Measurement of thermal conductivity by differential scanning calorimetry

A technique of measurement of thermal conductivity of solid materials by differential scanning calorimetry is presented. It concerns small samples having a diameter less than 8.0 mm, a height less than 2.0 mm and a low thermal conductivity. This method requires many samples with different heights which are heated in such a way that a calibration substance put on their top undergoes a first-order phase transition. The analysis of heat transfer of a such experiment predicts that the slope of the differential power during the transition is proportional to the factor 2 and inversely proportional to the sum of the thermal resistances. A measurement of the thermal conductivity of samples made of polytetrafluoroethylene powder, compressed at the density of 2.10±0.03 g cm⁻³, has been performed; the value obtained is 0.33±0.02 W m⁻¹ K⁻¹. Measurements of thermal conductivity of small metal hydride pellets are also presented. The precision of the measurements are on average 10%.     

Thermomechanical analysis (TMA) correlated to differential scanning calorimetry (DSC) for ageing study of some metallic glasses

To characterize the ageing of some metallic glasses, a correlated study of the differential scanning calorimetry method (DSC) and of the thermomechanical analysis (TMA) emphasizes the specificity of the latter. We analyzed metallic glasses which have been produced either by chemical methods or by melt spinning techniques. Using TMA and DSC, we have established that the relaxation of metallic glasses is strongly dependent on treatment applied: either thermal or mechanical history. Conversely, we do not observe large differences between DSC and TMA analysis for the crystallisation. From experimental data, we try to modelize the behaviour of this type of materials under operating conditions.The authors wish to thank Dr. H. Warlimont, Dr. Hilzinger and Dr. G. Herzer of Vaccumschmelze GmbH (Hanau F.R.G), Dr. E. Illekova and Dr. P. Duhaj of Institute of Physics (Bratislava, Tchecoslovaquie) for the scientific collaboration during which the melt spinned metallic glasses were supplied.     

Study of gelation using differential scanning calorimetry (DSC)

A new method for determining the degree of conversion of gelation (_gel) and gel time (t _gel) at gel point using a single technology, DSC, is discussed in this work. Four kinds of thermoset resins are evaluated. It is found that the mutation points of reduced reaction rate (V _r ) vs. reaction conversion () curves, corresponding with the changes of reaction mechanism, represents the gelation of the reaction. The at the mutation point is defined as _gel. From isothermal DSC curves, the point at _gel is defined ast _gel. Traditional techniques (ASTM D3532 and DSC method) are also used to determine _gel andt _gel in order to demonstrate this new method. We have found that the results obtained from this new method are very consistent with the results obtained from traditional methods.     

Differential scanning calorimetry study of haemin thermal stability

A differential scanning calorimetry study of the thermal behaviour of haemin in N,N-dimethylformamide solution was carried out. The samples were scanned with different scan rates in the temperature range 25-130°C. The UV VIS spectrophotometry was used as assistant measurement method. The scan rate dependent and irreversible exothermic peaks were found. The activation energies of observed transitions were calculated assuming kinetically controlled process. The nature of thermal behaviour of haemin in DMF solutions is discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

The limit of detection in differential scanning calorimetry

A procedure is described to determine the limit of detection of DSC instruments by using tiny signals from spontaneous polymorphic transitions of CsCl, K₂Cr₂O₇ and Na₂SO₄. It is shown how such signals can be found well-resolved in DSC diagrams of powder samples. To distinguish them from the baseline noise they should exhibit a height at least twice that of the baseline width. For the instrument employed the corresponding smallest amount of heat, i.e., the limit of detection, was found to be 0.1 mJ.The authors thank Mr. H. Maltry for technical help and the Deutsche Forschungsgemeinschaft for support.     

Effect of thermal history on kappa-carrageenan hydrogelation by differential scanning calorimetry

The effect of thermal history on gel-sol transition was investigated by highly sensitive differential scanning calorimetry (DSC) in order to clarify the non-equilibrium state of κ-carrageenan hydrogels. κ-Carrageenan with a concentration from 0.5% to 5.0% was used. When concentration of solution was lower than 2.0%, homogeneous κ-carrageenan gel was formed when aqueous solution was fully equilibrated. When concentration exceeded 3.0%, a sub-peak could be observed at the low temperature side of the main peak. It was indicated that helices having various sizes and different kinds of defects are present in the junction zone. Thermal histories, such as cooling rate from the sol state or annealing at around gel-sol transition temperature, markedly affect the junction zone formation. A large junction zone is formed at a slow gelation rate, and also that many small junction zones form at a fast gelation speed.     

Kinetic study of polyurethanes formation by using differential scanning calorimetry

Kinetics of polyurethane formation between several polyols and isocyanates with dibutyltin dilaurate (DBTDL) as the curing catalyst, were studied in the bulk state by differential scanning calorimetry (DSC) using an improved method of interpretation. The molar enthalpy of urethane formation from secondary hydroxyl groups and aliphatic isocyanates is 72±3 kJ mol^-1 and for aromatic isocyanates it is 55±2 kJ mol^-1 . In the case of a single second order reaction for aliphatic isocyanates reaction, activation energy is 70±5 kJ mol^-1 with oxypropylated polyols and 50±3 kJ mol^-1 with Castor oil. For aromatic isocyanates and oxypropylated polyols the activation energy is higher around 77 kJ mol^-1 . In the case of two parallel reactions (situation for IPDI and TDI 2-4) best fits are observed considering two different activation energies.     

Isothermal differential scanning calorimetry study of a glass/epoxy prepreg

Isothermal differential scanning calorimetry (DSC) was used to study the curing behavior of epoxy prepreg Hexply®1454 system, based on diglycidyl ether of bisphenol A (DEGBA)/dicyandiamid (DICY) reinforced by glass fiber. Cure kinetics of an autocatalytic‐type reaction were analyzed by general form of conversion‐dependent function. The characteristic feature of conversion‐dependent function was determined using a reduced‐plot method where the temperature‐dependent reaction rate constant was analytically separated from the isothermal data. An autocatalytic kinetic model was used; it can predict the overall kinetic behavior in the whole studied cure temperature range (115–130°C). The activation energy and pre‐exponential factor were determined as: E = 94.8 kJ/mol and A = 1.75 × 10¹⁰ sec^?1 and reaction order as 2.11 (m + n = 0.65 + 1.46 = 2.11). A kinetic model based on these values was developed by which the prediction is in good agreement with experimental values. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of codeine phosphate and codeine in thermal characterization by differential scanning calorimetry

Thermal behaviour of codeine phosphate and codeine crystallized at the several solvents system was studied by DSC, and then, the kinetic parameters and thermochemical data have been obtained. We have found that codeine phosphate and codeine exist in a number of polymorphic formes which may inflicence the bio-availability.     

A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

As a part of a study of the colloidal structures present in nonionic ointments, the interaction between polyoxyethylene and water is investigated. A series of mixtures of polyoxyethylene 1550 and water is studied using differential scanning calorimetry. Heating as well as cooling experiments are performed. The effects of the heat of mixing, supercooling and melting point depression on the measured enthalpy changes are discussed. From the non-freezing water fraction it is concluded that 2 water molecules per oxyethylene unit are tightly bound to the polymer chain. The observed differences between the cooling and the heating curves lead to a possible explanation for the alterations in the samples occurring at low temperatures. A hydrate structure of polyoxyethylene at low temperatures is proposed. Finally, comment is made on the phase diagram of the system polyoxyethylene/water.     

DSC and adiabatic calorimetry study of the polymorphs of paracetamol

Monoclinic (I) and orthorhombic (II) polymorphs of paracetamol were studied by DSC and adiabatic calorimetry in the temperature range 5 - 450 K. At all the stages of the study, the samples (single crystals and powders) were characterized using X-ray diffraction. A single crystal → polycrystal II→ I transformation was observed on heating polymorph II, after which polymorph I melted at 442 K. The previously reported fact that the two polymorphs melt at different temperatures could not be confirmed. The temperature of the II→I transformation varied from crystal to crystal. On cooling the crystals of paracetamol II from ambient temperature to 5 K, a II→ I transformation was also observed, if the 'cooling-heating' cycles were repeated several times. Inclusions of solvent (water) into the starting crystals were shown to be important for this transformation. The values of the low-temperature heat-capacity of the I and II polymorphs of paracetamol were compared, and the thermodynamic functions calculated for the two polymorphs. This revised version was published online in July 2006 with corrections to the Cover Date.     

Measurement of the sensitization of nitrocompounds by amines using differential scanning calorimetry

We report a new method of making empirical measurements of the sensitization of nitrocompounds by amines based on thermal analysis. The method is sensitive, accurate and reproducible. We have used this method to measure the sensitization of nitromethane, N-methyl-N-(2,4,6-trinitrophenyl) nitramine (tetryl), picric acid and trinitrotoluene (TNT) by a number of aliphatic amines.     

Effect of hydrothermal treatment on the gelatinisation properties of potato starch as measured by differential scanning calorimetry

Gelatinisation temperatures as a function of moisture content were determined for potato starch. The native starch was then hydrothermally treated at a temperature 3% (Kelvin degrees) below the gelatinisation peak temperature and at moisture levels varying from 20 to 67% (by weight). Gelatinisation temperatures, temperature ranges and enthalpy values were affected for all treated samples. However, two sample populations could be distinguished: those samples treated under limited moisture conditions and other samples treated in the presence of extragranular moisture. A two-step hydrothermal treatment further increased the gelatinisation temperature, but the effect of the second step was small in comparison to that of the first.We thank the Belgian Nationaal Fonds voor Wetenschappelijk Onderzoek for research positions as aspirant (H. Jacobs) and post-doctoraal onderzoeker (R. C. Eerlingen).     

Thermal analysis of the system KCL-LiCI by differential scanning calorimetry

Thermal analysis of the binary system KCl-LiCl in the composition range 0.368–0.812 mol fraction of LiCl was studied by differential scanning calorimetry (DSC). On the basis of the DSC curves, the experimental data for the phase-diagram, the latent heat of fusion, and the average specific heat in the liquid and solid states are presented as a function of the composition of the mixture. The experimental results compared with literature data. The following empirical correlation between the heat of fusion (H) and of compositions of the mixture in mol fraction of LiCl (x) was obtained: ·GH=26.95–50.20x+43.06x² with a minimum value of 11.8 kJ(g mol)^–1 at the eutectic point of 0.587 mol fraction of LiCl at 354.4°C. These results are required as basic data to develop thermal energy storage materials, based on the phase change of a molten mixture of KCl-LiCI.     

Differential scanning calorimetry (DSC) and Raman spectroscopy study of poly(dimethylsiloxane)

Poly(dimethylsiloxane) was studied by laser Raman spectroscopy and differential scanning calorimetry. The Si O Si skeletal mode at 489 cm⁻¹ and the C Si C deformation bands at 188 cm⁻¹ and 158 cm⁻¹ were studied as functions of temperature from ambient to −130°C, and effects of temperature interpreted in accordance with results from thermal analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2805–2810, 1998     

Temperature modulated differential scanning calorimetry (TMDSC) in the region of phase transitions. Part 1: theoretical considerations

For temperature modulated differential scanning calorimetry (TMDSC) a simple model, the low pass filter, is presented which allows to see and calculate the influence of heat transfer into the sample on magnitude and phase shift of the modulated part of the measured heat flow rate and the heat capacity determined from it. A formula is given which enables to correct the measured magnitude of the periodic heat flow rate function and the calculated heat capacity in dependence on the thermal resistance and heat capacity of the sample. The correction becomes very important in regions where the heat capacity changes considerably as in the melting region. The approach is successfully tested with model substances with well-known excess heat capacity in the transition region.     

A differential scanning calorimetry method to determine the isothermal crystallization kinetics of cocoa butter

This research aimed to reduce the variability on the data obtained from differential scanning calorimetric (DSC) analysis of the isothermal crystallization kinetics of cocoa butter.

To enable transformation of the DSC crystallization peak to a sigmoid crystallization curve, the DSC peak area has to be integrated. Usually, the start and end points of the crystallization peak are determined visually. The result of this visual determination appeared to be very much dependent on the operator, but also differed considerably when the same operator performed the integration several times. By proposing an objective calculation algorithm to determine the start and end points of integration, the variability caused by the operator during the integration procedure could be eliminated. Furthermore, sample preparation and the DSC heating protocol to melt the sample prior to crystallization were studied. Three heating protocols (65 °C for 15 min, 65 °C for 30 min and 80 °C for 15 min) were compared and it was shown that holding at 65 °C for 15 min was sufficient to eliminate any influence of sample history. Two different sample preparation procedures were compared and it appeared that a change in sample preparation procedure had a significant influence on the measured crystallization process. It is thus important to keep this method constant to eliminate the variability caused by it.