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  • Articles  (73)
  • DSC
  • Springer  (73)
  • American Association for the Advancement of Science
  • American Meteorological Society
  • 1995-1999  (52)
  • 1990-1994  (21)
  • 1999  (52)
  • 1992  (21)
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  • Articles  (73)
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  • Springer  (73)
  • American Association for the Advancement of Science
  • American Meteorological Society
  • Wiley-Blackwell  (5)
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  • 1995-1999  (52)
  • 1990-1994  (21)
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  • 1
    ISSN: 1572-8935
    Keywords: TDI-based polyurethane elastomers ; Tg ; Tglobal transition ; DSC ; TSC/RMA ; DMA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Thermal transitions of TDI-based polyurethane elastomers with PTMO as the soft segment were characterized by the depolarization technique in TSC and by using with the thermal windowing technique on selected specimens in the RMA measurements. Results indicate that the broadened thermal transition in the glass transition region as observed in the DSC thermogram is related to the combined Tg transition and the Tglobal transition in the TSC spectrum. This Tglobal transition is associated with the macromolecular property as detected by tan δ in DMA measurement. The increase in the Tg with a high NCO content may be explained by the structural modification found on the urethanic chain with the additional linkage of the hard segment that affects the cooperative motion of the molecular chain. Data measured from DSC, TSC/RMA and DMA with simulated DEA and wide angle X-ray data are presented for the characterization of the polyurethanes. The RMA measurement leads to a compensation search on Tg transition and provides pertinent thermokinetic data that correlates the NCO content with changes in enthalpy and entropy on the relaxation behaviors in the Tg transition of polyurethane elastomers.
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  • 2
    ISSN: 1432-1017
    Keywords: Halothane ; Dantrolene ; DPPC ; 31P-NMR ; DSC ; Model membranes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The action of the relaxing agent dantrolene on dipalmitoylphosphatidylcholine (DPPC) model membranes in the presence and absence of the general anesthetic halothane has been investigated by DSC and 31P-NMR. Dantrolene has a weak effect on both the thermodynamic and NMR parameters of the pure model membrane. When halothane is present in the system, the relaxing agent acts to counterbalance the strong anesthetic-induced membrane pertubation. This is reflected in DSC experiments by a change of the enthalpy variation (ΔH) and of the main gel-to-fluid phase transition temperature (Tc) towards the values of the pure lipid system. The amount of halothane-induced small tumbling vesicles, as detected by 31P-NMR by the superposition of an isotropic line on a lamellar-type powder spectrum, is considerably reduced upon dantrolene addition. This means that the relaxing agent “cures” the membrane de-structuring action promoted by halothane. Membranes first treated with dantrolene are also protected from the halothane perturbation. So, the relaxing agent is both “curative” and “preventative” against halothane. The optimum effect is obtained for 1 dantrolene molecule per ca 34 halothane molecules. The mechanisms of action were discussed in relation to membrane fluidity.
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  • 3
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    Journal of thermal analysis and calorimetry 38 (1992), S. 455-462 
    ISSN: 1572-8943
    Keywords: chemical education ; DSC ; polyethylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein überblick über die Leistungsfähigkeit von DSC in der Chemieausbildung, sowohl in der Hochschul-als auch in der Postgraduate-Phase vermittelt. Es wird ein Weg aufgezeigt, wie die Einführung von DSC in der Chemieausbildung erleichtert werden kann. Die ausführliche Beschreibung eines Hochschulexperimentes, das Schmelzverhalten von ultrahochmolekularem Polyethylenfiber wird gegeben. Es wird gezeigt, da\ derartige Experimente geeignet sind, verschiedene chemische und physikalische Vorgänge leicht demonstrieren zu können.
    Notes: Abstract An overview is given of the potential of DSC in chemical education, both in the under-graduate and in the graduate phase. The way in which the introduction of DSC in chemical education is facilitated, is outlined. A comprehensive description is given of a graduate experiment, the melting behaviour of ultra-high molecular weight polyethylene fiber. It is shown that, using such an experiment, various chemical and physical processes in substances can be easily demonstrated.
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  • 4
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    Journal of thermal analysis and calorimetry 38 (1992), S. 495-504 
    ISSN: 1572-8943
    Keywords: cement hydration ; DSC ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Bei der Untersuchung von Zement und des Einflusses von Additiven auf das Hydratationsverhalten von Zement finden thermoanalytische Methoden eine breite Anwendung. Der effektivste und meistbenutzte Beschleuniger für die Hydratation von Zement ist Calciumchlorid, aber die Ergebnisse hängen stark von der Dosiergeschwindigkeit ab. In vorliegender Studie wird mittels DSC-, TG- und Röntgendiffraktionsmethoden der Einflu\ der Dosierung von Calciumchlorid auf das Hydratationsverhalten von verschieden alten OPC-Zementbreiproben untersucht. Die Ergebnisse wurden in Bezug auf die relativen Mengen Calciumhydroxid und das gebildete Gesamtreaktionsprodukt gewertet. Bei Dosen von mehr als 1% Calciumchlorid konnte als Hydratationsprodukt Chloraluminat festgestellt werden. Sind Monochloraluminat und das Calciumaluminathydrat C4AH13 in geringen Mengen vorhanden, kann man zwischen den beiden mittels Röntgendiffraktion nicht unterscheiden. Thermoanalytische Methoden erwiesen sich als effektives Hilfsmittel bei der Charakterisierung der Produkte der Hydratation in Gegenwart von Chlorid.
    Notes: Abstract Thermal methods are used extensively in investigating cements and effects of additives on their hydration behaviour. Calcium chloride is the most effective and widely used accelerator for cement hydration, but the result is largely dependent on the rate at which it is added. In this study the influence of calcium chloride dosage on the hydration behaviour of OPC pastes aged for different periods has been investigated by means of differential scanning calorimetry (DSC), thermogravimetry (TG) and X-ray diffraction (XRD) methods. The results are discussed in relation to the relative amounts of calcium hydroxide and total reaction product formed. Chloroaluminate was a product of hydration in the samples dosed with greater than 1% calcium chloride. XRD was unable of itself to differentiate between monochloroaluminate and the calcium aluminate hydrate C4AH13 when present in small amounts. Thermal methods proved effective in characterising the products of hydration in the presence of chloride.
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  • 5
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    Journal of thermal analysis and calorimetry 38 (1992), S. 789-796 
    ISSN: 1572-8943
    Keywords: ETA ; DSC ; DTA ; silver cyano complex ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DTA und TG wurde [Phenyl2I][Ag(CN)2] untersucht in im festen Zustand bei Erhitzen in einer Argonatmosphäre bis 160°C als thermisch stabil befunden. Beim Erhitzen auf höhere Temperaturen erfolgt eine Zersetzungsvorgang, wobei flüchtige Produkte wie z.B. [Phenyl]I, [Phenyl]NC und (CN)2 entstehen. Bei Erhitzen auf 500°C erhält man metallisches Silber. Die festen Zwischen- und flüchtigen Produkte wurden mittels IR-Spektroskopie untersucht. Anhand der DTA- und ETA-Untersuchungen konnte festgestellt werden, daß bei Erhitzen und Abkühlen unterhalb 100°C reversible Einphasenumwandlungen stattfinden. Bei Erhitzen über 100°C schmilzt die Probe (SchmelzpunktT m=135°C). Die Schmelzenthalpie wurde mittels DSC ermittelt (H=−28 kJ/mol). Mit Hilfe von ETA wurde der Unordnungsgrad des Zersetzungsendproduktes geschätzt. Der Wert der Aktivierungsenergie für die Radondiffusion im Temperaturbereich 720°–500°C beträgt 32,6 kJ/mol.
    Notes: Abstract It was found by DTA and TG that [Phenyl2I][Ag(CN)2] in the solid state is chemically stable on heating in argon up to 160°C. During heating to higher temperatures it decomposes, forming volatile products such as [Phenyl]I, [Phenyl]NC and (CN)2 [1]. After heating the sample to 500°C metallic silver resulted. The volatile and intermediate solid products were analysed by IR-spectroscopy. It was found by means of DTA and ETA that an isophase reversible transition takes place when the sample is heated and cooled, not higher than 100°C. At heating higher than 100°C the sample melts (melting pointT m=135°C). The enthalpy melting was determined by means of DSC (ΔH=−28 kJ·mol−1). By means of ETA the disorder degree of the final decomposition product was estimated. The value of the activation energy of radon diffusion in the temperature range 720°–500°C equals 32.6 kJ·mol−1.
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  • 6
    ISSN: 1572-8943
    Keywords: DSC ; low molecolar compounds ; phase transitions ; polymers ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC- uns SAXS-Techniken wurden die Orientierung, Phasenzusammensetzung und Phasenumwandlungen einer Reihe von langkettigen niedermolekularen Verbindungen (LMC) wie z.B. Heneikosan, Zetylalkohol und normalen Fettsäuren untersucht, die in porösen Strukturen (Haarrissen) von in flüssigem Medium ausgerichteten polymeren Matrizen eingebracht wurden. Es konnten verschiedene LMC-Kristallit-TVpen in Haarrissen von polymeren Matrizen beobachtet werden. Es wurde gezeigt, daß der LMC-Phasenzustand in Haarrissen durch eine höhere Stabilität der Hochtemperatur-Polymermodifikationen charakterisiert ist. Die LMC Schmelztemperatur in Haarrissen nimmt im allgemeinen ab, genauso wie die Schmelzenthalpie (Wärme) und die Entropie. Der Grund für die beobachteten Veränderungen der LMC-Eigenschaften liegt in der großen Dispersität (40–100 nm) der LMC-Partikel in den Haarrissen, woraus sich ein sichtbarer Anstieg der Polymer/LMC Grenzflächeneinwirkung auf die grundlegenden thermodynamischen Parameter des untersuchten Systemes ergibt.
    Notes: Abstract Orientation, phase composition and phase transitions of a series of long chain low molecular weight compounds (LMC), such as heneicosane, cetyl alcohol, normal fatty acids, introduced into porous structure (crazes) of polymeric matrices oriented in liquid medium have been studied by means of DSC and SAXS techniques. Different types of LMC crystallites orientation in crazes of polymeric matrices have been observed. LMC phase state in crazes is shown to be characterized by higher stability of high-temperature polymer midifications. LMC melting temperature in crazes usually decreases as well as melting enthalpy (heat) and entropy. The origin of LMC properties changes observed is high dispersity (40–100nm) of LMC particles in crazes resulting in a marked growth of polymer/LMC interface influence on principal thermodynamic parameters of the systems studied.
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  • 7
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    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
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  • 8
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    Journal of thermal analysis and calorimetry 55 (1999), S. 67-76 
    ISSN: 1572-8943
    Keywords: activation energy ; DSC ; ethylene-vinyl acetate copolymer ; TG ; TG/IR ; thermal degradation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract When ethylene-vinyl acetate copolymer, EVA, is heated, a two-stage thermal degradation occurs following its melting. The vinyl acetate content of the copolymer was determined to be 43.8% by using TA 2950 and TA 2050 thermogravimetric instruments. TG/FTIR was used to detect the evolved gas. Acetic acid and trans-1-R-4-R'-cyclohexane were the main products evolved from EVA in the first and second stage, respectively. The apparent activation energies were determined for both stages by differential methods.
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  • 9
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    Journal of thermal analysis and calorimetry 55 (1999), S. 57-65 
    ISSN: 1572-8943
    Keywords: artificial ageing ; DSC ; dynamic crystallization ; isoconversional method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A crystallization kinetics analysis of several polypropylene-polyethylene (PP-PE), PP-rich copolymers was made by means of differential scanning calorimetry. The crystallization was studied via calorimetric measurements at different cooling rates. Several additives were added to the base material. Some test samples were subjected to artificial ageing processes. A modified isoconversional method was used to describe the crystallization process under non-isothermal conditions. The value of the Avrami parameter was determined for primary and secondary crystallization.
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  • 10
    ISSN: 1572-8943
    Keywords: dioximine complexes of Co ; DSC ; kinetic compensation effect ; kinetic parameters of thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 14 mixed Co(III) dioximine chelates of the types [Co(Diox·H)2(amine)2]X (X = Br, I, NO3, ClO4) and H[Co(Diox·H)2(N3)2], respectively (Diox·H2-1,2-cyclohexane dione dioxime (nyoxime), 1,2-cycloheptane dione dioxime (heptoxime) 1,2-cyclooctane dione dioxime (octoxime) were obtained and their thermal decompositions were studied in an argon atmosphere. After the dehydration of the crystallohydrates, both types of complexes exhibit 3 decomposition stages. For the [Co(Diox·H)2(amine)2]X type complexes (X = Br, I) the first endothermal stage is the substitution of an amine molecule for the external sphere anion and this process is followed by two exothermal decomposition stages. With H[Co(Diox·H)2(N3)2] type complexes the first and third processes are relatively slow, but the second process is very fast, corresponding to a vertical portion of the TG curves. From the TG curves kinetic parameters were derived for 11 processes and the validity of a non-linear compensation law was observed.
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  • 11
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    Journal of thermal analysis and calorimetry 56 (1999), S. 51-57 
    ISSN: 1572-8943
    Keywords: DSC ; enthalpies ; NaAlF4 ; Na5Al3F14
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Beside the two well-known minerals cryolite, Na3AlF6, and chiolite, Na5Al3F14, the binary system NaF-AlF3 also contains a third compound, NaAlF4, sodium tetrafluoroaluminate. Solid NaAlF4 has been prepared from its vapour under controlled conditions. The stability of NaAlF4 has been investigated by differential scanning calorimetry. It is shown that the disproportionation of the compound: 5NaAlF4(s)=Na5Al3F14(s)+2AlF3(s) takes place at considerable rate between 700 and 900 K. The enthalpy of this reaction is calculated and found to be -66.9 kJ. Enthalpies of the two solid state transitions α-Na3AlF6 → β-Na3AlF6 and α-AlF3 → β-AlF3 have also been measured and new values are reported. The enthalpy of formation of chiolite, Na5Al3F14, at 900 K has been recalculated from enthalpy increment data obtained by drop calorimetry. A value of ΔH900 o = -7513.6±12.0 kJ mol-1 has been obtained. This value is in disagreement with the recommended value given in JANAF Thermochemical Tables given at 900 K ΔHf o = -7559.2 kJ mol-1.
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  • 12
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    Journal of thermal analysis and calorimetry 56 (1999), S. 925-929 
    ISSN: 1572-8943
    Keywords: DSC ; equilibrium ; Fe-Ni distribution ; monosulfide solid solution ; pentlandite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two mixtures of pentlandite and the monosulfide solid solution (mss) have been synthesized. The bulk compositions of the samples are Fe6Ni3S8 and Fe3Ni6S8. Differential scanning calorimetry detected exothermic process in the samples under heating. The process takes place in temperature range between phase transition in the mss (near 400 K) and 690 K and is governed by diffusion. X-ray powder diffraction has showed that equilibrium Fe-Ni distribution between pentlandite and the mss is achieved after short-time heating up to 670 K.
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  • 13
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; epoxy resin ; SAN ; thermoplastic blends
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cure kinetics using a differential scanning calorimetry (DSC) technique were analyzed for a thermoplastic modified tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) epoxy resin cured with diaminodiphenylsulphone (DDS), an aromatic diamine. The neat resin and its blends with the poly(styrene-co-acrylonitrile) (SAN) of various compositions were studied by applying a phenomenological model proposed by Kamal. Kinetic parameters were determined by fitting experimental data. This model gives a good description of cure kinetics up to the onset of vitrification. Diffusion control was incorporated to describe the cure in the latter stages of cure. The results showed that the addition of SAN did not alter the nature of the reaction, but the reaction rates and final conversions decreased when SAN contents increase, due to reduction of mobility of the reacting species.
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  • 14
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1285-1304 
    ISSN: 1572-8943
    Keywords: amorphous state ; combined techniques ; drug design ; drug product development ; drug substance ; drug technology ; DSC ; excipients ; failure investigations ; hydrates ; MDSC ; microcalorimetry ; pharmaceuticals ; polymorphism ; polymers ; preformulation ; process optimization ; purity ; quality control ; solvates ; stability ; sub-ambient DSC ; TG ; temperature resolved X-ray diffraction ; water interactions ; thermal microscopy ; water sorption-desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Modern thermal analysis, microcalorimetry and new emerging combined techniques which deliver calorimetric, microscopic and spectroscopic data offer a powerful analytical battery for the study of pharmaceuticals. These techniques are very useful in all steps of development of new drug products as well as methods for quality control in production. The characterization of raw materials enables to understand the relationships between polymorphs, solvates and hydrates and to choose the proper development of new drug products with very small amount of material in a very short time. Information on stability, purity is valuable for new entities as well as for marketed drug substances from different suppliers. Excipients which vary from single organic or inorganic entity to complexes matrixes or polymers need to be characterized and properly controlled. The thermodynamic phase-diagrams are the basis of the studies of drug-excipients interactions. They are very useful for the development of new delivery systems. A great number of new formulations need proper knowledge of the behaviour of the glass transition temperature of the components. Semi-liquid systems, interactions in aqueous media are also successfully studied by these techniques.
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  • 15
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    Journal of thermal analysis and calorimetry 57 (1999), S. 61-73 
    ISSN: 1572-8943
    Keywords: amorphous ; combined techniques for polymorphism ; DSC ; MKS 492 ; polymorphism ; purine ; quantitative determination ofamorphous and polymorphs ; solvent mediated transitions ; temperature resolved X-ray diffraction ; TG ; thermodynamic relation between polymorphs ; xanthine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The polymorphic behaviour of the purine derivative MKS 492 was studied with investigations of suspensions of selected samples in different solvents and of samples obtained by crystallizations. The samples were analyzed by DSC, TG and X-ray diffraction. Six different crystalline modifications called A, B, B’, C, D and E and an amorphous form were identified. Four pure crystalline modifications, A, B, C and D have been manufactured and characterized by DSC, X-ray, IR, solubilities, densities, hygroscopicity and dissolution measurements. The four forms A, C, D and E are monotrop to the form B. The form B is enantiotrop to the form B’, which revealed the highest melting point of all known polymorphs. This form B’ is only stable at high temperature. Temperature resolved X-ray diffraction was very helpful for proper interpretation of the thermal events. The melting peaks of the forms A and C and the endothermic peak corresponding to the enantiotropic transition B into B’ occur in a narrow range of temperature. The form B which is the most stable one at room temperature has been chosen for further development. Quantitative methods to determine the content of the forms A, C and D in samples of form B or to determine the content of form A, B and D in form C have been developed by using X-ray diffraction. Limits of detection are 1 or 2%. For the quantitative determination of the amorphous fraction, X-ray diffraction and microcalorimetry are compared. For high amounts of the amorphous fraction, the X-ray diffraction method is preferred because it is faster. Microcalorimetry is very attractive for levels below 10% amorphous content. The lowest limit of detection is obtained by microcalorimetry, about 1%.
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  • 16
    ISSN: 1572-8943
    Keywords: crystal modifications ; DSC ; Gibbs free energy function ; molecular modelling ; solution calorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermodynamic energy relationship between two crystal modifications of cimetidine was investigated and compared with differences in their processing properties with respect to transformation from one modification to the other. The crystal energies of the two modifications A and D were found to be almost identical and therefore the polymorphs are regarded as virtually isoenergetic crystals. This statement is based on DSC measurements of the melting points and of the enthalpies of fusion for the two crystal forms, which enable the calculation of the Gibbs free energy functions. Furthermore, the statement is supported by measurements of the enthalpies of solution in two different solvents. Both DSC and solution experiments reveal a slightly higher stability of the D modification with respect to the A form. In addition, tribomechanical treatment also indicates modification D to be the more stable one, as well as the higher density of the D form. No transformation during DSC at low heating rate was found which could be used in a stability consideration. As the explicit crystal structures of the two modifications are resolved, it was possible to calculate crystal energies theoretically as well. The theoretical results showed a remarkable difference in the crystal energies at zero degree Kelvin. Furthermore, they were just contradicting experimental findings by stating A being more stable than D. Possible reasons for this discrepancy and the feasibility of today's calculation methods with respect to prediction of stability properties are discussed.
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  • 17
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    Journal of thermal analysis and calorimetry 57 (1999), S. 631-642 
    ISSN: 1572-8943
    Keywords: DSC ; fluorocarbon chain ; polymerizability ; polymorphic behaviors ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The molecular aggregation of acrylic and methacrylic acid esters containing long-fluorocarbon chains: 2-(perfluoroalkyl)ethyl acrylate (FFnEA) and 2-(perfluoroalkyl)ethyl methacrylate (FFnEMA) (F(CF2)nCH2CH2OCOC(X)=CH2, where X=H, CH3 and n=6, 8, 10) was investigated by differential scanning calorimetry (DSC) and temperature controlled X-ray powder diffraction measurement. These compounds exhibited some characteristic polymorphic behaviors depending on the length of fluorocarbon chain and the α-position methyl group. The solid-state polymerization by γ-ray irradiation was studied for these compounds in the various crystal forms. In the solid-state polymerization, highest polymerizability was observed in the crystal form that exists in the highest temperature region for each compound.
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  • 18
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    Journal of thermal analysis and calorimetry 58 (1999), S. 29-38 
    ISSN: 1572-8943
    Keywords: benzoicacid ; controlled release ; DSC ; ethyl cellulose ; FTIR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The physical state of benzoic acid (BA) and its interaction with ethyl cellulose (EC) were examined in ethyl cellulose—benzoic acid matrices by Differential Scanning Calorimetry (DSC). The glass transition temperature (Tg) of EC of various matrices having BA in solid solution form (upto 27.7%) was reduced. The BA in matrices containing more than 38.9% drug exhibited distinct melting endotherms due to crystalline form. The peak temperatures of these endotherms were lowered and they broadened as the concentration was lowered. The solubility of BA increased at its melting point as compared to ambient temperature. The melting enthalpy of BA, when plotted as a function of its concentration yielded a straight line with intercept of 330 mg g−1 of matrix. This is the solubility of BA in EC at its melting temperature. Fourier Transform Infra Red Spectroscopy (FTIR) investigations confirmed that hydrogen bonding occurred between EC and BA through hydroxyl groups.
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  • 19
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    Journal of thermal analysis and calorimetry 58 (1999), S. 363-368 
    ISSN: 1572-8943
    Keywords: DSC ; lipid ; phase behaviour ; synchrotron radiation ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The phase behaviour and phase stability of lipids are of importance in an understanding of the biological functions of cell membranes. Among a variety of physical techniques employed to study the phase behaviour and structural properties of polar lipids, differential scanning calorimetry and X-ray diffraction have proved to be successful and are the most frequently used methods. Applications involving a combination of the two techniques, particularly when synchrotron radiation is used as the light source of X-ray diffraction, are reviewed in this article.
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  • 20
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    Journal of thermal analysis and calorimetry 58 (1999), S. 653-662 
    ISSN: 1572-8943
    Keywords: dehydration ; DSC ; TG ; water ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A procedure for measurement of the heat of zeolite dehydration by scanning heating has been designed. Simultaneous data on heat flow (DSC) and mass loss (TG) are required for evaluation. The heating rate depends on the experimental conditions (point-spread function, sample mass, crucible design, and calorimetric reproducibility). Dehydration measurements have three advantages as compared with the sorption procedure: i) one can investigate samples with irreversible dehydration; ii) no approximation model is needed for calculation of the partial molar heat of dehydration; and iii) the procedure is not labor-consuming. The procedure was tested on the natural zeolites heulandite, chabazite and mordenite. The results are close to those measured by the sorption procedure. The partial molar heat of dehydration was found to depend on the water content. It increases from 50 to 87 J mol−1 K−1 for heulandite, from 53 to 81 J mol−1 K−1 for chabazite, and from 51 to 71 J mol−1 K−1 for mordenite. The approximation of the heat of sorption by linear regression was found to be wrong. Detection of a ‘phase transitioN’ after this approximation has no meaning.
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  • 21
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    Journal of thermal analysis and calorimetry 58 (1999), S. 725-739 
    ISSN: 1572-8943
    Keywords: DDC ; DSC ; DTA ; transformation-governed TA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The described instrumental method makes it possible that the quasi-static heating technique, well applicable to thermogravimetric measurements, (see Part I of this paper) can be used in the case of DTA and DSC examinations, too. Based on the new type of curves the characteristic transformation temperatures, the whole course of the transformation in dependence of sample temperature, the extent of the enthalpy change caused by the transformation or by its partial processes can accurately be determined. The essentially greater accuracy of the measurements — in comparison to the conventional ones — is due to the quasi-static heating technique which ensures that the transformations should take place under quasi-equilibrium conditions.
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  • 22
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1607-1626 
    ISSN: 1572-8943
    Keywords: binary systems of cholesteryl ; DSC ; esters ; induced smectic phases ; thermomicroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Acht binäre Systeme einer homologen Reihe von Cholesterylestern (Cholesterylpropionat bis Cholesteryldecanoat) mit trans-4-Propylcyclohexyl-4-(trans-4-pentylcyclohexyl) benzoat (Licristal 1223, Merck, Darmstadt) wurden thermomikroskopisch und DSC-analytisch untersucht. In sechs Fällen wurden induzierte smektische A-Phasen mit Umwandlungspunktmaxima festgestellt. Die cholesterischen bzw. nematischen Phasen bilden kontinuierliche Reihen von cholesterischen Mischkristallen, während die festkristallinen Phasen bei allen Systemen einfache Eutektika aufweisen.
    Notes: Abstract Eight binary systems of a homologous series of cholesteryl esters (from cholesteryl propionate to cholesteryl decanoate) with trans-4-propylcyclohexyl-4-(trans-4-pentyl-cyclohexyl) benzoate (Licristal 1223, Merck, Darmstadt) were examined by thermomicroscopy and DSC analysis. In six cases induced smectic A phases with transition point maxima were observed. The cholesteric resp. nematic phases form continuous series of cholesteric mixed crystals, while the solid phases show simple eutectics.
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  • 23
    ISSN: 1572-8943
    Keywords: alkylureas ; DOAB vesicles ; DSC ; gel-liquid transitions ; urea
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The gel to liquid-crystal transition for vesicles in aqueous solution formed by dimethyldi-n-octadecylammonium bromide (DOAB) occurs at 44.7°C. Moreover, the shapes of the scans recorded by a sensitive DSC microcalorimeter are very similar when the vesicular solutions are prepared starting with solid DOAB and comparable amounts of either solid urea or solid alkylureas. Therefore, the DOAB vesicles in aqueous solution accommodate this class of solutes without marked changes in the melting temperature and the enthalpy of the transition. The contrast with effects of added surfactants and simple organic solutes such as THF and ethanol is particularly significant.
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  • 24
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    Journal of thermal analysis and calorimetry 55 (1999), S. 807-816 
    ISSN: 1572-8943
    Keywords: DSC ; hydrogen-bond ; IR ; lithium formate monohydrate ; Raman spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) of lithium formate monohydrate (LiHCOO·H2O) were performed in the temperature range 300–700 K. The DSC/TG measurements show that the dehydration process to anhydrous lithium formate (LiHCOO) is complex and occurs in two stages. The data are correlated to the structure and to the arrangement of the molecules in the crystal, including the hydrogen-bonding. Infrared transmittance and Raman spectra of this crystal are reported and commented on.
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  • 25
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    Journal of thermal analysis and calorimetry 55 (1999), S. 789-796 
    ISSN: 1572-8943
    Keywords: alkaline earth malonates ; DSC ; DTA ; kinetic parameters ; TG ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition of strontium and barium malonates has been studied isothermally and non-isothermally employing simultaneous TG-DTG-DTA, DSC, XRD and IR spectroscopic techniques. DSC of these malonates has been recorded both in oxygen and nitrogen atmospheres. The decomposition is a single step process and the end product formed is carbonate. The energy of activation and frequency factor values for the decomposition of strontium malonate are 547 kJ mol−1 and 1041 s−1 respectively. The activation energy and frequency factor values for isothermal dehydration of barium malonate sester-hydrate are 57–111 kJ mol−1 and 107–1012 s−1 respectively and the corresponding values for decomposition from DSC are 499.5 kJ mol−1 and 1044 s−1 respectively. The higher thermal stability of strontium malonate as compared to that of barium salt is ascribed to its being anhydrous so that decomposition proceeds without restructuring. Their thermal stabilities have also been compared with that of respective oxalate salts.
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  • 26
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    Journal of thermal analysis and calorimetry 56 (1999), S. 7-15 
    ISSN: 1572-8943
    Keywords: ALE ; CVD ; DSC ; DTA ; EGA ; EL display ; solar cell ; sol-gel ; spray pyrolysis ; super-conductor ; TG ; thin films
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Processing thin films for advanced applications, for instance in electronics and optoelectronics, involves several steps starting from precursor synthesis and ending up with the devices. Especially when optimizing the first steps of this chain of processes, thermoanalytical techniques play an important role. The review will focus on the main chemical deposition methods (CVD, ALE, spray pyrolysis, sol-gel) giving selected examples of problem-solving by thermal analysis. The techniques discussed are TG, DTA/DSC, EGA and their combinations. High-temperature X-ray diffraction (HTXRD) is also a powerful tool for in situ studies of thin films. The examples are taken from solar cell, superconductor and flat panel electroluminescent display technologies.
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  • 27
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    Journal of thermal analysis and calorimetry 56 (1999), S. 429-435 
    ISSN: 1572-8943
    Keywords: DSC ; nickel sulphide ; TG ; toughened glass ; X-ray diffraction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Nickel sulphide (NiS) was characterised using X-ray diffraction, thermal gravimetric analysis (TG) and differential scanning calorimetry (DSC). The 'as received' Millerite, stoichiometric NiS, observed to be slightly nickel deficient, was found to readily decompose in a nitrogen atmosphere at elevated temperatures (450°C max.) to the sulphur deficient Godlevskite, Ni7S6. DSC and X-ray measurements demonstrated that the high temperature form of the Godlevskite was readily stabilised at room temperature. The kinetics of the α-β re-transformation in Godlevskite were then investigated using DSC and were observed to be first order.
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  • 28
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    Journal of thermal analysis and calorimetry 56 (1999), S. 547-552 
    ISSN: 1572-8943
    Keywords: cobalt oxysalts ; DSC ; enthalpy of decomposition ; enthalpy of dehydration ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was used to determine the molar enthalpies of dehydration and decomposition of CoC2O4·2H2O, Co(HCOO)2·2H2O and [Co(NH3)6]2(C2O4)3·4H2O. The first stage of dissociation of each compound is a single-step dehydration both in air and argon atmospheres. The next stages are decomposition processes influenced by experimental parameters. The enthalpies of dehydration and decomposition vary from compound to compound in each atmosphere. The obtained data have been related to the macromechanisms proposed for the thermal decomposition and the parallel-consecutive decomposition-oxidation processes.
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  • 29
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    Journal of thermal analysis and calorimetry 56 (1999), S. 783-792 
    ISSN: 1572-8943
    Keywords: complex process ; DSC ; isoconversional methods ; kinetics ; model-free kinetics ; peak maximum evolution methods ; simulations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In the case of a complex mechanism of two parallel independent reactions, peak maximum evolution methods and model-fitting methods give only a mean value of the kinetic parameters, while isoconversional methods are useful to describe the complexity of the mechanism. Isothermal and non-isothermal isoconversional methods can be used to elucidate the kinetics of the process. Nevertheless, isothermal isoconversional methods can be limited by restrictions on the temperature regions experimentally available because of duration times or detection limits.
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  • 30
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    Journal of thermal analysis and calorimetry 56 (1999), S. 947-951 
    ISSN: 1572-8943
    Keywords: combustion ; crude oil ; DSC ; TG/DTG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper investigates the minimum oil content necessary for self-sustained combustion, which is introduced as a criterion for the selection of suitable reservoirs for in-situ combustion processes. Differential scanning calorimetry was used to determine the heat values of oil-limestone mixtures. The minimum temperature required for the total consumption of the fuel was obtained by thermogravimetry (TG/DTG). The minimum amount of oil necessary to sustain combustion was calculated from these two parameters and compared with the oil content of the reservoir. Reservoirs with an oil content greater than or equal to this minimum value were considered feasible. It was seen that the fields examined are generally not suitable for in-situ combustion processes.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1155-1161 
    ISSN: 1572-8943
    Keywords: crystallisation ; DMA ; DSC ; PCL ; polymer ; temperature modulation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Temperature modulated dynamic mechanical analysis (TMDMA) was performed in the same way as temperature modulated DSC (TMDSC) measurements. As in TMDSC TMDMA allows the investigation of reversible and non-reversible phenomena during crystallisation of polymers. The advantage of TMDMA compared to TMDSC is the high sensitivity for small and slow changes in crystallinity, e.g. during re-crystallisation. The combination of TMDMA and TMDSC yields new information about local processes at the surface of polymer crystallites. It is shown that during and after isothermal crystallisation the surface of the individual crystallites is in equilibrium with the surrounding melt.
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  • 32
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1141-1146 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; heavy ion irradiation ; melting ; PBT films ; poly(butyleneterephthalate) films
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of heavy ion-irradiation (Ar 5.5 MeV amu-1, 5·1011 ion cm-2) on the melting and crystallization of two PBT films subjected to different modes of thermal treatment was investigated. Differences were observed between the processes occurring in both initial films, due to differences in crystalline phase content. The course of melting and crystallization in heavy ion-irradiated films during first heating, cooling and second heating differs from that in the initial films. The density data and DSC results indicate a decreased crystalline phase content in the PBT films after irradiation.
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  • 33
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1353-1357 
    ISSN: 1572-8943
    Keywords: DSC ; terpenoids ; TG ; thermal behaviour
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The terpenoids acetyl sitosterol, lupeol, acetyl diosgenin and stigmasterol were studied. Comparison of the thermogravimetric curves and the activation energies of the terpenoids suggested the following sequence of thermal stability: acetyl sitosterol 〈 acetyl diosgenin 〈 lupeol 〈 stigmasterol. The DSC curves allowed determination of the melting points and the degrees of purity. Comparison of the TG and DSC curves revealed the presence of phase transitions without mass loss that were attributed to rearrangements in the terpenoid molecules.
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  • 34
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    Journal of thermal analysis and calorimetry 57 (1999), S. 371-375 
    ISSN: 1572-8943
    Keywords: C14E8 ; detergent ; DSC ; polyethylene glycol tetradecyl ether ; thermal transition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A narrow, reversible endothermic main transition is found in the aqueous micellar phase of octaethylene glycol tetradecyl ether (C14E8) by DSC, characterized by a transition temperature of 41°C and a ΔH value of 0.5 kcal mol−1, which is not observed by light scattering. This transition is assigned to a cooperative conformational rearrangement of the assembled amphiphilic detergent molecules and not to a micelle aggregation process. It is suggested that the detergent’s polar head group is primarily involved in this rearrangement.
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  • 35
    ISSN: 1572-8943
    Keywords: DSC ; iron(II)-oxime complexes ; kinetic parameters ; Mössbauer spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A number of 15 [Fe(Diox#x00B7;H)2L2] type chelates and [Fe(Diox)3(BOR)2] clathrochelates (Diox#x00B7;H2 — dimethylglyoxime, glyoxime, propoxime, nyoxime, furyl-dioxime; L-pyridine, alkyl-pyridine derivatives, diethyl-phenyl-phosphine, diethyl-p-tolyl-phosphine) were obtained and characterized by means of far and middle FTIR and Mössbauer spectroscopic methods. Some structural problems were discussed on the basis of the optical data. The DSC measurements show the higher thermal stability of the clathrochelates without O—H⋯O intramolecular hydrogen bonds (with asymmetric octahedral structure), as compared to the [Fe(Diox#x00B7;H)2L2] trans, symmetric chelates containing O—H⋯O bonds. The kinetic parameters of the thermal decomposition of the complexes have been derived using the nomogram method.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 745-752 
    ISSN: 1572-8943
    Keywords: confinement effects ; DSC ; dynamic light scattering ; finite-size effects ; glass transition ; o-terphenyl
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Calorimetry is the method first used by Jackson and McKenna to study the effect of finite-size on the molecular dynamics of glass-formers confined in nano-meter scale pores. It was found that the glass transition is shifted to lower temperature as pore size decreases. Since then, other spectroscopic techniques have corroborated this finding and given more information on the molecular dynamics. These results are used to compare with the predictions of several theories of glass transition, and in particular the coupling model of the author.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 847-851 
    ISSN: 1572-8943
    Keywords: DSC ; linear low-density polyethylene(LLDPE) ; low density polyethylene (LDPE) ; polymer blend ; thermal properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A forensic sample consisting of melt-recrystallized polymers that was recovered from the scene of a fire in a factory was identified by differential scanning calorimetry. The factory commonly used two kinds of film sheets, A and B, made by different manufacturers. It was necessary to decide whether the forensic sample related to material A or B. The forensic sample and reference samples of materials A and B were subjected to infrared spectroscopy and pyrolysis gas chromatograph mass spectrometry measurements, which revealed their polyethylene nature. The thermal behaviour of the samples was examined by differential scanning calorimetry (DSC) and they were found to be blends of two kinds of polyethylenes, low-density polyethylene and linear low-density polyethylene. The samples could be identified and distinguished from each other via the DSC measurements.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 369-373 
    ISSN: 1572-8943
    Keywords: critical temperature ; DSC ; HNNC ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Two methods for estimating the critical temperature (Tb) of thermal explosion for the highly nitrated nitrocellulose (HNNC) are derived from the Semenov's thermal explosion theory and two non-isothermal kinetic equations, dα/dt=Af(α)e−E/RT and dα/dt=Af(α)[1+E/(RT)(1–To/T)]e−E/RT, using reasonable hypotheses. We can easily obtain the values of the thermal decomposition activation energy (E), the onset temperature (Te) and the initial temperature (To) at which DSC curve deviates from the baseline of the non-isothermal DSC curve of HNNC, and then calculate the critical temperature (Tb) of thermal explosion by the two derived formulae. The results obtained with the two methods for HNNC are in agreement to each other.
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  • 39
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2257-2272 
    ISSN: 1572-8943
    Keywords: heat capacity ; data analysis ; differential scanning calorimeter ; DSC ; single run
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es werden die Grundzüge für die Datenanalyse von Wärmekapazitätsmessungen durch Doppelproben- DSC mit Einfachdurchgängen beschrieben: 1. Korrektion des Wärmeflusses durch Subtraktion des Beitrages des Probenbehälters, einschließlich der Korrektion nicht angeglichener Behältermassen. 2. Korrektion des Wärme flusses und der Temperatur mit einer nichtlinearen Temperaturkalibrierung, Korrektion von Temperaturverzögerung und Aufheizgeschwindigkeit. 3. Berechnung der Zellen-konstanten für beide Zellenpositionen und Ermittlung des Asymmetriefaktors zwischen den Zellenpositionen A und B. 4. Kalibrierung der Wärmekapazität und Berechnung mit Anstiegs- und Asymmetriekorrektion. 5. Berechnung der Wärmekapazität für Mehrfachdurchgänge. 6. Kurvenanpassung für die Wärmekapazität.
    Notes: Abstract An outline for the data analysis of single-run heat capacity measurments by dual sample DSC is presented with the following features: 1. Heat flow correction by subtracting the contribution due to the sample pan, including correction for mismatched pan masses. 2. Heat flow and temperature correction with a nonlinear temperature calibration, temperature lag correction, and heating rate correction. 3. Calculation of the cell constants for both cell positions and evaluation of the asymmetry factor between cell positions A and B. 4. Heat capacity calibration and calculation with slope and asymmetry correction. 5. Calculation of heat capacity for multiple runs. 6. Data curve fitting for heat capacity.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2491-2499 
    ISSN: 1572-8943
    Keywords: DSC ; DTA ; M(IO3)2· 6H2O ; M(IO3)2·6D2O
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DTA- und DSC-Methoden wurden Me(IO3)2·6H2O und Me(IO3)2·6D2O (mitMe 2+=Ca2+ und Sr2+) thermisch und kalorimetrisch untersucht. Es wird ein Überblick über das thermische Verhalten ordentlicher und deuterierter Hydrate gegeben, in dem auch die Unterschiede zwischen beiden diskutiert werden. Die Enthalpien der untersuchten Phasenumwandlungen wurden bestimmt. Aus den Daten für Hdeh wurde Hf von Ca(IO3)2·6H2O, Ca(IO3)2H2O(D2O) und Sr(IO3)2·6H2O(D2O) berechnet und Bemerkungen zum beobachteten Isotopeneffektes gemacht.
    Notes: Abstract Thermal and calorimetric studies were carried out on M(IO3)2·6H2O and M(IO3)2·6D2O forM 2+=Ca2+ and Sr2+, using DTA and DSC methods. The thermal behaviour of the ordinary and deuterated hydrates is outlined and the differences observed between them are discussed. The enthalpies of the phase transitions were determined. The ΔH f o for Ca(IO3)2·6H2O, Ca(IO3)2·6H2O(D2O) and Sr(IO3)2·6H2O(D2O) were calculated from the ΔH deh data and comments are made on the isotope effect observed.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 303-311 
    ISSN: 1572-8943
    Keywords: DSC ; polyester ; polymerization
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Polymerisation von 3-benzyl-3-ethyl 2-oxetanon führt zu drei Polymer Typen: PolyRS (überschuss des Enantiomers,EE=0), PolyR oder PolyS (REE 〉 SEE) und Polyracemate. Alle Polymere sind kristallin und die thermischen Eigenschaften (T g, SchmelzeT M und δH M) hängen wesentlich vonEE des Polymers ab. Die Fortpflanzung der Polymerisation ist nicht stereospeeifisch. Die Verwendung von Aufheitzen Abkühl Zyklen führt zu einer reinen kristallinen Form, die bei der höchsten Temperatur schmilzt. Das Polyracemat verhält sich wie ein reines Polymer, das bei niedrigeren Temperatur schmilzt; es racemisiert im Laufe einer verlängerten Erhitzung im Schemlzfluss.
    Notes: Abstract The polymerization of 3-benzyl-3-ethyl 2-oxetanones leads to three types of polymers: polyRS (enantiomer excess,ee=0), polyR or polyS (Ree 〉See) and polyracemate. All these polymers are crystalline and the thermal properties (T g, meltingT M and δH M) depend mainly on theee of the polymer. The propagation of the polymerization is not stereospecific. The use of heating-cooling cycles leads to a pure crystalline form melting at the highest temperature. The polyracemate has the behaviour of a pure polymer which melts at a lower temperature, a prolonged heating in the melt induces a strong racemization.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 277-287 
    ISSN: 1572-8943
    Keywords: DSC ; limit of detection ; polymorphic transitions
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Anhand von sehr kleinen Signalen von spontanen polymorphen übergängen bei CsCl, K2Cr2O7 und Na2SO4 wird ein Verfahren zur Bestimmung der Nachweisgrenze von DSC-Geräten beschrieben. Es wird gezeigt, wie derartige Signale gut aufgelöst in DSC-Diagrammen von Pulverproben erhalten werden können. Um sie vom Rauschen der Basislinie zu unterscheiden, sollten sie eine Höhe von mindestens dem Doppelten der Basislinienbreite aufweisen. Für das angewendete Gerät beträgt die entsprechende geringste Wärmemenge, d.h. die Nachweisgrenze 0.1 mJ.
    Notes: Abstract 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.
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  • 43
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    Journal of thermal analysis and calorimetry 38 (1992), S. 409-420 
    ISSN: 1572-8943
    Keywords: metallic glasses ; DSC ; TMA
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Zur Charakterisierung des Alterns einiger metallischer Gläser wird in einer Vergleichsstudie der DSC-Methode und der thermomechanischen Analyse (TMA) die Spezifität letzterer hervorgehoben. Es wurden metallische Gläser untersucht, die entweder mittels chemischer Verfahren oder durch Schmelzverdüsen hergestellt wurden. Mittels DSC und TMA wurde festgestellt, da\ die Entspannung der metallischen Gläser stark von der Behandlungsweise abhängt, d.h. ob es sich um eine thermische oder mechanische Vorgeschichte handelt. Im Gegensatz dazu konnten bei der Kristallisation keine gro\en Unterschiede zwischen DSC und TMA gefunden werden. Anhand experimenteller Daten wurde versucht, das Verhalten derartiger Materialien unter den Betriebsbedingungen zu modellieren.
    Notes: Abstract 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.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 855-863 
    ISSN: 1572-8943
    Keywords: calibration materials ; DSC ; DTA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Als neue Referenzsubstanzen für Temperatur- und Energiekalibrierung von DTA- und DSC-Geräten wurden im Temperaturbereich 300–600 K einige organische Verbindungen, wie z.B. Phenanthren, Benzanilid, Anissäure, Triphenylen, 2-Chloranthrachinon, Hexachlorbenzol, Karbazol, 4-Jodbenzoesäure, Perylen und Anthrachinon untersucht.
    Notes: Abstract Several organic compounds like phenanthrene, benzanilide, anisic acid, triphenylene, 2-chloroanthraquinone, hexachlorobenzene, carbazole, 4-iodobenzoic acid, perylene, anthraquinone, as new reference materials for temperature and energy calibration of DTA and DSC apparatuses were studied in the range 300—600 K.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 989-996 
    ISSN: 1572-8943
    Keywords: aerospace industry ; DSC ; metal matrix composites (MMC)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Metallmatrixverbundwerkstoffe (MMC) sind für die Raumfahrtindustrie von großem Interesse, insbesondere zum Bau thermisch-struktureller Komponenten ist es wichtig, Methoden zur Verfügung zu haben, die leicht und einfach zur Charakterisierung der mechanischen Festigkeit der Materialien benutzt werden können. Es wurde gezeigt, daß DSC es ermöglicht, die Kohäsionsenergie im Fiber/Matrix-Grenzflächengebiet eines mit SiC-Whiskern verstärkten Aluminiumverbundstoffes quantitativ zu bestimmen. Diese Kohäsionsenergie ist abgängig vom Verstärkungsgrad bezogen auf die Matrixfestigkeit und berücksichtigt sowohl die chemischen als auch mechanischen Eigenschaften der Kohäsion im Fiber/Matrix-Grenzflächengebiet. In jedem Falle bedarf diese Methode einer systematischen Kalibrierung anhand von Test der mechanischen Eigenschaften.
    Notes: Abstract The metal matrix composites (MMC) being of very high interest for the aerospace industry, particularly to build up thermal-structural components, it is important to have available methods which are easy and simple to conduct for characterization of the mechanical strength of the material. This study shows that the differential scanning calorimetry (DSC) may enable us to quantify the energy of cohesion in the fiber/matrix interface area of an aluminium composite reinforced by SiC whiskers. The energy of cohesion is dependent on the state of reinforcement compared to the matrix strength and take into account both chemical and mechanical characteristics of the cohesion in the fiber/matrix interface area. However, this method would require a systematic calibration based on tests of mechanical characteristics.
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  • 46
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1123-1137 
    ISSN: 1572-8943
    Keywords: Ba-Y-Cu-O superconductor ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Für eine Reihe von Verbindungen der allgemeinen Formel Ba2YCu3Oy 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 ΔH(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.
    Notes: Abstract DSC investigations have been performed for a series of compounds Ba2YCu3Oy 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 ΔH 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.
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  • 47
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1189-1201 
    ISSN: 1572-8943
    Keywords: DSC ; gelatins ; glass transition temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC wurde im Bereich −50° bis +130°C die Temperaturabhängigkeit der Wärmekapazität für verschiedene Arten von Gelantine mit einem Wassergehalt von 2 bis 95% untersucht. Es wurde gezeigt, daß in allen untersuchten Fällen metastabile kollagenähnliche Strukturen in Gelen oder kristallinen Gelantinen gebildet werden, deren thermodynamische Parameter von den Bildungsbedingungen abhängen. Es wurden die charakteristischen Eigenschaften der Glasumwandlungen in amorphen Gelantinen und kristallinen Gelantinen mit unterschiedlichen Schmelzwärmen und einem unterschiedlichen Gehalt an geordneter Phase bestimmt. Spezielle Aufmerksamkeit wurde den strukturellen Eigenschaften von freiem und gebundenem Wasser gewidmet. Es wurde gezeigt, daß die Ab-hängigkeit der GlasumwandlungstemperaturT g vom Gehalt an gebundenem Wasser generell für viele denaturierte Biopolymere anwendbar ist. Im Unterschied zu gebundenem Wasser fungiert freies Wasser in Gelatinen nicht als ein Weichmacher, bildet aber eine starre Matrix, die die Glasumwandlung verhindert.
    Notes: Abstract In the range from −50° to +130°C, the temperature dependence of the heat capacity for different kinds of gelatins with water contents of from 2 to 95% was studied by the DSC method. It was shown that, in all studied cases, metastable collagen-like structures are formed in gels or crystalline gelatins, with thermodynamic parameters depending on the formation conditions. The characteristic properties of the glass transitions in amorphous gelatins and crystalline gelatins with different melting heats and different contents of the ordered phase were established. Special attention is paid to the structural properties of free and bound water. The dependence of the glass transition temperatureT g on the bound water content was shown to be of general applicability for many denatured biopolymers. Free water in gelatins, in distinction to the bound water, does not act as a plasticizer, but forms a rigid matrix inhibiting the glass transition.
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  • 48
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1215-1231 
    ISSN: 1572-8943
    Keywords: DSC ; irradiated polymers
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung DSC wurde zur Untersuchung des Einflusses von Bestrahlung mit schnellen Elektronen auf die molekulare Mobilität und den Schmelzvorgang von semikristallinen Polymeren und Kopolymeren von Ethylen und von Fluorkopolymer angewendet. Die Temperaturabhängigkeit der Wärmekapazität im Bereich 100 bis 500 K zeigte die besonderen Wesenszüge des Bestrahlungseffektes auf vier Relaxationsumwandlungen in Verbindung mit dem Auftreten von Segmentbewegungen in verschiedenen Molekülteilen der gestörten Regionen des Polymers. Man fand, daß die Bestrahlungsbeständigkeit der Kristallite eindeutig von der Vorgeschichte des untersuchten Objektes abhängt. Die Ergebnisse wurden ausgehend von der bestimmenden Rolle von Molekülbeweglichkeit und freiem Volumen für das Überwiegen der Strahlungsvernetzung der Moleküle gedeutet. Es wurden Zusammenhänge zwischen den Wesenszügen der thermischen Umwandlungen und den mechanischen Eigenschaften der bestrahlten Polymere festgestellt.
    Notes: Abstract DSC was used to study the influence of fast electron irradiation on the molecular mobility and melting of semicrystalline polymers and copolymers of ethylene and of fluorocopolymer. The heat capacity-temperature dependences obtained in the range from 100 K to 500 K revealed the specific features of the irradiation effect on four relaxational transitions associated with the appearance of segmental motion in different molecular elements of the disordered regions in the polymer. The pronounced dependence of the radiation stability of crystallites on the thermal prehistory of the object under study was found. The results were interpreted on the basis of the decisive role of the molecular mobility and free volume for the predominance of the radiation cross-linking of the molecules. Correlations were established between the characteristics of the thermal transitions and the mechanical properties of the irradiated polymers.
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  • 49
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1345-1355 
    ISSN: 1572-8943
    Keywords: ammonium cerium sulphate ; DSC ; kinetic parameters ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC und TG wurde die thermische Zersetzung von Ammoniumzersulfat untersucht. Die Ergebnisse zeigen in Sauerstoff einen fünfstufigen Zersetzungsprozeß im Temperaturbereich 364–1116 K. Ausgehend von den thermoanalytischen Angaben, der Elementaranalyse und den Messungen der magnetischen Suszeptibilität wurde eine Sequenz für die Zersetzung erstellt. Das Endprodukt wurde mittels Röntgendiffraktion als CeO2 identifiziert. Ammoniumzersulfat und die Produkte des ersten und des letzten Überganges enthalten Zerionen mit der Oxydationsstufe +4, während in den drei Zwischenschritten Zerionen mit der Oxydationsstufe +3 vorkommen. Anhand der nichtisothermen DSC-Untersuchungen wurden die kinetischen Parameter berechnet. Die isothermen Angaben zeigen, daß der Dehydratationsprozeß einem Ginstling-Brounstein Mechanismus folgt, während die folgenden drei Schritte durch das Mampelsche unimolekulare Gesetz der Randomkeimbildung bestimmt werden.
    Notes: Abstract Thermal decomposition of ammonium cerium sulphate has been studied by differential scanning calorimetry and thermogravimetry. The results show that the material decomposes in five steps in the temperature region 364–1116 K in oxygen. Based on the thermal data, elemental analysis and magnetic susceptibility measurements, sequence of decomposition has been established. The final product has been identified as CeO2 by X-ray diffractometry. Ammonium cerium sulphate and the products of the first and the final transitions contain cerium ion in 4+ oxidation state, while the three intermediate phases have cerium ion in 3+ oxidation state. From the non-isothermal DSC studies, kinetic parameters have been computed. The isothermal data show that the dehydration process follows Ginstling-Brounshtein mechanism, while the next three steps are governed by Mampel's unimolecular law of random nucleation.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1545-1562 
    ISSN: 1572-8943
    Keywords: camphor derivatives ; DSC ; IR ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC wurde eine Reihe von Kampferderivaten untersucht. Dabei konnte verschiedenes Verhalten mit dem Auftreten von glasartigen, amorphen, kristallinen und polymorphen Verbindungen und tautomeren Gemischen beobachtet werden. Die erhaltenen Resultate wurden durch IR-Spektroskopie und Röntgendiffraktion bestätigt.
    Notes: Abstract Thermal analysis of a series of camphor derivatives has been studied by differential scanning calorimetry. Different behaviors with the appearance of glassy, amorphous, crystalline, polymorphous compounds and tautomeric mixture were detected. These results have been confirmed by infrared spectroscopy and by X-ray diffraction.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 155-164 
    ISSN: 1572-8943
    Keywords: DSC ; glass ; relaxation ; structure
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The enthalpic relaxation of the title glasses, studied by differential scanning calorimetry, is well described by a mathematical model based on the stretched exponential relaxation function with the relaxation time proportional to the actual viscosity. The dependence of viscosity on temperature and the fictive temperature was expressed by Mazurin's approximation. The relaxation parameters obtained correlated significantly with the glass composition, indicating the changes in the structural of the TiO2 role near a TiO2 content of 3–4 mol%.
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  • 52
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    Journal of thermal analysis and calorimetry 55 (1999), S. 165-172 
    ISSN: 1572-8943
    Keywords: DSC ; nickel(II) squarate ; phase transition ; TG-DTA ; triamine
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    Topics: Chemistry and Pharmacology
    Notes: Abstract [NiL2]C4O4·nH2O [where n=2 when L=diethylenetriamine(dien) and N-(3-aminopropyl)-1,3-propanediamine (dpt); n=3 when L=N-(2-aminoethyl)-1,3-propanediamine (aepn); n=0 when L=N2-methyldiethylenetriamine (medien)] and Ni(tmdien)C4O4·2H2O (where tmdien=1,4,7 trimethyl-diethylenetriamine) have been synthesised and investigated thermally in the solid state. Ni(dpt)C4O4·H2O has also been synthesised pyrolytically in the solid state from the corresponding bis complex. All the complexes possess octahedral geometry. The squarate anion takes part in coordination only in monotriamine species. [Ni(medien)2]C4O4 upon heating undergoes phase transition (270–285°C; ΔH=4.9 kJ mol−1) accompanied by colour change pink to grey. Thermal stability decreases with increase in chain length of the triamines.
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  • 53
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    Journal of thermal analysis and calorimetry 56 (1999), S. 305-310 
    ISSN: 1572-8943
    Keywords: amorphous palladium alloys ; DSC ; hydrogenation ; mechanical alloying ; phenylacetylene ; structural characterization ; X-ray diffractometry ; X-ray photoelectron spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Amorphous PdZr, PdCuZr and PdCuSi alloy ribbons and powders are characterized by DSC, XRD and XPS in the as-received state and after treatments with oxygen, hydrogen or dilute hydrogen fluoride solution. Zr-containing alloys are shown to undergo substantial structural changes resulting in palladium enrichment on their surface, whereas no apparent changes in the bulk structure are found for PdCuSi. Catalytic activity and selectivity of the pretreated samples were tested in the hydrogenation of phenylacetylene.
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  • 54
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1203-1209 
    ISSN: 1572-8943
    Keywords: conformation of myosin ; DSC ; EPR ; spin labelling
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The internal dynamics and the thermal stability of myosin in rabbit psoas muscle fibres in different intermediate states of the ATP hydrolysis cycle were studied by differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) spectroscopy. Three overlapping endotherms were detected in rigor, in strongly binding and weakly binding state of myosin to actin. The transition at 58.4°C can be assigned to the nucleotide-binding domain. The transition at highest temperature represents the unfolding of the actin and the contributions arising from the actin-myosin interaction. The transition of 54°C reflects the interaction between the subunits of myosin. Nucleotide binding induced shifts of the melting temperatures and produced variations in the calorimetric enthalpy changes. The changes of the EPR parameters indicated local rearrangements of the internal structure in myosin heads.
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  • 55
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1323-1327 
    ISSN: 1572-8943
    Keywords: chloramphenicol ; DSC ; quality control ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability and thermal behaviour of chloramphenicol and various of its mixtures were investigated. The thermogravimetric and stability constant results showed that the chloramphenicol base is thermally more stable than the tablet in the studied formulation. The reduction in stability was attributed to the presence of starch in the formulation. The thermal decompositions of the chloramphenicol base and the tablet obey first-order kinetics.
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  • 56
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1311-1316 
    ISSN: 1572-8943
    Keywords: alumina ; aluminum oxide ; compact ; DSC ; particles ; pentaerythritol tetraacetate ; pharmaceuticals ; powder ; thermal resistance ; transient state
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The previously described method involving the use of transient DSC was applied to pharmaceutical powder compacts and to ceramic powder compacts. The samples were prepared by compressing powders of pentaerythritol tetraacetate and two kinds of alumina powder (differing in particle size distribution) up to a pressure of 20 MPa by using a jig. For pentaerythritol tetraacetate, a linear relationship was obtained between the parameter obtained by DSC and the compaction pressure.
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  • 57
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1005-1010 
    ISSN: 1572-8943
    Keywords: DSC ; enthalpic relaxation ; glass transition ; physical ageing
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpic relaxation has been used to model the development of the glass transition in polymers, using kinetic parameters determined separately. For this purpose the Kohlrausch-Williams-Watt stretched exponential function, relating the extent of relaxation, Φ(t), to time t and an average relaxation time, τa, i.e. $$1 - \Phi \left( t \right) = \exp \left( { - t/ta} \right)^{\beta }$$ where β is inversely related to the breadth of the relaxation spectrum, has been adopted. The relaxation time dependence on temperature was taken to follow the modified Arrhenius relationship, $$\tau _a = A\exp \left[ {\frac{{X\Delta H}}{{RT}} + \frac{{\left( {1 - X} \right)\Delta H}}{{RT'}}} \right]$$ where T is the storage and T′ the fictive temperature, X is the structure factor and ΔH the activation enthalpy. Both have been found to describe the process of enthalpic relaxation in polymer glasses and a direct comparison has been made with the change in specific heat observed with different cooling rates in DSC experiments. The effect of variables, such as activation enthalpies, pre-exponential factors, and the non-linear factors such as X and β on the observed Tgs and the temperature range over which the transition occurred have been determined.
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  • 58
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    Journal of thermal analysis and calorimetry 57 (1999), S. 283-291 
    ISSN: 1572-8943
    Keywords: DSC ; fish ; general proteolytic activity ; pyloric caeca ; ripening ; salted herring product
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermoanalytical behaviour of pyloric caeca during salting and ripening was investigated using a Perkin Elmer DSC 7. Not only the thermal stability of the muscle proteins was influenced by salting but also that of pyloric caeca. It was recognised that the salting itself leads to a remarkable increase of the transition temperature compared with raw herring. An influence of the salt:fish ratio could be observed. The higher the salt content the higher the increase of the denaturation temperature. During ripening the transition temperature remained on a high level or showed only a slight decrease during the investigation period. The dependency from the salt content remained evident. The increase of the transition temperature was accompanied by a decrease of the transition enthalpy. The increase of thermal stability is connected with a decrease of the general proteolytic activity in pyloric caeca. Possibly, the enzymes are diffusing from the pyloric caeca into the muscle and cause there an increase of enzymatic activity observable in North Sea herring accompanied by a decrease of activity in pyloric caeca itself. Simultaneous the thermal stability of pyloric caeca is lowered. The reason for the differences in ripening could be seen in some enzyme-inhibiting factors unknown until now.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 409-414 
    ISSN: 1572-8943
    Keywords: DSC ; thermal denaturation ; vegetative bacteria
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal stability of vegetative cells of Listeria monocytogenes, Escherichia coli and Lactobacillus plantarum was studied by counting viable fractions and determining DSC curves of their suspensions. DSC curves in the 5–99°C range showed a series of endothermic transitions between 50 and 60°C, where the heat destruction of cells occurred. Heat denaturation of DNA required a higher temperature than cell killing. Thermal death was strongly influenced by the pH, composition and NaCl content of the suspending buffer. A mathematical model developed by us enabled comparison of DSC peak temperatures and temperatures required for loss of viability.
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  • 60
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    Journal of thermal analysis and calorimetry 57 (1999), S. 517-526 
    ISSN: 1572-8943
    Keywords: DSC ; humic substances ; thermal properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential Scanning Calorimetry combined with Fourier transform infrared spectroscopy, was applied to the study of a number of fulvic and humic acids extracted from soils, peat, river and seawater. The thermal patterns obtained were related to the nature and origin of samples. The low-temperature endotherms were attributed to dehydration and loss of peripheral polysaccharide chains. The endotherm at 250°C observed for soil FA was ascribed to partial decarboxylation of more labile surface COOH groups, whereas the high-temperature exotherms at about 500°C were related to the degree of polycondensation of the aromatic network of the humic molecules.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 13-18 
    ISSN: 1572-8943
    Keywords: DSC ; enthalpic relaxation ; polyurethane ; TSDC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Polyurethane acrylate resins cured by two different ways, a thermal way and a photochemical way, are investigated by means of differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC). Even if both curing methods lead to the same material from a chemical point of view, we show that important differences exist between the thermocured resin and the photocured resin in terms of molecular relaxation behaviour.
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  • 62
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    Keywords: DMTA ; DSC ; mechanical properties ; metallocene catalysts ; polyethylene
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    Notes: Abstract A series of high density polyethylenes (HDPE) were synthesized via homogeneous polymerization with metallocene catalyst in two different reactors (glass and stainless steel). The thermal and mechanical properties of the polyethylenes, synthesized with two types of reactor and different reaction parameters, are discussed.
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  • 63
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    Colloid & polymer science 270 (1992), S. 1106-1115 
    ISSN: 1435-1536
    Keywords: Keratin ; thermal transitions ; water binding ; crystallinity ; DSC
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Differential Scanning Calorimetry (DSC) has been applied to study the interactions between components of human hair keratin. Keratin is a biopolymeric composite made of several proteins forming basically two phases: amorphous matrix and crystalline microfibrillar phase. Water, the content of which depends on atmospheric humidity, is also an integral part of keratin structure. The following processes are apparent from the DSC: removal of loosely bound water (ca. 70°C), a transition in the amorphous phase (155°C) and melting/denaturation of the α-crystalline phase (233°C). The process occurring in keratin at ca. 155°C has an opposite character to a glass transition; we refer to this process as the toughening transition. The area of the α-keratin peak increases significantly upon annealing at temperatures from 80°C to 150°C and decreases for higher annealing temperatures. Water affects both the crystalline and amorphous phases of keratin. The process similar in nature to annealing — induced recrystallization in synthetic polymers is strictly correlated with removal of strongly bound fraction of water in keratin.
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    Journal of inclusion phenomena and macrocyclic chemistry 14 (1992), S. 163-169 
    ISSN: 1573-1111
    Keywords: Zeolite ; phthalocyanines ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The template synthesis of copper(II) phthalocyanine by the condensation of dicyanobenzene within the supercages of Cu(II) exchanged X and Y type zeolites was studied using differential scanning calorimetry. The exotherms for intrazeolite and surface complexation have been resolved. These thermal events exhibit a dependence on the copper loading and hydration level which has been interpreted as a pressure effect.
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    Colloid & polymer science 270 (1992), S. 1182-1187 
    ISSN: 1435-1536
    Keywords: Amorphous phase ; crystallization ; SAXS ; DSC ; PET
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Crystallization of poly(ethylene terephthalate) from the amorphous state has been studied in the temperature range 90°–120°C to characterize the amorphous phase when crystalline microstructure is developing. Small-angle x-ray scattering, scanning electron microscopy, and density measurements were used to investigate the morphology of semi-crystalline materials. Differential scanning calorimetry and dynamical mechanical spectroscopy experiments were carried out on amorphous, partially crystallized and crystallized specimens and, when structural relaxation is allowed (thermal treatments close to but below glass transition temperature), strong evidence is obtained for the existence of two different amorphous phases with different mobilities.
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  • 66
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    Keywords: adducts ; cobalt complex ; DSC ; kinetics ; nickel complex ; O,O'-dialkyldithiophosphate ; pyridine ; TG-DTG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of tri(O,O'-diisopropyldithiophosphate)cobalt(III), Co(dptp)3 and bis (O,O'-diethyldithiophosphate)nickel(II), Ni(detp)2 and its adducts with pyridine, Ni(detp)2(py)2 or 4-methylpyridine, Ni(detp)(mpy)2 in a dynamic nitrogen atmosphere was investigated by TG-DTG and DSC techniques, which showed a medium endothermic peak for the evolution process of pyridine(or 4-methylpyridine) and a strong exothermic peak for that of O,O'-diethyldithiophosphate. The thermal stability and decomposition patterns for these compounds were compared and interpreted in terms of structural features such as bond character and steric effects. The kinetic parameters and mechanisms of every decomposition stage involved for all these complexes were obtained employing the non-isothermal kinetic analysis method suggested by Malek et al., which showed the kinetics mechanism for pyrolysis of pyridine(or 4-methylpyridine) is an S-B empirical model with lower activation energy, while that of O,O'-dialkyldithiophosphate is a diffusion model. These results are in accord with the fact that two ligands are of different type.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 85-92 
    ISSN: 1572-8943
    Keywords: DSC ; exothermic peak ; human serum albumin ; non-equilibrium state ; pyridine-n-hexane mixtures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Human serum albumin (HSA) immersed in pyridine-n-hexane mixtures was analyzed using differential scanning calorimetry (DSC). State of the solid HSA in organic solvent mixtures is the non-equilibrium state which is seen as the exothermic peak on the DSC curves. The enthalpy change corresponding to this exothermic peak approaches zero when going from pure pyridine to pure n-hexane. Dependence of the enthalpy change on the pyridine concentration is suggestive that the non-equilibrium state of the immersed HSA results from the HSA-pyridine interactions 'frozen' at the lower temperature. Most likely the temperature-initiated exothermic peak observed on the DSC curves reflects the swelling of HSA by pyridine.
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  • 68
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    Journal of thermal analysis and calorimetry 56 (1999), S. 437-446 
    ISSN: 1572-8943
    Keywords: Al-La-Ni amorphous ribbons ; DSC ; heating rate ; non-isothermal crystallization kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Crystallization kinetics of Al91La5Ni4 amorphous ribbons produced by a melt-spinning method were studied by DSC analysis and X-ray diffraction. The effect of heating rate (from 4 to 200°C min-1) was investigated in the temperature range from 298 to 700 K. Increases the heating rate from 4 to 200°C min-1 resulted in increases of the temperature difference between the two stages of the transformation process: crystallization of Al and crystallization of the Al compounds from 148.9 to 167.4 K. The apparent activation energies for the first step, related to Al crystallization, and to the second step related to crystallization of Al4La and Al3Ni, were found to be 161±9 and 199±10 kJ mol-1, respectively. The results indicate the possibility of tailoring the heating treatment to produce the required fraction of the amorphous phase.
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  • 69
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1211-1216 
    ISSN: 1572-8943
    Keywords: dispersion-type processed cheese ; DSC ; ELMI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In contrast with the traditional method of cheese processing, where Ca breaks down from the protein chain and protein is peptized, a new technology has been elaborated, during which cheese is dispersed without phosphate-containing processing salt, when the gel is formed by plant hydrocolloids. Raw material of constant composition was processed with a phosphate-containing salt or in the presence of hydrocolloids. Thermodynamic processes occurring during the processing and in the end-products were examined by an ultra-sensitive micro DSC method. The structures of end-products were also investigated by electronmicroscopy. The temperature ranges of the endothermal processes indicating the transformations of protein and hydrocolloids can be distinguished: 81-90°C for peptization processing and 61-72°C for processing without peptization. The differences are less in the end-products: 75-87°C in traditional processed cheese and 68-74°C in processed cheeses made without peptization. In contrast with the spongy structure of traditional processed cheeses consisting of peptized proteins, processed cheeses made without peptization involve structure-forming elements created by the interaction of linear macromolecules of hydrocolloids and cheese proteins.
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  • 70
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1317-1322 
    ISSN: 1572-8943
    Keywords: cyclodextrins ; drugs ; DSC ; excipients ; prochlorperazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry was used to examine the thermal behaviour of mixtures of the drug prochlorperazine with standard excipients, to assess potential interactions, and of mixtures with cyclodextrins, to investigate inclusion complexation which could increase the photostability of the drug. For most of the excipients (magnesium stearate, stearic acid, Explotab®, Ac-Di-Sol®, Encompress® and Ludipress®, lactose and Starch 1500) disappearance or broadening of the melting endotherm of the drug indicated interactions. Lubritab® was the only 'inert' excipient tested. Mixtures of prochlorperazine and the cyclodextrins gave incomplete inclusion complexation as shown by only partial disappearance of the melting endotherm of the drug.
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  • 71
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    Journal of thermal analysis and calorimetry 57 (1999), S. 599-605 
    ISSN: 1572-8943
    Keywords: DSC ; lead bromide ; melting ; systematic error
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 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.
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  • 72
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    Journal of thermal analysis and calorimetry 58 (1999), S. 243-248 
    ISSN: 1572-8943
    Keywords: actin ; cisplatin ; DSC ; thiol ; transplatin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 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.
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  • 73
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    Journal of thermal analysis and calorimetry 58 (1999), S. 569-577 
    ISSN: 1572-8943
    Keywords: counterion effect ; DSC ; membrane ; Nafion-H ; Nafion salts ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behavior of Nafion-117 membranes was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). TG measurements revealed that the mechanism of thermal degradation of a Nafion membrane in the acid form is different from that of Nafion in the sodium form. The DSC curves for the first heating, for both acid and salt forms, display two endothermic peaks, near 120 and 230°C. The high-temperature peak was assigned to the crystalline domains melting in Nafion, and the low-temperature peak was attributed to a transition into ionic clusters, since this transition exhibits significant changes depending on the nature of the counterion and the degree of hydration.
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