Thermal characteristics of mixtures of cyclonite and nitroglycerine or diazidonitrazapentane

The thermal characteristics of mixtures of cyclonite (RDX) and nitroglycerine (NG) and of RDX and diazidonitrazapentane (DIANP) were studied. The thermal decomposition processes of NG and RDX are not synchronous with those of RDX/NG mixtures. The DSC curves show two obviously exothermic peaks, one at 203°C for NG and other at 240°C for RDX. However, there is only a single exothermic peak in the DSC curves of RDX/DIANP mixtures within certain ratio limits, due to the coincidence of the exothermic decomposition peaks for both RDX and DIANP and their mutual dissolution. The effects of the different thermal characteristics of different explosives on the combustion performance are also discussed.     

Kinetic analysis of cis-trans thermal isomerization of polyacetylene

A single broad exothermic peak due to cis-trans isomerization appears near 140°C in the differential scanning calorimetry (DSC) curve of polyacetylene (PA) films, polymerized by a nonsolvent method using a high-temperature-aged catalyst. This exothermic peakis described by a two-state model, in which population probabilities for cis and trans states are assumed to change through the forward and backward reactions. The enthalpy difference between the two states is 1.69 kcal/mol, which was derived from the slope of the plot of heat of isomerization versus cis content. The activation energy was determined experimentally from the heating-rate dependence of the peak temperature. A single activated process with an activation energy of 28 kcal/mol was observed for the PA film. Other parameters such as the preexponential factor were estimated by comparing theoretical and experimental DSC curves.     

Application of thermal analysis to the study of antituberculosis drugs–excipient compatibility

First-line drugs (rifampicin, RIF; isoniazid, INH; ethambutol, ETA; and pyrazinamide, PZA) recommended in conventional treatment of tuberculosis were analyzed in 1:1 w/w binary mixtures with microcrystalline cellulose MC 101 (CEL) and lactose supertab^® (LAC) by differential scanning calorimetry (DSC), thermogravimetry (TG), differential thermal analysis (DTA), and Fourier transformed infrared analysis (FTIR) as part of development of fixed dose combination (FDC) tablets. Evidence of interaction between drug and pharmaceutical excipients was supposed when peaks disappearance or shifting were observed on DTA and DSC curves, as well as decreasing of decomposition temperature onset and TG profiles, comparing to pure species data submitted to the same conditions. LAC was showed to interact with RIF (absence of drug fusion and recrystallization events on DSC/DTA curves); INH (thermal events of the mixtures different from those observed for drug and excipient pure in DSC/DTA curves); PZA (decrease on drug fusion peak in DSC/DTA curves), and ETA (shift on drug onset fusion and absence of pure LAC events on DSC/DTA curves). In all cases, an important decrease on the temperature of drug decomposition was verified for the mixtures (TG analysis). However, FTIR analysis showed good correlation between theoretical and experimental drug-LAC spectra except for INH–LAC mixture, evidencing high incompatibility between these two species and suggesting that those interactions with PZA and RIF were thermally induced. No evidence of incompatibilities in CEL mixtures was observed to any of the four-studied drugs.     

Prediction of thermodynamic, transport and vapor-liquid equilibrium properties of binary mixtures of ethylene glycol and water

Equilibrium and non-equilibrium molecular dynamics and Monte Carlo simulation techniques were applied to predict various thermodynamic, transport and vapor-liquid equilibrium properties of binary mixtures of ethylene glycol and water (EG-W) based on OPLS-AA and SPC/E force fields. The properties predicted include density, vaporization enthalpy, enthalpy of mixing, heat capacities, diffusion coefficients, shear viscosities, thermal conductivities, vapor-liquid coexistence isotherms and isobaric curves, and saturation vapor pressures. Good agreements with experimental data were obtained for most of these properties. Errors are mostly related to inaccuracy found in predictions of pure fluids; a correction to prediction of pure substance can systematically improve prediction for the mixture. This work suggests that OPLS-AA and SPC/E force fields using the common combining rules are transferable for predicting multiple physical properties of EG-W mixtures.     

Studies on ignition and afterburning processes of KClO4/Mg pyrotechnics heated in air

Thermal behavior of KClO₄/Mg pyrotechnic mixtures heated in air was investigated by thermal analysis. Effects of oxygen balance and heating rates on the TG?CDSC curves of mixtures were examined. Results showed that DSC curves of the mixtures had two exothermic processes when heated from room temperature to 700?°C, and TG curve exhibited a slight mass gain followed by a two-stage mass fall and then a significant mass increase. The exothermic peak at lower temperature and higher temperature corresponded to the ignition process and afterburning process, respectively. Under the heating rate of 10?°C?min^?1, the peak temperatures for ignition and afterburning process of stoichiometric KClO₄/Mg (58.8/41.2) was 543 and 615?°C, respectively. When Mg content increased to 50%, the peak ignition temperature decreased to 530?°C, but the second exothermic peak changed little. Reaction kinetics of the two exothermic processes for the stoichiometric mixture was calculated using Kissinger method. Apparent activation energies for ignition and afterburning process were 153.6 and 289.5?kJ?mol^?1, respectively. A five-step reaction pathway was proposed for the ignition process in air, and activation energies for each step were also calculated. These results should provide reference for formula design and safety storage of KClO₄/Mg-containing pyrotechnics.     

苯胺溶剂中偶氮二异丁腈热分解特性及动力学

偶氮二异丁腈(AIBN)是一种典型的相变吸热与分解放热重叠的物质, 该重叠现象的存在不利于其动力学规律的研究. 为了正确解析AIBN相变吸热对其分解放热的影响, 并研究AIBN在溶剂中的非等温热行为, 利用差示扫描量热仪(DSC)对苯胺、AIBN及AIBN-苯胺溶液(22.18%(w))进行动态扫描, 得到不同升温速率下AIBN在苯胺溶剂中起始分解温度T_onset的范围为79.90-94.47 ℃, 比放热量较固态AIBN高291 J·g^-1左右, 该数值可以视为其比相变热. 基于Kissinger法计算的AIBN与AIBN-苯胺溶液的活化能E和指前因子A的结果相差不大. 采用Friedman法对AIBN与AIBN-苯胺溶液的热分解过程进行计算, 发现固态AIBN相变吸热对其分解放热的影响主要发生在反应进度α小于0.20的范围内, 当α大于0.20后, 两者活化能E(α)和ln(A(α)·f(α))随α的变化趋势基本一致. 分析认为, 相对于AIBN的分解反应而言, 苯胺可以视为一种惰性溶剂, 即其不会干扰AIBN的分解机理. AIBN在苯胺溶剂中的分解机理可以视为固态AIBN的分解机理. 结合Friedman法的计算结果, 采用一般积分法, 即Coats-Redfern法得到AIBN在苯胺溶剂中分解反应的机理函数为G(α)=α^3/2, 符合Mampel power法则,平均表观活化能为139.93 kJ·mol^-1.     

The use of high-speed differential scanning calorimetry (Hyper-DSC™) to study the thermal properties of carbamazepine polymorphs

The thermal properties of two polymorphs of the drug carbamazepine, Forms I and III, were studied using high-speed differential scanning calorimetry (DSC). Previously, accurate determination of the heat enthalpy of fusion of Form III has not been possible using DSC at typical heating rates, due to concurrent exothermic recrystallisation to the higher-melting Form I. Here, it is demonstrated that heating rates of 250° C/min altered the kinetics of the melting transition of Form III such that this concurrent exothermic recrystallisation was inhibited. This allowed direct measurement of the enthalpy of the melting endotherm for Form III from a single transition. The enthalpy of this transition was found to be 109.5 J/g. Further investigations were then performed to test the utility of this technique in quantifying relative amounts of Forms I and III in mixtures of the two polymorphs. It was demonstrated that a limit of detection of 1% (w/w) was possible in this system. However, accurate quantification was not possible due to seeding effects initiating recrystallisation to Form I in these mixtures, even at these elevated heating rates. The utility of this novel technique as a fast analytical tool for studying the polymorphic behaviour of metastable polymorphs has been successfully demonstrated.     

X‐ray studies on the double melting behavior of poly(butylene terephthalate)

The double melting behavior of poly(butylene terephthalate) (PBT) was studied with differential scanning calorimetry (DSC) and wide‐angle X‐ray analysis. DSC melting curves of melt‐crystallized PBT samples, which we prepared by cooling from the melt (250 °C) at various cooling rates, showed two endothermic peaks and an exothermic peak located between these melting peaks. The cooling rate effect on these peaks was investigated. The melt‐crystallized PBT sample cooled at 24 K min^?1 was heated at a rate of 1 K min^?1, and its diffraction patterns were obtained successively at a rate of one pattern per minute with an X‐ray measurement system equipped with a position‐sensitive proportional counter. The diffraction pattern did not change in the melting process, except for the change in its peak height. This suggests that the double melting behavior does not originate from a change in the crystal structure. The temperature dependence of the diffraction intensity was obtained from the diffraction patterns. With increasing temperature, the intensity decreased gradually in the low‐temperature region and then increased distinctly before a steep decrease due to the final melting. In other words, the temperature‐dependence curve of the diffraction intensity showed a peak that is interpreted as proof of the recrystallization in the melting process. The peak temperature was 216 °C. The temperature‐dependence curve of the enthalpy change obtained by the integration of the DSC curve almost coincided with that of the diffraction intensity. The double melting behavior in the heating process of PBT is concluded to originate from the increase of crystallinity, that is, recrystallization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2005–2015, 2001     

Thermal behaviour and firing characteristics of Zr/KClO4 primer mixture containing CuO

The effect of CuO on the thermal behaviour of Zr/KClO₄ primer mixtures was studied by thermoanalytical techniques, and the Bruceton method and its related calculation. It was found that the CuO catalytically promoted the decomposition of Zr/KClO₄ primer mixtures and shifted the exothermic peak of DSC curves to lower temperatures. In addition, the Zr/KClO₄ primer mixture containing CuO had a significant effect on the firing characteristics of electro-explosive devices.     

双烯类聚合物的热分析——Ⅲ.铁与其它催化体系聚1,2-丁二烯及其衍生物的热分析

<正> 由不同催化体系制得的聚1,2-丁二烯,由于其立体规整性(如等规、间规和无规)不同,其形态、热学性质也会有所不同。关于它们的热学性质文献报道不多。我们曾报道,由三乙酰基丙酮钴-三异丁基铝-二硫化碳催化体系制备的间规聚1,2-丁二烯是晶态的;而由正丁基锂和MoCl_4OR-(i-Bu),AlOR′制得的是无规聚1,2-丁二烯;是非晶态     

Modulated temperature DSC measurements relating to the cold crystallization process of poly(ethylene terephtalate)

The modulated temperature differential scanning calorimetric method (MT-DSC) yields three temperature dependent signals, an underlying heat capacity curve from the underlying heat flow rate (corresponding to the conventional DSC signal), and a complex heat capacity curve with a real part (storage heat capacity) and an imaginary part (loss heat capacity). These curves have been measured in the cold crystallization region for poly(ethylene terephtalate) with a modified Perkin-Elmer DSC-7. The underlying curve shows the well known large exothermic crystallization peak. The storage heat capacity shows a step change which reproduces the change in heat capacity during crystallization. This curve may be used as baseline, to separate the crystallization heat flow rate from the underlying heat flow rate curve. The loss heat capacity curve exhibits a small exothermic peak at the temperature of the step change of the storage curve. It could be caused by changes of the molecular mobility during crystallization.Dedicated to Professor Wunderlich on the occasion of his 65th birthday     

Thermal analysis of sulfurization of polyacrylonitrile with elemental sulfur

Thermal analysis of sulfurization of polyacrylonitrile (PAN) with elemental sulfur was investigated by thermogravimetry and differential thermal analysis of the mixture of polyacrylonitrile and elemental sulfur up to 600°C. Due to the volatilization of sulfur, the different heating rate (10 and 20 K min⁻¹) and different mixture proportion of polyacrylonitrile and elemental sulfur were adopted to run the analysis. The different heating rates make the DSC curves of sulfur different, but make the DSC curves of PAN similar. In the DSC curve of sulfur for the heating rate of 20 K min⁻¹ around 400°C, a small exothermic peak occurs at 400°C in the wide endothermic peak around 380∼420°C, indicative of that there is an exothermic reaction around 400°C. In the DSC curves of the mixture, the peaks around 320°C are exothermic as the content of sulfur is below 3.5:1 and endothermic as the content of sulfur is over 4:1, indicating that one of the reactions between PAN and sulfur takes place around 320°C. In the TG curves of the mixture, the mass losses begin at 220°C, and sharply drop down from 280°C. The curves for the low sulfur content obviously show two steps of mass loss, and curves for the high sulfur content show only one step of mass loss, indicative of more sulfur is benefit for the complete sulfurization of PAN. This study demonstrates that the TG/DSC analysis can give the parameter for the sulfurization, even if the starting mixture contains the volatile sulfur.     

Heating effect on the DSC melting curve of flaxseed oil

Flaxseed oil is rich in the alpha-linolenic acid. The effect of heating on the thermal properties of flaxseed oil extracted from flax seeds has been investigated. The flaxseed oils were heated at a certain temperature (75, 105, and 135 °C, respectively) for 48 h. The melting curve (from ?75 to 100 °C) of flaxseed oil was determined by differential scanning calorimetry (DSC) at intervals of 4 h. Three DSC parameters of exothermic event and endothermic event, namely, peak temperature (T _peak), enthalpy, and temperature range were determined. The initial flaxseed oil exhibited an exothermic peak, two endothermic peaks, and two endothermic shoulders between ?68 and ?5 °C in the melting profile. Heating temperature had a significant influence on the oxidative deterioration of flaxseed oil. The melting curve and parameters of flaxseed oil were almost not changed when flaxseed oil was heated at 75 °C. However, the endothermic peaks of melting curve decreased dramatically with the increasing of heating time when heating temperature was above 105 °C. There is almost no change of melting heat flow of flaxseed oil when heating time exceeded 32 h at 135 °C. The preliminary results suggest that the DSC melting profile can be used as a fast and direct way to assess the deterioration degree of flaxseed oil.     

DSC Studies of the Effects of Cisplatin and Transplatin on G-Actin

The effects of cisplatin and its trans isomer transplatin on the thermal denaturation of G-actin were studied with a Micro DSC-III differential scanning calorimeter. The denaturation enthalpy of G-actin was found to be 12 J g^–1, and the denaturation temperature was 328 K. The thermal denaturation curve showed that increasing cisplatin concentration decreased the enthalpy change. However, after the ratio of cisplatin to G-actin attained 8:1 (mol:mol), the denaturation enthalpy no longer decreased. Transplatin decreased the enthalpy change more rapidly. In contrast with cisplatin, the denaturation peak at 328 K disappeared, and a strong exothermic peak appeared at 341 K when the ratio of transplatin to G-actin was 8:1 (mol:mol). The enthalpy change was 75 J g^–1, which is far in excess of the range of weak interactions. This strong exothermic phenomenon probably reflects the agglutination of protein. The effects of cisplatin and transplatin on the number of the free thiol groups of G-actin are discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermodynamics of activated phase transitions of 8CB: DSC and MC calorimetry

The present paper reports the heating rate effect on the phase transitions of a pure liquid crystal octylcyanobiphenyl (8CB) with use of Differential Scanning Calorimetry (DSC) and Modulation Calorimetry (MC) techniques. The DSC runs were taken at various temperature ramp rates from 20 to 0.5 K/min for heating and cooling scans. Well-defined endothermic/exothermic peaks were found at the melting/crystallization, smectic-A to nematic (SmA-N), and nematic to isotropic (N-I) transitions on heating/cooling scans, respectively. All transitions shift in temperature significantly with different ramp rates. The temperature shift of C(p) peaks between heating and cooling scans indicates the order of the transitions. In addition, all transitions follow an Arrhenius behavior. The activation energy of a transition increases as the total energy involved in the transition decreases. The respective enthalpy and entropy change of each transition provides information on the Gibbs free energy. The significance of the results is discussed in terms of the order of transitions. A comparative analysis of MC and DSC techniques highlights the significance of the two techniques. MC is a practicable tool for observing the phase dynamics whereas DSC is a good tool for studying the rate kinematics of the transitions.     

Thermostimulated processes in starch-bis(hydroxymethyl)propionic acid mixtures subjected to high-pressure plastic deformation

DSC and thermogravimetry are employed to study starch, bis(hydroxymethyl)propionic acid, and their mixtures of different compositions subjected to plastic deformation under pressures of 1 and 3 GPa. An endothermic peak with an enthalpy of 300 J/g observed in the thermogram of starch is most likely related to the breakage of hydrogen bonds. Treatment under pressure greatly reduces the enthalpy of this peak. For initial mixtures, the enthalpies of the endothermic peak of starch and the endothermic peak of melting of the acid are lower than those for individual components because of chemical interaction occurring between the mixture components during heating. The high-pressure treatment makes the decrease in the enthalpy of endothermic processes much more pronounced for both components.     

Phase equilibria in phospholipid-water systems

This work is a critical account of phase studies of phospholipid-water mixtures. The Phase Rule and equations of thermodynamics of heterogeneous systems are applied in the analysis of calorimetric and dilatometric results for these systems. It is inferred that the approach in which a lipid-water mixture of low lipid content is regarded as a one-component system is misleading and unhelpful. A mixture containing water and a pure synthetic phospholipid is a binary system, and the Phase Rule can be applied to it in a straightforward manner. Non-isothermal transitions and invariant three-phase reactions of the eutectic, peritectic and polytectic type can be encountered in lipid-water systems, like in other binary mixtures. The concentration dependence of the enthalpy of the isothermal three-phase transition yields a well-known Tammann triangle. For the volume change at such transition an analog of the Tammann triangle can be drafted which can be useful in interpretation of dilatometric and densitometric data for heterogeneous binary systems.The literature thermodynamic data for the aqueous lipids are analyzed on the basis of the phase diagram of the DPPC-water system. The measured values of the transition enthalpy and volume change at the pre- and main transitions refer to invariant phase reactions. The measured heat capacities and thermal coefficients of expansion actually characterize the biphasic lipid-water mixtures and may reflect phenomena specific for heterogeneous binary systems only. A reinterpretation of the literature DSC data for the DPPC-water system at temperatures below zero is suggested.Experience gained in the study of equilibrium phase diagram, kinetic and colloidal aspects of phase behaviour of dioctadecyldimethylammonium chloride-water system indicates that the common procedures of the sample preparation of lipid-water mixtures may lead to the states which are non-equilibrium in two respects: the system contains a metastable phase, and the phase is dispersed to such an extent that an irreversible colloidal structure is formed. Definitive phase studies of the phase behaviour of phospholipid-water systems in the whole concentration range are urgently needed.     

Autooxidation of Unsaturated Fatty Acids and Their Esters

The shape of DSC curves of non-isothermal oxidation of fats was explained. Two main exothermic effects overlapped partially are caused by hydroperoxide formation (first peak) and by further oxidation of peroxides (second peak). The oxidation of oils and lipid analogues of various peroxide concentration showed that only the start of the oxidation process is affected by initial concentration of peroxides, other temperatures determined from DSC curves are not connected with this parameter. The computer simulations gave the best agreement of theoretical and experimental data for kinetic scheme of a two-step consecutive reaction with autocatalytic start. The comparison of activation energies calculated for isothermal and non-isothermal autooxidation of unsaturated fatty acids and their esters also confirmed this interpretation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Compatibility study between sitagliptin and pharmaceutical excipients used in solid dosage forms

Differential scanning calorimetry (DSC) is a primary technique for measuring the thermal properties of materials, which reflects the physico-chemical properties of drug substances. In the present study, it is used as a screening technique for assessing the compatibility of sitagliptin with some currently employed pharmaceutical excipients. The influence of processing conditions and their effects (simple blending, co-grinding or kneading) on drug stability was evaluated. Sitagliptin showed a sharp endothermic peak at 212.1 °C with an enthalpy change of 131.5 J g^?1 indicating melting of drug. Facile transformation of dehydrated sitagliptin to monohydrate form was observed in some mixtures, disappearance of sharp melting endothermic peak of sitagliptin was observed in some mixtures. On the basis of DSC results, sitagliptin was found to be compatible with micro crystalline cellulose, croscarmellose, and pregelatinized starch. Some excipient interaction was observed with magnesium stearate, ascorbic acid, and citric acid. X-ray diffractometry and FT-IR were used as supportive tools in interpreting the DSC results. Overall, the excipients selected were compatible with the API and the mixtures are stable within the tested conditions. These results would be useful for formulation development of the film coated tablets of sitaglitptin.     

The effect of various potato cultivars at different times during growth on starch content determined by DSC

Differential scanning calorimetry (DSC) was used to determine the starch content of potato dry matter isolated from various cultivars at different times during growth. When potato dry matter was heated in the presence of excess water, a symmetrical endothermic peak resulted, which was similar to the gelatinization peak of pure starch. From the enthalpy value of potato dry matter and pure potato starch at a moisture content of 70%, the starch content in the potato dry matter can be determined. Starch content increased as growth progressed to a maximum and then decreased. The effect of moisture content and sample mass on gelatinization of dry matter and starch was also investigated. Compared to other starch analysis technique, DSC is a simple and more rapid method.