -S. Li L. -X. Sun Y. Li 《Journal of Thermal Analysis and Calorimetry》2008,92(2):483-487
Synthesis, characterization and thermal analysis of polyaniline (PANI)/ZrO2 composite and PANI was reported in our early work. In this present, the kinetic analysis of decomposition process for these
two materials was performed under non-isothermal conditions. The activation energies were calculated through Friedman and
Ozawa-Flynn-Wall methods, and the possible kinetic model functions have been estimated through the multiple linear regression
method. The results show that the kinetic models for the decomposition process of PANI/ZrO2 composite and PANI are all D3, and the corresponding function is ƒ(α)=1.5(1−α)2/3[1−(1-α)1/3]−1. The correlated kinetic parameters are E
a=112.7±9.2 kJ mol−1, lnA=13.9 and E
a=81.8±5.6 kJ mol−1, lnA=8.8 for PANI/ZrO2 composite and PANI, respectively. 相似文献
3.
Fabiana S. Felix L. C. Cides da Silva L. Angnes J. R. Matos 《Journal of Thermal Analysis and Calorimetry》2009,95(3):877-880
The thermal decomposition of salbutamol (β2 — selective adrenoreceptor) was studied using differential scanning calorimetry (DSC) and thermogravimetry/derivative thermogravimetry
(TG/DTG). It was observed that the commercial sample showed a different thermal profile than the standard sample caused by
the presence of excipients. These compounds increase the thermal stability of the drug. Moreover, higher activation energy
was calculated for the pharmaceutical sample, which was estimated by isothermal and non-isothermal methods for the first stage
of the thermal decomposition process. For isothermal experiments the average values were E
act=130 kJ mol−1 (for standard sample) and E
act=252 kJ mol−1 (for pharmaceutical sample) in a dynamic nitrogen atmosphere (50 mL min−1). For non-isothermal method, activation energy was obtained from the plot of log heating rates vs. 1/T in dynamic air atmosphere (50 mL min−1). The calculated values were E
act=134 kJ mol−1 (for standard sample) and E
act=139 kJ mol−1 (for pharmaceutical sample). 相似文献
4.
Ammonium dinitramide (ADN) prills were prepared by emulsion crystallization and characterized by optical microscopic, thermogravimetric
(TG) and differential scanning calorimetric (DSC) techniques. The isothermal and non-isothermal decomposition kinetics of
ADN prills were studied by TG. The differential isoconversional method of Friedman (FR) and integral isoconversional method
of Vyazovkin were used to investigate the dependence of activation energy (E
a) with conversion (α) and the results were compared with literature data. The dependence of activation energy was also derived
from isothermal data. A strong dependence of E
a with α is observed for the ADN prills. All the methods showed an initial increase in E
a up to α=∼0.2 and later decreases over the rest of conversion. The apparent E
a values of FR method are higher than that of Vyazovkin method up to α=∼0.45. The calculated mean E
a values by FR, Vyazovkin and standard isoconversional method for α between 0.05 and 0.95 were 211.0, 203.9 and 156.9 kJ mol−1, respectively. 相似文献
5.
G. Z. Zhang S. H. Du J. Wang X. C. Wang 《Journal of Thermal Analysis and Calorimetry》2009,97(2):433-436
2,2-dinitropropyl acrylate (DNPA), 2,2-dinitrobutyl acrylate (DNBA) and 2,2-dinitrobutyl methacrylate (DNBMA) were synthesized
and the kinetics of their free-radical polymerization in the presence of 2,2′-azobisisobutyronitrile (AIBN) were investigated
by DSC in the non-isothermal mode. The kinetics of the free-radical polymerization as estimated by the Kissinger and Ozawa
methods showed that the reaction is disfavoured by increasing steric hindrance around the acrylyl double bond. The rate constants
calculated from the activation parameters showed the structural dependency. The polymerization kinetics revealed that the
polymerizability of three monomers decreased due to the presence of substituent methyl groups on the acrylyl double bond and
2,2-dinitrobutyl on ester group. Thus, the polymerization tendency increased in the order DNPA>DNBA>DNBMA. 相似文献
6.
In this work, a kinetic study on the thermal degradation of carbon fibre reinforced epoxy is presented. The degradation is
investigated by means of dynamic thermogravimetric analysis (TG) in air and inert atmosphere at heating rates from 0.5 to
20°C min−1 . Curves obtained by TG in air are quite different from those obtained in nitrogen. A three-step loss is observed during
dynamic TG in air while mass loss proceeded as a two step process in nitrogen at fast heating rate. To elucidate this difference,
a kinetic analysis is carried on. A kinetic model described by the Kissinger method or by the Ozawa method gives the kinetic
parameters of the composite decomposition. Apparent activation energy calculated by Kissinger method in oxidative atmosphere
for each step is between 40–50 kJ mol−1 upper than E
a calculated in inert atmosphere.
The thermo-oxidative degradation illustrated by Ozawa method shows a stable apparent activation energy (E
a ≈130 kJ mol−1 ) even though the thermal degradation in nitrogen flow presents a maximum E
a for 15% mass loss (E
a ≈60 kJ mol−1 ).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
7.
The non-isothermal decomposition process of the powder sample of palladium acetylacetonate [Pd(acac)2] was investigated by thermogravimetric (TG) and the X-ray diffraction (XRD) techniques. Model-free isoconversional method
of Tang, applied to the investigated decomposition process, yield practically constant apparent activation energy in the range
of 0.05≤α≤0.95. It was established, that the Coats-Redfern (CR) method gives several statistically equivalent reaction models,
but only for the phase-boundary reaction models (R2 and R3), the calculated value of the apparent activation energy (E) is nearest to the values of E obtained by the Tang’s and Kissinger’s methods.
The apparent activation energy value obtained by the IKP method (132.4 kJ mol−1) displays a good agreement with the value of E obtained using the model-free analysis (130.3 kJ mol−1). The artificial isokinetic relationship (aIKR) was used for the numerical reconstruction of the experimental integral model
function, g(α). It was established that the numerically reconstructed experimental function follows R3 reaction model in the range of
α, taken from model-free analysis. Generally, decomposition process of Pd(acac)2 starts with initial nucleation which was characterized by rapid onset of an acceleratory reaction without presence of induction
period. 相似文献
8.
The kinetics of free-radical cross-linking polymerization of methyl methacrylate (MM) in the presence of poly[2-(10-undecenoyloxy)ethyl methacrylate] (PUDEM) as a macromolecular cross-linker has been isothermally examined within the temperature range from 85–100°C using the differential scanning calorimetry (DSC). The activation energy found for this reaction, E
a=89.3 kJ mol–1, exceeds slightly the literature values of activation energy obtained for the mass polymerization of MM without any cross-linking agent. The activation energy has been also determined by the isoconversion method. It has been found that E
a decreases with the increase in the conversion, which may indicate a change in the reaction mechanism.This work was partly supported by the Committee for Research (KBN) in the framework of project No. 7 T08E 026 20 相似文献
9.
K. E. Ozbas 《Journal of Thermal Analysis and Calorimetry》2008,93(2):641-649
In this study, the relationship between particle size and pyrolysis characteristics of Elbistan lignite was examined by using
the thermogravimetric (TG/DTG) and differential thermal analysis (DTA) techniques. Lignite samples were separated into different
size fractions. Experiments were conducted at non-isothermal conditions with a heating rate of 10°C min−1 under nitrogen atmosphere up to 900°C. Pyrolysis regions, maximum pyrolysis rates and characteristic peak temperatures were
determined from TG/DTG curves. Thermogravimetric data were analyzed by a reaction rate model assuming first-order kinetics.
Apparent activation energy (E) and Arrhenius constant (A
r) of pyrolysis reaction of each particle size fraction were evaluated by applying Arrhenius kinetic model. The apparent activation
energies in the essential pyrolysis region were calculated as 27.36 and 28.81 kJ mol−1 for the largest (−2360+2000 μm) and finest (−38 μm) particle sizes, respectively. 相似文献
10.
S. Y. Sawant V. M. S. Verenkar S. C. Mojumdar 《Journal of Thermal Analysis and Calorimetry》2007,88(3):669-672
Samples of water based commercial acrylic resin paints were spread in a film form on slides, dried at room temperature and
exposed to solar radiation for up to eight months.
The characterization and quantification of resins and charges in the white paint emulsion were carried out for the thermal
decomposition. Besides this, X-ray diffractometry was used to identify CaCO3 as charge and TiO2 (rutile phase) as pigment.
It was observed through thermal techniques similar behavior to the samples even though with varied exposure time.
Kinetic studies of the samples allowed to obtain the activation energy (E
a) and Arrhenius parameters (A) to the thermal decomposition of acrylic resin to three different commercial emulsion (called P1, P2, P3) through non-isothermal procedures. The values of E
a varied regarding the exposition time (eight months) and solar radiation from 173 to 197 kJ mol−1 (P1 sample), from 175 to 226 kJ mol−1 (P2 sample) and 206 to 197 kJ mol−1 (P3 sample).
Kinetic Compensation Effect (KCE) observed for samples P2 and P3 indicate acrylic resin s present in these may be similar in nature. This aspect could be observed by a small difference in the thermal behavior of
the TG curves from P1 to P2 and P3 sample.
The simulated kinetic model to all the samples was the autocatalytic Šesták-Berggreen. 相似文献
11.
The solid state thermal behavior of trans-[Co(bpb)(amine)2]NCS⋅H2O complexes where (bpb)=[N,N’-bis(2-pyridinecarboxamido-N)-1,2-benzene], and amine=pyrrolidine (prldn)(1), and benzylamine (bzlan) (2), and trans-[Co(bpb)(piperidine)2]ClO4⋅H2O (3) (mixed with KSCN), has been studied using thermoanalytical techniques, infrared spectroscopy, and pyrolysis coupled
to both infrared and mass spectrometry, PY/FTIR and PY/MS. The deamination-anation reaction is clearly observed for all three
complexes. The estimated values of E
a for the deamination-anation are: E
a(1)=246.8 kJ mol−1, E
a(2)=255.7 kJ mol−1, E
a(3)=234.7 kJmol−1. The trend in E
a values is rationalized based on the ligand field strength of the amines and the structural effects. A novel decarbonylation
of the amide CO group from the equatorial ligand is observed after the release of one amine molecule. This process has been
monitored for complex (1) by FTIR in the carbonyl region and by mass spectrometry for the detection of CO2 at 280°C. The activation energy of this process is estimated for complex (1) (662.5 kJ mol−1). The reaction scheme for the observed reactions is proposed.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
12.
Gabriela Vlase T. Vlase Ramona Tudose Otilia Costişor N. Doca 《Journal of Thermal Analysis and Calorimetry》2007,88(3):637-640
Kinetics of thermal decomposition of three structurally similar complexes Co2Cu(C2O4)3 (R-diam)2, where R is ethyl, 1,2-propyl or 1,3-propyl, was studied under non-isothermal conditions and nitrogen dynamic atmosphere at heating
rates of 5, 7, 10, 12 and 15 K min−1.
For data processing the Flynn-Wall-Ozawa and a modified non-parametric kinetic methods were used. By both methods the activation
energy are in the range of 97–102 kJ mol−1. The formal kinetic is r=kα(1−α)2. Also a compensation effect between lnA and E was evidenced. The kinetic analysis lead to the conclusion of an identic decomposition mechanism by a single step process. 相似文献
13.
H. Sis 《Journal of Thermal Analysis and Calorimetry》2007,88(3):863-870
In this research, the relationship between particle size and combustion kinetics and combustion properties of lignite samples
was examined by utilizing the thermogravimetric (TG/DTG) and differential thermal analysis (DTA) techniques. The lignite samples
separated into different size fractions were subjected to non-isothermal thermogravimetric analysis between ambient and 900°C
in the presence of 50 mL min−1 air flow rate. Activation energy (E) and Arrhenius constant (A
r) of combustion reaction of each size was evaluated by applying Arrhenius kinetic model to the resulting data. Combustion
properties of the samples were interpreted by careful examination of the curves. The apparent activation energies in major
combustion region were calculated as 41.03 and 53.11 kJ mol−1 for the largest size (−2360+2000 μm) and the finest size (−38 μm), respectively. 相似文献
14.
V. P. Kheidorov Yu. A. Ershov G. Yu. Chalyi O. V. Titorovich 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(8):1358-1362
The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl−) in aqueous medium at 283–298 K and pH 8.2 was studied. The reaction order with respect to each component was determined
and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation.
The activation parameters of the reaction were measured: E
a
= 33.58 kJ/mol, ΔH
≠ = 31.12 kJ/mol, ΔS
≠ = −170.02 J/(K mol), ΔG
≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine
treated with OCl− is discussed. 相似文献
15.
Z. Fengqui H. Rongzu S. Jirong G. Hongxu 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2006,80(7):1034-1036
The kinetic parameters of the exothermic decomposition of the title compound in a temperatureprogrammed mode have been studied
by means of DSC. The DSC data obtained are fitted to the integral, differential, and exothermic rate equations by the linear
least-squares, iterative, combined dichotomous, and least-squares methods, respectively. After establishing the most probable
general expression of differential and integral mechanism functions by the logical choice method, the corresponding values
of the apparent activation energy (E
a), preexponential factor (A), and reaction order (n) are obtained by the exothermic rate equation. The results show that the empirical kinetic model function in differential
form and the values of E
a and A of this reaction are (1 − α)−4.08, 149.95 kJ mol−1, and 1014.06 s−1, respectively. With the help of the heating rate and kinetic parameters obtained, the kinetic equation of the exothermic
decomposition of the title compound is proposed. The critical temperature of thermal explosion of the compound is 155.71°C.
The above-mentioned kinetic parameters are quite useful for analyzing and evaluating the stability and thermal explosion rule
of the title compound.
The text was submitted by the authors in English. 相似文献
16.
F. Langmaier P. Mokrejs K. Kolomazník M. Mládek R. Karnas 《Journal of Thermal Analysis and Calorimetry》2007,88(3):857-862
Differential scanning calorimetry was employed to investigate the reaction of diglycidyl ethers of bisphenol A (DGEBA) of
mean molecular mass 348–480 Da, with collagen hydrolysate of chrome-tanned leather waste in a solvent-free environment. The
reaction leads to biodegradable polymers that might facilitate recycling of plastic parts in products of the automotive and/or
aeronautics industry provided with protective films on this basis. The reaction proceeds in a temperature interval of 205–220°C,
at temperatures approx. 30–40°C below temperature of thermal degradation of collagen hydrolysate. The found value of reaction
enthalpy, 519.19 J g−1 (= 101.24 kJ mol−1 of epoxide groups) corresponds with currently found enthalpy values of the reaction of oxirane ring with amino groups. Reaction
heat depends on the composition of reaction mixture (or on mass fraction of diglycidyl ethers in the reaction mixture); proving
the dependence of kinetic parameters of the reaction (Arrhenius pre-exponential factor A (min−1) and activation energy E
a (kJ mol−1)) did not succeed. Obtained values of kinetic parameters are on a level corresponding to the assumption that reaction kinetics
is determined by diffusion. 相似文献
17.
V. D. Živanović S. R. Grujić M. B. Tošić N. S. Blagojević J. D. Nikolić 《Journal of Thermal Analysis and Calorimetry》2009,96(2):427-432
The crystallization of K2O·TiO2·3GeO2 glass under non-isothermal condition was studied. In powdered glass with particle sizes less than 0.15 mm, surface crystallization
was dominant and an activation energy of crystal growth of E
a,s=327±50 kJ mol−1 was calculated. In the size range 0.15 to 0.45 mm, both surface and volume crystallization occurred. For particle sizes >0.45
mm, volume crystallization dominated with spherulitic morphology of the crystals growth and E
a,v=359±64 kJ mol−1 was calculated. 相似文献
18.
A. Cadenato J. M. Morancho X. Fernández-Francos J. M. Salla X. Ramis 《Journal of Thermal Analysis and Calorimetry》2007,89(1):233-244
The thermal polymerization kinetics of dimethacrylate monomers was studied by differential calorimetry using non-isothermal
experiments. The kinetic analysis compared the following procedures: isoconversional method (model-free method), reduced master
curves, the isokinetic relationship (IKR), the invariant kinetic parameters (IKP) method, the Coats-Redfern method and composite
integral method I. Although the study focused on the integral methods, we compared them to differential methods. We saw that
even relatively complex processes (in which the variations in the kinetic parameters were only slight) can be described reasonably
well using a single kinetic model, so long as the mean value of the activation energy is known (E). It is also shown the usefulness of isoconversional kinetic methods, which provide with reliable kinetic information suitable
for adequately choosing the kinetic model which best describes the curing process. For the system studied, we obtained the
following kinetic triplet: f(α)=α0.6(1−α)2.4, E=120.9 kJ mol−1 and lnA=38.28 min−1. 相似文献
19.
Rane S. Y. Gawali S. D. Kumbhar A. S. Padhye S. B. Bakare P. P. 《Journal of Thermal Analysis and Calorimetry》1999,55(1):249-258
Copper(II) complexes of lawsone (2-hydroxy-1,4-naphthaquinone, Lw) with variety of aqua ligation viz. Cu-1, [Cu(Lw)2(H2O)]2; Cu-2, [Cu(Lw)2(H2O)2] and Cu-3, [Cu(Lw)2(H2O)2]2 have been synthesized. The role of water as counter ligand on coordination propensity of redox active lawsone in naphthoquinone/naphthosemiquinone
(NQ/NSQ) forms is quantified by studies of pyrolytic reactions, using non-isothermal TG and DTA techniques, coupled with IR
studies. Mixed (NQ) (NSQ) ligation in Cu-1 and Cu-3 required energy of activation, Ea ∼67 kJ mol−1 of (NQ) and ∼41 kJ mol−1 of (NSQ). Comparable energies of aqua ligand (∼43 kJ mol−1) with NSQ ligand in Cu-1 and Cu-3, dictate charge distributions in lawsone coordinations. A large difference between Ea of aqua and p-NQ ligand indicates coordination of lawsone in its fully oxidised quinone form in Cu-2. From thermoanalytical
studies schematic oxidative decomposition mechanisms are proposed for Cu-1 and Cu-3. From pyrolytic reactions enthalpies are
estimated by DTA technique.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
20.
Abstact The reduction process of silica supported cobalt catalyst was studied by thermal analysis technique. The reduction of the
catalyst proceeds in two steps:
which was validated by the TPR and in-situ XRD experiments. The kinetic parameters of the reduction process were obtained with a comparative method. For the first step,
the activation energy, E
a, and the pre-exponential factor, A, were found to be 104.35 kJ mol−1 and 1.18·106∼2.45·109 s−1 respectively. The kinetic model was random nucleation and growth and the most probable mechanism function was found to be
f(α)=3/2(1−α)[−ln(1−α)]1/3 or in the integral form: g(α)=[−ln(1−α)]2/3. For the second step, the activation energy, E
a, and the pre-exponential factor, A, were found to be 118.20 kJ mol−1 and 1.75·107∼2.45 · 109s−1 respectively. The kinetic model was a second order reaction and the probable mechanism function was f(α)=(1−α)2 or in the integral form: g(α)=[1−α]−1−1. 相似文献