用Diamond TG/DTA热重/差热综合热分析仪在外加磁场下研究磁性材料相转变

介绍综合热分析仪Diamond TG/DTA在磁性材料研究中的应用.提出在外加磁场作用下,得到样品的热重曲线(TG),由TG曲线分析样品磁性相变及样品居里温度变化的原因,看到稀土铁基金属间化合物样品替代的Co元素的站位和元素之间相互作用对居里温度有很大影响.作为一种测量居里温度的方法,拓展Diamond TG/DTA热分析仪应用研究领域.     

Temperature Calibration of TMAs Using Modulated Temperature and Curie Temperature Reference Standards

This article presents the concept of calibrating temperature in thermomechanical analyzers (TMA) using reference standard magnetic materials whose Curie temperatures are well-known. This concept has not been tested experimentally to the best of the author's knowledge. Electrical current applied to a unifilarly wound furnace results in the furnace acting as an electrical inductor. A magnetic material sample located within such a furnace practically constitutes a solenoid core. A modulated temperature program directly results in a corresponding varying force exerted by the sample against the TMA probe, if the probe's axis and the central induced magnetic field line of force are coaxial, and, furthermore, if the direction of the central magnetic field line of force and the expansion direction of the probe are identical. If a sample undergoes a Curie transition, then the force which the sample exerts against the probe will diminish to zero as the transition goes to completion. Using a modulated temperature program throughout this phase transition allows determination of transition completion, by observation of the point at which the force required to maintain the sample's physical position reaches a steady state from it's previously non-steady state. This revised version was published online in August 2006 with corrections to the Cover Date.     

DTA/TG coupling

With the discovery of high temperature superconductivity an extraordinary field for investigations on new materials containing up to (more than) 8 or 9 components has been open. But, in addition to problems specifically related to superconductivity, we are faced with a prelimary difficulty: the preparation of well defined compounds which may have reproducible properties. This difficulty is smoothed out when the phase relations in the relevant systems are known. Differential Thermal Analysis (DTA) contributes to their establishment. However, in multicomponent systems, an isopletic line is expected to intercept various boundary surfaces and the analysis is obviously complicated, compared to low order systems. In addition, by the nature of high temperature superconductors the oxygen partial pressure used for their preparation is an important thermodynamic parameter which contributes to fix the oxygen content in the solid state. During heat treatments, the composition of the systems may change, due to oxygen or volatile oxides (Tl₂O₃, PbO₂ or HgO) release. A permanent composition control then requires thermogravimetric (TG) measurements associated to DTA.This paper attempts to demonstrate the efficiency of the assembly DTA/TG for the study of high temperature superconductors. Going beyond the frame of preparation and quality control, the system is also particularly useful for kinetic studies. Examples will be principally in the (Tl,Pb)-(Ba,Sr)-Ca-Cu-O systems.It is a pleasure to associate to this lecture my colleagues from research groups with which I collaborate from many years in the difficult field of elaboration and characterization of thalliumbased HTSC: T. K. Jondo, K. Lebbou. R. Abraham and M. T. Cohen-Adad in Lyon (Lab. PCM2), M. Couach and A. F. Khoder at the CEN in Grenoble (SPSMS), J. Muller and R. Flukiger at the DPMC in Geneva and of course C. Opagiste and Ph. Galez at the LSM in Annecy.     

Three model-free methods for calculation of activation energy in TG

Two well-known isoconversion methods, the first one developed by Ozawa-Flynn-Wall and the second one developed by Friedman, are confronted with calculations made using modulated thermogravimetry (MTG). The latter variant is free from a number of assumptions and restrictions made in the isoconversion computations. In particular, it allows the use of a single decomposition curve and it remains in force even in the case of multistage decomposition with conjugated processes.To obtain the model-fitting methods from the model-free methods one should replace some functions averaged over isoconversion levels by the functions calculated on the basis of kinetic models. In the Ozawa-Flynn-Wall method it is the averaged reduced time (integral of Arrhenius exponential over time). In the method of Friedman it is the averaged differential conversion function.In MTG, the perturbations caused by the sinusoidal temperature modulation are connected with derivatives of mass loss by simple scaling, where activation energy plays a role of a scaling parameter. The ratio of the experimentally measured perturbations to the experimental derivative is used for the model-free computation of activation energy. If a theoretical derivative replaces the experimental one, this procedure leads to the model-fitting method. Even a rough approximation of the experimental derivative should not lead to an excessive error in activation energy. If in a vicinity of peaks maxima in derivatives of mass loss the decomposition is controlled by single rate-limiting processes, modulated thermogravimetry should give realistic activation energies for these processes. Inasmuch as the results of MTG are weakly sensitive to selection of kinetic models, this method should have a high predictive force.     

Factors affecting the experimentally resolved shapes of TG curves

From a theoretical consideration concerning the factors affecting the experimentally resolved shapes of thermogravimetric curves, the possible way to increase the accuracy of the thermogravimetric measurements were discussed.

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Zusammenfassung Unter theoretischen Aspekten bezüglich derjenigen Faktoren, die die experimentelle Auflösung thermogravimetrischer Kurven beeinflussen, wird ein möglicher Weg zur Steigerung der Genauigkeit thermogravimetrischer Untersuchungen diskutiert.

     

Studies of Nanocrystalline Phase and Residual Amorphous Phase of FeCuNbSib Alloy Using TG(M) Technique

The —T and d/dT—T curves of the FeCuNbSiB amorphous alloy, which are the relationship between the total saturated magnetic moment per unit mass and temperature, are investigated by magnetic thermogravimetry analysis (TG(M)) technique. It is found that the crystallization process of the samples can be divided into five stages. The studies of samples annealed in temperature range of 480–610°C for 1h show that when the annealing temperature (T_a) is less than 540°C, the quantity of nanocrystalline -Fe(Si) phase increases evidently with T_a, and the Curie temperature (T_C) of residual amorphous phase also increases linearly with T_a, i.e. T_C=0.52T_a+91.7°C, with correlation coefficient =0.98. The variation of volume fraction of -Fe(Si) nanocrystalline phase or residual amorphous phase with T_a is measured by TG(M) technique.This revised version was published online in November 2005 with corrections to the Cover Date.     

The Quality of Standards in Least Squares Calibrations

Frequently, the Least Square Regression Model (LSRM) assumption related to standards quality is either forgotten or formulated in too strict of a way, making its application unsuccessful or difficult. This work posits that the LSRM requires calibration standards with concentration ratios affected by negligible uncertainties that are achievable for standard solutions with large relative uncertainties. Criterion to test this assumption and a model to take into account the uncertainty of standards in performed quantifications are presented. The developed models were successfully tested with a combination of experimental data about interpolation uncertainty, for the determination of hexachlorobenzene by GC-ECD, with simulated values of standards concentrations.     

High-resolution TG for the Characterization of Diesel Fuel Additives

High-resolution thermogravimetric analysis (Hi-Res^TM TG) in its variable heating rate mode was applied to commercially available diesel fuel additives under a nitrogen atmosphere. A TGA 2950 from TA Instruments was used to run the experiments. For the selected diesel fuel additives, the use of variable heating rate resulted in sharper transitions and clearer onset of degradation than in traditional constant heating rate experiments. Moreover, the time required for experiments giving reasonable resolution was remarkably reduced compared to constant heating rate experiments. The technique proved to be very useful in the study of multi-component systems, such as diesel fuel additives, since it provides more detailed information regarding mass changes in the sample as a result of heat treatment when total decomposition involves more than one stage i.e. mass changes stem from consecutive reactions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Vacancy Contents in MnZn Ferrites From TG Curves

Expressions for calculating the cation vacancy contents of MnZn ferrites from thermogravimetric curves are presented together with some experimental data. In a single-phase MnZn ferrite synthesized by conventional ceramic procedures, the O₂ evolution accompanying ferrite formation follows the formal equation. Mn²⁺ _σα Zn_σβ Fe³⁺ _2σ(1–γ) [V ]_{σ/4(1–2γ)} O₄ =σ'/σ Mn²⁺ _σ(α–2ϕ) Zn_σβ Fe²⁺ _2σθ Mn³⁺ _2σϕ Fe³⁺ _{2σ(1–γ–θ)} [V ]_{σ/4(1–2γ–3ϕ)} O₄ +σ'φ/2O₂ (g) where α and β denote the MnO and ZnO mole fractions in the primary mixture γ=α+β, θ and ϕ depend on the quantities of Fe²⁺ and Mn³⁺ formed, respectively, φ=θ–ϕ and σ'/σ is a function of the former parameters. Even though the relative amounts of Fe²⁺ /Fe³⁺ and Mn²⁺ /Mn³⁺ remain uncertain, the vacancy content [V ] of the ferrite can be determined because it depends on φ alone, which is related to the change in mass of the sample as the synthesis takes place through the equation φ=(1.5–γ) μ_β /μ_O2 (1–m _f /m _i ) Here, m _i and m _f are the masses of the sample before and after O₂ evolution, μ_B is the formula mass of the ferrite and μ_O2 is the O₂ molar mass. Practically vacancy-free single-phase MnZn ferrite samples were obtained by sintering in air at 1250°C and cooling in pure N₂ . This revised version was published online in July 2006 with corrections to the Cover Date.     

用软件定标技术扩展EM－360L核磁共振谱仪的温度适应范围

利用计算机控制和数据处理技术对进口核磁共振谱仪加以改造,使其测试所要求的环境温度由原来的恒温(20±1℃)降至室温.其精度保持不变,硬件方案简捷可靠、软件利用一个标准样品的已知参数来校正系统的刻度单位,算法采用动态的可调刻度单位标定其它样品的测试结果,取得了较为理想的效果.并对影响核磁共振谱仪数据精度的因素及规律作了讨论.     

TG and autoignition studies on forest fuels

The autoignition delay times of some important Mediterranean forest species: Arbutus adrachne, Abies cephallonica, Pinus brutia, Pinus halepensis, Pistacia lentiscus, Cupressus semprevirens, Olea europaea, Cistus incanus were determined in the range 460–600°C under precisely controlled temperature and airflow conditions. Based on these data the forest fuels examined were classified into two groups: the least and the most flammable species. The autoignition delay data were related to the thermal analysis measurements. The themogravimetric analysis in an inert (nitrogen) atmosphere showed that the thermal decomposition of cellulose in the range of 300–400°C as well as the mass residue at 600°C are directly related to the ignition behavior.This revised version was published online in November 2005 with corrections to the Cover Date.     

New Temperature Integral Approximate Formula for Non-isothermal Kinetic Analysis

A new approximate formula for temperature integral is proposed. The linear dependence of the new fomula on x has been established. Combining this linear dependence and integration-by-parts, new equation for the evaluation of kinetic parameters has been obtained from the above dependence. The validity of this equation has been tested with data from numerical calculating. And its deviation from the values calculated by Simpson's numerical integrating was discussed. Compared with several published approximate formulae, this new one is much superior to all other approximations and is the most suitable solution for the evaluation of kinetic parameters from TG experiments. This revised version was published online in August 2006 with corrections to the Cover Date.     

TG and DSC as tools for confirming hybrid vermiculites derived from intercalation

Vermiculite was prepared to react with aliphatic diamines (ethylene-, trimethylene-, tetramethylene- and hexamethylene-) diamine. The products were characterized by elemental analysis, infrared spectroscopy and X-ray diffraction. The amounts of diamines adsorbed were 0.89, 0.86, 0.79 and 0.68 mmol g^–1, respectively for NH₂(CH₂)⋅nNH₂ where n=2, 3, 4, 6. The basal spacings of the intercalated vermiculites varied between 1300 and 1470 pm. Thermogravimetry and DSC data confirmed intercalation of diamines in gallery space of vermiculite.     

Kinetics of the oxidation of magnetite using simultaneous TG/DSC

Kinetics of the oxidation of magnetite (Fe₃O₄) to hematite (a-Fe₂O₃) are studied in air using simultaneous TG/DSC. The mechanism is complex and the differences between the kinetic conclusions and Arrhenius parameters based on either TG or DSC are discussed. As in our previous work on CaCO₃ [1], the determination of a satisfactory baseline for the DSC results adds considerable uncertainty to those kinetic results. Consequently the calculations based on the TG data are considered superior. Solid state reactivity varies from one source of material to another and the results are compared for two different commercial samples of magnetite, both presumably prepared by wet chemical methods. These materials are much more reactive than the material studied previously [2], which had been coarsened and refined at high temperatures. In that earlier study, the metastable spinel, g-Fe₂O₃, was formed as an intermediate in the oxidation to the final stable form, a-Fe₂O₃. The exothermic reaction of the gamma to alpha form of the product during the oxidation process destroys the direct comparison between the TG and DSC results, since the former only detects the change in mass of the sample and not the crystallographic transformation. The TG results, however, represent the true oxidation process without superposition of the structural aspects. This revised version was published online in July 2006 with corrections to the Cover Date.     

Metrologically based procedures for the temperature, heat and heat flow rate calibration of DSC

Metrologically based measuring procedures and evaluation methods are recommended as guidance for practical temperature, heat and heat flow rate calibration of DSC instruments which are largely independent of instrumental, test and sample parameters. The relevant terms are defined, the measuring procedures and evaluation methods described, calibration materials and their characteristic data stated and guidance for the sample handling provided. Reference is made to three extended papers on calibration. The recommendations were developed by the working group Calibration of Scanning Calorimeters of the German Society of Thermal Analysis (GEFTA).Recommendation of the working group Calibration of scanning calorimeters of the Gesellschaft für Thermische Analyse e.V. (GEFTA)     

Hierarchical Fibrous Honeycomb Ceramics with High Load Capability and Low Light-Off Temperature for the Next-Generation Auto Emissions Standards

Novel and stringent automotive exhaust gas emissions standards are urgently needed to counter the problems posed by the worsening global climate and environment. However, the traditional cordierite-based honeycomb ceramics substrates with ultimate pore density have seriously restricted the establishment of new emission standards. Herein, we introduce a novel robust substrate with tailored volume-specific surface area and low heat capacity. This substrate employs the synergy of high-strength ceramic fibers and ultrathin TiO₂ nanosheets. The micro-sized fibers provide support to ensure structural strength during the catalytic reaction, while the nanosheets play the dual role of connecting the fibers and providing a high surface area for catalyst immobilization. The new three-dimensional (3D) microarchitecture exhibits a high volume-specific surface area of 3.59×10⁴ cm²/cm³, a compressive strength of 2.01 MPa, and remarkable stability after high-speed air erosion at 800 °C. The honeycomb-like structure exhibit low resistance to gas flow. Furthermore, after loading with Pt and Pd nanoparticles, the composite 3D microarchitecture delivered an excellent catalytic performance and prominent structural stability, with a super low light-off temperature of 150 °C. The outstanding mechanical and thermal stability and the high surface area and light-off temperature of the new substrate indicate its potential for use as a highly efficient catalytic carrier to meet the next-generation auto emissions standards.     

Uncertainty Budget for Simultaneous Determination of Minor and Major Ions in Seawater with Ion Chromatography Confronted with Uncertainties in Concentrations of Calibration Standards

This work deals with the development and application of the detailed uncertainty budget for simultaneous determination of minor and major ions in seawater and derived saline solutions. Combination and sequence of gravimetric or/and volumetric steps involved in introducing each particular ion into stock and final combined calibration standards; cross contamination of chemicals and dilution of samples were critically assessed and their significance to the combined uncertainty was evaluated. The main uncertainty components were identified and quantified for all anions and cations determined with ion chromatography in seawater and estuary water and confronted with uncertainties associated with concentrations of ions in combined calibration standards. Similar uncertainty components reflect very differently upon different ions.     

用软件定标技术扩展EM－360L核磁共振谱仪的温度适应范围

利用计算机控制和数据处理技术对进口核磁共振谱仪加以改造，使其测试所需要的环境温度由原来的恒温降至室温。其精度保持不变，硬件方案捷可靠，软件利用一个标准样品的已知参数来校正系统的刻度单位，算法采用动态的可调刻度单位标定其它样品的测试结果，取得了较为理想的效果。     

Determining moisture absorption/desorption properties of commercial membranes by thermogravimetry (TG)

A series of different commercial membranes were characterized by their moisture absorption and desorption properties under controlled humidity and temperature conditions. This work was made possible by combining the features of a constant humidity conditioning chamber with those of a thermogravimetric (TG) apparatus. These two modules were interconnected by tubing, rotameters, an atmosphere-recycling microbellows pump and switching valves. Under programmed heating and isothermal conditions reproducible data were obtained in terms of weight-gain or weight-lossvs. time and pore size. Evaluation of the resulting TG curves allowed us to report reasonable differences in the materials, some of which had been previously surface-modified by the manufacturer.     

Fractional analysis of technical polyoxaalkyl borates by TG

Results of preliminary thermoanalytical investigations (DSC/TG) of polyoxaalkyl esters of boric acid are presented. One aim of these investigations was the development of a method of characterization of the technical esterificate. The optimum parameters of quantitative thermogravimetric analysis of boric acid esters and the excess of polyoxaalkanols were assumed. The precision and accuracy of the developed method are discussed.