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1.
The thermal degradation of poly(furfuryl methacrylate) (PFM) has been studied by means of dynamic thermogravimetric analysis (TGA) in the temperature range 100–600°C under nitrogen and oxygen atmospheres at various heating rates, and the apparent activation energy for the interval 230–340°C corresponding to the first degradation step was determined. Isothermal TGA at 250°C, 275°C and 300°C was carried out and the apparent activation energy values obtained were compared with those determined in dynamic experiments. The residues from isothermal degradation experiments were analysed by infrared spectroscopy and the results seem to indicate that in the thermal degradation of PFM the formation of cyclic structures of 2,4-dimethylglutaric anhydride occurs in the macromolecular chains, together with partial depolymerization of polymer segments, as well as intermolecular crosslinking through oxidation of the C---H bond in position 5 of some furfuryl rings.  相似文献   

2.
The thermal degradation of a commercial, stabilized, unfilled nitrile (Buna-N) rubber material was investigated at temperatures in the range 85–140 °C. The resulting heterogeneous oxidation, due to diffusion limitations in oxygen availability, was studied using infrared microscopy and modulus profiling. Degradation-related spectral changes were observed primarily in the hydroxyl, carbonyl and ester regions; quantitative analysis revealed identical oxidation profiles for these chromophores. These chemical oxidation profiles (carbonyl formation) were correlated with mechanical modulus (hardness) profiles. Degradation of the sample proceeds via a linear increase in the carbonyl concentration, but an exponential increase in the modulus with time. It is concluded that the profile development and aging behavior can be described by a diffusion-limited autoxidation mechanism which can be modeled computationally. The results are compared to those of a previously studied carbon-black-filled material.  相似文献   

3.
The effect of acid treatment of multi-walled carbon nanotubes (MWCNTs) on the mechanical, thermal and mainly thermo-oxidative stability of isotactic polypropylene (iPP) was evaluated. From the acid treatment surface carboxylic groups were mainly formed, while the nanotubes' length was gradually reduced by increasing the treatment time. Young's modulus, tensile strength and storage modulus of the iPP/MWCNT nanocomposites were increased by increasing the treatment time of the MWCNTs, due to finer dispersion inside the polymer matrix, as revealed by TEM and micro-Raman spectroscopy. Furthermore, the nanotubes acted as nucleating agents, an effect more pronounced with finer filler dispersion. Thermal stability in an inert atmosphere also increased. Thermo-oxidative stability tests in air and O2 revealed that oxidative degradation took place in two stages. In the first stage, corresponding to temperatures up to 230 °C, the MWCNTs accelerated the oxidation of iPP, while at higher than 300 °C temperatures the trend was reversed. Incubation studies proved that, at the first stages, oxidation was due to random chain scission of iPP and oxygen uptake. This behaviour was accelerated by the MWCNTs' surface carboxylic groups and, as found by O2 permeability studies, was mainly a surface process. In the second stage, due to the shielding effect of MWCNTs, the removal of the gases produced during decomposition was hindered. At this stage the presence of MWCNTs resulted in more thermo-oxidatively stable nanocomposites.  相似文献   

4.
Surface and catalytic properties of Cu/Zn mixed oxide catalysts   总被引:1,自引:0,他引:1  
Copper catalysts supported on zinc oxide, with different loading (1–20 wt.% CuO), were prepared by impregnation of the basic zinc carbonate with a water solution of copper nitrate. The impregnated samples were dried at 120°C and calcined at 400–700°C. The surface and catalytic properties of CuO loaded on ZnO were determined by N2 adsorption measurements conducted at −196°C and CO oxidation by O2 at 150–300°C, respectively. The results obtained revealed that the surface and catalytic properties of different solids were dependent upon CuO content and calcination temperature. The specific surface areas of various adsorbents decreased monotonically as a function of both calcination temperature and extent of loading. However, the activation energy of sintering, ΔES, was found to increase by increasing the amount of CuO present. On the other hand, the CO oxidation activity on various catalysts was found to increase progressively by increasing the calcination temperature from 400 to 500°C, then decreased by increasing the temperature from 500 to 700°C. The augmentation of CuO content from 1 to 5 wt.% resulted in an increase in the CO oxidation activity, which decreased by increasing the extent of loading above this limit.  相似文献   

5.
The adsorption isotherms of Cu(II) ions from aqueous solutions in the concentration range 40–1000 mg l−1 on two samples of granulated and two samples of activated carbon fibres containing varying amounts of associated oxygen have been reported. The adsorption isotherms are type I of BET classification showing initially a rapid adsorption tending to be asymptotic at higher concentrations. The amounts of oxygen associated with the carbon surface has been enhanced by oxidation with nitric acid and ammonium persulphate in the solution phase and with oxygen gas at 350°C and decreased by degassing of the oxidized carbon samples at 400, 650 and 950°C. The adsorption of Cu(II) ions increases on oxidation and decreases on degassing. The increase in adsorption on oxidation depends on the nature of the oxidative treatment while the decrease in adsorption on degassing depends on the temperature of degassing. This has been attributed to the increase in the carbon–oxygen acidic surface groups on oxidation and their decrease on degassing. Suitable mechanisms consistent with the results have been proposed.  相似文献   

6.
The oxidation of cyclohexylamine was studied over tungsten, molybdenum and vanadium oxides containing catalysts supported on silica, γ-alumina or hydrotalcite in the temperature range 170°C–230°C. Depending on the catalyst and reaction conditions, the main products of the reaction are cyclohexanone oxime, cyclohexylidenecyclohexylamine or cyclohexanone. About 70% selectivity of cyclohexanone oxime formation at about 20% conversion of cyclohexylamine is obtained over tungsten catalysts. The activity of the tested catalysts usually passes through a maximum and, then, gradually decreases with time on stream. The deactivation of the catalyst is caused by the formation of tar products on the catalyst surface. The mechanism of oxidation involves formation of oxygen species on the catalyst surface which oxidizes cyclohexylamine.  相似文献   

7.
The mitigation of oxidative degradation under γ-irradiation promoted by eight commercial antioxidants: Ethanox 330, Hostanox O3, Irganox 1010, Topanol OC, Ionox 220, Santonox R, Santowhite, Cyanox 2246 loaded onto ethylene-propylene terpolymer at the concentration of 0.5 phr in respect of a pristine polymer was studied. The polymer samples were exposed to various doses up to 500 kGy. The kinetic parameters of oxidations: oxidation induction times, onset oxidation temperature, oxidation rates were evaluated by CL measurements. They validated the differences in the stabilisa-tion activities by limitation of the oxidation gradient. The high efficiency of some of the antioxidants studied, such as Ionox 220 and Santowhite, ensured the delay in degradation even at a high irradiation dose (500 kGy). For the environments with γ-radiation exposure, a relevant sequence in the increasing protection efficiency could be established: Topanol OC; Hostanox O3; Irganox 1010; Cyanox 2246; Santonox R; Ionox 220; Santowhite. The FT-IR spectra were recorded for the calculation of the radiochemical yields resulting from the modifications occuring in the concentrations of oxygenated structures. The accumulations of hydroxyl- and carbonyl-containing products were calculated to evaluate the irradiation effects in EPDM-based products during a severe accident. The options for EPDM stabilisation are discussed based on chemiluminescence and FTIR analyses.  相似文献   

8.
This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy–imine chelate ligands. The bis(phenoxy–imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C2 symmetric catalyst produces syndiotactic polypropylene. 13C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy–imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy–oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy–oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a Tm, 140 °C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy–oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy–imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene.  相似文献   

9.
Mercuric 5-nitrotetrazole is a possible replacement for lead azide. The thermal decomposition peak maximum ranged from 185 to 270°C as the heating rate increased from 0.1 to 100°C min−1. The activation energy and frequency factor for thermal decomposition were determined from dynamic and isothermal DSC and isothermal TG data; the average values were 38.8 kcal mol−1 and 3.56×1014 s−1. A half-life experiment confirmed the kinetic constants and indicated that the decomposition reaction was first order. The heat of explosion was determined by a pressure DSC test and found to be 2587 J g−1. The linear coefficient of expansion was 37±2×10−6°C−1 from −60 to 160°C and indicated secondary transitions near −10 and 90°C. The specific heat was 0.0003154T+0.1339 in the region −40–90°C. The critical temperature for a slab with a half-thickness of 0.035 cm was calculated to be 232 °C.  相似文献   

10.
Chemiluminescence (CL) has been applied to evaluate the oxidation susceptibility of various polyolefins: low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and isotactic polypropylene (i-PP). The intensity of CL emission in inert atmosphere could be related to the previous oxidation level. The thermal stability at 170 °C of the hydroperoxides in LDPE seems to be lower than that in LLDPE or HDPE. The kinetic parameters of the oxidation at 170 °C in oxygen, calculated from CL data, suggest the following stability order: HDPE > LLDPE > LDPEi-PP. The intensity of CL emission was related to the CH3 content as evaluated by Fourier transform infra-red spectroscopy.  相似文献   

11.
New elastomers with high content of 3,4 isoprene units have been developed during the last decades in an attempt to ensure superior performances of the final products and the present study is devoted to the investigation of some peculiarities of their ageing behaviour. On thermo-oxidative degradation, 3,4 isoprene units are less affected in comparison to cis-1, 4 and trans-1, 4 isoprene units. The degradation process consists mainly in splitting of the main chains at temperatures of 80–100 °C while at higher temperatures (120–130 °C) branching becomes a significant modification and this reaction is enhanced for the polymers containing preponderantly 3,4 units. Such behaviour leads to the fact that the processability of polymers containing high amounts of 1,2 and 1,3 isoprene units is less affected by thermo-oxidative degradation in comparison with cis-1, 4-polyisoprene, which could be explained by the fact that large amounts of double bonds are not present in the backbone of macromolecules but in the pendent groups.  相似文献   

12.
Lifetime prediction of polymeric materials often requires extrapolation of accelerated aging data with the suitability and confidence in such approaches being subject to ongoing discussions. This paper reviews the evidence of non-Arrhenius behaviour (curvature) instead of linear extrapolations in polymer degradation studies. Several studies have emphasized mechanistic variations in the degradation mechanism and demonstrated changes in activation energies but often data have not been fully quantified. To improve predictive capabilities a simple approach for dealing with curvature in Arrhenius plots is examined on a basis of two competing reactions. This allows for excellent fitting of experimental data as shown for some elastomers, does not require complex kinetic modelling, and individual activation energies are easily determined. Reviewing literature data for the thermal degradation of polypropylene a crossover temperature (temperature at which the two processes equally contribute) of 83 °C was determined, with the high temperature process having a considerably higher activation energy (107–156 kJ/mol) than the low temperature process (35–50 kJ/mol). Since low activation energy processes can dominate at low temperatures and longer extrapolations result in larger uncertainties in lifetime predictions, experiments focused on estimating Ea values at the lowest possible temperature instead of assuming straight line extrapolations will lead to more confident lifetime estimates.  相似文献   

13.
The thermal decomposition of zinc acetate dihydrate Zn(CH3CO2)2·2H2O in some humidity-controlled atmospheres has been successfully investigated by novel thermal analyses, which are sample-controlled thermogravimetry (SCTG), thermogravimety combined with evolved gas analysis using mass spectrometry (TG–MS) and simultaneous measurement of differential scanning calorimetry and X-ray diffractometry (XRD–DSC). The thermal processes of anhydrous zinc acetate in dry gas atmosphere by conventional linear heating experiment initiated with the sublimation around 180 °C, followed by the fusion and the decomposition over 250 °C. SCTG was useful to interpret clearly the successive reaction because the high-temperature parallel decompositions were effectively inhibited. The thermal behavior changed dramatically by introducing water vapor in the atmosphere and the thermal process was quite different from that in dry gas atmosphere. Zinc oxide (ZnO) was formed only in a humidity-controlled atmosphere, and could be easily synthesized at temperatures below 300 °C. XRD–DSC equipped with a humidity generator revealed directly the crystalline change from Zn(CH3CO2)2 to ZnO. A detailed thermal process of Zn(CH3CO2)2·2H2O and the effect of water vapor are discussed.  相似文献   

14.
Poly (nickel phthalocyanine) which has exceptional thermal stability is synthesized. Knowledge of modes of degradation of this polymer is found to be necessary for its high temperature applications. This polymer showed very high thermal stability with maximum polymer decomposition temperatures (PDTmax) of 500 °C in air and 890 °C in N2, with char yield 93% at 800 °C. Because of its excellent thermal stability, degradation study with MS as well as GC–MS techniques were found to be very difficult. The present publication deals with MS and GC–MS studies of nickel phthalocyanine sheet polymer at high temperatures ranging from 700 to 1000 °C. Tentative mechanisms are proposed for its modes of fragmentations and based on GC–MS studies, the most probable degradation products are identified.  相似文献   

15.
Oxynitride perovskites with bright and variable colour have the potential to be employed as non-toxic pigments, and to substitute colourants that contain harmful heavy metals. For this application it is extremely important to have a precise knowledge about the materials stability. The thermal stability of oxynitride perovskites in different atmospheres was measured by thermogravimetry in combination with mass spectroscopy (MS). The studied compounds, namely LaTiO2N, SrNbO2N and SrTaO2N, were heated up to 1200 °C in argon–oxygen mixtures with varying oxygen contents. It was found that the thermal behaviour of the studied oxynitrides changes drastically with the oxygen concentration. When heated up in pure argon the oxynitrides transform to oxides containing transition metals of lower oxidation state and/or binary nitrides. For oxygen contents between 0.5% and 20% the samples were completely oxidised. The oxidation rate increases with oxygen content. MS analysis of the gaseous products (including N2, NO and NO2) reveals a complex reaction mechanism, which is strongly modified by the composition of the atmosphere.  相似文献   

16.
The oxidation of sulphide minerals   总被引:2,自引:0,他引:2  
J. G. Dunn   《Thermochimica Acta》1997,300(1-2):127-139
The literature associated with the thermal behaviour of mineral sulphides has been selectively and critically reviewed. Particular attention has been paid to:

• • the importance of characterising the starting material, as well as intermediate products

• • the effect of experimental variables on the thermal analysis results

The various reactions that sulphides can undergo in inert and oxidising atmospheres are presented. Under mild oxidising conditions, such as an air atmosphere and heating rates of 10–20°C min−1, the oxidation occurs as a sequence of reactions usually controlled by oxygen diffusion, although in some situations decomposition of the sulphide with evolution of sulphur can occur. Besides the formation of oxides and sulphates, and the subsequent decomposition of the latter, solid-solid reactions can occur between sulphates and unreacted sulphides. In ternary systems, such as the iron-nickel sulphides, considerable ion diffusion can take place.

Under more vigorous oxidising conditions, such as an oxygen atmosphere with a heating rate in excess of 40°C min−1, some sulphides can be ignited. Under these conditions the relative ignition temperatures of sulphides can be measured, and the effects of variables such as particle size and stoichiometry on the ignition temperature examined.

The oxidation of pyrite is presented as a case study of the effects of experimental variables on the results of thermal analysis. The application of the results of studies to the industrial processing of sulphides of economic importance has been discussed.  相似文献   


17.
K. Kinoshita   《Thermochimica Acta》1977,20(3):297-308
The reactions between Pt oxides and carbon black in helium and air were examined by DTA. The thermograms were dependent on the mode of sample preparation. 20 wt.% PtO2 supported on carbon catalyst heated in He at 10°C min−1 produced an exotherm at approximately 400°C. Physical mixtures of PtO2 and carbon only reacted at a higher temperature (approximately 550°C) in He where PtO2 is thermally decomposed to Pt and O2. In air, Pt catalyzed the oxidation of cabon in the 20 wt.%Pt supported on carbon sample. On the other hand, PtO2 in the physical mixture did not appear to catalyze the oxidation of carbon in air. This difference in behavior is explained by assuming that atomic oxygen is produced in the supported catalyst sample which reacts at low temperature with carbon. In the physical mixture, thermal decomposition of PtO2 yields molecular oxygen which reacts with carbon at a higher temperature than does atomic oxygen.  相似文献   

18.
Palladium loaded calcium-hydroxyapatite, Pd(z)/CaHAp, and calcium-fluoroapatite, Pd(z)/CaFAp, were synthesised and characterised by TEM, XRD, IR and UV–vis–NIR spectroscopies. Introduction of palladium does not change the structure of CaHAp and CaFAp. The average size of PdO particles was found to be around 4–5 nm on Pd(1)/CaHAp but larger (6–7 nm) on Pd(1)/CaFap. The acid–base properties of the supports and of the catalysts were studied using butan-2-ol conversion. On CaHAp and CaFAp, the butenes yield (dehydration reaction) is very low either in the absence or in the presence of oxygen. The methyl ethyl ketone yield (dehydrogenation reaction) is significant only in the presence of oxygen and higher over CaFAp. Conversely, the performances of Pd(z)/CaHAp are better than those of Pd(z)/CaFAp below 180 °C. Above 180 °C, buta-2-ol combustion is favoured on Pd/CaHAp but not on Pd/CaFAp.

In methane oxidation, Pd(z)/CaHAp showed also a much larger activity than Pd(z)/CaFAp. On 2 wt% Pd loaded CaHAp, the methane oxidation reaches a conversion of almost 100% at 350 °C, which is comparable with the performance of conventional Pd/Al2O3 catalysts. The reducibility of PdO under methane–oxygen mixtures is lower on Pd(z)/CaHAp. For both reactions, the lower activity of Pd(z)/CaFAp is related to its higher acidity, resulting from the substitution of OH by F, and to the larger PdO particle size.  相似文献   


19.
The thermal degradation behavior of a range of ethylene-propylene-diene (EPDM) elastomers, covering the whole range of composition, has been examined under isothermal conditions between 410 and 440 °C using thermogravimetric analysis. The kinetic parameters of degradation for the polymers have been evaluated using different mathematical models based on different proposed mechanisms of degradation. The experimental data were fitted to the models using non-linear regression analysis technique based on Marquardt-Levenberg algorithm. It appears that the degradation of EPDMs follows the Avrami-Erofeev two-dimensional nucleation model or a random chain-scission mechanism. No observable trend was found between the ethylene content of EPDM and the activation energy of degradation.  相似文献   

20.
The drying and sintering processes of SiO2–ZrO2 alkoxide-derived gels have been studied by means of DSC technique. In the drying process, most part of water and alcohols are removed from the gels. For the SiO2 gel such elimination occurs at the end of the drying process, however for the ZrO2 gel this elimination occurs during the whole drying time. An intermediate behavior is observed for the binary system SiO2–ZrO2 gels. In the sintering process, the DSC technique allows to determine the elimination of water and alcohols retained within the structure (open or close pores) and the well-known hydroxyl condensation of silica gel between 700° and 800°C is also observed. The ZrO2 gel shows the final hydroxyl condensation at the heating temperature of 600°C. For the binary SiO2–ZrO2 gels, the hydroxyl condensation has been associated to the activation energy needed for the dissociation of silica hydroxyls. This energy decreases with the ZrO2 concentration in the gel resulting in a sintering treatment of 500°C leading to the entire hydroxyl condensation for the gel with 75% ZrO2–25% SiO2.

By studying the temperature of the DSC peaks, it is possible to know the temperature at which most part of water and alcohols are leaving the gel, and these results can be used in order to select the corresponding drying or sintering schedules for obtaining a well-fabricated material.  相似文献   


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