Determination of kinetic parameters in TG and DSC by means of direct overall evaluation of simple and complex reactions

For kinetic evaluation by TG and DSC of simple and complex reactions we used a direct fit on the basis of TG differential equations and DSC non-linear equations. The advantages of an overall evaluation, i.e. the simultaneous inclusion of all data sets at different heating rates, are described. TG and DSC measurements of the dehydration of calcium oxalate monohydrate and the decomposition of calcium oxalate are used as examples.     

Adapting a thermobalance to constrained rate thermogravimetry

A thermobalance has been converted to allow interactive control of the heating rate from the rate of mass loss of the sample (Constrained Rate Thermogravimetry). The interfacing of the balance and temperature controller both to an ACORN RISC microcomputer and to a PC microcomputer is described along with an outline of the software required. This provides an economic route for the conversion of existing thermobalances. Problems of achieving effective control and acceptable data recording are outlined. The nature of the TG curves obtained from interactive temperature control and the influence of control parameters is discussed.     

A new apparatus for simultaneous differential thermal analysis and gas evolution analysis

A new apparatus is described which permits the simultaneous recording of the differential thermal analysis and gas evolution curves for a given sample from ambient to 900°. The sample is pyrolyzed in a dynamic helium gas atmosphere using a conventional DTA furnace and sample holder assembly. The evolved decomposition products are detected in the helium gas stream by means of a thermistor thermal conductivity cell. From a knowledge of the GE curve and an analysis of the decomposition products, a more accurate interpretation of the DTA curve can be made.     

Effect of side chains in block polycarboxylate superplasticizers on early-age properties of cement paste

The design and development of a macro-thermogravimetric (TG) analyzer are presented. Two sources of measurement bias are studied: balance heating and the effect of viscous forces. Temperature regulation and measurement are discussed. In a second part of the study, results obtained with the newly developed macro-TG system for the dehydration of CuSO₄·5H₂O are compared with data obtained with a commercial thermobalance. The effects of mass and of the heating rate on TG and differential TG curves are discussed. Finally, the effect of the initial mass of a polyethylene sample on its combustion is studied as an example application of the macro-TG device.     

Kinetic analysis of complex decomposition reactions using evolved gas analysis

For complex decomposition reactions, traditional methods, such as TG and DSC cannot fully resolve all of the steps in the reaction. Evolved gas analysis (EGA) offers another tool to provide more information about the decomposition mechanism. The decomposition of sodium bicarbonate was studied by TG, DSC and EGA using a simultaneous thermal analysis unit coupled to a FTIR. The decomposition of sodium bicarbonate involves two reaction products H₂O and CO₂, which are not evident from either TG or DSC measurements alone. A comparison of the reaction kinetics from TG, DTG and EGA data were compared.     

Energy-dispersive X-ray fluorescence spectrometer for analysis of conventional and micro-samples: Preliminary assessment

The energy-dispersive X-ray fluorescence spectrometer for analysis of conventional and micro-samples using pinhole collimators of various sizes is developed. The measurements can be performed in the air or, in order to decrease the absorption of long-wavelength radiation of low-Z elements, in helium atmosphere. The sample is excited by the air-cooled Rh target X-ray tube of ca. 100 μm nominal focal spot size and maximum power 75 W. The X-ray spectra of the samples are collected by thermoelectrically cooled Si-PIN detector. The tungsten pinhole collimators of the size holes from 50 to 2000 μm are placed between primary filter and analyzed sample to reduce size of analyzed area. The sample can be moved using the X–Y stage. The position of the sample is monitored by CCD camera and two laser pointers. The beam spot sizes for various collimators are evaluated by the thin-wire and knife-edge methods. Beside the beam spot sizes, the loss of radiation intensity and the changes of spectral distribution of the incident radiation caused by applying various collimators are also investigated. The sample-surface-down geometry in the designed spectrometer allows for a simple analysis of various samples: solutions, loose powders, solid samples of conventional size and micro-samples.     

Thermal decomposition mechanism of synthesized copper octoate

Present study describes the synthesis and characterization of copper octoate. Attenuated total reflectance–Fourier transformation infra red (ATR–FTIR) and energy dispersive X-ray (EDX) spectrometric techniques have been used for the characterization of the synthesized compound. The surface morphology of the compound has been studied using scanning electron microscopy (SEM). Thermal behavior and decomposition mechanism of copper octoate has been explained on the basis of simultaneous thermo-gravimetry–differential thermal analysis–evolved gas analysis (TG–DTA–EGA) and high temperature X-ray diffraction (HTXRD) measurements. Copper octoate is stable up to 250 °C. The decomposition process consists of two overlapping steps. A plausible decomposition mechanism is proposed and details of the studies carried out are being discussed here.     

A novel direct coupling of simultaneous thermal analysis (STA) and Fourier transform-infrared (FT-IR) spectroscopy

Evolved gas analysis (EGA) from thermal analyzers such as thermogravimetry (TG) or simultaneous thermal analysis (STA) which refers to simultaneous TG–DSC is well established since it greatly enhances the value of TG or TG–DSC results. The sensitive and selective FT-IR technique is in particular useful for the analysis of organic molecules but also for infrared active permanent gases evolved during most decomposition processes. The coupling interface between thermal analyzers and FT-IR spectrometers usually consists of heated adapters and a flexible, heated transfer line. In this work, a novel direct coupling of an STA instrument and an FT-IR spectrometer without a transfer line is presented. A very small FT-IR spectrometer is directly mounted on top of the STA furnace leading to a compact and fully integrated STA–FT-IR coupling system. The possibilities and the value of simultaneous STA–FT-IR measurements are demonstrated for organic, biomass, and ceramic samples in the temperature range between room temperature and about 1,500 °C. Various samples from the field of inorganics and organics—especially polymers—were furthermore measured showing the advantages of the direct STA–FT-IR coupling compared to state-of-the-art STA–FT-IR coupling using a heated transfer line: we found that the time delay caused by the volume of the transfer line itself is rather negligible whereas a significantly better correlation between gas detection and TG results was observed in case of some highly condensable decomposition gases. Aspects of quantification of evolved gases are furthermore discussed as well as the known nonlinearity of FT-IR detection at higher gas concentrations.     

Measurement of heterogeneously catalyzed gas reactions by DSC

Gas reactions, catalyzed by solid catalysts, can be measured by DSC. In the experimental set-up an open sample pan with catalyst (powder or pellet) is placed on the sample side of the DSC sensor. The reactive gas mixture flows through the cell and reacts on the catalyst surface. The heat effect, caused by this reaction, results into a DSC signal.The calibration procedure is described for quantitative evaluation of the DSC measurements. For illustration four different reaction systems are discussed.     

Sample Preparation Techniques—An Important Part in Trace Element Analysis for Environmental Research and Monitoring

Abstract

For the determination of minute amounts of elements in environmental samples combined analytical procedures are frequently employed. The combination of suitable sample preparation techniques with adequate detection methods lead to powerful analytical procedures. Decomposition methods are an important part of combined procedures for the determination of trace elements in solid samples. After a short summary of the potential sources for systematic errors two new decomposition methods are described that are suitable for the ashing of organic environmental samples. In one method the organic sample is ashed in a high-frequency excited oxygen plasma. The second method is a high pressure decomposition that permits mineralization of the sample in sealed quartz vessels with nitric acid at temperatures up to 320°C.

For both methods the ratio of sample weight to decomposition reagents is comparatively high. This makes these methods in combination with adequate detection methods suitable for the determination of elements at very low concentrations.

X-ray fluorescence spectrometry combined with adequate preconcentration methods is very well suited for the simultaneous determination of trace elements. Following a critical evaluation of various preconcentration techniques the analytical characteristics of filter paper with immobilized complexing agents are described. Particular emphasis is given to filter papers with dithiocarbamates as chelating group.     

Design of an apparatus for polarization measurement in soft X-ray region

A novel apparatus for polarization measurement in the soft X-ray region has been designed, constructed, and installed in the evaluation beamline for soft X-ray optical elements (BL-11) at the SR Center of Ritsumeikan University, Shiga, Japan. It allows us to perform conventional reflection and transmission measurements including rocking curve measurement as well as polarimetric and ellipsometric measurements based on the rotating-analyzer method by using six independently movable motorized stages. As a preliminary test of the apparatus, the reflection profile of a Mo/SiO₂ multilayer mirror prepared by an ion beam sputtering technique, which is designed as a reflection polarizer for use of 13.9 nm, has been measured by the apparatus. The result is compared with that by an existing reflectometer, and the azimuth angle dependence of the reflection intensity has been demonstrated. Consequently, it is shown that the apparatus has the capability to perform the rotating-analyzer ellipsometry.     

Thermogravimetric investigation ofwastes from electrical and electronic equipment (WEEE)

Two components of electronic wastes (sample A – a mixture of three types of printed circuit boards, sample B – a mixture of electronic junctions with metal wires) were investigated using thermogravimetric analysis (TG). Thermogravimetric and derivative thermogravimetric data (TG and DTG) give information on the thermal stability of A and B samples and allows finding the correct conditions for their degradation using pyrolysis in an experimental system, built on the laboratory scale for utilization of hazardous wastes. X-ray fluorescence measurements prove that brominated flame retardant is present in sample A, whilst chlorinated flame retardant is a probable component of sample B. Preliminary liquid chromatography of oil products obtained as a result of thermal waste degradation shows that the hydrocarbons released during pyrolysis could be used as a fuel.     

Thermal decomposition of tetraalkylammonium iodides

A number of tetramethylammonium (TMA) iodides, including mono-, tri-, and pentaiodide, were synthesized. Thermal decomposition of samples was investigated by simultaneous TG–DSC analysis accompanied by gaseous IR- and mass-spectrometry analyses. Two different reaction pathways have been observed for TMA pentaiodide at different heating rates. At low heating rates (1–5 K min^?1), a gradual mass loss takes place and a stability plateau due to monoiodide formation exists on TG curve. At high heating rates (10, 15 and 7 K min^?1 as the in-between stage), there are only two peaks on DTG curve (instead of three for lower heating rates) and no monoiodide formation is observed as the sample decomposes completely before 350 °C.     

Electrical conductivity measurements during the thermal decomposition reaction of ammonium metavanadate

Electrical conductivity vs. temperature curve shows all characteristic peaks due to individual stages of the thermal decomposition reaction of NH₄VO₃, including the stage of formation of the anhydrous ammonium divanadate at ～150°, obtainable only under special experimental conditions on TG, DTG, and DTA curves. It is suggested that such measurements can be used for detecting and/or confirming the existence of intermediate solid products of decomposition in case they are difficult to be identified.     

Modern vacuumbalances

Different types of vacuum balances have been developed corresponding to the various applications [ 1 ]:

Special beam balances are applied for metrology and thermogravimetry and for the investigation of physical and chemical reactions of solid samples with the gas phase. Today, with all these balances the beam deflection is observed by an inductive or photoelectric sensor and electromagnetically restored.

In corrosive atmospheres or under very clean conditions e.g. for investigations in ultrahigh vacuum the magnetic suspension balance should be favoured. The sample tube is separated from the balance and can be hermetically sealed from the environment. It contains only the pan with the sample connected to a permanent magnet, suspended at a stable position in the field of a controlled electromagnet. The carrying balance is electrodynamically compensated.

The spring balance is an inexpensive alternative, if a minor relative resolution can be accepted. The simple design utilizing only few materials enables measurements under very clean conditions. A quartz spring allows for investigations in corrosive atmosphere. The extension of the spring is observed optically or by means of an inductive sensor.

Quartz resonators are used to control vacuum metallizing and other evaporating and sputtering processes. Resonator systems of any type need no gravitational field and can be applied, therefore, in space technology. The mass determination is restricted to samples which are strongly connected to the surface of the sensor.

     

Solid—liquid phase diagrams of mixtures containing substituted phenols and amine mixtures

The thermal decomposition of CaCO₃ was studied under high vacuum by means of both TG and the more recently developed constant decomposition rate thermal analysis (CRTA) which allows the monitoring of both reaction rate and the residual pressure over the sample. The reliability of the kinetic results seems to be much higher with the latter technique which actually allows the reduction of the reaction rate and therefore the heat and mass transfer effects over a broad range of sample size. For instance, it was necessary, by conventional TG started under a vacuum of 2 10^?6 torr with a heating rate of 0.5 K min^?1, to lower the amount of sample to 2 mg in order to obtain the same activation energy as that calculated from CRTA with various samples weighing up to 50 mg. The TG experimental conditions quoted above (and which are upper limits of mass and heating rate) are beyond the limit of sensitivity of most available conventional TG equipment.     

Monte Carlo simulation of RRKM unimolecular decomposition in molecular beam experiments. I. Basic considerations and calculational procedure

A simulation method is described for the comparison of a molecular decomposition theory, based on the fundamental RRKM theory, with crossed molecular beam experiments. In the present formulation, the method is applied to the case with long-lived collision complexes surrounded by a centrifugal barrier. The procedure uses Monte Carlo techniques to simulate the formation and decomposition of the complexes, thus effectively solving the high-dimensional integrals resulting but seldom solved in the analytical treatments. Several computational problems, like singularities in the c.m. angular distributions, have been circumvented in this procedure. Angular momentum conservation, the simultaneous interaction of several decomposition channels and strict flux conservation are included in the procedure. Dynamical features can be introduced, as will be shown in forthcoming papers.     

A simple automatic titrator based on a digital balance

A computer-controlled automatic titrator incorporating a weight burette is described. The titration vessel is mounted on the pan of a zero-displacement digital balance which records the weight of added sample as well as the weight of titrant added during the titration.     

Thermal decomposition of some metal sulphates

The thermal decomposition temperatures of some metal sulphates (iron, copper, cobalt, nickel, zinc and lead sulphates) have been investigated by TG and DTA. The mechanism of decomposition of these sulphates is discussed, making use of additional information obtained from isothermal studies and X-ray diffraction measurements. The activation energies of these reactions were calculated and found to increase, with almost the same increments, in the order Zn<Fe<Co<Ni<Cu.