Application of heat conduction calorimetry to high explosives

This paper describes some thermal analysis experiments conducted on high explosive samples. These employ differential scanning calorimetry to monitor thermal effects at elevated temperatures (around 200 °C) and heat conduction calorimetry to record thermal effects at much lower temperatures (below 100 °C).The work shows that, due to the generally high thermal stability of many high explosive compositions, heat generation rates are very low, if detectable at all, at normal storage temperatures, even when using a very sensitive instrument. The sensitivity and reproducibility of this technique has been investigated in detail by Wilker et al. [S. Wilker, U. Ticmanis, G. Pantel, Detailed investigation of sensitivity and reproducibility of heat flow calorimetry, in: Proceedings of the 11th Symposium on Chemical Problems Connected with the Stability of Explosives, Sweden, 1998] and shown to be capable of recording heat generation rates of less than a microwatt. This allows continuous measurement of decomposition processes in nitrate ester based propellants at temperatures as low as 40 °C. However, the measurement of very low levels of heat generation is difficult, time consuming and therefore expensive. If the assumption is made that the life limiting process is invariably the slow decomposition of the energetic component, this will frequently lead to very long service lifetime predictions.A number of possible complications are identified. Firstly, due to its low detection threshold, a heat conduction calorimeter may detect other reactions which will not lead to failure, but which may still dominate the heat flow signal. Secondly, the true failure process may generate little energy and be overlooked. In view of these considerations, at present it seems unwise to rely on heat conduction microcalorimetry as the only tool for the assessment of the life of high explosive energetic systems.Based on examples of life terminating processes in high explosives during storage and use, it is clear that decomposition of the energetic material is not invariably the cause of system failure. It is also by no means the only reaction that may take place in, and be observed by, a heat conduction calorimeter.     

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.     

Some remarks on heat capacity measurements by temperature-modulated calorimetry

In temperature-modulated calorimetry, the condition in sample amount, especially thickness, required for high-accuracy heat capacity measurement should be made clear. We propose the condition of maximum thickness of a sample for measuring heat capacity within an accuracy of 1%. The other important factor for high-accuracy heat capacity measurement is thermal contact conductance between a sample and a sample pan and also that between a pan and a base plate of an apparatus. The conditions in these thermal contact conductances required for high-accuracy heat capacity measurement are discussed. Among them, if only thermal contact conductance between a pan and a base plate is significant, there is an ingenious method to measure heat capacity with high accuracy. Furthermore, if the thermal contact conductance between a pan and a base plate is infinite, we offer a simple method to obtain complex heat capacity.     

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.     

Solution calorimetry to monitor swelling and dissolution of polymers and polymer blends

The observed rate of drug release from a polymeric drug delivery system is governed by a combination of diffusion, swelling and erosion. It is thus not a simple task to determine the effects of the polymer on the observed drug release rate, because the swelling characteristics of the polymer are inferred from the drug release profile. Here we propose to use solution calorimetry to monitor swelling. Powdered polymer samples (HPMC E4M, K4M, K15M and NaCMC, both alone and in a blend) were dispersed into water or buffer (pH 2.2 and 6.8 McIlvaine citrate buffers) in a calorimeter and the heat associated with the swelling phenomena (hydration, swelling, gelation and dissolution) was recorded. Plots of normalised cumulative heat (i.e. q_t/Q, where q_t is the heat released up to time t and Q the total amount of heat released) versus time were analysed by the power law model, in which a fitting parameter, n, imparts information on the mechanism of swelling.

For all systems the values of n were greater than 1, which indicated that dissolution occurred immediately following hydration of the polymer. However, while not suitable for determining reaction mechanism, the values of n for each polymer were significantly different and, moreover, were observed to vary both as a function of particle size and dissolution medium pH. Thus, the values of n may serve as comparative parameters. Properties of the polymer blends were observed to be different from those of either constituent and correlated with the behaviour seen for polymer tablets during dissolution experiments. The data imply that solution calorimetry could be used to construct quantitative structure–activity relationships (QSARs) and hence to optimise selection of polymer blends for specific applications.     

The advantages and disadvantages of direct and indirect calorimetry

Kleiber's definitions of what constitutes direct and indirect calorimetry are accepted as the beginning of a commentary on the advantages and disadvantages of direct and indirect calorimetry in which calorimetry is divided into a number of categories based on the kind of calorimetric measurement. For non-reaction calorimetry such as entropy determinations and differential scanning calorimetry, the only means of measurement is by direct calorimetry. For reaction calorimetry, a preference of direct over indirect calorimetry depends on the accuracy needed and the ability of the experimenter to define the system. The data necessary to correct the observed heat loss in direct calorimetry are often all that are needed to make an indirect calculation of the true heat loss. In general, because they are convenient and inexpensive to use, indirect calorimetric methods are preferable to direct methods. However, when possible, one method can be used to verify the results of the other.     

Investigation of the flammability of different textile fabrics using micro-scale combustion calorimetry

Evaluating and analyzing the performance of flame retardant (FR) textiles are a critical part of research and development of new FR textiles products by the industry. The testing methods currently used in the industry have significant limitations. Most analytical and testing techniques are not able to measure heat release rate (HRR), the single most important parameter in evaluating the fire hazard of materials. It is difficult to measure HRR of textile fabrics using cone calorimetry because textile fabrics are dimensionally thin samples. The recently developed micro-scale combustion calorimetry (MCC) is able to measure the following flammability parameters for textile using milligram sample sizes: heat release capacity, HRR, temperature at peak heat release rate (PHRR), total heat release and char yield. In this research, we applied MCC to evaluate the flammability of different textile fabrics including cotton, rayon, cellulose acetate, silk, nylon, polyester, polypropylene, acrylic fibers, Nomex and Kevlar. We also studied the cotton fabrics treated with different flame retardants. We found that MCC is able to differentiate small differences in flammability of textile materials treated with flame retardants. We were also be able to calculate the limiting oxygen index (LOI) using the thermal combustion properties of various textile samples measured by the MCC. The calculated LOI data have yielded good agreement with experimental LOI results. Thus, we conclude that MCC is an effective new analytical technique for measuring textile flammability and has great potentials in the research and development of new flame retardants for textiles.     

Pulsed bed calorimetry

Conventional calorimetry has always the difficulty of choosing between near to equilibrium working conditions and high thermal ramp rates. Thus, either the transport phenomena and sample homogeneities are good but the signals become weak due to thermal losses, or the signals are sharp, but strong gradients across the sample lead to chemical and thermal heterogeneities. The described pulsed fluidized bed technique, by strongly stirring the sample, allows good sample homogeneities even at high ramp rates. Moreover, the permanently regenerated cover gas allows as well a good heat transfer towards the thermocouples as a constant atmosphere composition leading to very precise onset temperatures.     

Advanced AC calorimetry of polycaprolactone in melting region

The new capabilities of AC calorimetry, when working at frequencies above the classical limit were demonstrated. The appropriate frequency range of classical AC calorimetry was substantially enlarged. It was shown that the advanced AC calorimetry can be applied for studying dynamic heat capacity of polymers in the frequency range 0.1–1 Hz. Thus, the processes with characteristic time as short as ca. 5 s was registered. The advanced AC technique was applied for investigation of the melting kinetics in polycaprolactone. It was found that melting in polycaprolactone is related to an activated process. The activation of the melting process after a step heating is described by a stretched exponent and the decay of the melting by only one exponent at short times. The dependencies of the exponent on temperature and thermal treatment were investigated at frequencies in the range 0.1–1Hz and modulation amplitudes 0.005–0.2 K.     

Reversibility of the low‐temperature transitions of polytetrafluoroethylene as revealed by temperature‐modulated differential scanning calorimetry

Temperature‐modulated differential scanning calorimetry reveals distinct differences in the kinetics of the low‐temperature phase transitions of polytetrafluoroethylene. The triclinic to trigonal transition at 292 K is partially reversible as long it is not complete. As soon as the total sample is converted, supercooling is required to nucleate the reversal of the helical untwisting involved in the transition. The trigonal phase can be annealed in the early stages after transformation with a relaxtion time of about 5 minutes. The dependence of the reversing heat capacity on the modulation amplitude, after a metastable equilibrium has been reached, is explained by a non‐linear, time‐independent increase of the heat‐flow rate, perhaps caused by an increased true heat capacity. The order‐disorder‐transition at 303 K from the trigonal to a hexagonal condis phase is completely reversible and time‐independent. It extends to temperatures as low as the transition at 292 K or even lower. Qualitatively, the thermal history and crystallization conditions of polytetrafluoroethylene do not affect the transition kinetics, that is, melt‐crystallized film and as‐polymerized powders show similar transition behaviors, despite largely different crystallinities. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 750–756, 2001     

Isothermal curing of an epoxy resin by alternating differential scanning calorimetry

The quasi-isothermal curing of a diepoxide resin with a triamine of polyoxypropylene was studied by alternating differential scanning calorimetry (ADSC), which is a temperature modulated DSC technique. The complex heat capacity measurements allows to analyse the vitrification process at curing temperatures (T_c) below the maximum glass transition of the fully cured epoxy (T_g∞=85.8°C). Initially, the modulus of the complex heat capacity, |C^*_p|, increases until a maximum (conversion between 0.42 and 0.56) and then decreases. This step is followed by an abrupt decay of |C^*_p|, due to the vitrification of the system, which allows the determination of the vitrification time. This value agrees well with that determined by the partial curing method. The phase angle and out-of-phase heat capacity show an asymmetric wide peak during the vitrification process. The change in |C^*_p| at vitrification decreases with the increase of T_c becoming zero at temperature T_g∞. This epoxy-triamine system shows a delay of the vitrification process respect to other model epoxy systems probably due to the presence of polyoxypropylene chains in the network.

The decay of |C^*_p| during vitrification may be normalised between unity and zero by defining a mobility factor. This mobility factor has been used to simulate the reaction rate during the stage where the reaction is controlled by diffusion. The observed reaction rate is simulated by the product of the kinetic reaction rate, determined by the autocatalytic model, and the mobility factor.     

Melting and crystallization of poly(butylene terephthalate) by temperature‐modulated and superfast calorimetry

Quantitative temperature‐modulated differential scanning calorimetry (TMDSC) and superfast thin‐film chip calorimetry (SFCC) are applied to poly(butylene terephthalate)s (PBT) of different thermal histories. The data are compared with those of earlier measured heat capacities of semicrystalline PBT by adiabatic calorimetry and standard DSC. The solid and liquid heat capacities, which were linked to the vibrational and conformational molecular motion, serve as references for the quantitative analyses. Using TMDSC, the thermodynamic and kinetic responses are separated between glass and melting temperature. The changes in crystallinity are evaluated, along with the mobile–amorphous and rigid–amorphous fractions with glass transitions centered at 314 and 375 K. The SFCC showed a surprising bimodal change in crystallization rates with temperature, which stretches down to 300 K. The earlier reported thermal activity at about 248 K was followed by SFCC and TMDSC and could be shown to be an irreversible endotherm and is not caused by a glass transition and rigid–amorphous fraction, as assumed earlier. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1364–1377, 2006     

Performance evaluation of differential accelerating rate calorimeter for the thermal runaway reaction of di-tert-butyl peroxide

The thermal behavior of di-tert-butyl peroxide (DTBP) has been studied by accelerating rate calorimetry (ARC), in order to obtain a better understanding of novel differential accelerating rate calorimetry (d-ARC) developed by OmniCal Inc. presently. Thermal analysis, kinetic analysis, and estimation of time to maximum rate (TMR_ad) of 5–20 mass% DTBP and toluene mixture were performed and compared with the past reports. From the experimental results, moderately hazardous mixture which was evaluated inaccurately by the conventional ARC was analyzed successfully by d-ARC. Kinetic parameters were determined to be 153–164 kJ mol^?1 of the activation energy and 3.3E+17 to 3.3E+18 min^?1 of the frequency factor by d-ARC, and agreed with the past reports. Meanwhile, the kinetics of low-concentrated DTBP mixture were calculated to be incorrect value by the conventional ARC. Furthermore, TMR_ad of low-concentrated DTBP mixture was successfully estimated by d-ARC, while incorrect estimations were obtained by the conventional ARC. It was concluded that d-ARC has better performance of adiabatic calorimetry and is useful tool of the thermal risk assessment for chemical process safety.     

Kinetic Studies of the Thermal Decomposition of KDNBF, a Primer for Explosives

KDNBF (potassium 4,6-dinitrobenzofuroxan) has been used as a primer explosive in igniters and detonators for many years. Considerable information about the sensitivity of KDNBF to various stimuli, such as impact, friction, shock and electrostatic charge, is known. However, the thermal sensitivity of KDNBF has been relatively unexplored. Hence, there is very little information available concerning the fundamental thermal properties of KDNBF. Therefore, as part of an extensive thermal hazard assessment, DSC, TG, accelerating rate calorimetry (ARC) and heat flux calorimetry (HFC) measurements have been undertaken on KDNBF. The results demonstrate that KDNBF decomposes via a multi-step exothermic process directly from the solid state. The decomposition process does not appear to depend on the nature of the atmosphere, except in the final stage of the TG decomposition in air, where remaining carbonaceous material is converted to CO₂. The first stage of the decomposition is sufficiently rapid that ignition occurs if too large a sample is used. Dynamic and isothermal methods were used to obtain the kinetic parameters and a range of activation energies were obtained, depending on the experimental conditions. The kinetic results have been analyzed in terms of various solid state decomposition models. This revised version was published online in August 2006 with corrections to the Cover Date.     

Application of heat flow calorimetry to the study of oilwell cements

The majority of previous studies of the hydration of cements using heat flow calorimetry have been carried out isothermally. However, with oilwell cements the slurry is mixed on the surface at ambient temperature and then gradually increases in temperature as it is pumped down the well. A Setaram C-80 calorimeter has been used to simulate the temperature ramp in API oilwell cement test schedules. This approach has enabled cementing reactions to be studied for the first time under conditions approaching those encountered in the field, and has shown that the results obtained from isothermal experiments may be misleading.The permission of the British Petroleum Company PLC to publish this paper is gratefully acknowledged.     

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.     

Modulated differential scanning calorimetry in the glass transition region

Temperature-modulated calorimetry (TMC) allows the experimental evaluation of the kinetic parameters of the glass transition from quasi-isothermal experiments. In this paper, model calculations based on experimental data are presented for the total and reversing apparent heat capacities on heating and cooling through the glass transition region as a function of heating rate and modulation frequency for the modulated differential scanning calorimeter (MDSC). Amorphous poly(ethylene terephthalate) (PET) is used as the example polymer and a simple first-order kinetics is fitted to the data. The total heat flow carries the hysteresis information (enthalpy relaxation, thermal history) and indications of changes in modulation frequency due to the glass transition. The reversing heat flow permits the assessment of the first and higher harmonics of the apparent heat capacities. The computations are carried out by numerical integrations with up to 5000 steps. Comparisons of the calculations with experiments are possible. As one moves further from equilibrium, i.e. the liquid state, cooperative kinetics must be used to match model and experiment.On leave from Toray Industries, Inc., Otsu, Shiga 520, Japan.This 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-AC05-96OR22464. Support for instrumentation came from TA Instruments, Inc. Research support was also given by ICI Paints, and Toray Industries, Inc.     

Applications of reaction calorimetry in chemical engineering

Reaction calorimetry strongly penetrated process development laboratories in the fine chemicals industry. Applications of calorimetry to different fields of process optimization, chemical reactions and physical unit operations were developed. Applications were first developed in the field of process safety. The thermal data of reaction obtained in the calorimeters allow us to check if a reaction will be controllable at full scale under normal operating conditions and in case of equipment failure. Further, the accurate temperature control and heat flow measurement opened the door to more engineering related data, in the fields of phase equilibria like vapour liquid, solubilities, crystallization and also in the mixing techniques. Some examples of developments in these different fields will be reviewed.     

Thermal study of HNIW(CL-20) and mixtures containing aluminum powder

The thermal behavior of the energetic material 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-tetracyclo-[5.5.0.0^5,9.0^3,11]-dodecane (HNIW or CL-20) and its mixtures with aluminum under linear temperature control condition and adiabatic condition were investigated by DSC-TG-MS-FT-IR and ARC. Two different particle sizes of aluminum powder (10 μm and 50 nm) were added into CL-20. The influence of particle size on the thermal behavior of CL-20 was studied by using of these apparatuses. The enthalpies of reaction and onset temperatures were determined for various heating rates. The kinetic parameters were found according to Kissinger method, Ozawa method, and Friedman method based on DSC data. The gaseous products from the decomposition of CL-20 and its mixtures were determined by simultaneous MS-FT-IR experiments. ARC measurements were performed to investigate the thermal stability of the samples. The onset temperature, adiabatic temperature rise, self-heat rate, time to maximum rate, and pressure–temperature profile were found from the data measured by ARC. Based on these results, the catalytic effect of aluminum powder was studied.     

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.