Closer relation between thermal analysis and calorimetry

Several DTA experiments followed by calorimetric works are reviewed here to emphasise the importance of complementary role of both techniques. The thermal analysis is advantageous in the sense that it gives quickly the overall view of thermal behaviour of a material under various conditions. Calorimetric work provides accurate heat capacity data which enable to derive thermodynamic functions including the enthalpy and entropy. The latter quantity is especially important in judging whether the material obeys the third law of thermodynamics. However, calorimetric work leads occasionally to an erroneous conclusion if the work is not preceded by thermal analysis performed under various conditions. Sometimes, quality of information obtained by DTA exceeds that obtained by laborious calorimetry.     

Numerical simulation and parametric analysis of latent heat thermal energy storage system

This paper presents the numerical analysis of the transient performance of the latent heat thermal energy storage unit established on finite difference method. The storage unit consists of a shell and tube arrangement with phase change material (PCM) filled in the shell space and the heat transfer fluid (HTF) flowing in the inner tube. The heat exchange between the HTF, wall and PCM has been investigated by developing a 2-D fully implicit numerical model for the storage module and solving the complete module as a conjugate problem using enthalpy transforming method. A comparative investigation of the total melting time of the PCM has been performed based on natural convection in liquid PCM during the charging process. The novelty of this paper lies in the fact it includes convection in PCM and this investigation includes a detailed parametric study which can be used as a reference to design latent heat storage. The results indicate that natural convection accelerates the melting process by a significant amount of time. In order to optimize the design of the thermal storage unit, parametric study has been accompanied to analyze the influence of various HTF working conditions and geometric dimensions on the total melting time of the PCM. Another important feature considered in this work is the influence of the inner wall of the tube carrying the HTF on the entire melting time of the PCM. An error of around 7.2% is reported when inner wall of the tube is ignored in the analysis.

     

Computer simulation of thermal analysis in heat-flux DSC applied to metal solidification

A general mathematical treatment for heat-flux differential scanning calorimetry is given. It combines equations derived for heat transfer in the calorimeter cell with an approach to the solidification of metal or alloy carried out in this type of instrument. The differences are discussed between temperature evolution, kinetics of latent heat and undercooling evolution within the sample, and temperature evolution, recorded signal and measured undercooling at the monitoring station.

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Zusammenfassung Es wird ein allgemeine mathematische Behandlung von Wärmefluß-DSC gegeben. Es verbindet Gleichungen für den Wärmetransport in der Kalorimeterzelle mit einer Annäherung der Verfestigung von Metall oder Legierung, die in diesem Gerätetyp durchgeführt werden. Es werden die Unterschiede zwischen: Temperaturevolution, Kinetik latenter Wärme und Unterkühlungsevolution innerhalb der Probe und zwischen: Temperaturevolution, aufgezeichnetes Signal und gemessene Unterkühlung an der Monitorstation diskutiert.

     

The modeling and simulation of the thermal analysis on the hydrogenerator stator winding insulation

This paper presents the modeling and simulation of the thermal analysis on the hydrogenerator stator winding. The insulation aging is predetermined first by the insulation temperatures that, in turn, are influenced by the environmental conditions and second by the speed increase of the high temperature chemical reaction in materials. By increasing the temperature in the electro-insulated material, many molecules enter in chemical reaction accelerating the insulation aging. The heat transfer is a natural process, caused by inner energy, between bodies with high temperature and bodies with lower temperature. This process can also take place between parts of the same body that have different temperatures. The heat is transmitted by conduction, convection, and radiation. The heat transfer and especially the thermal conduction are a domain in which the finite element method is successfully applied. The thermal conduction problems will be solved by the finite elements method. The analysis of the thermal transfer process was made using the modeling and simulation program with finite elements ANSYS, and the results of the simulations were compared with measurement values. The analyzed stator winding is supplied with high voltage of 11 kV that is used for a high power hydrogenerator. To realize the thermal analysis of the winding stator, the coil will be supplied with 11 kV. The results of the analysis on a prototype model present the thermal transfer in coil–insulation–air system when the coil is hot.     

Comparison between thermal analysis and mass spectroscopic studies of uranyl oxinates

The 5,7-dichloro, 5,7-dibromo, 5,7-diiodo and 5,6-dinitro derivatives of oxine (ligandsL ₁,–L ₄) were used to prepare uranyl chelates (A ₁–A ₄). Thermal analysis (DTA) and mass spectroscopic studies were performed. The stoichiometries of the chelates were determined by elemental analysis, molecular weight determination applying an -spectroscopic liquid scintillation counter and mass spectral measurements. The uranylligand ratios were found to be 11 for A₁, 13 for A₂, 12 (monohydrate) for A₃, and 12 forA ₄. The correlation between the thermal analysis and mass spectra was examined. The activation energy required for each step of thermal degradation of the ligands and chelates was calculated. The natures of most of the molecular ions obtained in the mass spectra were also explained.     

Comparative study on thermal behaviors between micrites and thrombolites using thermogravimetric analysis

Journal of Thermal Analysis and Calorimetry - Although micrites (abiotic limestone) and thrombolites (typical biotic limestone), according to the sedimentation and biological action, can be...     

High-temperature thermal analysis study of the reaction between magnesium oxide and silica

The reaction between SiO₂ and MgO at temperatures up to 1500°C was studied using thermal analysis, with X-ray diffraction being used to identify reaction products. The reaction is slow and results in the formation of Mg₂SiO₄ and MgSiO₃, with minor amounts of SiO₂·nH₂O and residual amounts of unreacted SiO₂ and MgO. Complete reaction of the starting materials to form Mg₂SiO₄ can only be achieved by maintaining the mixture at 1500°C for extended periods of time (>1 h).     

Synergy between theory and experiment in structure resolution of low-dimensional oxides

In this paper, I review recent progress in joint theoretical and experimental studies aiming at atomic structure determination of low-dimensional metal oxides. Low-dimensional systems can be generally defined as materials of unusual structure that extend to less than three dimensions. In recent years low-dimensional systems have attracted increasing attention of physicists and chemists, and the interest is expected to rise in the near future. Two- and one-dimensional structures in form of thin oxide films or elongated oxide chains have many potential applications including model supports for heterogeneous catalysts and insulating layers in semiconductor industry. The interest in zero-dimensional gas-phase oxide clusters ranges from astrophysics to studies of elementary steps in catalysis. The key prerequisite for understanding physical and chemical properties of low-dimensional systems is a detailed knowledge of their atomic structures. However, such systems frequently present complex structures to solve. Only in a few cases experimental data can provide some information about possible arrangement of atoms, but data interpretation relies to a large extent on intuition. Therefore, in the recent years quantum chemical calculations became an indispensable tool in structure identification of low-dimensional systems, yet the accuracy of theoretical tools is often limited. The results reviewed here demonstrate that often the only way of an unambiguous atomic structure determination of low-dimensional systems are experimental studies combined with theoretical calculations. Particularly the global optimization methods such as genetic algorithm in combination with the density functional theory prove very useful in automatic structure determination of the observed surface structures and gas-phase clusters.     

Studies on the number of contacts between ibuprofen and ethenzamide using thermal analysis

We studied a method of estimating the number of contacts in a solid dosage form using thermal analysis. Ibuprofen (IB) and Ethenzamide (ET) were used as model actives. IB and ET were granulated and sieved with each other. We prepared mixtures of IB and ET using different diameter granules. The number of contacts between the samples was calculated by the expression method of Ouchiyama and Tanaka. By thermal analysis, we measured the quantity of endotherm up to 60-63 degrees C from 56 degrees C. The quantity of endotherm up to 61 degrees C from 56 degrees C was in good proportion to the number of contacts calculated by the expression.     

Study of the interaction between caesium bromide and kaolinite by differential thermal analysis

The reaction occurring during the wet grinding of kaolinite with CsBr was studied by simultaneous Differential Thermal Analysis -Thermogravimetry (DTA-TG), supplemented by infrared spectroscopy of isothermally treated CsBr disks. The DTA and TG curves were compared with those of untreated kaolinite and of kaolinite mixed or air ground with different alkali halides. A new endothermic DTA peak at 75–115°, accompanied by weight loss, is due to the desorption of surface and interparticle water located mainly at the interface between the mineral and the salt. A second endothermic peak at about 500° represents the simultaneous dehydroxylation of the clay and thermal hydrolysis of CsBr. The presence of a separate CsBr phase was identified from two endothermic peaks which characterize melting and boiling of the salt; only mixtures with more than 140 mmol CsBr per 100 g kaolinite show the presence of this phase. All of the CsBr below this concentration occurs in the CsBrHOH-kaolinite intercalation complex. This degree of saturation is smaller than that obtained previously for CsCl.

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Zusammenfassung Mittels simultaner DTA-TG wurde die sich während des Naßmahlens von Kaolinit mit CsBr stattfindende Reaktion untersucht, ergänzt durch IR-spektroskopische Untersuchungen von isotherm wärmebehandelten CsBr-Plättchen. Die DTA und TG Kurven wurden mit denen von unbehandeltem Kaolinit und von Kaolinit, vermischt oder an Luft gemahlen mit verschiedenen Alkalihalogeniden. Ein neuer endothermer DTA-Peak bei 75–115°C., begleitet von einem Gewichtsverlust, wird der Desorption von Oberflächen- oder interpartikelgebundenem Wasser zugeschrieben, das hauptsächlich an den Übergangsflächen Mineral/Salz lokalisiert ist. Ein zweiter endothermer Peak bei 500°C steht für die gleichzeitige Dehydroxylierung der Tonerde und die thermische Hydrolyse von CsBr. Aus zwei für Schmelzen und Sieden des Salzes charakteristischen endothermen Peaks konnte auf eine separate CsBr-Phase geschlossen werden; nur Gemische mit mehr als 141 mmol CsBr pro 100 g Kaolinit zeigen die Gegenwart einer solchen Phase. Unterhalb dieser Konzentrationsgrenze ist alles CsBr in CsBr-HOH-Kaolinit Durchdringungskomplexen vorhanden. Dieser Sättigungsgrad ist niedriger als der für CsCl.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday

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S. Y. and A. N. are grateful to the Internal Fund of the Hebrew University of Jerusalem for financial support.     

Computational thermal and kinetic analysis

The complexation of β-lactam antibiotics, amoxicillin (AMPC), ampicillin (ABPC) and benzylpenicillin (PCG), with 2-hydroxypropyl-β-cyclodextrin (HPCD) was studied at various pH values using microcalorimetry, ¹H NMR spectroscopy, and molecular dynamic simulation. In the strong acid solution, two different types of inclusion complex with a 1:1 stoichiometry, Complex I with a phenyl ring of β-lactam antibiotics penetrated into the cavity of HPCD and Complex II with a penam included in the cavity, were formed by hydrophobic interaction, and Complex II was more stable than Complex I. In aqueous solution at pH≥4.5, only Complex I was formed, where the penam of PCG was more deeply penetrated into the cavity to keep it stable than those of AMPC and ABPC. The charged carboxyl-group on the penam was less affinity to form Complex II.     

Computational thermal and kinetic analysis

A software package to determine the non-isothermal kinetic parameters of heterogeneous reactions has been developed. The dynamic handle of conversion degree step and ranges, heating rates and kinetic models makes the evaluation of the activation parameters much faster. The standard procedure: ‘model-free’ kineitc, IKP and Perez-Maqueda et al. methods, is applied for the determination of the kinetic triplet corresponding to thermal induced transformations. The software is designed mainly for thermogravimetric, temperature programmed reduction and dilatometry data processing, but may also import already transformed numeric data.     

Emanation thermal analysis

A high pressure differential thermal analysis (DTA) apparatus is described which is capable of operation in the pressure range up to 500 MPa and at temperatures from 25 to 300°C. The requirements for quantitative DTA are examined. The apparatus enables the determination of heat of transition under high pressure by using small samples.     

Controlled-rate thermal analysis

Controlled-rate thermal analysis (CRTA) and differential scanning calorimetry (DSC) were used to investigate the adsorbed water layers and the surface properties of different commercial activated carbons. A simple method is proposed to obtain information on the properties of the adsorbed water film and the surface heterogeneity of the materials studied. This method utilizes TG mass loss and the first derivative of the DTG mass loss curves with respect to temperature and time, obtained during programmed liquid thermodesorption. The obtained TG mass loss curves, which reflect the energetic heterogeneity, consisted of steps and inflections which were associated with the mechanism of wetting of the solid surfaces. The heights of these steps and inflections depend on the adsorption capacity, the adsorption potential and the nature and number of the active centers of the carbon samples studied. The values of the total porosity and the surface phase capacity obtained by this method are in good agreement with those estimated on the basis of independent methods. The behaviour of water/carbon samples was studied by means of DSC at subambient and elevated temperatures. The experimental results provided novel data on the structural heterogeneity, the thermal stability of the water/carbon interface and its phase and structural transitions.Support from the Research Council of Kent State University (Ohio, USA) is acknowledged. The author is pleased to thank Drs M. Jaroniec, R. K. Gilpin, J. Choma and R. Dobrowolski for fruitful discussions and the active carbon samples.     

Oxyreactive thermal analysis

The paper presents the applicability of Oxyreactive Thermal Analysis (OTA) for the investigation of different kinds of carbon matter. For comparative reasons and more precise interpretation, along with OTA some physico-chemical properties of analyzed materials were used as the methods commonly applied for the investigations. The carbon materials of both natural (anthracites, graphite and diamonds) and synthetic origin (active carbon, glass carbon, expanded graphite, soot and synthetic diamonds) were investigated. It was stated that there is close relationship between structure parameters and physico-chemical properties and the thermal reactivity within the investigated groups of carbon matters. The results show that OTA can be accepted as a good investigative way for such materials. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dielectric-differential thermal analysis

A quantitative relation is given for the temperature function of the output voltage is thermodielectric analysis. Results obtained with zeolites show the validity of the equation.     

基于碳纳米管和铁氰酸镍纳米颗粒协同作用的葡萄糖生物传感器

将制备的铁氰酸镍纳米颗粒(NiNP)与多壁碳纳米管(CNT)混合, 分散于壳聚糖溶液中, 形成一种新的纳米复合成分(NiNP-CNT-CHIT), 将其修饰在玻碳电极表面. 新复合膜体现了NiNP和CNT之间的协同作用, 由于CNT的良好的传递电子性能, 促使NiNP催化氧化还原能力有了较大的提高. 此NiNP-CNT-CHIT复合膜修饰的玻碳电极在较低电位下对过氧化氢具有良好的电催化性能, 与NiNP-CHIT膜比较, 测定H₂O₂的灵敏度增大了50倍. 通过戊二醛在电极表面固定葡萄糖氧化酶制备了一种新的葡萄糖传感器. 该传感器在－0.2 V下对葡萄糖的线性范围为0.05～10 mmol/L, 检测下限为10 μmol/L.     

The relationship between differential thermal analysis data and the detonation characteristics of polynitroaromatic compounds

The thermal stabilities of 37 polynitroaromatic compounds are specified by means of non-isothermal DTA. The initial temperatures of the exotherms T_D, as well as the Piloyan decomposition activation energies, E, of the compounds are determined.A relationship is derived between ET^?1_D and the detonation characteristics of the compounds being measured. It is shown that allocation of the measured compounds to separate forms of the determined relationship is, in addition to thermochemical factors, also determined by the electron configuration and steric conditions in the reaction center of the given molecule.     

Synergy between Printex nano-carbons and silver nanoparticles for sensitive estimation of antioxidant activity

We report on the synthesis, characterization and applications of a Printex L6 carbon-silver hybrid nanomaterial (PC-Ag), which was obtained using a polyol method. In addition, we also highlight the use of Printex L6 nano-carbon as a much cheaper alternative to the use of carbon nanotubes and graphene. The silver nanoparticles (AgNP) were prepared directly on the surface of the Printex 6L carbon “nanocarbon” material using ethylene glycol as the reducing agent. The hybrid nanomaterial was characterized by High-angle annular dark-field transmission electron microscopy (HAADF-TEM), energy–dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), Raman spectroscopy and cyclic voltammetry. Optimized electrocatalytic activity on glassy carbon electrode was reached for the architecture GC/PC-Ag, the silver nanoparticles with size ranging between 1 and 2 nm were well–distributed throughout the hybrid material. The synergy between PC nano-carbons and AgNPs was verified by detection of gallic acid (GA) at a low applied potential (0.091 V vs. Ag/AgCl). GA detection was performed in a concentration range between 5.0 × 10⁻⁷ and 8.5 × 10⁻⁶ mol L⁻¹, with a detection limit of 6.63 × 10⁻⁸ mol L⁻¹ (66.3 nmol L⁻¹), which is considerably lower than similar devices. The approach for fabricating the reproducible GC/PC-Ag electrodes is entirely generic and may be explored for other types of (bio)sensors and devices.