ZnAc2·2H2O在空气中的热分解动力学研究

用TG/DTA,DSC和XRD技术研究了固态物质ZnAc2.2H2O在空气中的热分解过程.结果表明,ZnAc2.2H2O在空气中发生两步分解,其失重率与理论计算失重率相符.XRD结果表明,ZnAc2.2H2O分解的最终产物为ZnO.用Friedman法和Flynn-Wall-Ozawa(FWO)法求得分解过程的活化能E,并通过多元线性回归方法给出了可能的机理函数.ZnAc2.2H2O在空气中两步分解的活化能分别为119.82和66.82kJ/mol.     

Chemical Modification of Activated Carbons

Mesoporous activated carbons and silica gel (Kieselgel 100, Merck) were modified as follows: (i) treatment with vinyltrimethoxysilane; or (ii)chlorination with CCl₄ followed by the reaction with a Grignard reagent. Modification of silica gel was proved by methods FTIR, NMR-¹³C and element analysis on carbon. The chemical modification of coals by alkans and olefins was supported by comparison of results of thermogravimetry for modified coals and modified silica gels. Polymerization of vinyl groups on carbon surface is shown by methods thermogravimetric analysis and differential scanning calorimetry. This revised version was published online in August 2006 with corrections to the Cover Date.     

热分析技术在药物研究中的应用

本文简要介绍了热分析技术在药学领域中的重要性及其应用。由于热分析技术具有试样微量化、快速简便、不用分离试样、不用溶剂、适用范围广、曲线易于解析等优点,在药学研究和药品质量检验等方面,热分析技术将发挥更重要的作用。     

Feasibility Study of Crude Oil Fields by Thermal Analysis Techniques

This paper investigates the minimum oil content necessary for self-sustained combustion, which is introduced as a criterion for the selection of suitable reservoirs for in-situ combustion processes. Differential scanning calorimetry was used to determine the heat values of oil-limestone mixtures. The minimum temperature required for the total consumption of the fuel was obtained by thermogravimetry (TG/DTG). The minimum amount of oil necessary to sustain combustion was calculated from these two parameters and compared with the oil content of the reservoir. Reservoirs with an oil content greater than or equal to this minimum value were considered feasible. It was seen that the fields examined are generally not suitable for in-situ combustion processes. This revised version was published online in August 2006 with corrections to the Cover Date.     

消旋卡多曲在空气中的热分解动力学

用热分析(TG/DTA/DSC)技术研究了消旋卡多曲(C₂₁H₂₁NO₄S)在空气中的热分解过程. 热分析结果表明, 消旋卡多曲在空气中一步分解, 其熔点为77.4 ℃. 用Friedman法, Flynn-Wall-Ozawa (FWO)法和ASTM E698法求取了分解过程的活化能E, 并通过多元线性回归法给出了可能的机理函数.     

Study of Water Adsorption on Activated Carbons with Different Degrees of Surface Oxidation

A carbon of wood origin was oxidized with different oxidizing agents (nitric acid, hydrogen peroxide, and ammonium persulfate). The microstructural properties of the starting material and the oxidized samples were characterized using sorption of nitrogen. The surface acidity was determined using Boehm titration and potentiometric titration. The changes in the surface chemistry were also studied by diffuse reflectance FTIR. Water adsorption isotherms were measured at three different temperatures close to ambient (relative pressure from 0.001 to 0.3). From the isotherms the heats of adsorption were calculated using a virial equation. The results indicated that the isosteric heats of water adsorption are affected by the surface heterogeneity only at low surface coverage. In all cases the limiting heat of adsorption was equal to the heat of water condensation (45 kJ/mol).     

Thermal analysis of flammability

The present article describes the synthesis, structural features and thermal studies of the complexes of the type [M(SB)₂(H₂O)₂]·nH₂O [where HSB=pyridine-m-carboxaldene-o-aminobenzoic acid and M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)]. The complexes have been characterized on the basis of elemental analyses, magnetic susceptibility measurements, (FTIR and electronic) spectra and thermal studies. The nature of the bonding has been discussed on the basis of infrared spectral data. Magnetic susceptibility measurements and electronic spectral data suggest a six-coordinated structure of these complexes. The complexes of Mn(II), Co(II), Ni(II), Cu(II) are paramagnetic, while Zn(II) and Cd(II) are diamagnetic in nature. The thermal decomposition of the complexes have been studied and indicates that not only the crystallization and coordinated water are lost but also that the decomposition of the ligand from the complexes is necessary to interpret the successive mass losses. The kinetic parameters such as order of reaction (n) and the energy of activation (E _a) have been reported using Freeman–Carroll method. The entropy (S*), the pre-exponential factor (A), the enthalpy (H*) and the Gibbs free energy (G*) have been calculated.     

Thermal Analysis of Polymer-silicate Nanocomposites

The thermal behavior of epoxy-smectite nanocomposites (hybrids) is examined by non-isothermal thermogravimetry (TG, DTG and DTA) in air atmosphere. It has been shown that the thermal stability of hybrids is much greater than that of epoxy resin and strongly depends on both the smectite loading and the type of the gallery cations of organically modified smectites. The kinetics of degradation of nanocomposites is significantly influenced by the presence of smectites and proceeds in three stages. Stage I is attributed to the effect of quaternized ammonium ion exchanged smectite, as stages II and III are associated with the decomposition of the bulk epoxy resin. Because of the interfacial interactions and thesilicate-polymer multilayered nanoscale organization, the nanocomposites act as excellent heat insulator and mass transport barrier, which shift the thermal decomposition peaks towards much higher temperatures. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Synthesis of Levyne-Type Zeolite Studied by Thermal Analysis of Methylquinuclidine Aluminosilicate Gels

DSC, TG and quadrupole mass spectrometer data concerning methylquinuclidinium iodide (MeQ1), dried precursor gel, and crystalline levyne-type zeolite are discussed together with the thermal degradation of MeQ1 mixed with single inorganic components of the gel. It is shown that MeQ⁺ions play a role in the organization of the gel structure. This revised version was published online in July 2006 with corrections to the Cover Date.     

Determination of the Porous Structure of Activated Carbons Using the IAE Concept. Influence of the Local Adsorption Model

In this paper we study a method for the determination of the micropore volume distribution function of activated carbons. This method is based on the Integral Adsorption Equation concept (IAE). The micropore volume distribution function is assumed to be a Gaussian of which the parameters are unknown. These parameters are determined using adsorption isotherms of carbon dioxide on a given activated carbon (F30/470 CHEMVIRON CARBON) at 278, 288, 298, 303, 308, 318 and 328 K and for pressures up to 100 kPa. Several local adsorption models are used (Langmuir, Volmer, Fowler-Guggenheim, Hill-de Boer). The influence of the choice of the local model on the pore volume distribution function is discussed. The physical validity of this function and the performances of the different models are presented. It appears that the effect of the temperature on the adsorption isotherms is difficult to model over a wide range of relative pressure. The Hill-de Boer and the Langmuir local models are the most efficient (average errors respectively equal to 3.53% and 2.80% in the studied range of temperature and pressure). They provide the most meaningful parameters for the pore volume distribution function.     

A Study on Pre-Oxidation of Petroleum Pitch-Based Activated Carbons for Electric Double-Layer Capacitors

Electric double-layer capacitors (EDLCs) are an excellent electrochemical energy storage system (ESS) because of their superior power density, faster charge–discharge ability, and longer cycle life compared to those of other EES systems. Activated carbons (ACs) have been mainly used as the electrode materials for EDLCs because of their high specific surface area, superior chemical stability, and low cost. Petroleum pitch (PP) is a graphitizable carbon that is a promising precursor for ACs because of its high carbon content, which is obtained as an abundant by-product during the distillation of petroleum. However, the processibility of PP is poor because of its stable structure. In this study, pre-oxidized PP-derived AC (OPP-AC) was prepared to investigate the effects of pre-oxidation on the electrochemical behaviors of PP. The specific surface area and pore size distribution of OPP-AC were lower and narrower, respectively, compared to the textural properties of untreated PP-derived AC (PP-AC). On the other hand, the specific capacitance of OPP-AC was 25% higher than that of PP-AC. These results revealed that pre-oxidation of PP induces a highly developed micropore structure of ACs, resulting in improved electrochemical performance.     

Role of Microporosity of Activated Carbons on Their Adsorption Abilities for Phenols and Dyes

The amounts of adsorption of two commercial dyes, phenol, and 4-chlorophenol from water on activated carbons were measured at 30°C. The carbons were prepared from cane (bagasse) piths and were activated by steam. The activation temperature and time were in the ranges of 750–840°C and 2 h, respectively. It was shown that the isotherm data of all four solutes could be well fitted by the Langmuir equation under the conditions studied. The adsorption capacities of the solutes were correlated with the microporosity properties of the activated carbons including micropore volume and external surface area. Finally, the adsorption characteristics of the present carbons was compared with those prepared from various agricultural wastes.     

Thermal decomposition and indirect structural determination of rare earth element picrates with the dtso ligand

The complexes [Ln(pic)₃(DTSO)₃] (Ln=La, Lu and Y; pic=picrate; DTSO=1,3-dithiane-1-oxide) were synthesized and characterized. Indirect structural determination by far infrared spectroscopy is presented. Results from thermal decomposition of these complexes by TG/DTG and DSC techniques are reported. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal Analysis of Magnesium Tris(maleato) Ferrate(III) Dodecahydrate. Physico-chemical studies

Thermal analysis of magnesium tris(maleato) ferrate(III) dodecahydrate has been studied from ambient to 700°C in static air atmosphere employing TG, DTG, DTA, XRD, Mössbauer and infrared spectroscopic techniques. The precursor decomposes to iron(II) intermediate species along with magnesium maleate at 248°C. The iron(II) species then undergo oxidative decomposition to give α-Fe₂O₃ at 400°C. At higher temperatures magnesium maleate decomposes directly to magnesium oxide, MgO, which undergoes a solid state reaction with α-Fe₂O₃ to yield magnesium ferrite (MgFe₂O₄) at 600°C, a temperature much lower than for ceramic method. The results have been compared with those of the oxalate precursor.     

Effect of Heating Temperature on the Properties of Chars and Activated Carbons Prepared From Oil Palm Stones

The effects of heating temperature of pyrolysis and activation processes on the textural and chemical properties of the chars and activated carbons prepared from oil palm stones, an abundant palm-oil mill solid waste, were studied. For both pyrolysis and activation, relatively high temperature was essential to develop pore structures in the chars and activated carbons. However, too high temperature would cause pore narrowing and pore enlargement during pyrolysis and activation, respectively. The temperature had an insignificant effect on the inorganic components of the chars and activated carbons, but affected their surface organic functional groups significantly. This revised version was published online in August 2006 with corrections to the Cover Date.     

Application of Thermal Analysis to the Study of Some Waste Agricultural Products for the Preparation of Active Carbons

TG, DTG and DTA methods were used for the investigation of some waste agricultural products, such as grape seeds, walnut shells, plum and peach stones, which can serve as raw materials for the production of active carbons. It was demonstrated that thermo analytical methods are appropriate to study the thermal characteristics of the above wastes and the data obtained can be applied to the technological processes of active carbon preparation. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Mechanism of the Thermal Transformation From Goethite to Hematite

Synthetic pigments of goethite (Bayferrox^R) of different particle size were investigated by DTA, IR, DSC, TG and X-ray diffraction measurements. It follows that a so-called ‘hydrohematite’ described in the literature does not exist as a discrete intermediate during the dehydration course from goethite to hematite. Instead we observed a dependence of the dehydration mechanism on the particle size. Transformation enthalpies and activation energies for the dehydration process will be given. A plausible dehydration mechanism, which is compatible with our DTA/DSC results, is deduced from TEM investigations. This revised version was published online in August 2006 with corrections to the Cover Date.     

鲍鱼多糖Hal-A的热分析研究

采用热重、热重-红外谱联用及差示扫描量热法，对鲍鱼多糖进行热分析研究 ，结果表明鲍鱼多糖在空气和氮气氛中，230 ～ 340 ℃之间发生剧烈的分解反应 。氮气氛中，是吸热的分解过程；而空气氛中，是放热氧化反应，并且在453 ℃左 右，有另一个急剧的氧化裂解过程。与淀粉、肝素、甲壳素和半乳糖的热分析比较 ，含有硫酸酯的鲍鱼多糖和肝素热稳定性较低，含氨基的甲壳素最高，这反映出不 同基团对多糖热稳定性的影响。     

Thermal behavior of polystyrene synthesized in the presence of carboxymethyl cellulose

Summary Study of the decomposition kinetics is an important tool for the development of polymer recycling in industrial scale. In this work, parameters such as activation energy, frequency factor and reaction order, were measured under dynamic conditions. Flynn-Wall-Ozawa, Van Krevelen, Horowitz-Metzger, Coats-Redfern, Madhusudanan and Vyazovkin methods were used to determine the kinetic parameters. The analysis of the results obtained by the Coats-Redfern method shows that the thermal degradation process of LDPE and HDPE corresponds to a phase boundary controlled reaction (mechanism R2). This method shows that the reaction order values of LDPE and HDPE are about 0.7 and 0.6, respectively.     

Thermal analysis of gel-derived support for metallic catalyst

A series of Al₂O₃-SnO₂ catalysts with the molar ratio of Al₂O₃ to SnO₂ between 1:0 and 0:1 have been characterized by thermal analysis in reductive conditions, TPR and XRD methods. In the reductive conditions in temperatures up to about 1000 K, no reduction of the tin component to the metallic form takes place in the binary gel Al₂O₃-SnO₂. In the temperatures characteristic of the reforming process, only a reduction to SnO occurs in the above binary support. Thermal analysis of the gels in the reductive conditions and TPR results indicate stabilisation of the tin oxide species even in the systems of the molar ratio of Al₂O₃ to SnO₂ of 1:1. The metallic tin appears in the binary gel only after its reduction in the hydrogen atmosphere at temperatures close to ∼1100 K.