Search Results
Optimization of instrument response and resolution of standard- and high-speed power compensation DSC
Benefits for the study of crystallization, melting and thermal fractionation
Abstract
Normally, for Standard DSC, the PerkinElmer power-compensation setting is the low dynamic range mode (LDRM). In this mode, a noise filter is applied to decrease the noise-to-signal ratio, which concomitantly gives rise to a delay in time of the signal measured. In case the signal is expected to be of high intensity — experienced for instance at high scan rates using High Performance DSC (HPer DSC) — the noise filtering could be diminished by which the associated delay in time would be less, leading to a faster response of the instrument, also resulting in an improved resolution. In fact, such can be realized using the faster noise filter of the high dynamic range mode (HDRM) available for the Pyris 1 and Diamond DSCs, which DSCs are both equipped with the HyperDSCTM technique (HyperDSC being the commercial version of HPer DSC). The improvement in response is maximal for high rates like 100–500°C min−1 but even at low rates like 10°C min−1 it is still significant. Thus, taking advantage of HDRM, low-molar substances like indium and 4,4′-azoxyanisole show appreciable increasing height-to-width ratios for signals caused by crystallization, melting and the crystal <>liquid crystal transition respectively. Another advantage, the faster realization of steady state after the starting of the DSC, is of help in case of overlapping starting and transition signals during dynamic crystallization and melting, and during isothermal crystallization as elucidated for a HDPE. For 4,4′-azoxyanisole and for an ethylene-propylene copolymer having a broad melting range, it is shown that such faster response leads to a still better resolution with respect to temperature, even at high scan rates. Thus, the peaks belonging to the crystal-to-liquid crystal and the liquid crystal-to-isotropic liquid transitions of 4,4′-azoxyanisole were completely resolved while a thermal fractionation of the copolymer by the successive self-nucleation and annealing (SSA) technique with good resolution has been realized, both using rates as high as 200°C min−1.
Abstract
Initial plant scale trials of the nitrosation of an amino acid revealed a number of issues: _ Much lower yield compared to laboratory scale _ Considerable loss of mass balance _ Large excess of nitrosating agent required for complete reaction _ Highly reactive off-gases produced causing fires in the carbon absorber _ Reaction sensitive to agitation speed _ The by-product produces an impurity in the next process stage which has high human toxicity A kinetic and mechanistic study of the nitrosation reaction, using isothermal power compensation calorimetry and GC/mass spectrometry, has been undertaken in order to understand the above observations and to produce an improved manufacturing process - more robust, higher yielding, reduced effluent volumes and toxicity.
Abstract
A modulated temperature power compensated differential scanning calorimeter, MTDSC, has been built from a standard Perkin-Elmer DSC model-2 such that a computer generated voltage has been applied to induce a sinusoidal change in sample temperature superimposed on a linear heating rate. The effect of amplitude of the temperature fluctuation, modulation period and block temperature on the reversibility has been assessed from the Lissajous diagram of heat flow vs. sample temperature. From their reproducibility and symmetry the most effective conditions for operating the MTDSC has been deduced. The specific heat of sapphire has been measured using these operational conditions for comparison with conventional DSC. Phase separated blends of polycarbonate (PC) and polyethylene terephthalate (PET) have been analysed.
Abstract
A small scale (100 mL) calorimeter is developed. It includes a glass vessel submerged in a thermostatic bath, a compensation electrical heater, and a control system. The typical operation mode consists on introducing the solvents and part of the reactants into the vessel, to stabilise a temperature of the bath (T j) some degrees below the desired process temperature (T p) and to adjust the reaction mass temperature (T r) to T p using the electrical heater. An oscillating set point is established for Tr, which produces an oscillating response of the applied compensation power (Q c). Finally, the rest of reactants are dosed to the vessel. A small deviation of T r and T p is observed. Even though it can be avoided improving the tuning of the controller, it can be useful for enhancing the calculation of the heat capacity of the reaction mixture (C P). The signals of T r, Q c and T j are processed on-line using the FFT (Fast Fourier Transform) method as the mathematical tool used to analyse the data obtained, producing accurate values of the heat evolved (Q c) by the process, the heat transfer coefficient (UA), and the heat capacity of the reaction mixture (C P).
Abstract
Scanning calorimetric methods permit determination of heat capacities at high temperatures up to 1600C. For disk systems with power compensation application limits are in order of 700C, and for cylindrical systems with electrical calibration up to 1000C. For the high temperature range above 1000C DSC plates and a cylindrical calorimetric systems based on the CALVET principle ('MULTI HTC’) are known. For cylindrical calorimetric systems the precision of the Cp data is between 2 and 5% even at high temperatures without any requirements on the kind and shape of samples. These results are better than data provided by DSC plate systems.
Abstract
With some attention to temperature calibration but no other special precautions the temperatures of both solid-solid and melting transitions can be determined to within a few tenths of a Kelvin of absolute values in a range of heat-flux and power-compensation DSC instruments. Materials showing several solid-solid transitions are potentially useful multiple calibrants but require some work to define appropriate thermal treatments that lead to reproducible behaviour.
Abstract
The determination of heat capacity data with sawtooth-type, temperature-modulated differential scanning calorimetry is analyzed using the Mettler-Toledo 820 ADSC™temperature-modulated differential scanning calorimeter (TMDSC). Heat capacities were calculated via the amplitudes of the first and higher harmonics of the Fourier series of the heat flow and heating rates. At modulation periods lower than about 150 s, the heat capacity deviates increasingly to smaller values and requires a calibration as function of frequency. An earlier derived correction function which was applied to the sample temperature-controlled power compensation calorimeter enables an empirical correction down to modulation periods of about 20 s. The correction function is determined by analysis of the higher harmonics of the Fourier transform from a single measurement of sufficient long modulation period. The correction function reveals that the time constant of the instrument is about 5 s rad−1 when a standard aluminum pan is used. The influence of pan type and sample mass on the time constant is determined, the correction for the asymmetry of the system is described, and the effect of smoothing of the modulated heat flow rate data is discussed.
The thermal decomposition of NaHCO3 powders and single crystals
A study by DSC and optical microscopy
Abstract
The thermal decomposition of four commercial powders and of differently stored single crystals of sodium hydrogen carbonate is studied by power compensation DSC and by optical and FT-IR microscopy. Independently of manufacturer, specified purity and price, the thermal curves of all the commercial powders show a more or less pronounced low temperature peak preceding the one due to the main decomposition. Such small peak is not observed when samples of laboratory recrystallized material are used. However the thermal behaviour of the latter preparation differs remarkably depending on storage conditions: the material kept in closed glass containers decomposes at temperatures higher than those of the material stored in a dessiccator in the presence of concentrated H2SO4. The observation by optical microscopy of the behaviour of the surfaces of single crystals coming from different storage conditions when the temperature is raised in a Kofler heater helps the interpretation of the data collected. The mechanism of the decomposition is discussed and the relevant kinetic parameters reported.
A. Chebbo R. K. Aggarwal 2005 Genetic Algorithms for Optimal Reactive Power Compensation on the National Grid System IEEE
