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  • Springer  (58)
  • 2000-2004  (58)
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  • 1
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    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 719-730 
    ISSN: 1572-8943
    Keywords: DSC ; TSDC ; unsaturated polyester resin ; X-ray fluorescence spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This work reports on the curing kinetics of unsaturated polymer resins (UPRs) cured with styrene, studied by differential scanning calorimetry and Fourier transform infrared spectroscopy. The data lead to determination of the experimental conditions with which to obtain a fully cured material and open the way for study of the relaxation phenomena by means of thermally stimulated depolarization current analysis (TSDC). In relaxation studies on fully cured resins, the TSDC spectra revealed important overlapping of the main relaxation peak with an extra upper peak. The importance of this extra peak a priori prevents further analysis of the main relaxation. To identify the origins of this peak (space charge or other), the purity of the resin was checked by X-ray fluorescence spectroscopy. The use of UPR specimens with different compositions (in terms of the resin/activator/initiator ratio) demonstrated that the bulk of the impurities Cl, K, Ca, Sr, Zr and Ba are due to the promoter. Decoupling of the mixed peaks (α-relaxation and extra) revealed that the a peak is independent of the proportion of the promoter in the resin and that the extra peak is principally due to the presence of these impurities.
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  • 2
    ISSN: 1572-8943
    Keywords: chiral complex ; DSC ; hydrate ; optical resolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of O,O'-dibenzoyl-(2R,3R)-tartaric acid (DBTA), its monohydrate, and its potential supramolecular compounds with achiral alcohols and phenols were investigated with TG, DSC, EGD. The structural differences among the anhydrous DBTA, its monohydrate, and the supramolecular derivatives were investigated with X-ray powder diffraction. The thermal behaviour of DBTA-supramoleculars with isopropyl, tert-butyl, and 5-cyclohexyl alcohols is found to be similar to each other but essentially different from that of both DBTA and its monohydrate. On heating they melt and decompose between 60–180°C while they loose in one or two steps the bound alcohol. The thermal stability of the supramolecular compounds increases with the boiling point of the alcohol component. According to the X-ray powder diffraction patterns each supramolecular substance has different structure, that may also result in the different thermal stability of the compounds. The molar ratio of DBTA:achiral alcohol samples is 1:1.01–1:1.57 estimated from the corresponding mass losses. The XRD patterns of the prepared two DBTA-phenol materials are different from those of DBTA-achiral alcohol samples. The phenol compounds melt with slow mass losses and give an endothermic peak between 73–83°C but the melting point of the anhydrous DBTA cannot be observed. DBTA:phenol molar ratio is estimated to be 1:0.41 and 1:0.65 for phenol and 2-methylphenol, respectively.
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  • 3
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    Journal of thermal analysis and calorimetry 61 (2000), S. 731-743 
    ISSN: 1572-8943
    Keywords: DSC ; phase transition ; phospholipid ; phthalates ; plasticizers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Phthalic acid esters, and in particular bis-2-(ethylhexyl) phthalate, are common environmental contaminants with long-term toxic and carcinogenic effects that readily dissolve in lipid substances. DSC measurements of hydrated multilamellar dipalmitoyl phosphatidylcholine liposomes in the presence of different amounts of bis-2-(ethylhexyl) phthalate, dioctyl phthalate, dibutyl phthalate (DBP) and diethyl phthalate (DEP) were considered. The effects on the main transition temperature, ΔH, and the shape and width of the transition were studied. A decrease in Tm, without an accompanying decrease in ΔH,and increases in both the asymmetry and the width of the main transition peak were observed. In some cases, the calorimetric curve showed complex peak structures arising from the coexistence of various aggregates of different sizes. This was particularly evident in the liposomes with DEP and DBP contents ranging from 5.0 to 7.5% m/m. For all the considered model systems, the effects were noticeable even in the presence of small amounts of phthalates; in the presence of greater amounts, the overall structure of the bilayer was in some cases strongly modified, with the appearance of new different phases. Since the function of a membrane-associated protein is dependent on the lipid structure, phthalates could modify the function by modifying the membrane structure.
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  • 4
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    Journal of thermal analysis and calorimetry 61 (2000), S. 805-818 
    ISSN: 1572-8943
    Keywords: aluminium ; ARC ; DSC ; kinetics ; nanometric size ; SDT ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of Alex, a nanosized Al powder, were determined using various techniques, including DSC, TG, simultaneous TG-DTA (SDT) and accelerating rate calorimetry (ARC). The results demonstrate that the specific heat capacities of nano and micron size Al powders are similar between 30 and 400°C. Dynamic and isothermal methods were used to determine the kinetic parameters for the oxidation reaction of Alex, which was detected at an onset temperature of 481°C. The results obtained were in good agreement with each other. From the ARC experiments, exotherms were detected near 340 and 260°C for experiments started at ambient pressure and at 0.72 MPa, respectively.
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  • 5
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    Journal of thermal analysis and calorimetry 62 (2000), S. 51-62 
    ISSN: 1572-8943
    Keywords: DSC ; kinetic models ; protein denaturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract New approaches to the analysis of differential scanning calorimetry (DSC) data relating to proteins undergoing irreversible thermal denaturation have been demonstrated. The experimental approaches include obtaining a set of DSC curves at various scanning rates and protein concentrations, and also reheating experiments. The mathematical methods of analysis include construction of a linear anamorphosis and simultaneous fitting of a theoretical expression for the dependence of the excess heat capacity on temperature to a set of experimental DSC curves. Different kinetic models are discussed: the one-step irreversible model, the model including two consecutive irreversible steps, the Lumry and Eyring model with a fast equilibrating first step, and the whole kinetic Lumry and Eyring model.
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  • 6
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    Journal of thermal analysis and calorimetry 62 (2000), S. 715-719 
    ISSN: 1572-8943
    Keywords: computer simulation ; DSC ; non-isothermal crystallization kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The applicability of the kinetic analysis of data obtained by non-isothermal differential scanning calorimetry (DSC) is discussed. The Johnson-Mehl-Avrami (JMA) model was used for the computer simulation of DSC traces subsequently analysed by common methods of kinetic analysis of non-isothermal data. For the temperature-independent kinetic exponent n of the JMA equation, the kinetic analysis was shown to provide correct results, e.g. a correct kinetic model and apparent activation energy. On the other hand, for the temperature-dependent kinetic exponent, there is a great possibility of erroneous determination of the correct kinetic model and apparent activation energy, especially at higher heating rates. Since the temperature dependence of n cannot be determined on the basis of non-isothermal DSC experiments, conclusions must be drawn with appropriate caution.
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  • 7
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    Journal of polymer research 7 (2000), S. 257-266 
    ISSN: 1572-8935
    Keywords: Poly(ether sulfone) ; Epoxy resin ; Physical aging ; 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 , Physics
    Notes: Abstract The physical aging process of 4-4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with various molecular weights of poly(ether sulfone) (PES; Mn = 28,600, 10,600, and 6,137) was studied by DSC. For DGEBA/DDS system blended with a low MW PES-3 (Mn = 6,137), no phase separation of the polymer blend and only one enthalpic relaxation process due to physical aging was observed. Since the high MW PES-1 (Mn = 28,600) had a Tg close to that of fully cured DGEBA/DDS, the fully cured DGEBA/DDS/PES-1 blend had a broader glass transition than a neat DGEBA/DDS system. However, the DSC results showed two enthalpic relaxation processes due to the physical aging of PES-rich and cured epoxy-rich phases as the material was aged at 155 °C (30 °C below Tg). Since the Tgs of PES-1-rich and epoxy-rich phases overlapped with each other, the enthalpic relaxation processes corresponding to each phase coupled to each other in the earlier stage of physical aging. The medium MW PES-2 (Mn = 10,600) has a much lower Tg than that of fully cured DGEBA/DDS, two well separated Tgs were observed for the cured DGEBA/DDS/PES-2 blend, indicating the cured epoxy was immiscible with PES. Aging the polymer blend at 155 °C (24 °C below Tg1 of the PES-2-rich phase and 53 °C below Tg2 of the epoxy-rich phase) produced two well separated relaxation processes due to PES-2-rich and epoxy-rich phases. The experimental results suggested that aging the polymer blend at a suitable temperature would improve the phase separation between PES-1-rich and epoxy-rich phases.
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  • 8
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    Journal of thermal analysis and calorimetry 59 (2000), S. 83-92 
    ISSN: 1572-8943
    Keywords: cationic and photoinitiated polymerization ; DSC ; interfacial mixing ; interpenetrating polymer network (IPN) ; glass transition temperature ; NMR ; quantitative thermal analysis of phases ; reactive epoxy and acrylate systems ; Tg broadening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study NMR and DSC are used to probe the structure, thermal characteristics and morphology of a network formed from a diepoxide/acrylate system. Separate chemistries are employed to polymerize the diepoxide and acrylate components. The cationic polymerization of the diepoxide exhibits excellent selectivity in producing a crosslinked polyether network without affecting the acrylate monomer. Subsequent photoinitiated free-radical polymerization of the acrylate produces a phase separated, semi-interpenetrating polymer network (SIPN).
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  • 9
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    Journal of thermal analysis and calorimetry 59 (2000), S. 93-100 
    ISSN: 1572-8943
    Keywords: catalyst ; cure kinetics ; DSC ; HTPB ; kinetic compensation effect ; urethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of theurethane-forming cure reaction of hydroxyl terminated polybutadiene (HTPB) with isophorone diisocyanate (IPDI) in presence of ferric tris (acetyl acetonate) (FeAA) catalyst was investigated using differential scanning calorimetry (DSC). The Arrhenius activation parameters, viz., activation energy E and pre-exponential factor A were evaluated using the non-isothermal integral Coats-Redfern equation. The cure reaction was catalysed by ferric acetyl acetonate (FeAA), as revealed from the decrease in reaction temperatures and the increase in rate constants; however, the computed activation energy did not show any correlation to the catalyst concentration. The values of E and A for the uncatalysed reaction at different heating rates showed interdependence through kinetic compensation (KC) effect. Using KC correction, E values were normalised for the value of A for the uncatalysed reaction under identical conditions. The normalised E values decreased exponentially with increase in concentration of FeAA, showing high propensity of the HTPB-IPDI system for catalysis.
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  • 10
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    Journal of thermal analysis and calorimetry 59 (2000), S. 157-168 
    ISSN: 1572-8943
    Keywords: cellulose acetate ; DSC ; glass transition ; melting ; polycaprolactone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cellulose acetate-based polycaprolactones (CAPCL's) were synthesized by the polymerization of ε-caprolactone which was initiated by non-substituted OH group in cellulose acetate. The CL/OH (mol mol−1) ratios of the CAPCL's were changed from 2 to 20. Thermal and viscoelastic properties of the CAPCL sheets were studied by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Glass transition, cold crystallization and melting were determined by DSC. Dynamic modules (E'), dynamic loss modules (E'') and tanδ were measured in a temperature range from −150 to 50°C by DMA. Apparent activation energy of a dispersion was calculated from the frequency dependency of E'' peak temperature. It was found that the main chain motion of both CA and PCL is observed in a CL/OH ratio from 0 to 10 mol mol−1. However, when CL/OH ratio exceeds 10 mol mol−1, the crystalline region which is rearranged by the PCL chain association is observed and only the main chain motion of PCL can be detected.
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  • 11
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    Journal of thermal analysis and calorimetry 59 (2000), S. 245-255 
    ISSN: 1572-8943
    Keywords: DSC ; metallocene ; polyethylenes ; SAXS ; synchrotron radiation ; thermal fractionation ; WAXD ; Ziegler-Natta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, the stepwise isothermal crystallization or thermal fractionation of Ziegler—Natta and metallocene based polyethylenes (ZN-PE and m-PE) with two kinds of branch lengths (ethyl and hexyl) and branch compositions were studied using simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The crystal long period and the invariant were determined by SAXS, and the variations of crystal unit cell parameters and the degree of crystallinity were determined by WAXD. The arithmetic mean length (Ln), the weightedmean length (Lw) and the broadness index (Lw/Ln) of the studied polyethylenes were previously determined by DSC. Results from these studies were interpreted using the model of branch exclusion, which affects the ability of the chain-reentry into the crystal phase. Multiple SAXS peaks and step-change in crystallinity change (WAXD) were seen during heating, which corresponded well with the crystal thickness distribution induced by stepwise crystallization. The effects of the heterogeneity of the 1-olefin branch length and the distribution on the crystal long period and the invariant as well as the degree of crystallinity were discussed.
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  • 12
    ISSN: 1572-8943
    Keywords: annealing ; DSC ; self-nucleation ; SSA ; thermal fractionation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new technique to thermally fractionate polymers using DSC has been recently developed in our laboratory. The applications of the novel successive self-nucleation and annealing (SSA) technique to characterize polyolefins with very dissimilar molecular structures are presented as well as the optimum conditions to thermally fractionate any suitable polymer sample with SSA. For ethylene/α-olefin copolymers, the SSA technique can give information on the distribution of short chain branching and lamellar thickness. In the case of functionalized polyolefins, detailed examinations of SSA results can help to establish possible insertion sites of grafted molecules. The application of the technique to characterize crosslinked polyethylene and crystallizable blocks within ABC triblock copolymers is also presented.
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  • 13
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    Journal of thermal analysis and calorimetry 59 (2000), S. 497-508 
    ISSN: 1572-8943
    Keywords: Avrami equation ; crystallization ; dibenzylidene sorbitol ; DSC ; isothermal kinetics ; nucleating agents ; nucleation ; pine crystal ; polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of nucleating agents such as dibenzylidene sorbitol (DBS) (a derivative of sorbitol), pine crystal 1500, sodium and potassium benzoates in commercial grade isotactic polypropylene iPP are studied using differential scanning calorimetry (DSC). Isothermal crystallization kinetics of polypropylene to the alpha phase have been analyzed using Avrami's model. Results indicate that dibenzylidene sorbitol and pine crystal are very effective in increasing the crystallization temperature of the polymer and number of nuclei formed during crystallization.
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  • 14
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    Journal of thermal analysis and calorimetry 59 (2000), S. 559-570 
    ISSN: 1572-8943
    Keywords: adhesive ; composition analysis ; curing kinetics ; DMA ; DSC ; TGA ; thermal cure ; thermoplastic/thermoset blend
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC, TGA and DMA thermal analysis techniques are used to characterize a complex adhesive blend. The chemical and thermomechanical property development shown to follow a two-stage process. Beneficial synergy between these analysis tools is demonstrated in this study.
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  • 15
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    Journal of thermal analysis and calorimetry 59 (2000), S. 23-31 
    ISSN: 1572-8943
    Keywords: DSC ; fullerene ; glass transition ; star-like polystyrene ; segmental dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Segmental dynamics around Tg in the 4- and 6-arm fullerene (C60) core star-like polystyrenes with different preset arm lengths was studied by DSC as compared to that in the linear PS and PS/C60 blend. The ‘anomalies’ in glass transition behavior were found for the stars including both suppression and facilitation of segmental motion, and pronounced dynamic heterogeneity within a transition range. The results are interpreted in terms of breakdown of intermolecular cooperativity of segmental motions and PS-C60 interactions.
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  • 16
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    Journal of thermal analysis and calorimetry 59 (2000), S. 675-680 
    ISSN: 1572-8943
    Keywords: conducting polymer ; DSC ; kinetic analysis ; PPV ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The title polymer was obtained electrochemically by the reduction of 4,4'-bis(dibromomethyl)-2,2'-dimethoxybiphenyl under very smooth conditions. The DSC and TG/DTG curves registered at four different heating rates showed that the polymer is stable in air up to 150°C, where smooth degradation starts. Above 300°C, decomposition is fast and exothermic (ΔH= –323 J g–1) . The activation energy (116±4 kJ mol–1 ) was determined by Ozawa's method.
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  • 17
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    Journal of thermal analysis and calorimetry 59 (2000), S. 721-727 
    ISSN: 1572-8943
    Keywords: ageing ; annealing ; DSC ; polyaniline ; relaxation transition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermally treated films of polyaniline-emeraldine base (PANI-EB) cast from NMP solution were studied by using differential scanning calorimetry. Dependence of the thermodynamic parameters of the relaxation transitions on temperature and annealing period as well as the effect of the thermal history of the samples upon the crosslinking processes were investigated. For the first time DSC analysis of PANI-EB films after prolonged ageing was performed. It was found that relaxation transitions can be registered only for crosslinked PANI-EB. The crosslinking processes proceed both upon short-time heating of the polymer studied over80°C and during long-time storage at room temperature.
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  • 18
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    Journal of thermal analysis and calorimetry 59 (2000), S. 711-719 
    ISSN: 1572-8943
    Keywords: cure ; dicyandiamide ; DSC ; epoxy ; hermetic ; solvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The curing characteristics of adicyandiamide-cured epoxy system under the influence of solvents in a closed environment were studied by means of isothermal differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The DSC analyses revealed that the presence of solvent results in decreases in the curing exotherm, the initial curing rate, the glass transition temperature, the reaction rate and the reaction order of the epoxy resin. The greatest decreases were caused by the solvent with the highest boiling temperature. A change in temperature-dependent curing route due to the heat absorbed during solvent evaporation is responsible for the difference. The FTIR analyses confirmed that the composition of the cured resin is affected by the solvent, the curing temperature and the specimen configuration. As compared with those obtained from open systems, specimens produced in a closed environment have an enhanced curing exotherm, initial curing rate, glass transition temperature, reaction rate and reaction order because of the retention of volatile catalytic by-products.
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  • 19
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    Journal of thermal analysis and calorimetry 61 (2000), S. 579-587 
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; modified epoxy-amine ; epoxy rubber system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this work the curing kinetics behaviour of a rubber modified epoxy amine system is investigated through calorimetric analysis. This study is part of a wider investigation on new epoxy formulations to be used as matrices of composite materials. The aim is to enhance both the processing behaviour and the mechanical properties of the matrix in order to obtain higher performance composites for more demanding applications. The epoxy system is blended with a high molecular mass rubber containing functional groups reactive towards the epoxies. The formation of a rubber/epoxy network can be achieved by means of a 'pre-reaction' between the epoxy monomers and the rubber functional groups, carried out in the presence of a suitable catalyst and before the resin is cured with the amino hardener. In this work the influence of both the rubber and the catalyst on the resin cure kinetics is analysed.
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  • 20
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    Journal of thermal analysis and calorimetry 61 (2000), S. 565-578 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; PK99 ; rigid amorphous fraction ; WAXD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the whole range between the glass transition temperature (T g) and the melting temperature (T m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy. The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer, and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques. The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions. Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does not relax at T g.
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  • 21
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    Journal of thermal analysis and calorimetry 61 (2000), S. 607-614 
    ISSN: 1572-8943
    Keywords: composted materials ; DSC ; thermal characterization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was applied to the study of material composted from sawdust, used coffee, farmyard manure and the organic fraction of domestic solid waste. Composting trials were carried out in Morocco and samples were collected after different periods of composting. The results obtained provided evidence that sawdust substrate is not a suitable source for composting due to the high content of lignin; samples from used coffee are characterized by a degree of aromaticity that is lower and a functional group heterogeneity that is higher than those of organic wastes from manure and the organic fraction of domestic wastes. The latter organic waste substrates appear to be easily degraded and humified and to give DSC curves that at the end of composting are vary close to those of native soil humic acids.
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  • 22
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    Journal of thermal analysis and calorimetry 61 (2000), S. 711-718 
    ISSN: 1572-8943
    Keywords: DSC ; PEG ; T-CR-T
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified isoconversional method is applied to perform the kinetic analysis of non-isothermal processes. The solidification process of a polyethylene glycol with a mean molecular of 4000 (PEG 4000) was here analyzed. It was stated that the Avrami model provides a good description of the solidification process. Temperature-cooling rate-transformation diagrams were constructed and there was a good agreement between experimental data and the calculated T-CR-T curves. Moreover, morphological qualitative analysis has been performed by means of scanning electron microscopy.
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  • 23
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    Journal of thermal analysis and calorimetry 61 (2000), S. 771-778 
    ISSN: 1572-8943
    Keywords: burning rate ; DATH ; DSC ; TG ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition characteristics of1,7-diazido-2,4,6-trinitrazaheptane (DATH) and multi-component systems containing DATH were studied by using DSC, TG and DTG techniques. Three –NO2 groups in the DATH molecule break away first from the main chain when DATH is heated up to 200°C. Following this process, the azido groups and the residual molecule decompose rapidly to release a great deal of heat within a short time. In the multi-component systems, DATH undergoes a strong interaction with the binder of the double-base propellant and a weak interaction with RDX. The burning rates of the two propellants were determined by using a Crawford bomb. The results showed that the burning rate rises by about 19–66% when 23.5%DATH is substituted for RDX in a minimum smoke propellant. Meanwhile, the N2 level in the combustion gases is enhanced, which is valuable for a reduction of the signal level of the solid propellant.
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  • 24
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    Journal of thermal analysis and calorimetry 62 (2000), S. 177-186 
    ISSN: 1572-8943
    Keywords: binary phase diagram ; DSC ; enthalpic method ; eutectic composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We construct with a differential scanning calorimeter (DSC) a phase diagram for the ethylene carbonate (EC)-dimethyl carbonate (DMC) binary system for its liquid-solid phase equilibria. We determine the eutectic composition of the binary system using an enthalpic method that we devised based on the composition dependence of the enthalpy of solidus melting, with highly consistent results. We also discuss the merits and limitations of this enthalpic method.
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  • 25
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    Journal of thermal analysis and calorimetry 63 (2000), S. 397-413 
    ISSN: 1572-8943
    Keywords: Cu–5 at%Zn ; DSC ; F.C.C. (Face Centered Cubic) ; kinetics ; short-range-order ; solute-vacancy complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value of 89.5±0.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
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  • 26
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    Journal of thermal analysis and calorimetry 61 (2000), S. 551-564 
    ISSN: 1572-8943
    Keywords: amphiphile oligomers ; DSC ; thermo-reversible gelation ; water states
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Symmetrical block oligomers having in common terminal groups (A) consisting of polyoxyethylene (20) stearyl ether are materials of pharmaceutical and cosmetic interest. Phase properties of their aqueous systems and amounts of water typologies were determined by differential scanning calorimetry (DSC). The overall amount of water absorbed by each investigated oligomer was not significantly influenced by the type of central bridging block, whereas the amount of free water decreased with increasing oligomer concentration in the gel. A number of 60–70 moles of water was found to solvate the oligomer chain. The oligomers studied presented a thermo-reversible gelation with and precipitation under determined temperature conditions.
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  • 27
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    Journal of thermal analysis and calorimetry 61 (2000), S. 889-896 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; Fe40Ni40P14B6 glassy alloy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this paper a DSC study is reported of the behavior of Fe40Ni40P14B6 alloy produced by rapid quenching. The experimental results show that relaxation phenomena can be studied directly from the DSC curves. From these experiments, the spread of the E c values in the literature is attributed to differences in the quenching rates and the presence of variable number of quenched-in nuclei. It is also shown that the microstructure (number and size of crystals) of the non-isothermally devitrified metallic alloy changes with the heating rate; this is a consequence of the shift of crystallization temperatures and, therefore, of the change of the ratio of nucleation and crystal growth rates.
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  • 28
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    Journal of thermal analysis and calorimetry 62 (2000), S. 163-171 
    ISSN: 1572-8943
    Keywords: alkylcyclohexanes ; binary phase diagrams ; DSC ; metastable solutions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was used to construct phase diagrams of binary mixtures of alkylcyclohexanes and to characterize metastable phases formed in the binary mixtures. The experimentally measured liquidus curves were compared to the liquidus curves calculated using ideal solution theory. The measured phase diagrams of pentadecylcyclohexane/nonadecylcyclohexane and octadecylcyclohexane/nonadecylcyclohexane binary mixtures are consistent with theoretical phase diagrams constructed based on the assumption that these mixtures form eutectic systems. It was also observed that a metastable phase formed in some binary mixtures of pentadecylcyclohexane/nonadecylcyclohexane under fast cooling conditions. It is hypothesized that this metastable phase recrystallizes into the eutectic phase upon heating.
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  • 29
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    Journal of thermal analysis and calorimetry 59 (2000), S. 999-1015 
    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Some DSC calorimeters such as the model Setaram DSC 111 allow the user to set the parameters of temperature programming. Default values furnished by the constructor are often used, but it is very interesting to study the thermal behaviour of the regulation of the calorimeter under different conditions and kinds of set point temperatures. For this research we have developed in C a set of softwares in order to show the behaviour of the proportional integral derivative (PID) controller of the DSC. It can help the user to choose correct values for P, I and D parameters according to the kind of experiment conducted. The software allows studies for extra parameters such as the sampling rate of the computerized PID controller or the determination of filtering of the correction.
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  • 30
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    Journal of thermal analysis and calorimetry 59 (2000), S. 1023-1027 
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; fibers ; polybenzimidazole ; secondary transitions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Fibers drawn form poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI) were studied by DSC and DMA. PBI is a high temperature polymer T g is between 387 and450°C depending on the measurement technique used. The as-spun fiber is free of orientation. The oriented fiber exhibits considerable dependence on whether the DSC measurements were carried out in free-to-shrink or fixed-length modes. The β-relaxation is at 290°C, and was associated with loss of water. The γ-transition at 20°C was not identified, while theδ-transition at –90°C seems to correspond to rotation of the m-phenylene ring.
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  • 31
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    Journal of thermal analysis and calorimetry 63 (2000), S. 339-344 
    ISSN: 1572-8943
    Keywords: amphiphile ; DSC ; D-xylose ; derivatives ; lyotropy ; thermotropy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We studied the phase transition temperatures of a series of amphiphilic D-xylopyranose and D-xylofuranose derivatives in which the lipophilic part is an alkyl chain R (n-CnH2n+1), regiospecifically linked to D-xylose, at different positions, by Z which is an atom or a functional group (O, S, O–(CH2)3–S). The alkyl chain was moved from the C-1 to the C-5 position in the xylose moiety, thereby allowing us to compare directly the phase transition temperatures of the individual materials. These compounds give thermotropic and/or lyotropic liquid crystals. In some cases, we also observed solid–solid phase transitions.
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  • 32
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    Journal of thermal analysis and calorimetry 60 (2000), S. 25-33 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; thermal decomposition ; 2,4,6-trinitrotoluene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An autocatalytic model involving the limited solubility of volatile catalytic products was applied to the thermal decomposition of 2,4,6-trinitrotoluene. The critical supersaturation of the thermal decomposition products with the catalytic properties was higher at a low heating rate. Decrease of the sample mass led to an increased critical supersaturation of the decomposition products. This is probably a result of the greater contribution of products adsorption on the aluminium pan surface. It is presumed that the differences observed in the rate constant are connected with the uncontrolled critical supersaturation of the volatile thermal decomposition products.
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  • 33
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    Journal of thermal analysis and calorimetry 60 (2000), S. 45-52 
    ISSN: 1572-8943
    Keywords: compatibilization ; DMTA ; DSC ; polyamide 6/thermoplastic polyurethane blends
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Blends obtained from polyamide 6 and a thermoplastic polyurethane compatibilized by diblock copolyurethaneamides were investigated by means of DMTA and DSC. The blends were prepared by compounding in a Brabender mixer. The compatibilizer affected the glass transition temperature of the amorphous phase of the blends. The non-isothermal crystallization temperature of the polyamide phase was lowered in the presence of the polyurethane and the copolyurethaneamide.
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  • 34
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    Journal of thermal analysis and calorimetry 60 (2000), S. 117-121 
    ISSN: 1572-8943
    Keywords: biopol/polyamide 6 blends ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Blends obtained from Biopol D600G and polyamide 6 reveal in DSC investigations multiphase structure with a distinct crystalline polyamide 6 phase. Due to rapid crystallization of the polyamide 6 the crystallization of the Biopol D600G is retarded. The grade of crystallization of Biopol D600G is lower in the blends than in the pure state, as calculated from the melting enthalpies. Crystallization of polyamide 6 in the blends is faster and results in increasing of the grade of crystallization of polyamide 6 phase comparing to the unblended component.
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  • 35
    ISSN: 1572-8943
    Keywords: cyanazine ; DSC ; kinetics ; thermal stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyanazine was taken as an example for investigations under the influence of different conditions on thermal decomposition of triazine herbicides. DSC measurements were carried out under atmospheric pressure and hermetically closed, under pressure 1.3 kPa. The influence of the pressure on the constant reaction rate of decomposition of cyanazine was discussed. It was also proved that the predicted reaction constant rates from isothermal and non-isothermal measurements are consistent.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 111-116 
    ISSN: 1572-8943
    Keywords: DMTA ; DSC ; HMDI ; mesogenic chain extender ; polyurethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract New polyurethanes with mesogenic units in the main chain due to the use of a liquid crystalline chain extender were synthesized from 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI)using diisocyanates of different trans, trans isomer content, a low molecular diol4,4'-bis(6-hydroxyhexoxy)biphenyl (BHHBP) and a high molecular poly(hexyleneadipate)diol (PHA). The growth of trans, trans isomer content in HMDI used to syntheses of PU induces monotonic growth of melting point, rectilinear growth of crystallization temperatures and the growth of crystallization enthalpy, both for hard segment polyurethanes and block polyurethanes. The increase of trans, trans isomer content in HMDI increases also glass transition temperatures and dynamic storage modulus of the polyurethanes.
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  • 37
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    Journal of thermal analysis and calorimetry 60 (2000), S. 163-166 
    ISSN: 1572-8943
    Keywords: comparison ; decomposition ; DSC ; enthalpy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The comparison of thermal and calorimetric properties of metal derivatives of 6-aminopicolinic acid (APH) is presented. The salts and complexes of APH with Cr(III), Cd(II), Cu(II), Ni(II), Pb(II), Co(II)and Ag(I) have been studied by TG-DTA and DSC methods up to 1200°C in a nitrogen atmosphere. Decomposition processes are proposed. The decarboxylation, deamination and carbonation of the organic fragments of molecules take place. The compounds decompose to metal or to metal oxides. The values of the transition enthalpy were determinated.
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  • 38
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; physical aging ; TGDDM epoxy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The physical aging of a system containing tetraglycidyl-4-4′-diaminodiphenylmethane (TGDDM), with a multifunctional novolac glycidyl ether resin hardened by 4,4′-diaminodiphenylsulphone (DDS) has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Samples fully cured were aged at temperatures between 200 and 250°C, during periods of time from 1 to a maximum of 336 h. Furthermore, the dynamic mechanical relaxation behaviour annealed at temperature of 220°C, was studied, aging during 24 and 168 h. The effect of the enthalpy relaxation during DSC heating scan is shown by the presence of an endothermic peak whose position and intensity depends on the aging conditions, both temperature and time. DSC studies suggest that enthalpy relaxation increases gradually with aging time to a limiting value for each temperature where structural equilibrium is reached. DMA results show that the effect of aging is to cause chain stiffening and a decrease in the height of the peak value of the loss factor.
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  • 39
    ISSN: 1572-8943
    Keywords: 2-benzylamino-butanol ; DSC ; mandelic acid ; melting phase diagram ; optical resolution
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The optical resolution of racemic mandelic acid (I) by S-2-benzylamino-butanol (II) was performed in water, ethyl acetate, and water saturated ethyl acetate. It was found that the efficiency of the resolution is three times higher in water saturated ethyl acetate than in either water or ethyl acetate. The salt mixtures produced during the resolutions and the pure diastereoisomeric salts were analyzed by TG, DSC and X-ray powder diffraction measurements. The R-(-)-I×S-(+)-II salt has the higher melting point and heat of fusion value which indicates that this is the more stable salt. Though the general assumption is that diastereoisomeric salt pairs of successful optical resolutions form eutectic systems, the R-mandelic acid-S-2-benzylamino-butanol and the S-mandelic acid-S-2-benzylamino-butanol system was found to behave in a different way. Melting did not start at or near the estimated eutectic temperature. The difference can be explained either by miscibility in the solid phase (solid solution) or by a blocked interaction between the crystals of the two solid salts. This unusual behaviour of the salt pair should be responsible for the unusual difference in the efficiency of the resolutions performed in different solvents
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  • 40
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    Journal of thermal analysis and calorimetry 60 (2000), S. 535-539 
    ISSN: 1572-8943
    Keywords: DSC ; ferrite ; Mössbauer spectra ; TG ; thermal decomposition ; zinc ferriformate
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis of zinc hexa(formato)ferrate(III) decahydrate, Zn3 [Fe(HCOO)6]2 10H2O has been investigated up to 800°C in static air atmosphere employing TG, DSC, XRD, IR, ESR and Mössbauer spectroscopic techniques. After dehydration at 160°C, the anhydrous complex decomposes into α-Fe2 O3 and zinc carbonate in successive stages. Subsequently the cations remix to yield fine particles of zinc ferrite, ZnFe2 O4 , as a result of solid state reaction between α-Fe2 O3 and zinc carbonate at a temperature (600°C) much lower than for ceramic method.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 595-604 
    ISSN: 1572-8943
    Keywords: crystal structure ; DSC ; oxides ; X-ray diffraction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of TiO2 prepared by hydrolysis method was presented. Thermodynamics and kinetics of anatase crystallization reaction were investigated. Differential method of kinetic data evaluation in non-isothermal conditions according toKissinger, Ozawa and Kazeev-Yerofeev was applied. Starting, crystallized and thermally treated powders were determined using X-ray powder diffraction analysis. The characteristic parameters (the activation energy, constant rate and formal kinetic order of reaction) of TiO2 formation were calculated using DSC data.
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  • 42
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    Journal of thermal analysis and calorimetry 60 (2000), S. 683-689 
    ISSN: 1572-8943
    Keywords: DSC ; heat capacity ; mixed oxide TiO2-RuO2 ; RuO2 ; TiO2
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    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC was used for heat capacity measurements of pure RuO2 in the temperature range from 300 to 1170 K of solid solutions corresponding to the compositions of (Ti1−x Rux )O2 (x ≤0.15 and x ≥0.85) and in the temperature range from 300 to 1550 K of pure TiO2. The analysis of experimental data obtained within ±2% of accuracy has shown that the characteristic temperatures representing the harmonic lattice vibrations do not strongly depend on the chemical composition x . It was demonstrated that non-harmonic heat capacity is strongly correlated to x. The existence of additional excess heat capacity was observed with the mixed oxide solid solution samples of low Ru content and explained by the defect formation model.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 333-343 
    ISSN: 1572-8943
    Keywords: base line ; DSC ; kinetics ; modeling ; thermodynamics ; TMDSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.
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  • 44
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    Journal of thermal analysis and calorimetry 60 (2000), S. 357-369 
    ISSN: 1572-8943
    Keywords: blends of polyamides ; copolyamides ; crystallization ; DSC ; melting point ; structure
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The DSC method was used to obtain more information on changes of thermal properties connected with different comonomers bound in the (co)polymer chains. The copolyamides propered were block ones which were less crystalline and compatible with poly-ε-caprolactam. The results have confirmed the crystalline nature of polyamides and copolyamides.
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  • 45
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    Journal of thermal analysis and calorimetry 60 (2000), S. 345-355 
    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Some DSC calorimeters, such as the model DSC 111, built by the society Setaram, allow the user to set the temperature programming parameters. Usually default values furnished by the constructor are often used, but it is very interesting to study the thermal behaviour of the regulation of the calorimeter under different conditions and with different kinds of set point temperatures. For this research, we have developed in C language a set of software in order to demonstrate the behaviour of the (proportional integral derivative) PID controller of the DSC. It can help the user to choose correct values for P, I and D parameters according to the kind of experiment conducted. The software allows studies of extra parameters, such as the sampling rate of the computerized PID controller or the determination of filtering of the correction.
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  • 46
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    Journal of thermal analysis and calorimetry 60 (2000), S. 917-926 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; KDNBF ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract KDNBF (potassium 4,6-dinitrobenzofuroxan) has been used as a primer explosive in igniters and detonators for many years. Considerable information about the sensitivity of KDNBF to various stimuli, such as impact, friction, shock and electrostatic charge, is known. However, the thermal sensitivity of KDNBF has been relatively unexplored. Hence, there is very little information available concerning the fundamental thermal properties of KDNBF. Therefore, as part of an extensive thermal hazard assessment, DSC, TG, accelerating rate calorimetry (ARC) and heat flux calorimetry (HFC) measurements have been undertaken on KDNBF. The results demonstrate that KDNBF decomposes via a multi-step exothermic process directly from the solid state. The decomposition process does not appear to depend on the nature of the atmosphere, except in the final stage of the TG decomposition in air, where remaining carbonaceous material is converted to CO2. The first stage of the decomposition is sufficiently rapid that ignition occurs if too large a sample is used. Dynamic and isothermal methods were used to obtain the kinetic parameters and a range of activation energies were obtained, depending on the experimental conditions. The kinetic results have been analyzed in terms of various solid state decomposition models.
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  • 47
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    Journal of thermal analysis and calorimetry 61 (2000), S. 75-89 
    ISSN: 1572-8943
    Keywords: DSC ; Fourier transformation ; heat capacity ; sawtooth-modulation ; TMDSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The determination of heat capacity data with sawtooth-type, temperature-modulated differential scanning calorimetry is analyzed using the Mettler-Toledo 820 ADSC™temperature-modulated differential scanning calorimeter (TMDSC). Heat capacities were calculated via the amplitudes of the first and higher harmonics of the Fourier series of the heat flow and heating rates. At modulation periods lower than about 150 s, the heat capacity deviates increasingly to smaller values and requires a calibration as function of frequency. An earlier derived correction function which was applied to the sample temperature-controlled power compensation calorimeter enables an empirical correction down to modulation periods of about 20 s. The correction function is determined by analysis of the higher harmonics of the Fourier transform from a single measurement of sufficient long modulation period. The correction function reveals that the time constant of the instrument is about 5 s rad−1 when a standard aluminum pan is used. The influence of pan type and sample mass on the time constant is determined, the correction for the asymmetry of the system is described, and the effect of smoothing of the modulated heat flow rate data is discussed.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 91-98 
    ISSN: 1572-8943
    Keywords: DSC ; heat flow calibration ; temperature calibration
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermoanalytical instruments are extensively used in R&D as well as in industrial quality control. A quantitative analysis of the data of a thermoanalytical measurement requires a careful calibration of the instrument. In differential scanning calorimetry (DSC) the quantities that have to be calibrated are the temperature and the heat flow. These two quantities are usually calibrated by evaluating melting or solid-solid transitions of some reference materials with well known transition enthalpies and temperatures. In this contribution we investigate temperature and heat flow calibration in the temperature range between −100 and 160°C. We included 9 different samples for the analysis and established some general rules for the calibration process. As a result we found that with a well calibrated instrument the heat flow can be measured with 90% confidence to about ± 3% accuracy in this temperature range. With respect to temperature calibration we find that accuracies of ±0.8°C (90% confidence) may be expected. These values represent general accuracy limitations of DSC’s due to varying heat transfer conditions within the samples.
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  • 49
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    Journal of thermal analysis and calorimetry 61 (2000), S. 363-368 
    ISSN: 1572-8943
    Keywords: DSC ; glycosylated ribonuclease ; thermodynamic stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermodynamic stability of pancreatic ribonuclease B (RNase B), which possesses identical protein structure of pancreatic ribonuclease A (RNase A), but differs by the presence of a carbohydrate chain attached to Asn 34, was studied by means of differential scanning calorimetry (DSC) at different pH conditions. The comparison between the two proteins has shown a little but significant stabilization of RNase B with respect to the unglycosylated one at pH values higher than 7.0. The thermodynamic analysis reveals the carbohydrate moiety to have a small stabilization effect of 3 kJ mol–1 at pH 8.0 and 63°C on the protein.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 341-350 
    ISSN: 1572-8943
    Keywords: DSC ; polymorphism ; X-ray
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the hydrocarbon chain length in the formation of interdigitated and non-interdigitated bilayers in n -alkylammonium chlorides has been investigated for chain lengths varying between 8 and 14 carbon atoms. The formation of non-interdigitated bilayers during crystallization from solution is favoured for shorter chains whilst the interdigitated structure is predominant for larger chains. The thermodynamic parameters of the solid to solid phase transitions in the non-interdigitated samples depend on chain length showing the odd-even alternation that characterized homologous series in n -paraffins. The solid to liquid crystal phase transition temperatures and enthalpies show a linear dependence with the chain length.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 369-376 
    ISSN: 1572-8943
    Keywords: diclofenac ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry was applied to the determination of diclofenac in three 'Voltaren' formulas. The pharmaceutical products (soluble tablets, suppositories and vials) were selected in order to show that calorimetric analysis is an easy technique to perform and can be competitive with other conventional methods. In the tablets diclofenac (DH) was determined, without any pre-treatment, from the area of the endothermic peak which occurs at about 180°C in the DSC curve obtained in N2 atmosphere. In the analysis of the suppositories and vials, nitrilotriacetic acid (NTA) was added to transform the diclofenac sodium salt (DS) into the thermally active form (DH). In both cases, it was necessary to eliminate the interference of excipient by cyclohexane extraction (suppositories) or by a multistep program for the DSC run (vials). The accuracy of the results and the simplicity of the procedure justify the important role of DSC in the analysis of these drugs and certainly of several other commercial products.
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  • 52
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    Journal of thermal analysis and calorimetry 61 (2000), S. 389-396 
    ISSN: 1572-8943
    Keywords: compost ; DSC ; organic matter ; TG ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The possibility to use thermal analysis for a quick characterisation of chemical changes in the organic matter of composted materials was tested. Nine samples were taken at progressive stages of maturation from the same trench of a fully automated composting plant. DSC and TG were simultaneously performed in static air conditions on whole ground composts. Progressive stages in the composting process yielded samples whose DSC traces revealed appreciable modifications in thermal patterns that agreed well with quantitative data obtained from TG measurements. The ratio between the mass losses associated with the two main exothermic reactions (R1) showed a good sensitivity in detecting the changes in the level of stabilisation during the composting process. Thermal methods seem to be a valid comparative method in evaluating the level of bio-transformation of materials during a composting process.
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  • 53
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    Journal of thermal analysis and calorimetry 61 (2000), S. 411-423 
    ISSN: 1572-8943
    Keywords: bread baking ; DSC ; starch gelatinization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Starch gelatinization in wheat flour dough of various moisture contents was quantitatively evaluated by means of DSC. The experimental records were worked out in the form of excess heat capacity vs. T traces which were deconvoluted to single out the contribution of starch gelatinization from that of the decomposition of amylose-lipid complexes. The quantitative procedure used put into evidence that a third endothermic process would take place in the dough with a poor moisture content. DSC runs carried out with sealed pans (i.e., at constant moisture level) and open pans (from which some water was free to evaporate) allow simulation of two extreme conditions of a real baking process, namely that relevant to the central core and to superficial layer of a dough loaf, respectively. The extent of starch gelatinization occurred in these conditions was quantitatively assessed. These data were collected at various heating rates and used to define temperature-time-transformation(TTT) diagrams which are useful tools to predict the progress of baking for any given thermal history of the system.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 451-459 
    ISSN: 1572-8943
    Keywords: DSC ; gelatin films ; high angle X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry and high angle X-ray diffraction analyses were performed on gelatin films, air dried at different values of constant elongation, crosslinked with glutaraldehyde and examined at constant relative humidity of 75%. Drawing induces a preferential orientation of the chain segments of gelatin parallel to the stretching direction,and a linear increase of the renaturation level, calculated as the ratio between the denaturationenthalpy of gelatin films and that of tendon collagen. The comparison with the results previously obtained on the mechanical properties of the films, puts into evidence the different contributions of orientation and renaturation on the improvement of the mechanical parameters on drawing. The results offer important information on the role of glutaraldehyde (GTA) crosslinking on the stability of collagenous materials.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 797-807 
    ISSN: 1572-8943
    Keywords: dimenhydrinate ; DSC ; film coating ; HPMC ; thermal conductivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Dimenhydrinate is a heat-sensitive antihistamine with a low melting point. The heat-sensitive feature is of importance if direct compression is used. Direct measurement of the heat originating in the texture of tablets during compression is very difficult. Thermoanalytical methods were used as indirect methods to describe the changes in material properties at high temperature: differential scanning calorimetry, thermomicroscopy and thermogravimetric analysis. Film coating method is widely used in pharmaceutical technology. A fluidized bed apparatus was applied to coat the crystals. The coating film forming agent was hydroxy-propyl-methylcellulose (HPMC), which is a gastric-soluble polymer. Thermoanalytical measurements reveal that dimenhydrinate crystals are sensitive to heat. Film coating method does not alter the shape of the DSC curve of dimenhydrinate, but increases the melting point. The presence of a macromolecular film reduces the thermal conductivity, because it separates the particles.
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  • 56
    ISSN: 1572-9001
    Keywords: Dynamic NMR ; 15N NMR ; 13C NMR ; DSC ; tautomerism ; melting point
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The behavior of neat 3(5)-methylpyrazole has been studied at low temperatures by DSC and by NMR (13C and 15N). The main conclusion is that the supercooled liquid is a mixture of four trimers formed by 3-methyl and 5-methyl tautomers.
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  • 57
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 837-846 
    ISSN: 1572-8943
    Keywords: DSC ; γ-irradiation ; laser Raman ; microelectrophoresis ; XRD ; zeta-potential ; zirconium hydroxide ; ZrO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Zirconium hydroxide particles produced by rapid precipitation at pH 10.4, 7 or 2 were subjected toγ-irradiation up to a final dose of 20 MGy. The effects of the γ-irradiation were examined by X-ray powder diffraction, laser Raman spectroscopy, differential scanning calorimetry and microelectrophoretic measurements. It was found that γ-irradiation had no influence on the behaviour of zirconium hydroxide during calcination and subsequent cooling. The results of microelectrophoretic measurements showed that γ-irradiation influences the surface properties of zirconium hydroxide as a function of the precipitation pH. Zirconium hydroxide precipitated at pH 2 proved to be the most susceptible to γ-irradiation, while the sameγ-irradiation had very little (if any) effect on the surface properties of zirconium hydroxide precipitated at pH 10.5. After γ-irradiation, the electrophoretic mobility of zirconium hydroxide precipitated at pH 2 was increased at both low and high pH, thereby indicating an increase in its adsorption capacity. The analogy observed between the pH-dependence of the effects of γ-irradiation on the electrokinetic behaviour of zirconium hydroxide and the influence of ball-milling on the thermal behaviour of zirconium hydroxide [8] suggested that the susceptibility of amorphous zirconium hydroxide increases with decrease of the precipitation pH.
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  • 58
    ISSN: 1573-4978
    Keywords: chromatin ; DNA ; DSC ; thermal denaturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The thermal denaturation of calf thymus total chromatin and of fractions enriched in heterochromatin or euchromatin, has been investigated by differential scanning calorimetry and compared to that of calf thymus DNA and DNA-histone complexes. In our experimental conditions, chromatin melts in three thermal transitions: the main one, assigned to separation of the DNA double helix, occurs at 83 °C, while the other two occur at 63 °C and 74 °C. The data show that: (a) the transition enthalpy for denaturation of DNA in the total chromatin and in DNA-histone complexes is nearly the same as that of DNA in solution; (b) the transition at 63 °C is present in the thermogram of the heterocromatin enriched fraction, while it is completely absent in that of the euchromatin enriched one. The results suggest that this transition can be attributed to the higher order structures of heterochromatin.
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