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  • DSC  (107)
  • Fisheries
  • General Chemistry
  • Theoretical, Physical and Computational Chemistry
  • Springer  (109)
  • 1995-1999  (109)
  • 1945-1949
  • 1940-1944
  • 1997  (59)
  • 1996  (50)
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  • 1995-1999  (109)
  • 1945-1949
  • 1940-1944
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  • 1
    ISSN: 1572-882X
    Keywords: cellulose alkyl esters ; poly(∈-caprolactone) ; blends ; miscibility ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Cellulose alkyl esters, CELL- OCOCnH2n+1(n = 1 ∼ 6), were synthesized by a homogeneous reaction of cotton cellulose with different acyl chlorides in N,N-dimethylacetamide--lithium chloride solution. The miscibility of the esterified celluloses with poly(∈-caprolactone) (PCL) was investigated, mainly through thermal analysis by differential scanning calorimetry (DSC). A polymer pair, cellulose butyrate (CB)/PCL, showed the highest miscibility of all the binary blends examined here; this is usual when relatively high-substituted esters (DS ≥ 2.0) are used as the respective component. The butyl ester derivatives with DS ≤ 1.5 showed poor miscibility with PCL
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  • 2
    ISSN: 1432-1017
    Keywords: Key words Phosphatidylcholine ; Phosphatidylglycerol ; DSC ; Phase diagrams ; Miscibility ; Nonideality parameter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The miscibility of phosphatidylcholine (PC) and phosphatidylglycerol (PG) with different chain lengths (n = 14, 16) was examined by differential scanning calorimetry (DSC) at pH 2 and pH 7. The determination of the coexistence curves of the phase diagrams was performed using a new procedure, namely the direct simulation of the heat capacity curves as described recently (Johann et al. 1996, Garidel et al. 1997). From the simulations of the heat capacity curves first estimates for the nonideality parameters for nonideal mixing as a function of composition were obtained and phase diagrams were constructed using temperatures for the onset and offset of melting which were corrected for the broadening effect caused by a decrease in cooperativity of the transition. In most cases, the composition dependence of the nonideality parameters indicated nonsymmetric mixing behavior. The phase diagrams were further refined by simulations of the coexisting curves using a four-parameter model to account for nonideal and nonsymmetric mixing in the gel as well as in the liquid-crystalline phase. The mixing behavior of the systems was analyzed as a function of pH and chain length difference to elucidate the effect of these two parameters on the shape of the phase diagrams. At pH 7 the phase boundaries are much closer together and a narrower coexistence range is obtained compared to the corresponding phase diagrams at pH 2. For DPPC/DMPG at pH 2, the shape of the phase diagram and the strongly positive nonideality parameter ρ 1 for the liquid-crystalline phase indicates an upper azeotropic point. This indicates an unusual behavior of the system, namely more pronounced clustering of like molecules in the liquid-crystalline phase compared to the gel phase.
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  • 3
    ISSN: 1572-8943
    Keywords: DSC ; polyethylenes ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In thermal analysis polyethylenes can be characterized by their melting temperature. With the polyethylene mixtures studied, we obtained the best results during solidification. Crystallization temperature decreased in the order: high density PE, low density PE linear, radical low density PE. Calorimetric measurement of crystallization enthalpies allowed the determination of the composition of each of the polyethylenes, in regenerated and recycled mixtures in relation with the frame of the plastic waste valorisation process. The rate of crystallization obtained from X-ray diffraction spectra of these polymers is function of their volumic mass. A good agreement has been observed between these two techniques.
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  • 4
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    Journal of thermal analysis and calorimetry 49 (1997), S. 79-85 
    ISSN: 1572-8943
    Keywords: cross-linking degree ; DSC ; enthalpy relaxation ; epoxy resins ; physical aging ; reactive diluent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Structural relaxation in different epoxy-anhydride and epoxy-diamine resins has been investigated by differential scanning calorimetry using annealing and cooling rate experiments. The annealing experiments lead to the determination of enthalpy loss,δH, at an equivalent annealing temperatureT a=T g-20, and for periods of annealing time, ta, between 1 h and 4 months. The variation ofδH with logta, defines a relaxation rate per decade,rrpd, which is very sensitive to changes of the epoxy network. The cooling rate experiments allow the determination of the apparent activation energy,δh *. The effect of the degree of crosslinking, the addition of a reactive diluent, which acts as flexibilizer, and the length of cross-link onrrpd and δh* was studied.
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  • 5
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    Journal of thermal analysis and calorimetry 49 (1997), S. 149-154 
    ISSN: 1572-8943
    Keywords: DSC ; heterogeneity in polymer network ; poly(methacrylic acid)-net-poly(oxytetramethylene) ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract TG and DSC were carried out on PMAA-net-POTM in order to elucidate the relation between the heterogeneity and the thermal changes; moreover, TG and DSC were carried out on PPOTMDM and PMAA to compare the results. The onset temperature in the last stage in the TG curve of PMAA-net-POTM increases as the concentrations of DMF and POTMDM in the polymerization decrease. This is explained in terms of plasticizers effects. A single peak due to fusion of POTM chains appears in the DSC curves of most copolymers. However, it is not seen in the DSC curves of copolymers with high heterogeneity. This is explained in terms of the freezing of POTM chains by frozen heterogeneous moieties.
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  • 6
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    Journal of thermal analysis and calorimetry 49 (1997), S. 177-182 
    ISSN: 1572-8943
    Keywords: bismaleimide resin ; CTBN ; curing behaviour ; DSC ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Bismaleimide resin (Compimide 353) was modified with the liquid elastomer carboxyl-terminated acrylonitrile butadiene (CTBN). The prereaction synthesis and curing of the CTBN-bismaleimide resin is discussed. The structure of the modified resin was identified by IR and NMR spectroscopy. The basic curing mechanism is also discussed. DSC and TG were used to study the curing behaviour and kinetic parameters, viz. the order of reaction, energy of activation and preexponential factor. Adhesive properties such as lap shear strength and peel strength at room temperature and elevated temperature were evaluated and are discussed.
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  • 7
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    Journal of thermal analysis and calorimetry 49 (1997), S. 343-349 
    ISSN: 1572-8943
    Keywords: double melting peak ; DSC ; fiber ; polyethylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The multiple melting peaks observed on differential scanning calorimetry (DSC) of ultrahigh molar-mass polyethylene fibers (UHMMPE) are analyzed as a function of sample mass. Using modern DSC capable of recognizing single fibers of microgram size, it is shown that the multiple peaks are in part or completely due to sample packing. Loosely packed fibers fill the entire volume of the pan with rather large thermal resistance to heat flow. On melting, the fibers contract and flow to collect ultimately at the bottom of the pan. This process seems to be able to cause an artifact of multistage melting dependent on the properties of the fibers. A method is proposed to greatly reduce, or even eliminate, errors of this type. The crucial elements of the analysis of melting behavior and melting temperature are decreasing the sample size and packing the individual fibers in a proper geometry, or to introduce inert media to enhance heat transport.
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  • 8
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    Journal of thermal analysis and calorimetry 49 (1997), S. 399-405 
    ISSN: 1572-8943
    Keywords: DSC ; polyimide fiber ; TMA ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A commercially available polyimide fiber was investigated as a possible precursor for the formation of carbon fibers. The thermal response of the fiber was thoroughly investigated using DSC, TMA and TG. These responses were dependent on the atmosphere and tension during scanning. The fiber was stabilized at high temperatures both in inert and oxidative environments and the effect of these stabilization treatments on the structure and properties of the fiber was carefully followed. During heating, the fiber showed shrinkage tendency at small tensions, but at higher tensions the fibers could be stretched. Among the two environments investigated, air was more effective than nitrogen in getting a more stable fiber.
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  • 9
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    Journal of thermal analysis and calorimetry 49 (1997), S. 407-415 
    ISSN: 1572-8943
    Keywords: compatibility ; covulcanization ; derivative heat flow (δW/δT) ; DSC ; microheterogeneous
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Derivative heat flow curves give much more information about the phase heterogeneity of binary blends composed of NR, SBR and BR elastomers thanT g. In blend compositions, the areas under the derivative heat flow curves appear to be an additive function of the concentration of elastomers in the case of incompatible blends (NR/BR, NR/SBR). They are less than additive for either a partially compatible blend (uncured SBR/BR) or a compatible blend (covulcanized SBR/BR). In the case of 60/40 SBR/BR blends, a DSC (T 0.5) reveals a singleT g, in conformity with the earlier investigators, whereas the derivative heat flow curve shows two peaks (T p) indicating incomplete homogenization of the phases. This is a new observation not mentioned in the published literature. Thus, derivative heat flow traces are likely to provide a unique tool to determine compatibility of elastomers. The study also reveals the importance of sample contact with the DSC pan in quantitative determinations.
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  • 10
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    Journal of thermal analysis and calorimetry 49 (1997), S. 449-454 
    ISSN: 1572-8943
    Keywords: DSC ; network ; polyethylene ; turbidimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Semicrystalline polymers are made of a crystalline phase and of an amorphous phase. Recently, NMR, Raman and FTIR experiments have identified a third phase comprised of defects such as tie-molecules, in the organization of chains. Our investigation of physical gels has led us to believe that by following the heat flow in a very slow temperature ramp (0.05 K min−1), phasechanges, unnoticed in the usual fast ramp, could be detected. These are associated to a physical network strained in the temperature ramp. In order to obtain more information on the network phase, the polymer has been crosslinked The characteristics obtained by slow calorimetry and turbidimetry of the original and modified materials are compared.
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  • 11
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    Journal of thermal analysis and calorimetry 49 (1997), S. 483-490 
    ISSN: 1572-8943
    Keywords: carboxyterminated polybutadiene ; DSC ; DMA ; SEM ; toughened epoxy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new type of toughened epoxy polymer based on epoxy cresol novolac resin (ECN) and carboxy terminated polybutadiene (CTPB) liquid functional rubber has been studied. ECN has been synthesized in the laboratory and CTPB used was also of indigenised origin. Rubber modified epoxies were characterized with the help of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) techniques.
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  • 12
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    Journal of thermal analysis and calorimetry 49 (1997), S. 477-481 
    ISSN: 1572-8943
    Keywords: DSC ; EVA blends ; phenolic resin ; TG-DTG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The properties of polymeric blends originate from the synergistic association of their components. In this investigation, phenolic resins obtained by the reaction of cashew-nut shell liquid (CNSL) and aldehyde are used in several applications. Mixtures of CNSL with industrial reject ethylene-co-vinyl acetate (EVA reject) were prepared with an EVA reject content up to 70%. The thermal compatibility and stability were evaluated by means of thermogravimetry (TG), derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC). For blends containing a high percentage of EVA reject, the TG curves clearly show two decomposition stages, one at 350
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  • 13
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    Journal of thermal analysis and calorimetry 49 (1997), S. 513-520 
    ISSN: 1572-8943
    Keywords: DSC ; glass transition ; heat capacity ; melting transition ; nanophases ; polymers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Polymer molecules have contour lengths which may exceed the dimension of microphases. Especially in semicrystalline samples a single molecule may traverse several phase areas, giving rise to structures in the nanometer region. While microphases have properties that are dominated by surface effects, nanometer-size domains are dominated by interaction between opposing surfaces. Calorimetry can identify such size effects by shifts in the phase-transition temperatures and shapes, as well as changes in heat capacity. Specially restrictive phase structures exist in drawn fibers and in mesophase structures of polymers with alternating rigid and flexible segments. On several samples shifts in glass and melting temperatures will be documented. The proof of rigid amorphous sections at crystal interfaces will be given by comparison with structure analyses by X-ray diffraction and detection of motion by solid state NMR. Finally, it will be pointed out that nanophases need special attention if they are to be studied by thermal analysis since traditional ‘phase’ properties may not exist.
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  • 14
    ISSN: 1572-8943
    Keywords: dielectric spectroscopy (DETA) ; DSC ; dynamic mechanical (DMA) spectroscopy ; glass transition ; PET ; polymers ; relaxation ; rigid amorphous ; temperature modulated DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The relaxation strength at the glass transition for semi-crystalline polymers observed by different experimental methods shows significant deviations from a simple two-phase model. Introduction of a rigid amorphous fraction, which is non-crystalline but does not participate in the glass transition, allows a description of the relaxation behavior of such systems. The question arises when does this amorphous material vitrify. Our measurements on PET identify no separate glass transition and no devitrification over a broad temperature range. Measurements on a low molecular weight compound which partly crystallizes supports the idea that vitrification of the rigid amorphous material occurs during formation of crystallites. The reason for vitrification is the immobilization of co-operative motions due to the fixation of parts of the molecules in the crystallites. Local movements (Β-relaxation) are only slightly influenced by the crystallites and occur in the whole non-crystalline fraction.
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  • 15
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    Journal of thermal analysis and calorimetry 49 (1997), S. 745-753 
    ISSN: 1572-8943
    Keywords: DSC ; kerogen ; oxidation ; pyrolysis ; type determination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate of pyrolysis and oxidation of 8 different samples of oil shale kerogen concentrate (KC) were investigated using DSC analysis. Recently performed thermogravimetric studies (TG and DTG) with the same samples of KC indicated that the activation energy of the pyrolysis of specific KCs increases with increasing paraffinic structure in the KC. An opposite effect, i.e. a decrease of the activation energy with an increase of paraffinic structure was determined in the case of KC oxidation. In this study, using the standard ASTM E-698 method based on the determined temperature at which the maximum heat effect could be observed (exo in the case of oxidation and endo in the case of pyrolysis), an activation energy for the pyrolysis, as well as for the oxidation process was determined and also successfully correlated with the content of paraffinic structure of KC. Thus, the higher content of paraffinic structure in KCs indicates that higher values of the activation energy could be determined either in the case of pyrolysis or oxidation followed by DSC analysis.
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  • 16
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    Journal of thermal analysis and calorimetry 49 (1997), S. 795-799 
    ISSN: 1572-8943
    Keywords: butter ; butter oil ; DSC ; recombined butter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC can be used to quickly determine if a product labeled as butter is actually a recombined butter made without milk. Recombined butter is manufactured from anhydrous milk fat, skim milk powder, water, salt, and lecithin. Melting profiles of tempered samples of natural butter and recombined butter were alike, but DSC curves from 5 to 25°C of untempered refrigerated samples revealed that the enthalpy of the melting transition around 17–20°C was much higher for natural butter than for recombined butter. The procedure for differentiating the two products can be completed in less than 20 min.
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  • 17
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    Journal of thermal analysis and calorimetry 49 (1997), S. 809-816 
    ISSN: 1572-8943
    Keywords: dehydration ; drying method ; DSC ; lactitol ; lactitol monohydrate ; TG ; X-ray powder diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The purpose of this study is to find out the effect of the crystal water content on the crystal structure of lactitol monohydrate. Crystal water was removed by drying over silicagel at 40°C and by using phosphorus pentoxide as drying agent at 20°C. The amouts of water removals were identified by thermogravimetry, the melting points and the heat of fusions were calculated from the results of differential scanning calorimetry measurements and the structure of samples were identified by X-ray powder diffraction method. Over 23 w/w% of total water content could removed by gently drying until significant structural changes could be detected. The melting point of anhydrous lactitol obtained by drying lactitol monohydrate was 120°C and the melting enthalpy was 102 J g−1 when measured with heating rate 10°C min−1 by DSC.
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  • 18
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    Journal of thermal analysis and calorimetry 49 (1997), S. 831-837 
    ISSN: 1572-8943
    Keywords: DSC ; enzymatic hydrolysis ; functional properties ; hemisphaericin ; mexicain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC was used to study the extent of denaturation of hemisphaericin and mexicain hydrolysates from corn gluten, soybean and sunflower meals. It was observed that the defatted meals studied exhibited only one broad peak transition. The data obtained demonstrated that the partial protein denaturation found with hemisphaericin or mexicain is correlated to modifications of functional properties. The two enzymes display different modes of action, according to the protein source.
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  • 19
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    Journal of thermal analysis and calorimetry 49 (1997), S. 913-927 
    ISSN: 1572-8943
    Keywords: anesthetic drugs ; bupivacaine hydrochloride ; dibucaine hydrochloride ; DSC ; polymorphism ; prilocaine hydrochloride ; procaine hydrochloride ; solvent mediated transitions ; temperature resolved X-ray diffraction ; tetracaine base ; tetracaine hydrochloride ; thermodynamic relationships
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The local anesthetic drug tetracaine hydrochloride is described in the Europ. Pharmacopea with a melting point of 148°C or with a range of 134 to 147°C due to the melting points of two other forms. The polymorphic behaviour of tetracaine hydrochloride has been studied by using thermal treatments, storage at 92% r.h., crystallizations and equilibrations with saturated solutions. Samples were characterized by X-ray diffraction, IR, thermal analysis and elemental analysis. Since some findings were difficult to interpret, temperature resolved X-ray diffraction was used additionally for the understanding of the thermal behaviour of tetracaine hydrochloride. In this study the polymorphic behaviour of some other local anesthetic drugs is compared. Ten different forms of tetracaine hydrochloride: six anhydrous crystalline forms, an amorphous form, a hemihydrate, a monohydrate and a tetrahydrate were identified. The relationships between all forms are given. The heating curve of the commercial form 1 is very dependent on the heating rate. This anhydrous form 1 is the thermodynamic stable modification at ambient temperature. The form 2 is reversibly enantiotrope to form 1. The four other modifications called 3, 4, 5 and 6 are monotropes of form 1. Only forms 1 and 5 are stable at ambient temperature. Form 1 is hygroscopic only at high humidity level of 92% r.h., form 5 is hygroscopic at 61% r.h. Both transform into the monohy-drate. No polymorphic forms of tetracaine base, dibucaine hydrochloride, procaine hydrochloride or prilocaine hydrochloride were found. The commercial form of bupivacaine hydrochloride is a monohydrate. Thermal treatment at 200°C gives one anhydrous form. As demonstrated by temperature resolved X-ray diffraction two other forms are detected by heating and cooling processes between 100 and 170°C. Equilibrations and crystallization experiments show that solvates are easily obtained in different solvents. Temperature resolved X-ray diffraction is a very efficient tool as a support to DSC for the identification of the transition processes and interpretation of thermal events and thermodynamic relationships. Equilibration experiments are very adequate to find out the thermodynamically stable form at ambient temperature (solvent mediated transitions).
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  • 20
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    Journal of thermal analysis and calorimetry 49 (1997), S. 961-970 
    ISSN: 1572-8943
    Keywords: distribution constant ; DSC ; powder compact ; Rosin-Rammler particle size distribution ; thermal resistance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract How a DSC result is influenced by the particle size distribution of a powder sample is shown, and a simple and optimal method to be included in a routine DSC analysis (e.g., purity determination) to improve the reliability of the analysis is proposed. In case ofα-Al2O3 powder, most reliable heat capacity data can be obtained by preparing a powder with a self-similar particle size distribution with a distribution constant of 0.7, and by compressing it under a pressure of 1.5 MPa for a duration of 5 min or longer.
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  • 21
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    Journal of thermal analysis and calorimetry 49 (1997), S. 999-1005 
    ISSN: 1572-8943
    Keywords: DSC ; finite element method ; temperature gradients ; polymer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential Scanning Calorimetry is frequently used for measurements of thermal properties on all kinds of substances. The temperature lag in the samples depend on the thermal properties and the thermal contact between sample and sample holder. In the paper, we discuss the temperature distribution in samples of comparatively low thermal conductivity, such as polymers. The purpose of this study is to pinpoint the substantial temperature differences that may occur in such bad conducting samples under different conditions. The calculations of the temperature gradients have been carried out by using a finite element software package.
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  • 22
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    Journal of thermal analysis and calorimetry 49 (1997), S. 991-998 
    ISSN: 1572-8943
    Keywords: cryo-microscopy ; crystallization ; DSC ; ICE ; microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A simultaneous differential scanning calorimeter (DSC)-optical video microscope instrument has been developed. The instrument development included slight modifications to the sample head of a Perkin-Elmer DSC-7, along with the use of a CCD camera and magnifying lenses. The instrument permitted simultaneous following of optical and thermal events during isothermal and non-isothermal DSC experiments. The DSC curves were almost identical to those given by a standard DSC-7. The operational temperature range of the instrument is between −160 to 600°C. The capabilities of the DSC-video microscope are illustrated by examples of ice crystallization data in aqueous solutions of glycerol and dimethyl sulphoxide.
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  • 23
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    Journal of thermal analysis and calorimetry 48 (1997), S. 19-38 
    ISSN: 1572-8943
    Keywords: chalcedony ; crystalline disorder ; DSC ; DTA ; high-low quartz inversion ; silcretes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The paper reviews studies on possible applications of the high-low quartz inversion in petrology. Since the first suggestions of Fenner and Tuttle, nearly fifty papers have dealt with the subject, including ten by the present authors. The detailed discussion of the preparative and instrumental factors which may influence the quartz inversion behaviour reveals that the DTA (DSC) runs have to be made under highly standardized conditions to permit measurement of the ‘material inherent factors’ (mainly crystal physical factors) which cause variations in shape and temperatures. The most striking variations in shape and temperatures of the inversion effect (e.g. including temperatures more than 70°C lower than the ‘textbook value’ of 573°C for the quartz inversion) are observed for microcrystalline quartz crystals. The literature and the authors' own investigation demonstrate that the most interesting field of application of the method is that of authigenic quartz formation in sediments and soils. The characterization of metamorphic quartz is more complicated. Four fields of study are chosen to demonstrate the possible application of the quartz inversion characterization for petrogenetic interpretations: (1) the differentiation between authigenic and inherited quartz crystals in sediments, (2) the characterization of the contact-metamorphic aureoles around granites, (3) special regional-metamorphic terrains and (4) (from a few so far unpublished studies) the differentiation between sedimentary and soil silcretes.
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  • 24
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    Journal of thermal analysis and calorimetry 48 (1997), S. 259-266 
    ISSN: 1572-8943
    Keywords: DSC ; freezable water ; muscle water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The freezable water contents of samples obtained from previously chilled semimembranous muscle of middle-aged beef carcasses after a 24 h cooling period a room at in 5±1
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  • 25
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    Journal of thermal analysis and calorimetry 48 (1997), S. 473-483 
    ISSN: 1572-8943
    Keywords: dosage form ; drug products ; DSC ; identification ; quantitation ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis techniques, DSC and TG can advantageously be used in quality control of drug products. The methods are commonly used in preformulation for the study of polymorphism and for the study of the interactions drug substance-excipients, since these physical interactions can be the basis of the dosage form performance. For routine control of the drug products, DSC and TG methods which are quick, which require only few mg of the samples and which are automated, are very attractive for routine analysis of drug products. A single scan can give several qualitative and quantitative informations. DSC offer analytical possibilities only if the drug substance and the excipients do not have physical interactions or limited interactions (e.g. eutectic behaviour). About twenty marketed products have been analyzed by DSC and TG. In most of them identification of drug substance is easy. Several excipients could be identified in a tablet. Quantitations are demonstrated for some drug substances and excipients. DSC purity calculations have been applied to acetyl salicylic acid, paracetamol, cimetidine, pindolol, ibuprofen.
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  • 26
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    Journal of thermal analysis and calorimetry 48 (1997), S. 437-445 
    ISSN: 1572-8943
    Keywords: cardiac glycoside binding ; DSC ; membrane protein ; membrane receptor binding ; Na+ ; K+-ATPase ; thermal unfolding ; titration calorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC studies are carried out to characterize Na+,K+-ATPase isolated from pig kidney in its natural membrane environment as well as in its purified state upon detergent treatment. The transition temperatures of the investigated thermal protein unfolding process, observed between 43 and 64.5° C, depend on the local membrane environment as well as onpH. In addition, the transition temperature is significantly increased upon binding of different cations and ligands which are known to interact with the enzyme. Evidence for a lipid phase transition around 23 °C in the original biological membrane is reported. The application of a calorimeter equipped with removable cells appears to be more suitable for the investigation of this type of membrane sample than an instrument with fixed capillary cells. Filling the sample capillary cell with an usual syringe, consisting of a long and thin needle, can influence the experimental results. Na+, K+ -ATPase acts as the receptor for cardiac glycoside binding. The thermodynamic parameters of this binding process are determined by titration calorimetry. The binding of ouabain, as a typical example, is unusually slow and is enthalpy driven. The enthalpy change upon binding enthalpy is −75 kJ mol−1 at 25 °C. The surprisingly low stoichiometric coefficient, resulting from an evaluation based on a simple one step binding model, is interpreted in terms of a dimeric receptor unit.
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  • 27
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    Journal of thermal analysis and calorimetry 48 (1997), S. 647-656 
    ISSN: 1572-8943
    Keywords: aluminate sodalite ceramics ; ceramics ; dielectric properties ; DSC ; ferroelectric transitions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Aluminate sodalite ceramics, (Sr8Al12O24)(CrO4)2) — SACR, have been prepared from solution spray-dried precursors. The spray drying of a mixed aqueous nitrate solution gave an anhydrous powder which was thermally decomposed in air at 1350 °C to give a crystalline SACR powder with a median volume diameter of 4–6 μm. The SACR powder was dry pressed and sintered to 〉90% density. The yellow SACR powder showed two phase transitions between 10 and 45 °C with a 25 ° intermediate phase region indicative of a low defect concentration in the crystalline structure. A colour change observed in the sintered ceramic (changing to a mixed green/yellow) and a narrowing of the phase transition region (15–40 °C) are discussed. Dielectric measurements were consistent with the presence of two extrinsic ferroelectric transitions at 17 and 35 °C.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 691-696 
    ISSN: 1572-8943
    Keywords: conglomerate ; DSC ; melting phase diagram ; recemic compound
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The phenomena of conglomerate formation-racemic compound formation were investigated in a series of five (N-alkyl)-2′,6′-pipecoloxylidides. The optically active enantiomers were prepared by optical resolution of the racemates using 2R,3R-tartaric acid and 0,0′-dibenzoyl-2R,3R-tartaric acid as resolving agent. By DSC measurement of the racemates and the enantiomer the binary phase diagrams were determined. Among the four racemic molecular compounds the N-methyl derivative is the more stable. By increasing the length of the alkyl chain the stability of the racemic compound decreased, and in case of the longest -butyl-chain conglomerate formation was observed.
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  • 29
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    Journal of thermal analysis and calorimetry 48 (1997), S. 727-734 
    ISSN: 1572-8943
    Keywords: DSC ; monosulfide solid solution ; system Fe-Ni-S
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The decay of a monosulphide solid solution (mss) with the composition (Fe1−1Nix)0.96S was investigated by means of differential scanning calorimetry in the temperature range, from 20 to 305
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  • 30
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1305-1314 
    ISSN: 1572-8943
    Keywords: DSC ; electrolytic capacitors ; etched Al foils ; thermal resistance ; transient state
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A DSC method for evaluating the surface area of etched Al foils for use in high performance electrolytic capacitors is presented. A linear relationship between the etching degree (effective surface area) and the thermal resistance of the sample is obtained by means of DSC, based on the transient phenomenon. This method using the transient state in DSC measurement is not only novel, but also rapid and simple in evaluating the surface area of an etched aluminum foil. The method is effective even when the Al foil has a naturally oxidized surface.
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  • 31
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1357-1364 
    ISSN: 1572-8943
    Keywords: chemisorption ; desorption ; DSC ; dynamic FT-IR silver powder ; XPS
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The mechanism of adsorption and desorption of ethyl cellulose (EC) on and from silver powder was studied. After analysis with DSC, XPS and dynamic FT-IR, which could be heated by a program-controlled heater, applied to observe the states of pure EC and of EC adsorbed on silver powder, and also the thermal decomposition of EC from silver powder, the chemisorption bonding bridge between the oxygen atoms of EC and the silver atoms investigated. The differences in thermal decomposition between pure EC and EC adsorbed in silver powder were also studied. It was concluded that the chemisorption bonding between the oxygen atoms of EC and the silver atoms mainly involved the lone-pair electrons of the oxygen atoms on the EC chain and the outer empty 5 sp3 hybrid orbital of the silver. Because of the formation of this bridge, the bonds between neighboring carbon and oxygen atoms are weakened. As a result of this effect, the C-O bonds in the EC chain are broken more easily than the C-H bonds, which leads to the observation of -C-H- fragments in the upper space when EC adsorbed on silver is heated. When the same experiments were carried out on pure EC, almost all kinds of broken fragments of the EC molecule, including -C-H-, -C=O- and -C-O- appeared simultaneously.
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  • 32
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1467-1475 
    ISSN: 1572-8943
    Keywords: CRTA ; DSC ; kinetics ; synthetic brochantite ; TG-DTA ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction pathway of the thermal decomposition of synthetic brochantite, Cu4(OH)6SO4, to copper(II) oxide was investigated through the detailed kinetic characterization of the thermal dehydration and desulferation processes. The dehydration process was characterized by dividing into two overlapped kinetic processes with a possible formation of an intermediate compound, Cu4O(OH)4SO4. The dehydrated sample, Cu4O3SO4, was found first to be amorphous by means of XRD, followed by the crystallization to a mixture of CuO and CuO-CuSO4 at around 776 K. The specific surface area and the crystallization behaviour of the amorphous dehydrated compound depend largely on the dehydration conditions. The thermal desulferation process is influenced by the gross diffusion of the gaseous product SO3, which is governed by the advancement of the overall reaction interface from the top surface of the sample particle assemblage to the bottom.
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  • 33
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    Journal of thermal analysis and calorimetry 50 (1997), S. 365-373 
    ISSN: 1572-8943
    Keywords: DSC ; heat capacity ; indium ; linearity ; modulated DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Experiments using a commercial modulated DSC (MDSC) for the measurement of specific heat capacity of a sample have been carried out. It is found that because the amplitude of heat flow of MDSC is a complicated non-linear function of various experimental conditions such as the modulation frequency and the heat capacities of a sample and pan, the methodology of heat capacity determination using an MDSC in a single run has not been justified. The experimental results, on the other hand, agree with the theoretical equation of one of the authors. It is therefore concluded that the capabilities of MDSC should be further examined.
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  • 34
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    Journal of thermal analysis and calorimetry 50 (1997), S. 625-632 
    ISSN: 1572-8943
    Keywords: DSC ; NMR ; 8-quinolinol compounds ; TG-DTG ; stability ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Solid M-Ox compounds, whereM represents Mg(II), Zn(II), Pb(II) and NbO(III), and Ox is 8-quinolinol, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) and infrared absorption spectra (IR) have been used to characterize and to study the thermal stability and thermal decomposition of these compounds.
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  • 35
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1125-1134 
    ISSN: 1572-8943
    Keywords: calibration material ; calibration procedure ; DSC ; heat calibration ; heat flow rate calibration ; standards ; temperature calibration
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Metrologically based measuring procedures and evaluation methods are recommended as guidance for practical temperature, heat and heat flow rate calibration of DSC instruments which are largely independent of instrumental, test and sample parameters. The relevant terms are defined, the measuring procedures and evaluation methods described, calibration materials and their characteristic data stated and guidance for the sample handling provided. Reference is made to three extended papers on calibration. The recommendations were developed by the working group ‘Calibration of Scanning Calorimeters’ of the German Society of Thermal Analysis (GEFTA).
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    Journal of thermal analysis and calorimetry 50 (1997), S. 773-783 
    ISSN: 1572-8943
    Keywords: DSC ; FT-IR ; kinetics and mechanism ; SEM ; sodium hydrogencarbonate ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract New EGA findings revealed that the small endothermal event preceding that of the main decomposition of commercial NaHCO3 involves the simultaneous evolution of water and CO2. At very high sensitivity, EGA experiments evidenced that the above (limited) evolution of gases also took place from the recrystallized material for which thermal methods gave no indication of endotherms. Careful reexamination of previous DSC results indicated that for one kind of recrystallized material a very small endotherm had been neglected. Renewed experiments revealed that this endotherm can be enhanced if the samples are prepared by crushing and sieving in a wet atmosphere. Parallel FT-IR experiments on commercial and recrystallized materials demonstrated the presence of carbonate in samples that had previously been taken just beyond the first small endotherm; this confirmed the EGA results. SEM experiments showed that surface texture changes take place when samples are heated to temperatures just above that of the preliminary endotherm. On the basis of these new findings, the interpretation previously given to the small endotherm is revised and detailed knowledge is gained on the mechanism of decomposition of NaHCO3.
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  • 37
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    Journal of thermal analysis and calorimetry 48 (1997), S. 287-295 
    ISSN: 1572-8943
    Keywords: (AgxK1−x)NO3 ; DSC ; IR ; solid solution
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of partial replacement of K+ by Ag+ in the mixed system of KNO3 and AgNO3 during a set of DSC heating cycles was studied by means of a modern computerized DSC system. Thermal analysis was performed in the vicinity of the phase transition II → I for pure KNO3. The results revealed a large change in enthalpy and the phase transition temperature close to the morphotropic boundary x=0.5–0.6. At this boundary, the transformation enthalpy reached the maximum value of ∼101 J g−1. On the basis of the data obtained from this accurate thermal analysis work, a model is suggested for the energy barrier of rotation of the nitrate ion in the mixed nitrate system.
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  • 38
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    Journal of thermal analysis and calorimetry 48 (1997), S. 683-690 
    ISSN: 1572-8943
    Keywords: calorimetry ; DSC ; egg white ; egg white fractions ; fractionation ; thermoph-pr
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Egg white is of great interest for many culinary and industrial applications. Egg white is used for coating, gluing, thickening and so on in pasta, desserts, etc. There is thus a great interest from the industrial point of view to better know this raw material, used in very large amounts in the dessert production for example, and to obtain egg white fractions with different functional properties. Various egg white fractions prepared by selected procedures were analyzed by differential scanning calorimetry (DSC). The products resulting from a given fractionation procedure can thus be described by the thermal denaturation parameters (temperatures and enthalpies) of the egg white proteins. This work demonstrates the interest of the DSC technique and proves that the fractionation procedures selected here give the expected protein fractions.
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  • 39
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    Journal of thermal analysis and calorimetry 48 (1997), S. 903-907 
    ISSN: 1572-8943
    Keywords: DSC ; liquid-crystalline ; PMMS-PMOBAOB ; PMOBAOB ; transformation kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The transformation kinetics of liquid-crystalline 1,4-phenylene 4-n-methoxybenzoate-4-allyl-oxybenzoate (PMOBAOB) and a liquid-crystalline poly(mesogen/methyl) siloxane (PMMS) was studied by means of a non-isothermal method using differential scanning calorimetry. This determination led to an apparent activation energy of transformation of 639.0 and 306.5 kJ mol−1, respectively. The values of the Avrami exponentn were 1.8 and 1.1. The results show that the process of transformation of PMOBAOB involves a constant number of nuclei growing in two dimensions at a constant rate, while the process of transformation of PMMS-PMOBAOB involves a constant number of nuclei growing in one dimension at a constant rate.
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  • 40
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    Journal of thermal analysis and calorimetry 48 (1997), S. 1229-1248 
    ISSN: 1572-8943
    Keywords: α-Cu-Al alloys ; dislocations ; DSC ; energetics ; recrystallization ; rolled ; segregation ; short-range-order
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A general model is discussed for assessing the energy release due to the pinning of solute atoms to partial dislocations. The present approach discloses the influence of dislocation character distributions on the magnitude of this energy. In order to test its validity in αCu-Al alloys, differential scanning calorimetry (DSC) evaluations associated with the different peaks involved during linear heating were performed employing both cold worked and quenched materials. Dislocation densities were calculated from recrystallization traces. On the basis of this model it was concluded that the observed energy difference between the deformed and the quenched materials during the exothermic peak designated as Stage 2 corresponds to the pinning process. It was also concluded that nearly equal number of edge and screw dislocations are present in the dislocation configuration of deformed alloys. Nevertheless, it is proposed that dislocation-induced order might also occur as a consequence of enhanced solute concentration around the partials.
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  • 41
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    Journal of thermal analysis and calorimetry 48 (1997), S. 1299-1310 
    ISSN: 1572-8943
    Keywords: compatibility ; DSC ; master curves ; mechanical measurements ; rubber blends
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The compatibility of some technically important polymer blends, namely BR/NR, NR/NBR and CR/NBR, has been investigated using the DSC method. In addition, dynamic mechanical measurements have been carried out for the NR/NBR blends over the frequency range of 10−4 Hz –200 Hz and temperatures ranging from −70 to +70°C. The results obtained show that the three rubber blends are not compatible over the entire composition range as proven by the DSC and mechanical measurements. By analyzing the heat capacity increases at the glass transitions of the separate phases in the NR/BR blend, it was possible to suggest the presence of a limited compatibility at the boundaries of the two phases. By comparing this work with prior measurements, it was possible to conclude that the calorimetric method is a more efficient tool for the study of compatibility of polymer blends when compared to ultrasonic and viscosity methods. Furthermore, it was found that polymers that show compatibility when measured with an ultrasonic method could behave compatible, semicompatible or incompatible when analyzed by DSC. On the other hand, blends that show incompatibility by the ultrasonic method are always incompatible by the DSC method.
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  • 42
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    Journal of thermal analysis and calorimetry 49 (1997), S. 115-121 
    ISSN: 1572-8943
    Keywords: comb-like polymer ; DSC ; fluorocarbon chain ; side-chain crystallization ; X-ray diffraction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal properties of acrylate and methacrylate monomers containing long-fluorocarbon chains (H(CF2)nCH2OCOCH=CH2, (FnA) and H(CF2)nCH2OCOC(CH3)=CH2, (FnMA), wheren=6, 8, 10) and their comb-like polymers have been investigated by differential scanning calorimeter (DSC) and X-ray diffraction. The comb-like polymers (PF10A and PF10MA) with sufficiently long-fluorocarbon chains showed a simple melting and crystallizing behavior. For the fusion of PF10A in 1st heating, enthalpy change δH f was 18 kJ mol−1 and entropy change δS f was 45 J K−1 mol−1, while for PF10MA the values δH f and δSf were 5.3 kJ mol−1 and 14 J K−1 mol−1, respectively. Melted PF8A crystallized slowly, whereas PF8MA with same fluorocarbon chain and also both of PF6A and PF6MA with shorter fluorocarbon chains can hardly crystallize by the aggregation of side-chains. Effects of the length of side-chain and the flexibility of main chain on the side-chain crystallization of comb-like polymers are clear. Crystallization process of the methacrylate monomers was sensitively affected by the scanning rate of DSC measurement and the length of fluorocarbon chains.
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  • 43
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    Journal of thermal analysis and calorimetry 49 (1997), S. 193-199 
    ISSN: 1572-8943
    Keywords: DSC ; liquid crystals ; temperature calibration
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The temperature calibration of a TA Instruments 3200-2920 DSC has been performed on cooling using the isotropic → nematic, isotropic → cholesteric and other liquid crystal → liquid crystal transitions of thermally stable, high purity liquid crystals. The thermal stability of these liquid crystals has been verified by measuring the temperature of the mentioned transitions during cyclic heating and cooling experiments. Correspondence has been established between the real and indicated temperature during cooling for all combinations of heating and cooling rates of practical interest: correction values were determined to the indicated temperature in order to obtain the real temperature on cooling. These correction values were calculated as the average from the temperatures of four or five different liquid crystal transitions for each heating-cooling rate combination. The accuracy of the temperature calibration on cooling is ca. 0.2
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    Journal of thermal analysis and calorimetry 49 (1997), S. 227-234 
    ISSN: 1572-8943
    Keywords: DSC ; EVA ; interaction parameter ; polymer blends ; PVC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In order to provide additional information on the miscibility of the PVC/EVA system, calorimetric parameters such as ΔC pi,T gi and ΔT gi were obtained with a different approach. A qualitative and quantitative measure of the blend composition at the interface was obtained. This indicated that the domains are rich in each component and the presence of the second component in the phase has little effect on the main chain relaxation. The PVC fraction in the EVA-rich phase is always larger than the EVA fraction in the PVC-rich phase. Positive and small values of the Flory-Huggins interaction parameter were obtained from calorimetric data.
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  • 45
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    Journal of thermal analysis and calorimetry 49 (1997), S. 235-245 
    ISSN: 1572-8943
    Keywords: DSC ; EVA ; interaction parameter ; polymer blends ; PVC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Poly(vinyl chloride) was blended with ethylene-vinyl acetate copolymer containing 70 wt% of vinyl acetate. The system shows a single glass transition temperature for all compositions, indicating their miscibility. TheT g vs. composition curves display an inflection, which changes with the chemical environment of the initial solution. The best fit to the shape of the curve was well reproduced by the Kovacs-Braun equation. The δT g values reveal local heterogeneity, which means no total miscibility at a molecular level. Negative values of the Flory-Huggins interaction parameter were obtained from the calorimetric data.
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  • 46
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    Journal of thermal analysis and calorimetry 49 (1997), S. 293-301 
    ISSN: 1572-8943
    Keywords: characterization ; cis- ; trans isomers ; crystallinity ; DEA ; degradation ; DMA ; DSC ; DTG ; enthalpy ; glass transition temperature ; isomers ; vinyl
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Many of the isomers of polybutadiene and polyisoprene elastomers can be characterized by thermal analysis.T g is sensitive to side chain units (1,2 or 3,4 structure) for both polymers. Crystallinity measurements can characterizecis andtrans isomers. DMA and DEA master curves provide an idea of the heterogeneity of the chain units from the width of the loss factor curves in theT g region. Thermal and thermooxidative degradation, as followed by DSC and DTG, can differentiate specific natural and synthetic isomers of polyisoprenes in raw and vulcanized states.
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  • 47
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    Journal of thermal analysis and calorimetry 49 (1997), S. 303-310 
    ISSN: 1572-8943
    Keywords: curing ; DSC ; epoxy ; gel time ; gelation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method for determining the degree of conversion of gelation (αgel) and gel time (t gel) at gel point using a single technology, DSC, is discussed in this work. Four kinds of thermoset resins are evaluated. It is found that the mutation points of reduced reaction rate (V r ) vs. reaction conversion (α) curves, corresponding with the changes of reaction mechanism, represents the gelation of the reaction. The α at the mutation point is defined as αgel. From isothermal DSC curves, the point at αgel is defined ast gel. Traditional techniques (ASTM D3532 and DSC method) are also used to determine αgel andt gel in order to demonstrate this new method. We have found that the results obtained from this new method are very consistent with the results obtained from traditional methods.
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  • 48
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    Journal of thermal analysis and calorimetry 49 (1997), S. 693-702 
    ISSN: 1572-8943
    Keywords: DSC ; helical conformation ; poly(α-n-alkyl-L-aspartate)s
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of poly(α-n-alkyl β-L-aspartate)s (n being the number of carbon atoms in the linear alkyl side chain, withn=1, 2, 4, 6, 8, 12, 18 and 22), was studied by differential scanning calorimetry and thermogravimetric analysis. The effect of the length of the alkyl group on thermal properties such as stability, melting and crystallization of side chains, was investigated. For the polymers with n≥12, two endothermic peaks at T1 and T2 were detected separating three distinct phases A, B and C. The peak at T1 corresponds to the melting of the crystallized paraffinic side chains (transition A-B), and the peak: at T2 may be attributed to a transition (B-C), implying a liquid crystal phase.
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  • 49
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1105-1114 
    ISSN: 1572-8943
    Keywords: DSC ; resolution ; sensitivity ; test
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The Dutch Society for Thermal Analysis has developed tests to measure the resolution and the sensitivity of Differential Scanning Calorimeters. For this test the substance 4,4′-azoxyanisole is used. This substance shows two transitions: a solid to liquid crystal transition at about 117°C (ΔH≈120 J g−1) and a liquid crystal to isotropic liquid transition at about 134°C (ΔH≈2 J g−1). The resolution test is performed using an amount of 5 mg substance and a high heating rate of 20°C min−1. The resolution is evaluated by measuring how well the two peaks are separated. An amount of 0.25 mg substance and a low heating rate of 0.1 °C min−1 is used for the sensitivity test. The sensitivity is evaluated as the ratio of the peak height of the LC-transition and the top-top noise level. Members of the TAWN were asked to participate in the test. Each participant was provided with an amount of sample and a test procedure. 47 Contributions were received and these results are presented.
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  • 50
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1321-1326 
    ISSN: 1572-8943
    Keywords: alkali metal compounds ; DSC ; heat capacity ; high temperature ; thermodynamic data
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The heat capacities of selected inorganic binary and ternary alkali metal compounds are determined using differential scanning calorimetry (DSC). As part of an ongoing research program at Battelle Memorial Institute since 1983, the heat capacities of cesium and rubidium chalcogenides, aluminates, silicates and uranates in the temperature range 310 to 800 K have been added to the series of compounds. The measured data is to be combined with the standard enthalpies of formation and low temperature heat capacities to obtain reliable thermodynamic data on the alkali metal compounds to high temperatures.
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  • 51
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    Journal of thermal analysis and calorimetry 50 (1997), S. 617-624 
    ISSN: 1572-8943
    Keywords: bound water ; DSC ; free water
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The differences in bound water content of beef semimembranous muscle samples obtained from previously chilled (24 h at +4°C) middle-aged beef carcasses were determined by the use of DSC. Initially, samples obtained from fresh, unprocessed meat were frozen at −40, −50 or −65°C to determine their melting peaks for freezable water (free water) content with the use of DSC. The samples were then subjected to an environment with an ambient temperature of −30, −35, −40 or −45°C, with no air circulation, or with an air circulation speed of 2 m s−1, until a thermal core temperature of −18°C was attained; this was followed by thawing the samples until a thermal core temperature of 0°C was reached. This process was followed by subjecting the samples to the ambient temperatures mentioned above, to accomplish complete freezing and thawing of the samples, with DSC, and thereby determination of the freezable water contents, which were then used to determine the peaks of melting. The calculated peak areas were divided by the latent heat of melting for pure water, to determine the freezable water contents of the samples. The percentage freezable water content of each sample was determined by dividing its freezable water content by its total water content; and the bound water content of each sample was determined by subtracting the percentage free water content from the total. In view of the fact that the free water content of a sample is completely in the frozen phase at temperatures of −40°C and below, the calculations of free and bound water contents of the samples were based on the averages of values obtained at three different temperatures.
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  • 52
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    Journal of thermal analysis and calorimetry 50 (1997), S. 347-354 
    ISSN: 1572-8943
    Keywords: DSC ; eutectic composition ; LiCl-KCl system ; phase diagram
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis of the binary system KCl-LiCl in the composition range 0.368–0.812 mol fraction of LiCl was studied by differential scanning calorimetry (DSC). On the basis of the DSC curves, the experimental data for the phase-diagram, the latent heat of fusion, and the average specific heat in the liquid and solid states are presented as a function of the composition of the mixture. The experimental results compared with literature data. The following empirical correlation between the heat of fusion (ΔH) and of compositions of the mixture in mol fraction of LiCl (x) was obtained: ·GH=26.95−50.20x+43.06x2 with a minimum value of 11.8 kJ(g mol)−1 at the eutectic point of 0.587 mol fraction of LiCl at 354.4°C. These results are required as basic data to develop thermal energy storage materials, based on the phase change of a molten mixture of KCl-LiCI.
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  • 53
    ISSN: 1573-4846
    Keywords: thorium ; tin ; phosphate xerogels ; EPR ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Different transparent phosphate xerogels were synthesized usingconcentrated solutions of metal chlorides and phosphoric acid with aproper mole ratio of both components. By this method we prepared bulksamples of thorium and tin(IV) phosphate xerogels by drying at room temperature or at 350 K. Some properties of these amorphous materialswere studied by means of differential scanning calorimetry (DSC) andelectron paramagnetic resonance (EPR) techniques. Depending on moleratio $$\frac{{{\text{metal}}}}{{{\text{phosphate}}}}$$ , these xerogels show, near 180 K, inflection points which we interpret as T g . Samples dried at 425 K lose their transparency and have no T g . Thus, it seems that the “glassy” state is due to water molecules remaining in the material. The same properties wereconfirmed by EPR studies of the xerogels doped with Cr3+ andFe3+ ions as probes. These results show the existence of twodifferent phases in the xerogels: a liquid-like one, in the range from190 K to 350 K and a solid-like one, in the range from 4 K to 190 K.
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  • 54
    ISSN: 1573-4846
    Keywords: thorium ; tin ; phosphate xerogels ; EPR ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different transparent phosphate xerogels were synthesized using concentrated solutions of metal chlorides and phosphoric acid with a proper mole ratio of both components. By this method we prepared bulk samples of thorium and tin(IV) phosphate xerogels by drying at room temperature or at 350 K. Some properties of these amorphous materials were studied by means of differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) techniques. Depending on mole ratio metal/phosphate, these xerogels show, near 180 K, inflection points which we interpret asT g . Samples dried at 425 K lose their transparency and have noT g . Thus, it seems that the “glassy” state is due to water molecules remaining in the material. The same properties were confirmed by EPR studies of the xerogels doped with Cr3+ and Fe3+ ions as probes. These results show the existence of two different phases in the xerogels: a liquid-like one, in the range from 190 K to 350 K and a solid-like one, in the range from 4 K to 190 K.
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  • 55
    ISSN: 1573-904X
    Keywords: solution ; protein stability ; factor VIII ; formulation ; kinetics ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To investigate the influence of various nonreducing disaccharides and sugar alcohols on the inactivation kinetics of recombinant factor VIII SQ (r-VIII SQ) in aqueous solution not containing albumin as a stabiliser. Methods. The stability of r-VIII SQ was followed using measurement of activity (VIII: C) and HPLC gel filtration at different temperatures. The thermal stability was investigated using differential scanning calorimetry (DSC). Results. The decline in VIII:C followed pseudo-first order kinetics. However, the Arrhenius plot was not linear for formulations without carbohydrate, demonstrating a distinct, reproducible curvature. The reaction rate at 5°C was faster than expected from the Arrhenius kinetics. The energy of activation (Ea) for formulations without added carbohydrates, derived from the linear part of the Arrhenius plot, varied between 77 and 86 kJ/mole in the temperature range 20−37°C. The addition of 600 mg/ml sucrose increased the Ea to 104 kJ/mole. DSC measurements showed thatTm′ was 64.2 ± 0.2°C for r-VIII SQ without stabiliser. This value increased linearly with increasing concentrations of carbohydrate. This stabilising effect is most probably explained by the theory of preferential hydration. Conclusions. The inactivation kinetics of r-VIII SQ in aqueous solution without addition of carbohydrates followed pseudo-first order kinetics but the Arrhenius plot was nonlinear. Sucrose and sorbitol both had highly stabilising effects on r-VIII SQ at concentrations above 300 mg/ml. The preparation containing 600 mg/ml sucrose was stable for at least 12 months at 5°C and 6 months at 25°C.
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  • 56
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    Pharmaceutical research 14 (1997), S. 899-904 
    ISSN: 1573-904X
    Keywords: amorphous material ; crystallization ; solid state reaction kinetics ; XRPD ; DSC ; microcalorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The purpose of the work was to study the crystallization kinetics of amorphous sterotex K at different temperatures and with different methods, and to compare the obtained kinetic and thermodynamic results. Methods. Isothermal microcalorimetry was the principal technique to determine the crystallization behavior of sterotex K. X-ray powder diffraction and differential scanning calorimetry were employed to interpret the microcalorimetric heat flow curves and compare the kinetics and the calculated value for the transition enthalpy. Results. The best way to analyze the x-ray diffractograms was the statistic Wakelin's correlation method. The method gave consistent quantitative results with microcalorimetry and both methods showed crystallization to consist of two partially parallel part-processes, which attached probably to the different growing rates of the forms consisting of different lattice planes having the same spacing. The quantitative analysis of differential scanning calorimetry scans was troublesome to perform but the obtained average value of −51 J/g for the enthalpy of the crystallization was in good agreement with the values obtained with the other methods, the average being −52 J/g. Calculating heat flow versus released energy plots from the microcalorimetric data the crystallization mechanism was observed to change as a function of temperature. Conclusions. A sensitive isothermal microcalorimeter can give precise and fast knowledge about possible solid state transition mechanism, but the source of the heat flow signal must be verified with other analytical methods to avoid incorrect conclusions. Due to the sensitivity and the real-time data the microcalorimetry can show up the mechanism of the transition for varying as a function of temperature and reveal the uselessness of the conventional Arrhenius relationship for extrapolations.
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  • 57
    ISSN: 1435-1536
    Keywords: Key words Poly(ethylene-co-5.4 mol% 3 ; 5 ; 5-trimethylhexyl methacrythlate) ; poly(dimethyl-siloxane) ; miscibility ; permeability ; dynamic elastic measurement ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Blends of poly(ethylene- co-5.4 mol% 3,5,5-trimethylhexyl methacrylate) (PE-TMHM) with poly(dimethylsiloxane) (PDMS) were prepared in the PDMS content range from 0 to 20%. The miscibility was studied for PE-TMHM–PDMS blends by DSC, dynamic mechanical and microscopic spectroscopy, and the gas permeability was measured for O2, N2 and CO2 as function of PDMS content. PE-TMHM and PDMS were partially miscible with each other below 20 wt% of PDMS content. The permeability coefficients (P) for O2, N2 and CO2 were increased by the blending of PDMS to PE-TMHM. The change of P for O2 with PDMS content well reflected the partially miscible phase separation behavior.
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  • 58
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; etherification ; TGDDM epoxy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was applied to study the cure kinetics of an epoxy system containing both tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) and a multifunctional Novolac glycidyl ether resin, cured with 4,4′-diaminodiphenylsulfone (DDS). The experimental data were analyzed in terms of a mechanistic model proposed by Cole, which includes the etherification reaction. The kinetics can be completely described in terms of three rate constants, which obey the Arrhenius relationship. This model gives a good description of the cure kinetics up to the onset of vitrification. The effect of diffusion control was incorporated to describe the cure in the later stages. By combining the model and a diffusion factor, it was possible to predict the cure kinetics over the whole range of conversion, including an analysis of the evolution of different chemical species during the curing process. Good agreement with the experimental DSC data was achieved with this mechanistic model over the whole range of cure when the etherification reaction was assumed to be of first order with respect to the concentrations of epoxide groups, hydroxy groups, and the tertiary amine groups formed in the epoxide amine reaction.
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  • 59
    ISSN: 1572-8943
    Keywords: DTA ; DSC ; hydantion ; new ring ; tropane ; X-ray
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Several derivatives containing a new organic ring system, the tropane-6-spiro-5′-hydantoin structure (namely 8-alkyl-8-azabicyclo [3.2.1.] octane-6-spiro-5′-imidazoline-2′,4′-diones) have been characterized by thermal (DSC and simultaneous DTA-TG-DTG) and spectroscopic techniques (IR,1 H-NMR,13 C-NMR). X-ray powder diffraction and elemental analysis were applied for structural and molecular characterization. All the compounds melt in the range 160–250°C and undergo decomposition with progressive mass loss after the solid-liquid thermal transition with molecular degradation. It was found that tropane-6-spiro-5′-hydantoin derivatives with the hydantoin ring in β position are thermally less stable than those containing this ring in α position.
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  • 60
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    European biophysics journal 24 (1996), S. 293-299 
    ISSN: 1432-1017
    Keywords: Phase transition ; NMR ; DSC ; X-ray diffraction ; Bonnet Transformation
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    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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    Environmental management 20 (1996), S. 523-539 
    ISSN: 1432-1009
    Keywords: Water control ; Floodplain ; Fisheries ; Bangladesh ; Chandpur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Bangladesh is a very flat delta built up by the Ganges—Brahmaputra—Meghna/Barak river systems. Because of its geographical location, floods cause huge destruction of lives and properties almost every year. Water control programs have been undertaken to enhance development through mitigating the threat of disasters. This structural approach to flood hazard has severely affected floodplain fisheries that supply the major share of protein to rural Bangladesh, as exemplified by the Chandpur Irrigation Project. Although the regulated environment of the Chandpur project has become favorable for closed-water cultured fish farming, the natural open-water fishery loss has been substantial. Results from research show that fish yields were better under preproject conditions. Under project conditions per capita fish consumption has dropped significantly, and the price of fish has risen beyond the means of the poor people, so that fish protein in the diet of poor people is gradually declining. Bangladesh is planning to expand water control facilities to the remaining flood-prone areas in the next 15–20 years. This will cause further loss of floodplain fisheries. If prices for closed-water fish remain beyond the buying power of the poor, alternative sources of cheap protein will be required.
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  • 62
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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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    Journal of thermal analysis and calorimetry 47 (1996), S. 181-194 
    ISSN: 1572-8943
    Keywords: DSC ; gelatinization
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    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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    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Keywords: compensation effect ; DSC ; kinetics ; TG
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    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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    Journal of thermal analysis and calorimetry 47 (1996), S. 685-695 
    ISSN: 1572-8943
    Keywords: DSC ; polymers ; resins ; TG
    Source: Springer Online Journal Archives 1860-2000
    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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  • 66
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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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    Journal of thermal analysis and calorimetry 47 (1996), S. 1179-1200 
    ISSN: 1572-8943
    Keywords: DSC ; isothermal microcalorimetry ; retrogradation ; starch
    Source: Springer Online Journal Archives 1860-2000
    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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  • 68
    ISSN: 1572-8943
    Keywords: cooling/heating rate ; DSC ; fragility parameter ; glass transition temperature ; sorbitol-fructose
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    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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    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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    Journal of thermal analysis and calorimetry 46 (1996), S. 5-14 
    ISSN: 1572-8943
    Keywords: cadmium phenoxyacetate ; complexes ; DSC ; mercury(II) phenoxyacetate ; TG
    Source: Springer Online Journal Archives 1860-2000
    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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    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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    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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    Journal of thermal analysis and calorimetry 46 (1996), S. 619-626 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; filled polypropylene ; nucleation ; structural modification
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    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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    Journal of thermal analysis and calorimetry 46 (1996), S. 643-679 
    ISSN: 1572-8943
    Keywords: DDTA ; DSC ; macromolecules
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    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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    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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    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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 77
    ISSN: 1572-8943
    Keywords: DSC ; gelatinisation ; potato starch
    Source: Springer Online Journal Archives 1860-2000
    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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    Journal of thermal analysis and calorimetry 47 (1996), S. 1299-1314 
    ISSN: 1572-8943
    Keywords: baked goods ; cookies ; crackers ; DSC ; pretzels ; starch
    Source: Springer Online Journal Archives 1860-2000
    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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  • 79
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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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 80
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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
    Source: Springer Online Journal Archives 1860-2000
    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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  • 81
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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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  • 82
    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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  • 83
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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
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    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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  • 84
    ISSN: 1572-8943
    Keywords: complexes ; DSC ; guest-host interactions ; X-ray
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    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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  • 85
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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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  • 86
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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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  • 87
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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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  • 88
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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
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    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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  • 89
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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
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    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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  • 90
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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
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    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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  • 91
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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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  • 92
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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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  • 93
    ISSN: 1572-8943
    Keywords: DSC ; pharmaceutical technology ; polymer
    Source: Springer Online Journal Archives 1860-2000
    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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  • 94
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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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  • 95
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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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  • 96
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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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  • 97
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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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  • 98
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1339-1347 
    ISSN: 1572-8943
    Keywords: boehmite ; DSC ; gibbsite
    Source: Springer Online Journal Archives 1860-2000
    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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    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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    Journal of thermal analysis and calorimetry 47 (1996), S. 117-121 
    ISSN: 1572-8943
    Keywords: baseline ; DSC ; heat of fusion ; polyethylene
    Source: Springer Online Journal Archives 1860-2000
    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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