Modeling the heat flow and heat capacity of modulated differential scanning calorimetry

Modulated differential scanning calorimetry (MDSC) uses an abbreviated Fourier transformation ?r the data analysis and separation of the reversing component of the heat flow and temperature signals. In this paper a simple spread-sheet analysis will be presented that can be used to better understand and explore the effects observed in MDSC and their link to actual changes in the instrument and sample. The analysis assumes that instrument lags and other kinetic effects are either avoided or corrected for.     

Closer relation between thermal analysis and calorimetry

Several DTA experiments followed by calorimetric works are reviewed here to emphasise the importance of complementary role of both techniques. The thermal analysis is advantageous in the sense that it gives quickly the overall view of thermal behaviour of a material under various conditions. Calorimetric work provides accurate heat capacity data which enable to derive thermodynamic functions including the enthalpy and entropy. The latter quantity is especially important in judging whether the material obeys the third law of thermodynamics. However, calorimetric work leads occasionally to an erroneous conclusion if the work is not preceded by thermal analysis performed under various conditions. Sometimes, quality of information obtained by DTA exceeds that obtained by laborious calorimetry.     

Thermal conductivity of Tetryl by modulated differential scanning calorimetry

An investigation of the use of modulated differential scanning calorimeter (MDSC) to measure thermal conductivity (κ) of the explosive Tetryl using isothermal and non-isothermal methods. Issues surrounding the use of silicone oil as a heat transfer aid are discussed. Using these methods the calculated isothermal and non-isothermal properties of specific heat capacity were observed to be 0.844 and 0.863 J/(g K) and the calculated thermal conductivity values were found to be 0.165 and 0.186 W/K. Calibration experiments using polystyrene indicate that the non-isothermal method is more reproducible but has a larger offset (35%) from the true value. Our corrected values for Tetryl fall in the middle of the considerable range of values reported in the literature.     

The application of modulated differential scanning calorimetry to the glass transition

The modulated differential scanning calorimetry (MDSC) technique superimposes upon the conventional DSC heating rate a sinusoidally varying modulation. The result of this modulation of the heating rate is a periodically varying heat flow, which can be analysed in various ways. In particular, MDSC yields two components (reversing and non reversing) of the heat flow, and a phase angle. These each show a characteristic behaviour in the glass transition region, but their interpretation has hitherto been unclear. The present work clarifies this situation by a theoretical analysis of the technique of MDSC, which introduces a kinetic response of the glass in the transition region. This analysis is able to describe all the usual features observed by MDSC in the glass transition region. In addition, the model is also able to predict the effects of the modulation variables, and some of these are discussed briefly.Financial support has been provided by the DGICYT (Project no.PB93/1241). J.M.H. wishes to acknowledge financial assistance for a sabbatical period from the Generalitat de Catalunya.     

Evaluation of interfacial region of microphase-separated SEBS using modulated differential scanning calorimetry and dynamic mechanical thermal analysis

The continuous structural changes of Poly(styrene-b-ethylene-butylene-b-styrene) [SEBS] due to the effect of temperature are hard to evaluate using conventional differential scanning calorimetry (DSC). This paper presents an accurate and simple way to evaluate microstructural and glass transitions of SEBS using modulated differential scanning calorimetry (MDSC). The weak crystalline nature of –(CH₂-CH₂)–_n in the ethylene-butylene (EB) block melted around 36 °C. The premature molecular moment and Tg of the styrene block were at 62 °C and 96 °C, respectively. The interfacial region at high temperature was explained with respect to order-order transition (OOT) at 144 °C and a prominent Order-Disorder Transition (ODT) at around 202 °C. Dynamic mechanical thermal analysis (DMTA) and dynamic mechanical rheological testing (DMRT) measurements also revealed that the T_g of the PS transition were consistent at around 96 °C.     

The application of thermal analysis and conduction calorimetry on the formation and hydration of calcium aluminoferrite

DTA was used to study the formation of calcium aluminoferrite from CaO, Al₂O₃ and Fe₂O₃ (proportion=2 x 1–x),x=0-3/4) and the effects of C4A₃ C₁₁ A₇·CacF₂, -C₂S and MgO on that process. The fusion of CF and the eutectic of CaO-Fe₂O₃, CA-C₁₂A₇, CA-C₃A, C₁₂A₇-CA-C₃A and CA-C₂A_xF_(1–x) will be favourable for the formation. The presence of -C₂S and MgO will decrease its formation temperature by an extra eutectic while C₄A₃ . and C₁₁A₇·CaF₂ will not.The early heat evolution during the hydration of C₂A_xF_(1–x) were measured by the conduction calorimeter made by ourselves and the products after 1 day hydration were examined by TG and DTA. The results revealed that the peak of heat evolution rise, the amount of the hydrating product iron hydrate gel decreases, CAH₁₀ and C₃(A, F)H₆ increase with the increase of the value x. The more MgO (up to 5%) soluted in C₆AF₂, the higher the hydration heat for this solid solution is, when TiO₂ soluted in C₆AF₂ is 2%, the hydration heat for the system reaches the highest.This project is supported by National Natural Science Fundation of China and by the National Science and Technology Developing Fundation in Building Materials Field.     

Isothermal crystallization of concentrated amorphous starch systems measured by modulated differential scanning calorimetry

The slow isothermal crystallization of concentrated amorphous starch systems is measured by Modulated Differential Scanning Calorimetry (MDSC). It can be followed continuously by the evolution (stepwise decrease) of the MDSC heat capacity signal (Cp), as confirmed with data from X-ray diffractometry, Dynamic Mechanical Analysis, Raman spectroscopy, and conventional Differential Scanning Calorimetry. Isothermal MDSC measurements enable a systematic study of the slow crystallization process of a concentrated starch system, such as a pregelatinized waxy corn starch with 24 wt % water and 76 wt % starch. After isothermal crystallization, a broad melting endotherm with a bimodal distribution is observed, starting about 10°C beyond the crystallization temperature. The bulk glass transition temperature (T_g) decreases about 15°C during crystallization. The isothermal crystallization rate goes through a maximum as a function of crystallization time. The maximum rate is characterized by the time at the local extreme in the derivative of Cp (t_max), or by the time to reach half the decrease in Cp (t_1/2). Both t_max and t_1/2 show a bell-shaped curve as a function of crystallization temperature. The temperature of maximum crystallization rate, for the system studied, lies as high as 75°C. This is approximately 65°C above the initial value of T_g. Normalized Cp curves indicate the temperature dependence of the starch crystallization mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2881–2892, 1999     

The study of 'DSP' binding systems by thermogravimetry and differential thermal analysis

The so-called DSP (Densified Systems containing homogenously arranged Particles) systems represent a high-performance class of inorganic binders. The hydration and hardening processes of some DSP systems, based on calcium silicates (C₃S and C₂S) or Portland cement/clinker with silica fume additions, were assessed, in this paper, using the thermogravimetry (TG) and differential thermal analysis (DTA). These data permit a qualitative and quantitative study of the formed hydrates as well as the estimation of hydration process kinetics. This revised version was published online in August 2006 with corrections to the Cover Date.     

Evaluation of the stability of substituted InF3 glasses by differential thermal analysis

The thermal properties and devitrification behaviour of substituted InF₃ glasses were studied by means of differential thermal analysis. A comparison of various simple quantitative methods to assess the level of stability of multicomponent fluoride glass systems was also made. Most of these methods are based on critical temperatures. In this paper, a new parameter,k _d(T), is introduced to the stability criteria. The stabilities of several substituted InF₃ glasses were evaluated experimentally and correlated with the activation energies of crystallization via this new kinetic criterion and compared with those evaluated by other criteria.     

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.     

Temperature modulated DSC at intermediate-low temperatures

In this paper we present a new cooling system for temperature modulated DSC (TMDSC) working down to about 60 K. In order to demonstrate the features of this new system in combination with commercial TMDSC apparatus, we present measurements of the specific heat capacity (c_p) around the phase transitions of betaine borate and betaine phosphate. For SilGel 604 we report c_p and sound velocity data around the melt, as well as around the glass transition.     

Thermogravimetric and differential thermal analytical investigations on sewage farm soils

Soil substrates of sewage farms (inflow of sewage areas) and of closed sewage farms were investigated by means of thermogravimetry and differential thermal analysis. The results were compared with those obtained for control samples from outside the sewage farms.The organic matter of actively used sewage areas (inflow) contains a remarkable amount of easily oxidizable compounds brought to the inflows by suspended matter.Beside these compounds, macromolecular organic substances predominate in the composition of the organic matter and are responsible for an immense heat release in the high temperature range of the thermal studies.In the substrates of closed sewage farm inflows or of other sewage farm areas which do not belong to the inflows, the amounts of volatile and easily oxidizable compounds decrease rapidly. The substrates hardly differ in their reaction temperatures from control samples. The influence of single macromolecules on the exothermic oxidation is reduced with increasing humification.     

Fusion temperatures and enthalpies of high-temperature materials determined by differential thermal methods

The temperature and enthalpy of fusion of silver were measured in a differential thermal analyzer with gold and aluminum as reference materials. The measurement procedures and the data calibration (or correction) procedures used successfully in our laboratory for differential scanning calorimetry were applied. The experimental fusion temperature, (1233.9±1.0)K, and enthalpy, (108.4±3.3) J·g⁻¹, are compared with the assigned value of temperature for the IPTS-68 scale, 1235.08 K, and with a value for enthalpy, 110.75 J·g⁻¹. Work done at the National Institute of Standards and Technology. Not subject to copyright.     

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.     

Study of initiation reactivity of some plastic explosives by vacuum stability test and non-isothermal differential thermal analysis

On the basis of measurements of 18 high explosives by means of the Czech Vacuum Stability Test (VST) STABIL, a relationship has been specified between the results of this test and those of Russian manometric method. The said relationship was used to predict the Arrhenius parameters (E_a and log A values) of four plastic explosives based on RDX and one high explosive based on PETN (Semtex). The slopes E_aR⁻¹ of Kissinger's equation were specified by means of non-isothermal differential thermal analysis (DTA) and evaluation of the measurement results by means of the Kissinger method. The role played by binders and plasticizers in thermal decomposition of nitramines was pointed out on the basis of relationship between the E_a values obtained from VST and the E_aR⁻¹ values obtained from DTA, both for plastic explosives, eight nitramines, Composition B and PETN. The relationships between the E_aR⁻¹ values and thermostability threshold was specified for the given group of explosives. The relationship classify some of the studied plastic explosives as belonging to nitramines with steric hindrance in the molecule (CPX, TNAZ and HNIW). The relationship between E_aR⁻¹ values and drop energies, E_dr, sharply differentiates between plastic explosives and individual nitramines. From the relationship between the E_dr and D² values it was found that the increasing performance of the studied nitramines and plastic explosives is connected with the decrease in their impact sensitivity. Also specified are the approximate linear dependences between the peak temperatures of exothermic decomposition of all the explosives studied and their ignition temperatures, T_ig, or critical temperatures, T_c; these dependences were applied to prediction of T_ig and T_c of both the studied plastic explosives and some of the nitramines.     

The thermal analysis of polymers at high pressures

The extension of two techniques of thermal analysis into the region high pressures (50–100 MPa) are discussed. One is the extension of dilatometry (thus becoming pressure-volume-temperature measurements, PVT). This technique has been well established over the past few years. Some results obtained on typical polymer systems are presented and discussed. The second is the extension of the differential thermal analysis (DTA) principle to high pressures, trying to maintain some of the advantages of the DTA technique when compared to the PVT method, such as small sample size and productivity. DTA determinations of the pressure dependence of the melting points of pure metals and polymers are presented and compared with results from the PVT technique. Satisfactory agreement is obtained. The advantages and limitations of our current high-pressure DTA method are discussed.We gratefully acknowledge the partial financial support of the high-pressure DTA development by Metler Instrumente AG, Switzerland.     

Cell asymmetry correction for temperature modulated differential scanning calorimetry

The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on strict symmetry of the twin calorimeter. This symmetry is of particular importance for temperature-modulated DSC (TMDSC) since positive and negative deviations from symmetry cannot be distinguished in the most popular analysis methods. The heat capacities for sapphire-filled and empty aluminum calorimeters (pans) under designed cell imbalance caused by different pan-masses were measured. In addition, the positive and negative signs of asymmetry have been explored by analyzing the phase-shift between temperature and heat flow for sapphire and empty runs. The phase shifts change by more than 180° depending on the sign of the asymmetry. Once the sign of asymmetry is determined, the asymmetry correction for temperature-modulated DSC can be made.On leave from Toray Research Center, Inc., Otsu, Shiga 520, JapanThis work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U.S. Department of Energy, under contract number DE-AC05-960R22464.     

Calorimetric study and thermal analysis of crystalline nicotinic acid

As one primary component of Vitamin B₃, nicotinic acid [pyridine 3-carboxylic acid] was synthesized, and calorimetric study and thermal analysis for this compound were performed. The low-temperature heat capacity of nicotinic acid was measured with a precise automated adiabatic calorimeter over the temperature rang from 79 to 368 K. No thermal anomaly or phase transition was observed in this temperature range. A solid-to-solid transition at T _trs=451.4 K, a solid-to-liquid transition at T _fus=509.1 K and a thermal decomposition at T _d=538.8 K were found through the DSC and TG-DTG techniques. The molar enthalpies of these transitions were determined to be Δ_trs H _m=0.81 kJ mol^-1, Δ_fus H _m=27.57 kJ mol^-1 and Δ_d H _m=62.38 kJ mol^-1, respectively, by the integrals of the peak areas of the DSC curves. This revised version was published online in August 2006 with corrections to the Cover Date.     

Time-domain and frequency-domain differential calorimetry

The heat capacityC _p of a sample can be considered as a frequency dependent quantity; its behaviour can reflect the dynamics of enthalpy fluctuations. In order to take into account the dynamic nature of the measured quantity, calorimetry can mimic experimental methods as those of dielectrometry, performing experiments in time domain or in frequency domain.In this paper, an instrument is presented which is based on a calorimetric method meeting these requirements, and thus allowing to study sample dynamics of very viscous systems as glasses and some supercooled liquids. Moreover, experimental procedures permitting investigation of samples undergoing chemical and/or physical transformations by simultaneous measurements of enthalpy variation, heat capacity and, under certain conditions, thermal conductivity, are discussed.