Glass transition of hydrated wheat gliadin powders

Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorption ranged from 2.30 db%to 18.21 db%.Glass transition temperature(I_g)of dry wheat gliadin was estimated according to the Gordon Taylor equation.Structural heterogeneity at high degrees of hydration was revealed in dielectric temperature and frequency spectra.The activation energies(E_a)of the two relaxations were calculated from Arrhenius equation.     

Relaxation dynamics and fragility during liquid–glass transitions of poly(propylene glycol)s

The acoustic and thermal properties of the liquid–glass transitions of propylene glycol and its oligomers, poly (propylene glycol)s, were studied by temperature modulated DSC and Brillouin scattering. The fragility indices were determined from Angell plots using the observed modulation frequency dependence of the complex heat capacity. The variation in the glass transition temperatures is discussed on the basis of the free volume theory. The relaxation time of the structural relaxation obeys the Vogel–Fulcher law, and its high frequency end is in good agreement with the result of the dielectric measurement in the literature. The correlation between the observed thermal expansion coefficients and the glass transition temperature is discussed based on the free volume theory. The sound velocity and attenuation were accurately determined as a function of the temperature by Brillouin scattering by combination with the refractive index measurement. The relaxation dynamics were discussed by considering the relaxation from segmental motions. All of these physical properties were discussed based on the third-order anharmonicity and the Grüneisen parameter.     

Square modulated differential thermal analysis

KMnF₃ and DKDP crystals have been studied around their phase transitions using a conduction calorimetry technique where a long periodical square thermal pulse (0.05 K in amplitude) is superposed to a heating or cooling ramp as low as 0.06 K h⁻¹. Specific heat data obtained in the dissipation and relaxation semiperiods of the square pulse become different inside the phase transition interval. The electromotive force developed by the heat fluxmeters at the end of the relaxation semiperiod (underlying signal) is compared with the DTA trace obtained in a second run with the same temperature ramp but without the modulated perturbation. The comparison between the DTA trace and specific heat data obtained in the first run allows us to determine the value of the latent heat and to obtain information about the kinetic of the phase transition.     

Thermal properties of polypropylene post-consumer waste (PP PCW)

Differential scanning calorimetry has been used to study the heat flow during melting and crystallisation of a range of polypropylene post-consumer waste (PP PCW) grades and blends. The heat flow curves and the heat capacity curves indicated that the PP PCW grades and blends contained contaminants even after manual sorting and a cleaning process. The enthalpies of the PP PCW grades were lower than that for the virgin grades, as a result of degradation. Small amounts of polymeric contaminants (up to 10%) did not affect the enthalpies of PP PCW although other contaminants may have had some effect. The enthalpies of the PCW blends could in general be predicted by a linear additive rule, which is of importance for recycling a variety of PP PCW products.The authors would like to thank Dr. M. Killen (Basell Australia Pty. Ltd.), Mr. P. Slaven (Citiwide MRF), Dasma Valley Waste Prop. Ltd. and Mr. I. Janetzki (Huhtamaki Australia Ltd.) for supplying materials for this project. Financial support for the project was provided by Basell Australia and Ecorecycle Victoria, Australia.     

Non isothermal heat capacities and chemical reactions using a modulated DSC

An evaluation of measurements of heat capacities by modulated differential scanning calorimetry, MDSC is presented. Heat capacities were obtained from 130 to 550 K by a non isothermal technique in which a periodic modulation was added to the linear heating rate. Effects of amplitude and period of modulation, sample weight, sample type, pan type, and cell imbalance are described. Results are compared with those obtained using the isothermal technique. Heat capacity could be measured well into the decomposition region and separated from the non reversing signal due to chemical reaction (degradation), thus allowing a precise detection of onsets of the thermal degradation. This additional information will aid in the interpretation of the degradation chemistry, a field vital for the petroleum-industry.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayPart of this paper was presented at the 23rd Conference of the North American Thermal Analysis Society, Toronto, Canada, September 25–28, 1994.The author (MVN) acknowledges the experimental assistance provided by J. Balogh of Exxon Research and Engineering Company, Linden. Helpful discussions with A. Boller of the University of Tennessee at Knoxville, Dr. Y. Jin, General Electrical, and Dr. S. Sauerbrunn formerly of TA Instruments are also acknowledged.     

Reversible Melting of Semi-Crystalline Polymers 2. Annealing Near to the Melting Point

Annealing experiments have been carried out at a few degrees below the melting point of different polyethylenes (LDPE, LLDPE, HDPE), of polypropylene (PP) and of Nylon-6. The heat capacities decrease during the annealing, within a 2-4 min time scale, to a lower value which corresponds to the extrapolated heat capacity values obtained for the cooling cycle when the polymer is cooled from the melt. Heat capacities in the heating cycle following the cooling cycle of PP, Nylon-6 and HDPE have the same value as during the cooling section. This is not the case for LDPE and LLDPE. Exothermic total heat flow in the cooling section following the annealing indicates that the crystallisation takes place during the cooling rather than during the annealing period. The total melting enthalpy measured before and after the annealing cycle is the same. The reversing heat flow shows an excellent fit to the change of the crystallinity measured by small angle scattering of synchrotron radiation during a heating cycle at temperatures below the melting peak. A coupled thermodynamic interaction of the crystalline and the amorphous phases is concluded from this study. This kind of interaction is possible at the lateral end of polymeric chains incorporated into the crystalline phase. This is an indication of the portion of tie molecules in the system, i.e. the portion of fringed micelle type of crystalline morphology with respect to that of folded chain lamellae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of the influence of isomerism on the curing properties of the epoxy system DGEBA (n=0)/1,2 DCH by DEA and MDSC

Summary Modulated differential scanning calorimetry (MDSC) and dielectric analysis (DEA) have been used to characterize the cure process of the system diglycidyl ether of bisphenol A (DGEBA(n=0)/1,2 diaminocyclohexane (1,2 DCH). The trans isomer and a mixture cis/trans(30-70% respectively) of 1,2 DCH were used to find their different behaviour. The study allowed to check the influence of the cisisomer on the thermoset curing process. Gelation times were obtained through the equation proposed by Johari and vitrification times from the point of inflection of the complex calorific capacity modulus.     

Thermal Analysis,Microcalorimetry and Combined Techniques for the Study of Pharmaceuticals

Modern thermal analysis, microcalorimetry and new emerging combined techniques which deliver calorimetric, microscopic and spectroscopic data offer a powerful analytical battery for the study of pharmaceuticals. These techniques are very useful in all steps of development of new drug products as well as methods for quality control in production. The characterization of raw materials enables to understand the relationships between polymorphs, solvates and hydrates and to choose the proper development of new drug products with very small amount of material in a very short time. Information on stability, purity is valuable for new entities as well as for marketed drug substances from different suppliers. Excipients which vary from single organic or inorganic entity to complexes matrixes or polymers need to be characterized and properly controlled. The thermodynamic phase-diagrams are the basis of the studies of drug-excipients interactions. They are very useful for the development of new delivery systems. A great number of new formulations need proper knowledge of the behaviour of the glass transition temperature of the components. Semi-liquid systems, interactions in aqueous media are also successfully studied by these techniques. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influence of the chain length on the nematic-to-isotropic phase transition for the odd members of a highly non-symmetric pyrene-based series of liquid crystal dimers

This paper describes a detailed study of the nematic (N)-isotropic (I) phase transition in the homologous series of liquid crystal dimers, the α-(4-cyanobiphenyl-4?-oxy)-ω-(1-pyreniminebenzylidene-4?-oxy)alkanes (CBOnO.Py) by means of calorimetric and dielectric measurements as a function of temperature. It is concluded that for this transition, the latent heat or the entropy change decreases as the chain length of the odd dimers decreases, and this decrease is consistent with the observed tricritical behaviour.     

调制差示扫描量热法在高分子材料中的应用

调制差示扫描量热法(MDSC)是在传统线性变温基础上叠加一个正弦震荡温度程序,将总热流量分解为可逆热流(热容成分)和不可逆热流(动力学成分),同时具有较高的灵敏度和分辨率,在研究高分子材料复杂相变时具有独特的优势。近年来,MDSC在研究高分子材料的玻璃化转变、结晶-熔融、热容变化等领域得到了较为广泛的应用。本文对MDSC近年来在高分子材料中的最新研究应用做了详细介绍。