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  • DSC  (48)
  • Springer  (48)
  • American Meteorological Society
  • 1995-1999  (48)
  • 1996  (48)
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  • 1995-1999  (48)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 24 (1996), S. 293-299 
    ISSN: 1432-1017
    Keywords: Phase transition ; NMR ; DSC ; X-ray diffraction ; Bonnet Transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Ternary systems of palmitoyl-oleoyl-phosphatidylcholine (POPC) and the non-ionic surfactant C12EO2 (di-ethylene-oxide-mono-dodecyl-ether) in water have been studied with optical microscopy, NMR, DSC and X-rays from ambient temperatures to 45 °C. Below 29 °C the system is in the lamellar liquid crystalline state. Between 30 and 32 °C it transforms into a cubic Ia3d structure which converts into the cubic Pn3m phase at 39 °C. The transitions are fully reversible. An epitaxial relationship between all three phases was found, which is an elegant and convenient way to rearrange molecules from lamellar bilayers to a network of curved surfaces. The la3d (Q230) to Pn3m (Q224) transition occurs without measurable enthalpy change. This, together with the metric relation of 1.60 between the cubic lattice constants is strong evidence for a Bonnet transformation, where the structural changes occur without change in curvature. The potential significance of the cubic phases as intermediate structures for biological processes, e. g. transport across a bilayer or fusion of membranes, are discussed.
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  • 2
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    Journal of thermal analysis and calorimetry 46 (1996), S. 465-470 
    ISSN: 1572-8943
    Keywords: ABS polymer ; DSC ; lifetime estimation ; thermooxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The service life of ABS polymer, stabilized by 2-(3,5-di-tert-butyl-4-hydroxyanilino)-4,6-bis(octylthio)-1,3,5-triazine and containing 50% of a modifying rubber component, was estimated from oxidative induction times measured by DSC in isothermal mode in the temperature interval 140–170°C. The lifetime of ABS powder at the actual temperature of drying was predicted by linear extrapolation according to Arrhenius. However, the extrapolated value was much longer than the real lifetime determined from the long-term oven aging tests at 70 and 90°C, simulating the industrial drying process. The effect of changes in the apparent activation energy of oxidation due to antioxidant consumption during polymer aging is discussed.
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  • 3
    ISSN: 1572-8943
    Keywords: complexes ; DSC ; guest-host interactions ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stoichiometry of thermal decomposition and the thermochemistry were studied for [NiL4(NCS)2] (I) as a host complex, and for its clathrates of type [NiL4(NCS)2]·2G, where L=4-ethylpyridine and guest molecule G=1-methylnaphthalene in clathrate (II), 1-chloronaphthalene in (III) or 1-bromonaphthalene in (IV). For I, the loss of volatile components proceeds in three steps (−2L, −L, −L); the first steps for II–IV also involve the release of G (−2G, −2L). DSC and X-ray powder measurements indicated a phase transition in the host lattice, and allowed differentiation of the escape of G and L molecules. The enthalpy changes give the following sequence of thermodynamic stability for the studied chlathrates: I〉II〉III.
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  • 4
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    Journal of thermal analysis and calorimetry 46 (1996), S. 753-771 
    ISSN: 1572-8943
    Keywords: crystal-crystal transitions ; crystal forms ; DMA ; DSC ; Nylon M5T ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Poly(2-methylpentamethylene terephthalamide) (Nylon M5T) is a new high temperature aromatic polyamide developed by Hoechst Celanese. In this paper thermal properties of Nylon M5T chips, as well as as-spun and drawn fibers were studied by DSC, DMA, hot stage microscopy and WAXS.T g of the fully amorphous Nylon M5T is 143°C when measured by DSC;T g increases with crystallinity to 151°C. The temperature dependence of the solid and melt specific heat capacities has also been determined. The heat capacity increase at the glass transition of the amorphous polymer is 103.9 J °C−1 mol−1.T g by DMA for the as-spun fiber is 155°C, for a drawn fiber is 180°C. Three secondary transitions were observed by DMA in addition to the glass transition. These correspond to a local mode relaxation of the methylene groups at −120°C, onset of rotation of the amide-groups at −65°C and the onset of the rotation of the phenylenegroups (at 63°C). The crystallinity of Nylon M5T strongly depends on the rate of cooling from the melt. The isothermal crystallization data are melt temperature dependent: two-dimensional crystallization takes place when the samples are crystallized from higher melt temperatures, and this phase changes into a spherulitic structure during cooling to room temperature. Spherulitic crystallization occurs when lower melt temperatures are used. This polymer has three crystal forms as indicated by DSC, DMA and WAXS data. The crystal to crystal transitions are clearly visible when amorphous samples are heated in the DSC, or the DMA curves of as-spun fibers are recorded. It is experimentally shown that a considerable melting of the lower temperature crystal forms takes place during the crystal to crystal transitions. The equilibrium melting point as measured by the Hoffman-Weeks method, has been determined to be 339°C.
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  • 5
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    Journal of thermal analysis and calorimetry 46 (1996), S. 871-878 
    ISSN: 1572-8943
    Keywords: DSC ; melting point ; polyethylene ; Raman-active longitudinal acoustical mode ; semi-crystalline polymers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This is a study for criteria to judge the melting point of semi-crystalline polymers from the DSC endotherm for polymer melting. Beyond standard indium DSC melting results an evaluation has been made on a series of polyethylenes for which crystal sizes were measured and predicted from Raman LAM analysis. The results confirm the conclusion of Prof. Wunderlich that the DSC content of melting is the proper basis of reporting melting points.
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  • 6
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    Journal of thermal analysis and calorimetry 46 (1996), S. 893-903 
    ISSN: 1572-8943
    Keywords: cold crystallization ; DSC ; heat capacity ; modulated temperature DSC ; poly(ethylene terephtalate)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The modulated temperature differential scanning calorimetric method (MT-DSC) yields three temperature dependent signals, an underlying heat capacity curve from the underlying heat flow rate (corresponding to the conventional DSC signal), and a complex heat capacity curve with a real part (storage heat capacity) and an imaginary part (loss heat capacity). These curves have been measured in the cold crystallization region for poly(ethylene terephtalate) with a modified Perkin-Elmer DSC-7. The underlying curve shows the well known large exothermic crystallization peak. The storage heat capacity shows a step change which reproduces the change in heat capacity during crystallization. This curve may be used as baseline, to separate the crystallization heat flow rate from the underlying heat flow rate curve. The loss heat capacity curve exhibits a small exothermic peak at the temperature of the step change of the storage curve. It could be caused by changes of the molecular mobility during crystallization.
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  • 7
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1251-1258 
    ISSN: 1572-8943
    Keywords: boiling points ; DSC ; TGA ; vapour pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A TGA instrument has been adapted for rapid measurement of boiling points and vapour pressure at temperatures from ambient up to 400°C and pressures from ambient down to 20 mm Hg. Samples were contained in sealed holders having a laser-drilled aperture. Several organic liquids in the 100 to 300 gMW range showed good agreement with reference vapour pressure data. Sample mass, heating rate, and use of inert diluents were important variables affecting accuracy of vapour pressure measurements.
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  • 8
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    Journal of thermal analysis and calorimetry 47 (1996), S. 181-194 
    ISSN: 1572-8943
    Keywords: DSC ; gelatinization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Data obtained by dynamic mechanical analysis and DSC analysis of durum wheat dough are presented and discussed. Doughs with water contents ranging from 45 to 55% (w/w) were subjected to sinusoidal shearing by means of a dynamic mechanical spectrometer (Rheometrics, RFS2) equipped with parallel plate geometry, 0.1 strain amplitude and 1 rad/min frequency. The tests were carried on in temperature sweep mode at a heating rate of 2°C min−1. Wheat samples with water contents in the range between 7.5 and 37.5% and doughs with 37.5% moisture content were mixed for different times and subjected to DSC analysis (Perkin-Elmer, DSC-7) at a heating rate of 20°C min−1. Dynamic mechanical analysis revealed that the relationship between the dynamic properties of the dough and the temperature was modified as the water content of the dough increased and was quite different from that for gluten. A similar response was observed in the course of temperature scans made by means of DSC. These experimental findings suggest that the water-starch interaction in the presence of a protein matrix is affected by the availability of water and that the protein system is a competitor with respect to starch.
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  • 9
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    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Keywords: compensation effect ; DSC ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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  • 10
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    Journal of thermal analysis and calorimetry 47 (1996), S. 957-973 
    ISSN: 1572-8943
    Keywords: DSC ; Gibbs energy ; liquid crystalline polyethers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of polyethers have been synthesized from 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl)propane and α, Ω-dibromoalkanes having different numbers of methylene units [TPPs]. Both odd- and even-numbered TPPs [TPP(n=odd)s and TPP(n=even)s) exhibit multiple transitions during cooling and heating and they show little supercooling dependence, indicating close-to-equilibrium nature of these transitions. Combining the structural characterization obtainedvia wide angle X-ray diffraction powder and fiber patterns at different temperatures and the morphological observations from microscopy techniques, not only the nematic liquid crystalline phase but also highly ordered smecticF, smectic crystalG andH phases have been identified. The phase diagrams for both TPP(n=odd)s and TPP(n=even)s have been constructed [1–3]. Thermodynamic properties (enthalpy and entropy changes) during these transitions are studied based on differential scanning calorimetry experiments. The contributions of the mesogenic groups and methylene units to each ordering process can be separated and they indicate the characteristics of these processes thereby providing estimations of the transition types.
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  • 11
    ISSN: 1572-8943
    Keywords: cooling/heating rate ; DSC ; fragility parameter ; glass transition temperature ; sorbitol-fructose
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The glass transition temperatures of sorbitol and fructose were characterized by four points determined on DSC heating thermograms (onset, mid-point, peak and end-point), plus the limit fictive temperature. The variations of these temperature values, observed as functions of cooling and heating rates, were used to determine the fragility parameter, as defined by Angell [1] to characterize the temperature dependence of the dynamic behavior of glass-forming liquids in the temperature range above the glass transition. The apparent activation energy values, determined for the different temperatures studied, were similar for fructose and sorbitol. These values were compared to data obtained from other techniques, such as mechanical spectroscopy. The variations of the apparent activation values, observed in experiments involving cooling and heating at the same rate, slow cooling followed by rate-heating, or rate-cooling followed by fast heating, were explained by aging effects occurring during the heating step.
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  • 12
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1545-1565 
    ISSN: 1572-8943
    Keywords: cocoa butter ; fat crystallization ; DSC ; fat polymorphism ; fat structure ; fats ; lard ; milk fat ; triacylglycerols ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behavior of three ural fats (displaying very different composition), cocoa butter (CB)2, lard, and a stearin obtained from anhydrous milk-fat (AMF) fractionation, were studied by both DSC and X-ray diffraction as a function of temperature (XRDT). To perform temperature explorations between −30
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  • 13
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1743-1753 
    ISSN: 1572-8943
    Keywords: DSC ; HSM ; oxazepam ; PEG 4000 ; solid dispersion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A thermal study using DSC and Hot Stage Microscopy (HSM) was carried out to investigate the interaction in solid state of the binary system PEG 4000 — oxazepam, and to establish their phase diagram. The eutectic composition, which melting occurs at lower temperature as compared with the pure components, has been determined. The results obtained by DSC and HSM have indicated that PEG 4000 — oxazepam mixtures displays no obvious incompatibilities, and that the system shows a typical eutectic behaviour. However because of the closeness of the melting of PEG 4000 to the eutectic temperature, it was difficult to determine precisely the eutectic composition and temperature on the basis of DSC measurements alone. The use of heats of fusion corresponding to physical mixtures allowed an estimation of the eutectic composition at 6% w/w oxazepam. Additional information of temperature (57.6
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  • 14
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1755-1758 
    ISSN: 1572-8943
    Keywords: combustion calorimetry ; DSC ; sulphamide type compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two compounds of sulphamide type:p-amino-benzene sulphonamide (I) and 3,4-dimethylisoxazol 5-sulphanylamide (II) were studied by combustion calorimetry and by differential scanning calorimetry (DSC). The enthalpies in solid state at 298,15 K of combustion, δc H m o (I)=-2788,5±1,6 kJ mol−1, δc H m o (II)=-5036±3,8 kJ mol−1 and of formation, δf H m o (I)=-458,3±1,6 kJ mol−1, δfH m o (II)=-180,1±3,8 kJ mol−1 were determined. The thermal effects concerning the melting and phase transition of this compounds were also measured.
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  • 15
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1787-1803 
    ISSN: 1572-8943
    Keywords: DSC ; food components ; food microbiology ; food quality
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) is the most widely used thermal analytical technique in food research and it has a great utility in quality assurance of food. Proteins are the most studied food components by thermal analysis including studies on conformation changes of food proteins as affected by various environmental factors, thermal denaturation of tissue proteins, food enzymes and enzyme preparations for the food industry, as well as effects of various additives on their thermal properties. Freezing-induced denaturation of food proteins and the effect of cryoprotectants are also monitored by DSC. Polymer characterization based on DSC of polysaccharides, gelatinization behaviour of starches and interaction of starch with other food components can be determined, and phase transitions during baking processes can be studied by DSC. Studies on crystallization and melting behaviour of fats observed by DSC indicate changes in lipid composition or help characterizing products. Thermal oxidative decomposition of edible oils examined by DSC can be used for predicting oil stability. Using DSC in the freezing range has a great potential for measuring and modelling frozen food thermal properties, and to estimate the state of water in foods and food ingredients. Research in food microbiology utilizes DSC in better understanding thermoadaptive mechanisms or heat killing of food-borne microorganisms. Isothermic microcalorimetric techniques provide informative data regarding microbial growth and microbial metabolism.
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  • 16
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    Journal of thermal analysis and calorimetry 46 (1996), S. 177-186 
    ISSN: 1572-8943
    Keywords: activation energy ; chalcogenide glass ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Results of differential scanning calorimetry (DSC) at different heating rates on Se2Ge0.2Sb0.8 chalcogenide glass are reported and discussed. As the heating rate (α) changed, also the glass transition temperature (T g) and onset temperature of crystallization (T c) changed. As the value of the transition activation energyE t changed, the crystallization fraction (χ), heat flow (Δq and the crystallization peak temperature (T p) also changed. The value of the effective activation energy of crystallizationE c was calculated by means of six different methods. The Se2Ge0.2Sb0.8 chalcogenide glass has two crystallization mechanisms, a one-dimensional and an other surface crystallization growth. The average value ofE t for Se2Ge0.2Sb0.8 is equal to 194.95±3.9 kJ·mol−1 and the average value ofE c is equal to 164±3.3 kJ·mol−1.
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  • 17
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    Journal of thermal analysis and calorimetry 46 (1996), S. 619-626 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; filled polypropylene ; nucleation ; structural modification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of high concentration of BaSO4 as nucleating agent on crystallization of fiber-forming polypropylene was studied by DSC. The work presents experimental and calculated values of melting and crystallization enthalpies of filled polypropylene and the influence on the formation of interface interactions between filler and polymers. These results show minimal interactions of components (BaSO4 and polypropylene) under experimental conditions.
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  • 18
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    Journal of thermal analysis and calorimetry 46 (1996), S. 643-679 
    ISSN: 1572-8943
    Keywords: DDTA ; DSC ; macromolecules
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This review traces the development of thermal analysis over the last 40 years as it was experienced and contributed to by the author. The article touches upon the beginning of calorimetry and thermal analysis of polymers, the development of differential scanning calorimetry (DSC), single run DSC and other special instrumentations, up to the recent addition of modulation to calorimetry. Many new words and phrases have been introduced to the field by the author and his students, leaving a trail of the varied interests one can have over 40 years. It began with “cold crystallization” and most recently the term “oriented, intermediate phase” was coined, creating in-between: “extended chain crystals,” the “irreversible thermodynamics of melting of polymer crystals,” “dynamic differential thermal analysis” (DDTA), “the rule of constant increase ofC p per mobile bead within a molecule at the glass transition temperature,” “superheating of polymer crystals,” “melting kinetics,” “crystallization during polymerization,” the “chain-folding principle, “molecular nucleation,” “rigid amorphous phase,” a “system of classifying molecules,” “macroconformations,” “amorphous defects,” “rules for the entropy of fusion based on molecular shape and flexibility,” “single-molecule single-crystals,” “a system of classifying phases and mesophases,” and “condis phase.”
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  • 19
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    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
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  • 20
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1081-1092 
    ISSN: 1572-8943
    Keywords: chemical ionization MS ; constrained dye ; DSC ; dye-amylose inclusion complex ; Tandem MS ; TGA ; Thermal Desorption MS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of a dye molecule (guest) inside the cavity of a host amylose helix were studied by TGA, DSC, and Thermal Desorption MS. The results show that the degradation temperature of dye shifts to a higher temperature by approximately 20°C.
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  • 21
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1093-1111 
    ISSN: 1572-8943
    Keywords: conformational disorder ; crystal ; DSC ; glass ; glass transition ; heat capacity ; melting transition ; tetra[methyleneoxycarbonyl (2,4,4-trimethyl) pentyl] methane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Quantitative thermal analysis was carried out for tetra[methyleneoxycarbonyl(2,4,4-trimethyl)pentyl]methane. The ester has a glass transition temperature of 219 K and a melting temperature of 304 K. The heat of fusion is 51.3 kJ mol−1, and the increase in heat capacity at the glass transition is 250 J K−1 mol−1. The measured and calculated heat capacities of the solid and liquid states from 130 to 420 K are reported and a discussion of the glass and melting transitions is presented. The computation of the heat capacity made use of the Advanced Thermal Analysis System, ATHAS, using an approximate group-vibration spectrum and a Tarasov treatment of the skeletal vibrations. The experimental and calculated heat capacities of the solid ester were compared over the whole temperature range to detect changes in order and the presence of large-amplitude motion. An addition scheme for heat capacities of this and related esters was developed and used for the extrapolation of the heat capacity of the liquid state for this ester. The liquid heat capacity for the title ester is well represented by 691.1+1.668T [J K−1 mol−1]. A deficit in the entropy and enthalpy of fusion was observed relative to values estimated from empirical addition schemes, but no gradual disordering was noted outside the transition region. The final interpretation of this deficit of conformational entropy needs structure and mobility analysis by solid state13C NMR and X-ray diffraction. These analyses are reported in part II of this investigation.
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  • 22
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1113-1132 
    ISSN: 1572-8943
    Keywords: chiral molecule ; conformational disorder and motion ; crystal ; DSC ; heat capacity ; γ-gauche effect ; glass ; glass transition ; melting transition ; molecular mechanics computations ; tetra[methyleneoxycarbonyl (2,4,4-trimethyl) pentyl] methane ; solid state13C NMR ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The symmetric neopolyol ester tetra[methyleneoxycarbonyl(2,4,4-trirnethyl)pentyl]methane (MOCPM) has been studied by variable-temperature solid-state13C NMR and X-ray powder diffraction and compared to molecular mechanics calculations of the molecular structure. Between melting and glass transition temperatures the material is semicrystalline, consisting of two conformationally and motionally distinguishable phases. The more mobile phase is liquid-like and is, thus attributed to an amorphous phase (≈16%). The branches of the molecules in the crystal exhibit two conformationally distinguishable behaviors. In one, the branches are well ordered (≈56%), in the other, the branches are conformationally disordered (≈28%). Different branches of the same molecule may show different conformational order. This unique character of the rigid phase is the reason for the deficit of the entropy of fusion observed earlier by DSC. In the melt, solid state NMR can identify two bonds that are rotationally immobile, even though the molecules as a whole have liquid-like mobility. This partial rigidity of the branches accounts quantitatively for the observed increase in heat capacity at the glass transition. The reason for this unique behavior of MOCPM, a small molecule, is the existence of one chiral centers in each of the four arms of the molecule. A statistical model assuming that at least two of the chiral centers must fit into the order of the crystal can explain the crystallization behavior and would require 12.5% amorphous phase, 28.1% conformational disorder, and 59.4% crystallinity, close to the observed maximum perfection.
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  • 23
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1177-1189 
    ISSN: 1572-8943
    Keywords: DSC ; mercury porosimetry ; pore size distribution ; porous glass ; thermoporosimetry ; water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pore size distributions (PSDs) of microporous glass, which were controlled by acid leaching subsequent to phase separation of CaO-Al2O3-B2O3-SiO2 glass, were determined via both mercury porosimetry and thermoporosimetry (thermal porosimetry). As a result, the pore radii, the cumulative pore volumes, and the surface areas determined via thermoporosimetry were in good agreement with those determined via mercury porosimetry. It was revealed that thermoporosimetry could be applied to pore structure analysis for porous materials having pore sizes at least up to 58 nm in radius.
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  • 24
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1541-1550 
    ISSN: 1572-8943
    Keywords: DSC ; FTIR ; grafting ; IDSC ; kinetic parameters ; polymerization ; TG ; thermodynamic parameters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal polymerization of pentabromobenzyl (mono)acrylate (PBB-MA) on the surface of the inorganic fillers Mg(OH)2 and CaCO3 was studied. FTIR spectroscopy and extraction of the polymer in bromobenzene show that polypentabromobenzyl acrylate (PBB-PA) was mostly grafted on the surface of Mg(OH)2. Thermal analysis (TG, DSC, isothermal DSC (IDSC)) demonstrated an increase in polymerization starting temperature, and differences in polymerization enthalpy and apparent activation energy when an inorganic filler is added. These differences depend on the chemical composition of the filler used.
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  • 25
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    Journal of thermal analysis and calorimetry 47 (1996), S. 445-452 
    ISSN: 1572-8943
    Keywords: catalysts ; catalyst activity ; catalyst deactivation ; DSC ; gas reactions ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Gas reactions, catalyzed by solid catalysts, can be measured by DSC. In the experimental set-up an open sample pan with catalyst (powder or pellet) is placed on the sample side of the DSC sensor. The reactive gas mixture flows through the cell and reacts on the catalyst surface. The heat effect, caused by this reaction, results into a DSC signal. The calibration procedure is described for quantitative evaluation of the DSC measurements. For illustration four different reaction systems are discussed.
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  • 26
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    Journal of thermal analysis and calorimetry 47 (1996), S. 503-514 
    ISSN: 1572-8943
    Keywords: cardiac myosin ; DSC ; flexibility of myosin heads ; spin-labelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Conventional and saturation transfer electron paramagnetic resonance spectroscopy (EPR and ST EPR) and differential scanning calorimetry (DSC) were used to study the motional dynamics and segmental flexibility of cardiac myosins. Cardiac myosins isolated from bovine and human heart muscle were spin-labelled with isothiocyanate- or maleimide-based probe molecules at the reactive sulfhydryl sites (Cys-697 and Cys-707) of the motor domain. The maleimide probe molecules attached to human cardiac myosin rotated with an effective rotational correlation time of 33 ns which was at least eight times shorter than the rotational correlation time of the same label on skeletal myosin (260 ns). In the presence of MgADP and MgADP plus orthovanadate, flexibility changes in the multisubunit structure of myosins were detected, but this did not lead to changes of the overall rotational property of the myosin heads. Significant difference in the internal flexibility was detected on myosin samples isolated from ischemic tissue, the rotational correlation time decreased to 25 ns. DSC measurements supported the view that addition of nucleotides produced additional loosening in the multisubunit structure of cardiac myosin. It is postulated that there is an intersite communication between the nucleotide binding domain and the 20 kDa subunit where the reactive thiol sites are located.
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  • 27
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    Journal of thermal analysis and calorimetry 47 (1996), S. 887-896 
    ISSN: 1572-8943
    Keywords: compensation temperature ; DSC ; fictive temperature ; poly(ethylene terephthalate) ; thermally stimulated depolarization current
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This work deals with a comparison of data obtained from differential scanning calorimetry (DSC) and thermally stimulated depolarization current (TSDC) investigations. Measurements were performed on various poly(ethylene terephthalate) films: a wholly amorphous, a thermally crystallized and drawn samples. For each specimen, the TSDC complex spectra, resolved into elementary ones, led to the determination of the classical compensation temperature (T c ). The glass transition temperature (T g) and the fictive equilibrium temperature (T f) were determined by means of DSC. It appears thatT c is different fromT g and very close toT f.
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  • 28
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    Journal of thermal analysis and calorimetry 47 (1996), S. 931-939 
    ISSN: 1572-8943
    Keywords: DSC ; isothermal melt crystallization ; kinetic parameters ; Mathematica® ; new kinetic model ; poly(L-lactic acid)
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A DSC study was carried out of the isothermal melt crystallization kinetics of poly(L-lactic acid), PLLA, at 110, 115, 120, 125 and 130
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  • 29
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1201-1212 
    ISSN: 1572-8943
    Keywords: aging ; amylopectin ; DSC ; gels ; glass transition ; recrystallization ; retrogradation ; rice starch ; sugars
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal characterization of gelatinized binary rice starch-water and ternary starch-sugar-water gels before and after aging was carried out using differential scanning calorimetry. The glass transition temperature of the maximally freeze-concentrated solution (T′g) in both fresh and aged gels was observed to decrease progressively with increasing sugar concentration. Aging of the gels generally shiftedT′g to higher temperatures, but had little or no effect on the ice melting peak temperature (T m). The presence of various sugars could either accelerate or retard starch (amylopectin) recrystallization, depending on the type and concentration of sugar, as well as on starch/water ratio. A hypothesis based on the dual antiplasticizing-plasticizing effects of sugars was postulated to explain the observed effects. Of the sugars studied, xylose and fructose appeared to display exceptional retardative and accelerative effects, respectively, on retrogradation.
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  • 30
    ISSN: 1572-8943
    Keywords: DSC ; gelatinisation ; potato starch
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Gelatinisation temperatures as a function of moisture content were determined for potato starch. The native starch was then hydrothermally treated at a temperature 3% (Kelvin degrees) below the gelatinisation peak temperature and at moisture levels varying from 20 to 67% (by weight). Gelatinisation temperatures, temperature ranges and enthalpy values were affected for all treated samples. However, two sample populations could be distinguished: those samples treated under ‘limited’ moisture conditions and other samples treated in the presence of ‘extragranular’ moisture. A two-step hydrothermal treatment further increased the gelatinisation temperature, but the effect of the second step was small in comparison to that of the first.
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  • 31
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1299-1314 
    ISSN: 1572-8943
    Keywords: baked goods ; cookies ; crackers ; DSC ; pretzels ; starch
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We describe an application of DSC as an analytical ‘fingerprinting’ method that has been used to characterize the thermal properties of wheat starch in low-moisture, wheat-flour-based baked products, including cookies, crackers, and pretzels. This use of DSC has enabled us to relate starch thermal properties, on the one hand, to starch structure, and on the other hand, to starch functionality, in terms of baking performance and finished-product quality.
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  • 32
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1339-1360 
    ISSN: 1572-8943
    Keywords: bread crumb ; bread dough ; DSC ; hydrocolloid ; mechanical properties ; pentosans ; protein
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of hydrocolloids (guar and locust bean gums), soluble pentosans, and whey proteins on staling of bread crumb were investigated by means of DSC, rheometry, and image analyis. One current hypothesis, that these ingredients would behave as “water binders” and, at least the former two, as anti-staling agents, was indeed confirmed, although this action might be indirect. All the samples considered showed an exothermic DSC peak preceding the endotherm of the amylopectin fusion. According to a previous work, this signal was attributed to a water-dependent cross-linking process that would involve next-neighbouring polymer chains. To check the effect produced by molecular modifications that were expected to increase the water uptake of these ingredients, doughs containing added succinylated pentosans and whey proteins, and a polycarboxylate polymer, PEMULEN TR-1, were examined. These modifications enhanced starch retrogradation and yielded a firmer crumb. It was tentatively concluded that some direct interaction between these modified molecules and the crumb polymers might have taken place. In line with the food polymer science approach, the use of Time-Temperature-Transformation (TTT) diagrams is also discussed.
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  • 33
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1513-1525 
    ISSN: 1572-8943
    Keywords: Β-lactoglobulin ; DSC ; protein modification ; thermal properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of Β-lactoglobulin (Β-LG) were studied by differential scanning calorimetry (DSC) under different medium conditions.pH, neutral salts, protein perturbants, and polyols all affected the DSC characteristics of Β-LG. Acylation with fatty acids also changed the thermal properties, particularly peak width at half-height. The results suggest that the structural stability of Β-LG is controlled by non-covalent forces, particularly electrostatic and hydrophobic interactions. Disulfide bonds did not contribute to the thermal response of Β-LG. Fatty N-acyl-amino acids caused marked increases in thermal stability and decreases in denaturation enthalpy, and additional peaks were observed in the presence of some palmitoyl derivatives.
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  • 34
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    Journal of thermal analysis and calorimetry 46 (1996), S. 347-352 
    ISSN: 1572-8943
    Keywords: DSC ; optical densities ; thermal stability ; three-component interpolymer complexes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new type of three-component interpolymer complexes (3IPCM) formed by two similarly charged polyelectrolytes and an oppositely charged low molar mass compound was studied by DSC, NMR and X-ray methods. The low molar mass monobasic compounds in these complexes act as mediators. This type of complexes differs from earlier-obtained 3IPCM, which contained a dibasic low molar mass mediator. The present 3IPCM were obtained from two polymers (polyacrylic acid and sodium polyphosphate) and bases such as 4-vinylpyridine and 2-methyl-5-vinylpyridine.
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  • 35
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; epoxy resins ; gelation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract By employing differential scanning calorimetry (DSC) we have studied the kinetic of the cure reaction for a system containing a diglycidyl ether of bisphenol A (DGEBA) and 1,3-bisaminomethylcyclohexane (1,3-BAC) as a curing agent, using an isothermal approach over the temperature range of 60–110°C. We have determined the reached conversions at several cure temperatures and the reaction rates. The results showed that this cure reaction is autocatalytic. The experimental data were compared with the autocatalytic model proposed by Kamal, which includes two rate constants and two reaction orders. This model gives a good description of cure kinetics up to vitrification point. The activation energies for these rate constants were 44-57 kJ mol−1. From the gel time measurements the value obtained for the overall activation energy was 49.5 kJ mol−1.
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  • 36
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    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Keywords: bone cement ; DSC ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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  • 37
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    Journal of thermal analysis and calorimetry 47 (1996), S. 685-695 
    ISSN: 1572-8943
    Keywords: DSC ; polymers ; resins ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The paper describes the co-curing studies of ethynyl and ethenyl end-capped imide resins. The effect of composition and chemical structure of ethenyl end-capped resins (nadicimides) on thermal behavior of ethynyl end-capped resins was evaluated using DSC and thermogravimetric analysis. An increase in char yield was observed on co-curing of few resin formulations. A mechanism has been proposed to account for this observation.
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  • 38
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1213-1228 
    ISSN: 1572-8943
    Keywords: cassava starch ; DSC ; starch thermal properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Order-disorder transitions were investigated in native cassava starch at intermediate moisture contents (35 to 60% wt. water), using Differential Scanning Calorimetry (DSC) and dynamic Wide Angle X-ray Diffractometry (WAXS) with a synchrotron radiation source. The gelatinization of granules occurs as a cooperative process, due to constraints induced in crystallites by the amorphous areas. Variations of water content (water volume fraction from 0.28 to 0.86) and heating rate (0.2–10
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  • 39
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1179-1200 
    ISSN: 1572-8943
    Keywords: DSC ; isothermal microcalorimetry ; retrogradation ; starch
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In the present study, isothermal microcalorimetry was introduced as a tool to investigate properties of starch retrogradation during the first 24 h. The study was made on purified amylose and amylopectin from corn, as well as on native starches, such as wheat, potato, maize, waxy maize and amylomaize, differing in their amylose content. The results were obtained in the form ofP-t traces (thermal powervs. time), and integration of these traces gave a net exothermic enthalpy of reaction, caused by the crystallization of amylose and amylopectin. TheP-t traces reflected the quantities of amylose and amylopectin in the starch studied. Depending on the amylose content and the botanical source of the starch, the rate of crystallization of amylose was high and predominated over that of amylopectin during the first 5–10 h. The contribution from amylose crystallization to the measured exothermic enthalpy was very substantial during this period. After ∼10 h, amylose crystallized at a lower constant rate. During the first 24 h, amylopectin crystallized at a low steady rate. The exothermic enthalpies obtained by the isothermal microcalorimetric investigations during the first 24 h of retrogradation were generally low in relation to the endothermic melting enthalpies observed by differential scanning calorimetry (DSC) measurements after 24 h of storage. The discrepancies in enthalpy values between the two methods are discussed in relation to phase separation and the endothermic effects owing to the decrease in polymer-water interactions when polymer-rich regions in the starch gel separate. Besides the exothermic enthalpies obtained, theP-t traces also made it possible to study the initial gelation properties of amylose from different botanical sources. The present study further demonstrated that isothermal microcalorimetry can provide a possible way to investigate the antistaling effect of certain polar lipids, such as sodium dodecylsulphate (SDS) and 1-monolauroyl-rac-glycerol (GML), when added to starches of different botanical origin. The net exothermic heat of reaction for starch retrogradation during the first 24 h was decreased when GML or SDS was added to the starch gels. The recordedP-t traces also showed how the effect of the added lipid influenced different periods during the first 24 h of starch retrogradation, and that the effect depended mainly on the amylose content, the botanical source of the starch, and the type of lipid used. When GML or SDS was added to waxy maize, the isothermal microcalorimetric studies clearly indicated some interaction between amylopectin and the polar lipids. These results concerning the action of anti-staling agents are further discussed in relation to the helical inclusion complexes formed between amylose-polar lipid and amylopectin-polar lipid.
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  • 40
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    Journal of thermal analysis and calorimetry 46 (1996), S. 5-14 
    ISSN: 1572-8943
    Keywords: cadmium phenoxyacetate ; complexes ; DSC ; mercury(II) phenoxyacetate ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Solid cadmium and mercury(II) phenoxyacetates were prepared and investigated by DSC and TG techniques. The cadmium salt decomposed in two steps with the loss of 1.5 water molecules at first and the successive formation of CdCO3 as final product. Δdeh H * associated with the loss of one water molecule was compared with the corresponding values obtained for other phenoxyacetates previously studied and the obtained results were discussed. Anhydrous mercury(II) phenoxyacetate gave, on heating, HgCO3 which successively decomposed with the formation of gaseous products and a little amount of solid residue.
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  • 41
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    Journal of thermal analysis and calorimetry 46 (1996), S. 237-243 
    ISSN: 1572-8943
    Keywords: DSC ; DTG ; polyacetylene films ; TMA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Polyacetylene films irradiated byγ-rays up to 100 MRad were studied by means of TMA, DTG and DSC methods. It is shown that as the irradiation dose increases the concentration of topological branching knots into the polymer chains and theT g values decrease, the total mass loss and the enthalpy of the thermal isomerization reaction also decrease.
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  • 42
    ISSN: 1572-8943
    Keywords: DSC ; pharmaceutical technology ; polymer
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In the present study, the effect of the molecular weight and thermal treatments on commercial polyethylene glycols (PEG) samples used in the pharmaceutical processing technology, has been analyzed using DSC and HSM. The molecular weight of these polymers range from 1500 to 200000. Thermal investigations on the melting behavior of original PEG samples (as received from the manufacturer) showed only one single melting DSC endotherm effect before 373 K. This fact was associated to the presence of only one type of polymeric chain. Using standard conditions, PEG samples were solidified from the melt at 373 K, either by flash cooling (using liquid nitrogen and an ice bath) and by slow cooling, soaked and by slow cooling at room temperature. They were further studied by DSC. It was found that after cooling, PEG with molecular weight 1500 and 15000 showed DSC thermograms with a single endothermic peak. However, thermograms for PEG 4000 and 6000 produced a splitted melting endotherm. This fact was attributed to the presence of two types of chains, that are the folded and extended chains. Ageing time influences also the shape of the DSC endothermal effects. It was concluded that the endotherms obtained after heating these PEG indicate that the thermal history determine the structure (extended or folded chain type forms) and the degree of crystallinity, as evidenced by changes in heat of fusion values, melting points and structures after crystallization. The relationships between melting enthalpies and melting points, as deduced from DSC diagrams, with molecular weight of the polymers are also presented.
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  • 43
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1339-1347 
    ISSN: 1572-8943
    Keywords: boehmite ; DSC ; gibbsite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The dehydroxylation of gibbsite into boehmite was investigated by means of DSC analysis under non-isothermal conditions in the temperature range 453–673 K at heating rates from 2.5 to 20.0 K min−1. Mathematical analysis of the experimental DSC curves revealed the mechanism and kinetics of the gibbsite dehydroxylation process. The kinetic curvesα=f(t) andα=f(T) are sigmoidal in shape; their inflection points and the νm point of the curvesν=f(T) andν=f(T) are interrelated and are defined by the concept of a stationary point. The activation energy for the first stage of gibbsite dehydroxylation in the temperature range 453–673 K is 132.92±8.33–142.26±8.33 kJ mol−1.
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  • 44
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    Journal of thermal analysis and calorimetry 47 (1996), S. 117-121 
    ISSN: 1572-8943
    Keywords: baseline ; DSC ; heat of fusion ; polyethylene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A technique is proposed for improving the accuracy of the heat of fusion of semicrystalline polymers by DSC. The results of three commercially available instruments are compared.
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  • 45
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    Journal of thermal analysis and calorimetry 47 (1996), S. 195-213 
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; rheological impacts ; thermomechanical properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermomechanical properties of bread components can be used to characterize various events that have direct rheological impacts. The objective is to observe changes that occur during staling and toughening of a bread or similar products. In this article, characterization of bread polymers, starch and gluten, were examined by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA).
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  • 46
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    Journal of thermal analysis and calorimetry 47 (1996), S. 765-774 
    ISSN: 1572-8943
    Keywords: calcium aluminates ; cement ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimeter (DSC) has been used to study the dehydration characteristics of hydrated calcium aluminates such as CA, CA2 and C12A7 where C and A stand for CaO and Al2O3 respectively. Dehydration of CAH10 and C2AH8 (whereH=H2O) occur ∼ at 160–180°C and 200–280°C respectively. These two phases are unstable and ultimately get transformed to AH3 and C3AH6. Dehydration of AH3 and C3AH6 occur between 290 and 350°C and overlap at lower scanning rate. The activation energy for dehydration of the stable AH3 and C2AH6 phases has been found to be 107.16 and 35.58 kJ mol−1 respectively. The compressive strength of the hydrated calcium aluminates has been determined. The result shows that in the case of CA, almost 90% of ultimate strength has been attained in 1 day whereas in CA2, ultimate strength has been attained in 14 days and in C12A7 in 1 day. DSC results have been correlated with the rate of strength developments.
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  • 47
    ISSN: 1572-8943
    Keywords: crown-ethers (CE) ; 12-C-4 ; 15-C-5 ; DC 18-C-6anti ; DC 18-C-6syn ; DSC ; LiAlH4-CE complexes ; glass-transition ; solvates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of complexes [Li+-EC](AlH4)− withEC=12-C-4, 15-C-5, DC 18-C-6 (cis-anti-cis andcis-syn-cis isomers) was investigated by Differential Scanning Calorimetry (DSC). These complexes were prepared as solids from benzene solutions. Pure EC and several solvated species [Li+-EC](AlH4)−·nC6H6 (EC=15-C-5, DC 18-C-6syn) were also studied. DSC has revealed various phenomena. Solid-solid transitions were observed before melting for [Li+-EC](AlH4)− withEC=12-C-4 and 15-C-5. They are probably explained by small molecular modifications strongly dependent on the thermal history of the sample. A glass-transition was found for the pure crown-ether DC 18-C-6anti, the complex [Li+-EC](A1H4)− withEC=DC-18-C-6anti and the two solvates mentioned above.
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  • 48
    ISSN: 1573-1111
    Keywords: Biliar acid ; 2-hydroxypropyl-β-cyclodextrin ; interaction studies ; IR ; NMR ; DSC ; XRD
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction of two biliar acids (chenodeoxycholic acid and cholic acid) with 2-hydroxypropyl-β-cyclodextrin (HPβCD) in solution and in the solid state was studied using different techniques. The formation of an inclusion complex with a 1:1 stoichiometry was suggested by the phase solubility studies. Both differential scanning calorimetry and X-ray diffractometry exhibited the amorphous state of the complex. The inclusion of both biliar acids into the HPβCD cavity was confirmed by the13C-NMR studies. Cholic acid showed a weaker affinity with respect to chenodeoxycholic acid probably owing to the presence of a hydroxyl group onC(12) (12α) close to the complexation site.
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