Prediction of shock response of pyrotechnic mixtures from thermal analysis

The thermal behavior of metal, oxide, and oxidizer mixtures, some with fluorine compound additions, has been studied in order to examine the influence of thermal properties on the initiation conditions for chemical reaction of pyrotechnic powders under dynamic loading conditions. The autoignition energies of the mixtures obtained from thermal analyses were compared with shock initiation energies, determined from planar shock measurements. Although some mixtures showed an approximate equivalency between the energies obtained from the two different experiments, the experimental results indicated that any comparison should be made with great care.We thank A. J. Lindfors and S. Pockrandt for the planar shock measurements.     

Comparative study of specific heat capacities of some vegetable oils obtained by DSC and microwave oven

Summary TG and DSC analyses were carried out in this work to evaluate the changes in the denaturation of human hair keratin submitted to different chemical effects. Hair bleaching and chlorinating treatments caused changes in the denaturation temperatures and denaturation enthalpies of hair keratin. Bleached hair and hair kept in a chlorinated solution presented a lower denaturation enthalpy and a higher denaturation temperature compared to the control hair sample. The TG and DSC analyses allowed to quantify the degradation level of hair fibers after the chemical treatments. AFM was also utilized to characterize the morphological alterations in the hair fiber surfaces caused by the chlorinating and bleaching treatments.     

Experimental investigation into the heat capacity measurement using an modulated DSC

Experiments using a commercial modulated DSC (MDSC) for the measurement of specific heat capacity of a sample have been carried out. It is found that because the amplitude of heat flow of MDSC is a complicated non-linear function of various experimental conditions such as the modulation frequency and the heat capacities of a sample and pan, the methodology of heat capacity determination using an MDSC in a single run has not been justified. The experimental results, on the other hand, agree with the theoretical equation of one of the authors. It is therefore concluded that the capabilities of MDSC should be further examined.     

DSC investigation of oxygen subsystem in Ba-Y-Cu-O superconductors

DSC investigations have been performed for a series of compounds Ba₂YCu₃O_y with the oxygen content varying in the rangey=6.0...6.9 by means of various heat treatments at 800–1200 K followed by quenching, or through the chemical extraction of oxygen by placing the sample in dihydrogen at 470–490 K. The sample preserving a constant oxygen content during heating in nitrogen exhibited exothermal effects between 450 and 850 K. It has been shown that the H vs. y function reaches maximum aty 6.5. Kinetic measurements have shown that the diffusive mobility of oxygen atoms in the lattice is responsible for these effects, viz. the Arrhenius and cooperative processes of reorganization in the non-equilibrium oxygen subsystem of the bulk.

---

Zusammenfassung Für eine Reihe von Verbindungen der allgemeinen Formel Ba₂YCu₃O_y und einem Sauerstoffgehalt vony=6.0....6.9 wurden mittels verschiedener Wärmebehandlungen bei 800–1200 K, gefolgt durch Abschrecken oder beim chemischen Sauerstoffentzug durch Einbringen der Probe in Diwasserstoff bei 470–490 K DSC-Untersuchungen durchgeführt. Wird die Probe in Stickstoff erhitzt, so behält sie ihren Sauerstoffgehalt bei und zeigt bei 450–850 K einen exothermen Effekt. Es wurde gezeigt, daß die Funktion H(y) bei etwa y=6.5 ein Maximum erreicht. Kinetische Messungen zeigen, daß für diesen Effekt die diffusive Beweglichkeit der Sauerstoffatome im Gitter verantwortlich ist.

     

DSC investigation of isothermal bulk copolymerization of alkylaryl methacrylates

The free radical copolymerization of phenyl methacrylate (PhMA) witho-methylphenyl-methacrylate(o-MPhMA) ando-ethylphenyl methacrylate (o-EPhMA) was carried out and the enthalpies of copolymerization, overall rate constants and copolymerization parameters were determined for different molar ratios of comonomers in the temperature range 353–373 K.     

Melting of PbBr2: A DSC investigation

The melting of PbBr₂ in sealed crucibles was investigated by means of DSC. Three factors were considered to affect melting point: i) impurities, ii) the bromine pressure over the PbBr₂, and iii) photolysis. Both crystals and powders were investigated. The peak of the melting changed after sample grinding. The bromine pressure over the PbBr₂ was found to cause a significant error in the determination of the melting point.Lead bromide melts at 370.6±0.2°C. The heat of melting is 42.9±1.8 J g^–1.This revised version was published online in November 2005 with corrections to the Cover Date.     

DSC investigation of early pregnant uterus of the rat

The aim of the present work was the characterization of nonpregnant and early pregnant myometrium (days 3–6) of the rat by means of differential scanning calorimetry (DSC). The spontaneous motor activity as well as the KCl-evoked contractions of isolated uterine rings was additionally recorded. A relatively close correlation was found between calorimetric enthalpy (ΔH) and the contractility of the uterus samples. Our results indicate that DSC is a useful tool for the investigation of the functions of developing myometrium and it can be considered as supplementing the traditional structural and functional methods.     

Application of DSC as a tool for honey floral species characterization and adulteration detection

The thermal behaviour of authentic honeys and sugar syrups (industrial and homemade) was investigated by DSC. To confirm the first previous results concerning the effect of adulteration on the thermal behaviour of authentic honeys, 30 honey samples (Robinia, Lavender, Chestnut and Fir) were analyzed by DSC and their T _g were measured following a suited experimental protocol. The results indicated that this parameter was useful to characterize and to distinguish significantly these varieties between them. Applied to honey samples artificially adulterated with different industrial syrups, DSC showed a detection level of 5–10% depending on the type of syrup. An endothermic phenomenon occurring between 40–90°C during the heating was studied by TMDSC and a new thermal transition similar to a glass-transition was highlighted.This revised version was published online in November 2005 with corrections to the Cover Date.     

Li_2O-Al_2O_3-SiO_2系统微晶玻璃的晶化对其热学性质的影响

用X光衍射方法确定了Li_2-Al_2O_3-SiO_2系统微晶玻璃中的结晶相,并由此得出其结晶度。用1090B热分析仪测量其热膨胀特性,得出了热膨胀和结晶度的关系,以及热膨胀和晶化温度的关系。用差热分析方法得出了微晶玻璃的比热几乎不随结晶度变化而变化的结论。     

DSC Study on Brain Tubulin and the Effect of Cisplatin

Microtubules, a class of cytoskeletal elements, appear to be present in all eukaryoticcells. The temporal and spatial control of assembly and disassembly of microtubulesis believed to be a key factor in cellular function. Microtubules and their subunits(Q-0 tubulin heterodimers, MW 1 10,000) maintain a dynamic equilibrium in the cellcytoplasm. In addition, it is postulated that the lability of cytoplasmic microtubulescaused by drug is related to their equilibrium. Calorimetry method has been…     

Thermal behavior of polyacrylonitrile polymers synthesized under different conditions and comonomer compositions

Polyacrylonitrile (PAN) polymers are used as precursors for carbon fiber production. This process requires an oxidative stabilization step, which can be studied by differential scanning calorimetry (DSC). In this sense, thermal behavior of PAN based terpolymers by different polymerization processes, compositions and itaconic acid concentrations in the reaction media were investigated. The obtained results showed that the addition of itaconic acid and methyl acrylate as comonomers resulted a lower heat flow during the process comparing to the PAN homopolymer. It suggested that these comonomers aid the oxidative stabilization stage for all studied process. The redox system polymerization at 40°C resulted in a lower heat flow. Itaconic acid decreases slightly initial and peak temperatures of the terpolymer and heat flow until concentration of 3y. The cyclization temperature decreases when MAis incorporated into the terpolymer compared to the MMA terpolymer and increases when MAA is the acidic monomer. Among terpolymers the AN/MA/AA polymer showed the best thermal behavior for carbon fiber producing.     

Comparative DSC study of human and bovine serum albumin

The thermal denaturation process of bovine and human both fatty acid containing and fatty acid free albumins in aqueous solution was studied by use of differential scanning calorimetry. Human serum albumins were found to be more stable than their bovine counterparts. Fatty acid free albumins were characterized as generally less stable, more susceptible to aggregation, their unfolding endothermic transition was less cooperative and with the smaller degree of reversibility. Deconvolution analysis with using a non-two-state model with two component transitions showed essential differences in the thermodynamic parameters between all studied albumins, particularly regarding the high-temperature component transition.     

Characterizing blends of linear low-density and low-density polyethylene by DSC

Summary A two-step isothermal annealing (TSIA) procedure is described that enables the endothermic peaks of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and their blends, to be satisfactorily resolved during analysis by differential scanning calorimetry. A modified form of multistep isothermal annealing, the TSIA procedure produces a highly characteristic profile of the blend components by facilitating the segregation of the phases based on branch density. It is proposed that the TSIA procedure may have significant merit in the identification and quantification of the components in an unknown blend as well as increasing the sensitivity in analytical procedures aimed at blend component quantification.     

Comparison of simulated and actual DSC measurements for first-order transitions

A system of differential equations modeling a heat flux DSC is solved and the results are compared with those obtained using a TA Instruments Q1000™ DSC.¹ It incorporates a new heat flow rate measurement technique that determines the heat flow rate between the sample and its pan. Two types of first-order transitions are investigated: melting of a pure substance and solidification of a pure substance including super-cooling. In both transitions, the peak shape obtained using the new heat flow rate measurement and predicted by the model is quite different from that measured using conventional DSC. It is shown that the differences are the result of simplifications implicit in the conventional heat flow rate measurement that is based solely on the difference between sample and reference calorimeter temperatures. Heat flow rates measured using the improved measurement agree very well with the model predictions for heat exchange between the sample and its pan.     

DSC analysis of post-yield deformed pbt. Effects of thermal history

The effect of the deformation temperature on the energy stored in post-yield deformed poly(butylene terephthalate) PBT, was studied by means of DSC tests. Deformed specimens were rapidly cooled after unloading, in order to avoid the energy relaxation processes occurring before the DSC measurements. Cooling revealed to have a significant contribution on the whole stored energy, as shown by DSC tests conducted on undeformed PBT specimens conditioned at various temperatures. This work is aimed at separating the effects due to cooling and those ascribed to deformation on the energy storage and release processes, permitting to better understand previous findings on post-yield compressed PBT.     

Technological quality determination of pharmaceutical disintegrant by DSC cooling and DSC photovisual

A number of disintegrants are available on the market. They improve tablets’ disintegration. The objective of this work is the comparison of the technological quality parameters of disintegrants using different analytical techniques. Three batches of disintegrants and their binary mixtures (water:disintegrants) were investigated. Cooling experiments were used from –30 up to 200°C. The data obtained showed calorimetric differences between the samples. In the binary mixtures water showed different crystallization behaviour from the one found in the literature. According to the results DSC technique helped the quality control of different disintegrants.     

Thermal hazards of cracker mixture using DSC

DSC studies of cracker mixtures of different compositions of potassium nitrate, sulphur and aluminum have shown some critical characteristics either with the increase or decrease in the composition of the components. Specifically, sulphur composition below 8% showed no exothermic activity. The studies revealed that a minimum of 11% to a maximum of 17% of sulphur is required for good cracking characteristics. The kinetics of decomposition of cracker mixture is carried out employing DSC multiple heating rate kinetic method. Increase in sulphur content decrease the energy of activation facilitating easy ignition of the cracker mixtures. Arrhenius parameters for cracker mixture decomposition are reported in this paper.     

Effects of high electrolyte concentration on DPPC-multilayers: an ESR and DSC investigation

The effects of salinity on the lateral headgroup interactions of dipalmitoylphosphatidylcholine (DPPC) molecules in fully hydrated multilayers have been investigated by spin label electron spin resonance (ESR) spectroscopy and differential scanning calorimetry (DSC).By increasing the NaCl concentration from 0 to 3 M in the multilayers' dispersion medium, the ESR measurements performed with the 5-stearic acid spin label and di-tert-butyl-nitroxide show an increase in the orientational degree of order of the lipid molecules, mainly in the gel phase, and a decrease of the membrane permeability. An upward shift from 31.5° to 36.5°C and from 40.5° to 41.9°C of the pre- and main DPPC phase transition temperatures, respectively, is observed with 5-SASL, while slightly higher values are detected with DTBN. Small effects are evident on the properties of the liquid crystalline phase of the DPPC multilayers.The DSC measurements also reveal an upward shift of the pre- and main transition temperatures. The shifts, however, are more marked if compared to the ones observed with the ESR technique.The findings suggest an increase in the packing density of the DPPC molecules in the multilayers in presence of high salt concentration. Dehydration of the DPPC interfacial region with a variation of the lateral electrostatic interactions between phospholipid polar heads trigger the phenomena observed.     

Can one measure precise heat capacities with DSC or TMDSC?</o:p>

Summary During a prior study of gel-spun fibers of ultrahigh-molar-mass polyethylene, a substantial error was observed on calculating the heat capacity with a deformed pan, caused by the lateral expansion of the fibers on shrinking during fusion. In this paper, the causes of this and other effects that limit the precision of heat capacity measurements by DSC and TMDSC are explored. It is shown that the major cause of error in the DSC is not a change in thermal resistance due to the limited contact of the fibers with the pan or the deformed pan with the platform, but a change in the baseline. In TMDSC, the frequency-dependence is changed. Since irreversible changes in the baseline can occur also for other reasons, inspections of the pan after the measurement are necessary for precision measurements.