RheoDSC: design and validation of a new hybrid measurement technique

A newly developed hyphenated technique is presented that combines an existing rheometer and differential scanning calorimeter (DSC) into a single experimental setup. Through the development of a fixation accessory inside the cell of the calorimeter and the introduction of an add-on unit for the rheometer, the simultaneous calorimetric and rheological measurement inside the well-controlled thermal environment of a Tzero™ DSC cell opens new experimental possibilities. The evolution of thermal and flow properties of a material can be simultaneously monitored during steady or oscillatory shear flow and regular or modulated temperature DSC measurements. The technique offers interesting opportunities for the investigation of flow-induced transitions, such as crystallization or phase separation, and provides a possibility for high-throughput screening of materials. The signal quality of the novel technique in comparison to the stand-alone techniques is demonstrated by the evaluation of the calibration factors and by measurements on standard materials. Finally, combined rheological and calorimetric melting and crystallization experiments on polycaprolacton are performed.     

Thermal analysis of the rice and by-products

The thermogravimetry (TG) is a technique used in the quality control of foods. In this work the moisture and ash contents in the rice and by-products (bran and husk), the thermal stability and the gelatinization process by conventional, thermogravimetric and calorimetric methods were studied. The moisture and ash contents obtained by TG and conventional methods did not present significant differences. The rice presented higher starch content, while the bran presented higher protein content. The thermogravimetric data presented the following thermal stability order: rice>bran>husk. The calorimetric curves indicated the gelatinization of the starch. The kinetic parameters were compatible. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electrochemical heat flow calorimeter

A device designed for research of heat phenomena occurring in chemical power sources (CPS) is described. The device includes two functional blocks: electrochemical and calorimetrical, operating under single control, which allows simultaneously performing electrochemical and calorimetric measurements. The calorimetric block is a heat flow calorimeter. The calorimetric chamber design provides the possibility of studying thermal processes in laboratory electrochemical cells and CPS of planar, disk, and prismatic design. The absolute measurement error of the heat flow is ±50 μW at the resolution of 1 μW. The operating temperature range of the calorimetric chamber is 0–90°C. The basis of the electrochemical block is a module of a four–range potentiostat–galvanostat. The maximum polarizing current of the potentiostat is ±200 mA at the maximum voltage on the auxiliary electrode of ±10 V. Multiuser remote access from the user computers over Ethernet to the device is provided for control and treatment of experimental data. Digital deconvolution filters allowing to compensate the response rate of the heat flow meter are used for processing primary data of calorimetric measurements.     

Thermophysical property determination of high temperature alloys by thermal analysis

Differential scanning calorimetric measurements to determine solidus and liquidus temperatures and latent heat of fusion of two high temperature materials, PWA1484 and an experimental gamma titanium aluminide alloy, are presented. The solidus and liquidus temperatures of PWA1484 are 1340 and 1404°C. The solidus and liquidus temperatures of the titanium aluminide alloy are 1453 and 1522°C. Solidus and liquidus temperatures determined from actual heating and cooling curves, which were measured using imbedded thermocouples and analyzed by a pseudo-differential thermal analysis technique are found to be in good agreement with the differential scanning calorimetric measurements. This revised version was published online in July 2006 with corrections to the Cover Date.     

Integrated circuit thermopile as a new type of temperature modulated calorimeter

Thermopiles, integrated into a thin silicon membrane, are used in some calorimetric applications (e.g. Setaram SETline120 portable thermal analyzer) that utilize temperature ramps of the thermostat to obtain the caloric response. A new calorimetric method is proposed, which uses an integrated circuit thermopile (ICT) in an oscillating mode. A heater integrated into the membrane drives temperature oscillations and the thermopile senses the temperature gradient across the membrane. ac calorimetry and the 3-omega method do not measure total heat losses and have an inherent quasi-adiabatic low frequency limit. On the other hand, the thermopile setup can measure total heat losses that permits one to monitor enthalpy changes in a sample, e.g. during crystallization. Low frequency measurements are limited only by sensor sensitivity. Preliminary results show that the same experimental setup can be used to make dynamic heat capacity measurements over a frequency range from 1 mHz to 100 Hz. At high frequencies (1 Hz and higher), heat capacity of nanogram samples can be measured.     

Investigations of phase transitions in liquid crystals by means of adiabatic scanning calorimetry

High-resolution calorimetric techniques have substantially contributed in characterising and understanding the delicate thermal behaviour near many phase transitions in liquid crystals. In this paper we describe a high-resolution adiabatic scanning calorimetric technique that has proven to be an important tool in discriminating between first-order and second-order phase transitions in addition to rendering high-resolution information on fluctuations-induced pretransitional specific heat capacity behaviour. The capabilities of adiabatic scanning calorimetry are illustrated with experimental results for the isotropic to nematic and the isotropic to smectic A transitions for a series of alkylcyanobiphenyl compounds. For the nematic to smectic A transition results are presented for pure compounds and mixtures of liquid crystals as well as on the effects of added non-mesogenic solutes and nanoparticles. For chiral molecules results for phase transitions involving blue phases and twist grain boundary phases are considered.     

Three important calorimetric applications of a classic thermodynamic equation

The thermodynamic background to three calorimetric techniques is discussed; (i) titration microcalorimetry, (ii) adiabatic calorimetry, and (iii) heat conduction calorimetry. Relevant equations for each technique are derived from a common equation for the enthalpy H of a closed system. General patterns which emerge in the measured parameters are presented for adiabatic and heat conduction calorimeters linked to applications of these techniques.     

Signal processing and uncertainty in an isothermal titration calorimeter

In this paper, it is made a study of the accuracy of an isothermal titration calorimeter in the operating mode of ‘continuous injection’. The experimental equipment has been a TAM2277-201/2250 by Thermometric AB and the liquid mixtures used in the calibration have been the mixture cyclohexane+benzene and the mixture water+ethanol. The calibration contemplates different effects that affect the uncertainty in the determination of the sensitivity, the effect of the liquid injection, the treatment of the calorimetric signal, the variation of the experimental baseline and the different noises included in the calorimetric signal.     

An evaluation and comparison of micro-techniques for concentration of volatile components from dilute solutions

Summary Several micro-techniques for the removal of solvent from dilute solutions of volatile compounds have been compared. Large solute losses were experienced when the conventional blow-down technique was applied. Better yields could be obtained with static evaporation procedures, as long as an effective reflux was maintained. However, careful optimization of the vessel design and operating conditions is necessary. The most efficient volume reduction technique was shown to be chromatographic evaporation. Quantitative recoveries were obtained for the compounds tested and the process was significantly faster than static concentration. Moreover, operating conditions (gas flow, temperature) are less critical. With modifications, the principle can be used for the concentration of large sample volumes down to a few microliters.     

量热分析化学放大方法及技术

该文从提高选择性、灵敏度和分析性能的角度,在富集、缓冲液放大、非水溶液体系、级联反应等方面评述了量热分析化学热焓放大的原理、方法以及关键技术,其中,富集是通过集聚提升待测物浓度来提高反应焓变;缓冲液放大利用缓冲液的质子焓变增强反应焓变;非水溶液体系可从热容量的角度提升量热灵敏度;级联反应由系列反应或循环完成,最终焓变是系列反应焓变的叠加,达到热焓放大目的。通过结合最新的研究成果和应用进一步阐明化学放大方法实现热焓放大能有效改善和提高量热分析系统的信噪比和降低检出限,并大大加强量热分析方法在现场、实际试样分析测试中的固有应用优势。同时,对当前存在的问题、挑战及未来的研究方向进行了探讨,并展望了其发展趋势和前景。     

Uncertainty analysis of theoretical methods for adiabatic temperature rise determination in calorimetry

The main methods for the determination of the temperature rise in calorimetric experiments corrected of heat losses to surroundings (called adiabatic temperature rise) are described thereafter. This corrected temperature rise is obtained analytically from experimental temperature–time curves. The general scheme reported by Henri Régnault and Leopold Pfaundler for the first time in the 19th century is considered as the basis for all methods elaborated afterwards. A bibliographical study raised five methods including Régnault–Pfaundler’s. These methods have been applied on five experimental temperature–time curves obtained with an isoperibolic reference gas calorimeter at the French national metrology and testing institute (LNE) on combustion of pure methane. This paper deeply details a new analytical method elaborated at LNE exposing best heat transfer phenomena representation occurring in the water bath calorimeter. A comparative study of the five methods of the temperature rise determination and of their associated uncertainties is here presented.     

Calorimetric study of the alpha-tocopherol solubility in reversed AOT micelles

The experimental data of heat of mixing (Q) for heterogeneous system alpha-tocopherol/AOT/n-heptane with and without water at 25 degrees C are presented. The Q dependence on AOT (sodium bis (2-ethylhexyl) sulfosuccinate) concentration, and R parameter defined as R=[H2O]/[AOT] with flow calorimetric method were investigated. Using the D'Aprano model (which is formally identical to that used earlier by Magid et al.) the binding constant (K), the distribution constant of alpha-tocopherol (K distr) between hydrocarbon and the micellar phase, and the standard enthalpy of transfer (DeltaH tr 0) of alpha-tocopherol from the hydrocarbon to AOT reversed micelles were calculated. The solubility of alpha-tocopherol in AOT reversed micelles explored with the calorimetric technique was compared to the literature data obtained respectively with UV spectrophotometry for reversed micelles and by other techniques for the phospholipid bilayer.     

Effect of testing conditions on the laser flash thermal diffusivity measurements of ceramics

Several experimental techniques either under steady state or transient heat transfer conditions, have been developed to evaluate thermal conductivity and thermal diffusivity of materials. However, testing difficulties resulting from specimen size, extended testing time and heat losses, have somewhat impaired the applicability of many of them. In this respect, the use of the laser flash technique for thermal diffusivity measurements, is a very convenient alternative, considering its basic modeling equation is independent of the temperature gradient as well as the heat flow, and in addition the heat losses can be analytically treated. Another important advantage of the technique is its rapid experimental execution. In this work, it is presented as an investigation concerning how the testing conditions such as specimen coating, laser power and pulse duration, base line adoption, heat losses correction methods, and specimen thickness, may affect the thermal diffusivity measurements of some ceramic materials using the laser flash technique.     

Column switching applied to capillary gas chromatography/fourier transform infrared spectroscopy

A dual oven gas chromatograph incorporating a micro, mechanical switching valve has been interfaced to an FTIR spectrometer. With this system, each oven can be operated with independent temperature control. Complete choice of the columns' type and capacity gives flexibility in the separation prior to spectroscopic evaluation. An application which demonstrates some of the advantages of column switching in GC/FTIR is presented. Minor sample components have been successfully analyzed by heart-cutting the appropriate section of the separation from a high to a low capacity column. In this way, the dynamic range of the technique is effectively increased while an efficient chromatographic inlet to the FTIR is maintained.     

Rapid, practical and predictive excipient compatibility screening using isothermal microcalorimetry

Conditions for conducting excipient compatibility studies via isothermal microcalorimetry were explored using model reactions. The resulting recommended procedure for rapid and practical screening consisted of using binary mixtures (100 mg of each component), the addition of 20% (w/w) water, and monitoring the mixture at 50°C for 3 days using an isothermal microcalorimeter. The correlation between calorimetric excipient compatibility results and formulation stability was investigated for two developmental drugs. A comparison of calorimetric results to actual formulation stability suggested that it was possible to predict relative stability within functional classes. However, caution should be exercised in such predictions, because apparent reaction enthalpies were found to vary three-fold among excipients in the same functional class. Based on these observations, a two-step procedure is suggested for efficient development of stable formulations. First, excipient compatibility screening should be conducted using a rapid calorimetric technique. The calorimetric results are then used to evaluate relative risk of incompatibility for each excipient within a particular functional class. The calorimetric data and the functional requirements of the dosage form are then integrated in developing a limited number of model formulations that are likely to succeed from both a performance and a stability perspective. The second step of the process is to conduct traditional HPLC-based accelerated stability studies on the limited number of model formulations.     

Some problerns in adsorption and calorimetric studies of the steps of catalytic processes

Principal side factors as well as technical and procedural peculiarities capable of distorting the results of measurements of adsorbed and desorbed amounts, of falsifying the nature of the processes proceeding in the systems under study, and of promoting artifacts in calorimetric and other studies of gas chemisorption on powders are considered. Modified techniques and procedures allowing the elimination of sources of side phenomena and artifacts and freeing traditional glass static adsorption apparatuses and experimental procedures from undesirable factors and peculiarities are proposed. Some available chemisorption and calorimetric data representing artifacts and also some data that are not artifacts but, due to imperfections of chemisorption techniques, show up as artifacts are presented and discussed. Several applications of the improved techniques and procedures to calorimetric and adsorption studies of the steps of catalytic processes proceeding on the basis of natural gas and of products of its pr     

Application of thermal analysis in solid industrial wastes treatment

The choice of an appropriate and safe disposal alternative should be based on the wide range of physicochemical examination thermal analysis in conjunction with other data enables identification of wastes, allows determination of weight losses at any stage of thermal decomposition and characterization of the combustible properties of wastes. In this paper the physicochemical composition of some industrial wastes, which create serious hazards to the natural environment is presented. The following waste materials were investigated:

tar wastes from several departments of the coking plant

paint-shop wastes from a metallurgical factory.

Thermoanalytic measurements were carried out in the dynamic atmosphere of air. Enthalpic values were calculated from the peak areas of the DTA curves. Thermoanalytic data were compared with calorimetric results obtained from an oxygen bomb. The disposal methods for above-mentioned wastes are proposed.     

Simultaneous determination of fundamental parameters for ferroelectric liquid crystals

An analysis of an experimental technique which allows for a simultaneous determination of several parameters with special interest for ferroelectric liquid crystals is presented. These parameters are the spontaneous polarization, the rotational viscosity and the switching time. In addition, the susceptibility associated with the soft mode free of contributions related to the helicoidal structure can also be obtained. The experimental results for these parameters for the ferroelectric liquid crystal HDOBACEEC are reported. A comparison between the switching time values deduced from the rotational viscosity and those obtained by optical measurements is performed.     

Surface oxidation and reduction of small platinum particles observed by in-situ X-ray diffraction

A new method is presented, in which the constructive Bragg interference intensity of small metallic clusters during the formation or decay of a surface compound is measured by an in situ X-ray technique. First results for a series of platinum catalysts supported on silica gel show intensity losses on the 111-peak of up to 40% under oxygen following a standard pretreatment. These losses are restored reversibly under hydrogen. The average thickness of the disrupted surface layer ranges between 0.9 to 4.0 Å depending on the treatment temperature and platinum crystallite size.     

Calorimetric methods for catalytic investigations of novel catalysts based on metallized S-layer preparations

The contribution will show the first results from calorimetric screening of novel catalysts. Biotemplated platinum nanoclusters were prepared on the basis of S-layer—bacterial surface proteins—on different supports. Methods were contrived and examined, permitting both the investigation of catalytic bulk material, and the investigation of sensory interesting coatings. The calorimetric measurements were carried out using conventional calorimetric technique (DSC 111, firm SETARAM) and miniaturized calorimetric systems (integrated circuit calorimeter - IC-calorimeter and a sensor platform). The results of the calorimetric investigations to the selected model reactions (oxidation of hydrogen, carbon monoxide and propane) demonstrate the interesting characteristics of these new catalysts.