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  • kinetics  (77)
  • DSC  (58)
  • climate change  (49)
  • Springer  (179)
  • MDPI Publishing
  • 2000-2004  (179)
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  • Springer  (179)
  • MDPI Publishing
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  • 1
    Electronic Resource
    Electronic Resource
    Why Does the Linear Driving Force Model for Adsorption Kinetics Work? (2000)
    Springer
    Adsorption 6 (2000), S. 137-147 
    Details
    ISSN: 1572-8757
    Keywords: adsorption ; kinetics ; linear driving force model ; process design
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Linear Driving Force (LDF) model for gas adsorption kinetics is frequently and successfully used for analysis of adsorption column dynamic data and for adsorptive process designs because it is simple, analytic, and physically consistent. Yet, there is a substantial difference in the characteristics of isothermal batch uptake curves on adsorbent particles by the LDF and the more rigorous Fickian Diffusion (FD) model. It is demonstrated by using simple model systems that the characteristics of the adsorption kinetics at the single pore or the adsorbent particle level are lost in (a) evaluating overall uptake on a heterogeneous porous solid, (b) calculating breakthrough curves from a packed adsorbent column, and (c) establishing the efficiency of separation by an adsorptive process due to repeated averaging of the base kinetic property. That is why the LDF model works in practice.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008965317983
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  • 2
    Electronic Resource
    Electronic Resource
    Effect of K, Cs and Ba on the kinetics of NH3 synthesis over carbon-based ruthenium catalysts (2000)
    Springer
    Catalysis letters 68 (2000), S. 163-168 
    Details
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; kinetics ; ruthenium catalysts ; promotional effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of NH3 synthesis over carbon-based ruthenium catalysts promoted with barium or alkali was studied. Both the ammonia partial pressure dependencies of the reaction rates (T = 400°C, p = 63 bar, H2 : N2 = 3 : 1) and the pressure variations of the activity (T = 370°C, p= 4–63 bar, H2 : NN2 = 3 : 1) were found to be different for Ba and for the alkali (K, Cs). Ba–Ru/C proved to be more sensitive to the NH3 content and to the total pressure. The rate of synthesis over the alkali-promoted catalysts is, in turn, much stronger influenced by the ruthenium dispersion. TOFs of NH3 synthesis for the promoted samples at 370°C and 4 bar (Ba 0.085 1/s, Cs 0.05 1/s, K 0.035 1/s) are significantly higher than that for the Ru(0001) basal plane (0.0085 1/s results from the literature data at 370°C, 2 bar). The most active Ru/C samples (Ba or Cs) exceed significantly the fused iron catalyst, especially at high conversions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019024629261
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  • 3
    Electronic Resource
    Electronic Resource
    Physical aging of epoxy resin blended with poly(ether sulfone): Effect of poly(ether sulfone) molecular weight (2000)
    Springer
    Journal of polymer research 7 (2000), S. 257-266 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s10965-006-0128-6
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  • 4
    Electronic Resource
    Electronic Resource
    Mechanism of the hydrodenitrogenation of o-toluidine and methylcyclohexylamine over NiMo/γ-Al2O3 (2000)
    Springer
    Topics in catalysis 11-12 (2000), S. 327-333 
    Details
    ISSN: 1572-9028
    Keywords: hydrodenitrogenation ; toluidine ; methylcyclohexylamine ; kinetics ; nickel-promoted molybdenum sulphide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The hydrodenitrogenation (HDN) of o-toluidine and its reaction intermediates was studied over a NiMo/γ-Al2O3 catalyst. The kinetics of the HDN of methylcyclohexylamine and of the hydrogenation of cyclohexene were also studied. Hydrogenation of o-toluidine alone produces methylcyclohexene and methylcyclohexane. When a sufficient quantity of cyclohexene is added during the HDN of toluidine, methylcyclohexylamine, the first intermediate in the hydrogenation of toluidine, becomes detectable. Because of its strong adsorption constant and high rate constant for reacting further to methylcyclohexene and methylcyclohexane, methylcyclohexylamine is not observed in the HDN of toluidine. Adding cyclohexene decreases the adsorption of methylcyclohexylamine, thus enabling its detection. The rate and adsorption constants of methylcyclohexylamine and cyclohexene in the HDN of methylcyclohexylamine were calculated by fitting the kinetic data to a Langmuir–Hinshelwood equation. A two-site model was used to describe the surface reactions, with one site for the methylcyclohexylamine reactions and the other for the cyclohexene reaction.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1027208200169
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  • 5
    Electronic Resource
    Electronic Resource
    Static and Kinetic Studies on the Adsorption Behavior of Sulfadiazene (2000)
    Springer
    Adsorption 6 (2000), S. 349-357 
    Details
    ISSN: 1572-8757
    Keywords: sulfadiazene ; adsorption ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10−3 mol cm−3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl−, SO2− 4 and PO3− 4 (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026517117239
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  • 6
    Electronic Resource
    Electronic Resource
    NO reduction over La2O3 using methanol (2000)
    Springer
    Catalysis letters 64 (2000), S. 65-75 
    Details
    ISSN: 1572-879X
    Keywords: NO reduction ; CH3OH ; La2O3 ; methyl nitrite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Nitric oxide (NO) reduction by methanol was studied over La2O3 in the presence and absence of oxygen. In the absence of O2, CH3OH reduced NO to both N2O and N2, with selectivity to dinitrogen formation decreasing from around 85% at 623 K to 50–70% at 723 K. With 1% O2 in the feed, rates were 4–8 times higher, but the selectivity to N2 dropped from 50% at 623 K to 10% at 723 K. The specific activities with La2O3 for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of 35 μmol NO/s m2 was obtained whereas that for methanol was 600 μmol NO/s m2. The Arrhenius plots were linear under differential reaction conditions, and the apparent activation energy was consistently near 14 kcal/mol with CH3OH. Linear partial pressure dependencies based on a power rate law were obtained and showed a near‐zero order in CH3OH and a near‐first order in H2. In the absence of O2, a Langmuir–Hinshelwood type model assuming a surface reaction between adsorbed CH3OH and adsorbed NO as the slow step satisfactorily fitted the data, and the model invoking two types of sites provided the best fit and gave thermodynamically consistent rate constants. In the presence of O2 a homogeneous gas‐phase reaction between O2, NO, and CH3OH occurred to yield methyl nitrite. This reaction converted more than 30% of the methanol at 300 K and continued to occur up to temperatures where methanol was fully oxidized. Quantitative kinetic studies of the heterogeneous reaction with O2 present were significantly complicated by this homogeneous reaction.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019036431195
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  • 7
    Electronic Resource
    Electronic Resource
    Oxidation of dicyclopentadiene catalyzed by palladium(II) acetate and p-benzoquinone in the presence of inorganic acid (2000)
    Springer
    Catalysis letters 69 (2000), S. 103-107 
    Details
    ISSN: 1572-879X
    Keywords: dicyclopentadiene ; Wacker oxidation ; Pd(AcO)2 ; benzoquinone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of dicyclopentadiene catalyzed by palladium(II) acetate and benzoquinone in the presence of perchloric acid was studied. Tricyclodecenone in high selectivity (85–98%) at a conversion of dicyclopentadiene up to 76% was obtained. The kinetic model assumed the significant inhibition complexation between dicyclopentadiene and tricyclodecenone with the catalytic species.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019053402854
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  • 8
    Electronic Resource
    Electronic Resource
    Late-glacial and early-Holocene Trichoptera (Insecta) from Kråkenes Lake, western Norway (2000)
    Springer
    Journal of paleolimnology 23 (2000), S. 49-56 
    Details
    ISSN: 1573-0417
    Keywords: Trichoptera ; caddisflies ; late glacial ; Allerød ; Younger Dryas ; early Holocene ; Kråkenes ; palaeolimnology ; climate change
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Fossil Trichoptera (caddisfly) remains have been identified and quantitatively recorded in the late-glacial and early-Holocene sediments from Kråkenes Lake, western Norway. The sediment sequence was deposited between 12,300 and 8850 14C BP, covering the Allerød, Younger Dryas, and early-Holocene periods. The first Trichoptera were recorded at 12,000 14C BP, and during the Allerod a diverse assemblage of Limnephilidae taxa developed in the lake. By about 11,400 14C BP the relatively thermophilous Polycentropus flavomaculatus and Limnephilus rhombicus were present, suggesting that the summer water temperature was at least 17 °C. This temperature fell by 5-8 °C at the start of the Younger Dryas, and the thermophilous taxa were replaced within 20-40 14C yrs by Apatania spp., including the arctic-alpine A. zonella, suggesting a maximum summer water temperature of 10-12 °C. The Trichoptera assemblage was impoverished in numbers and in diversity over the next 200 yrs as the severe conditions of the Younger Dryas developed. As soon as temperatures rose and glacial meltwater and silt input ended about 700 14C yrs later, the resident Apatania assemblage expanded immediately, within 10 yrs. About 130 yrs later, thermophilous taxa replaced Apatania, and a much more diverse assemblage than in the Allerod occupied the varied habitats made available by the development of the Holocene lake ecosystem. The 130 yr delay may have been caused by a gradual temperature increase crossing a critical threshold, or by the time taken for thermophilous taxa to migrate from their Younger Dryas refugia.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008064831048
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  • 9
    Electronic Resource
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    Evidence for mid-Eemian cooling in continental climatic record from Lake Baikal (2000)
    Springer
    Journal of paleolimnology 23 (2000), S. 365-371 
    Details
    ISSN: 1573-0417
    Keywords: Lake Baikal ; diatoms ; biogenic silica ; Eemian ; climate change ; Siberia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract The discussion on climatic instability observed in Greenland ice cores during the Eemian period (substage 5e) resulted in discovery of a pronounced mid-Eemian cooling event. We report that the mid-Eemian cooling is found for the first time in the biogenic silica climatic record and microfossil abundance record of Lake Baikal. Timing of this event in Lake Baikal correlates well with timing of the European pollen records and marine sedimentary records. The presence of the mid-Eemian cooling signal in the Lake Baikal record suggests a much closer link between Asian climate influenced by strong pressure fields over the vast land masses and the climate-controlling processes in the North Atlantic during interglacial periods, than what was generally believed. Furthermore, the Lake Baikal record suggests that after the mid-Eemian cooling, the climatic conditions returned close to the warmth of the 5e optimum and thus argues that the warm conditions of the last interglacial persisted in Siberia throughout 5e, and did not end with the mid-Eemian cooling as suggested by several published marine records.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008188100542
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  • 10
    Electronic Resource
    Electronic Resource
    Holocene lake sediment records of Arctic hydrology (2000)
    Springer
    Journal of paleolimnology 24 (2000), S. 1-13 
    Details
    ISSN: 1573-0417
    Keywords: Arctic ; Holocene ; paleohydrology ; paleolimnology ; climate change
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Although paleoclimatic research in the Arctic has most often focused on variations in temperature, the Arctic has also experienced changes in hydrologic balance. Changes in Arctic precipitation and evaporation rates affects soils, permafrost, lakes, wetlands, rivers, ice and vegetation. Changes in Arctic soils, permafrost, runoff, and vegetation can influence global climate by changing atmospheric methane and carbon dioxide concentrations, thermohaline circulation, and high latitude albedo. Documenting past variations in Arctic hydrological conditions is important for understanding Arctic climate and the potential response and role of the Arctic in regards to future climate change. Methods for reconstructing past changes in Arctic hydrology from the stratigraphic, isotopic, geochemical and fossil records of lake sediments are being developed, refined and applied in a number of regions. These records suggest that hydrological variations in the Arctic have been regionally asynchronous, reflecting the impacts of different forcing factors including orbitally controlled insolation changes, changes in geography related to coastal emergence, ocean currents, sea ice extent, and atmospheric circulation. Despite considerable progress, much work remains to be done on the development of paleohydrological proxies and their application to the Arctic.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008100714795
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  • 11
    Electronic Resource
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    Diatom transfer-functions for quantifying past air temperature, pH and total organic carbon concentration from lakes in northern Sweden (2000)
    Springer
    Journal of paleolimnology 24 (2000), S. 109-123 
    Details
    ISSN: 1573-0417
    Keywords: diatoms ; climate change ; temperature ; pH ; transfer functions ; lake sediments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract The relationships between diatoms (Bacillariophyceae) in surface sediments of lakes and summer air temperature, pH and total organic carbon concentration (TOC) were explored along a steep climatic gradient in northern Sweden to provide a tool to infer past climate conditions from sediment cores. The study sites are in an area with low human impact and range from boreal forest to alpine tundra. Canonical correspondence analysis (CCA) constrained to mean July air temperature and pH clearly showed that diatom community composition was different between lakes situated in conifer-, mountain birch- and alpine-vegetation zones. As a consequence, diatoms and multivariate ordination methods can be used to infer past changes in treeline position and dominant forest type. Quantitative inference models were developed to estimate mean July air temperature, pH and TOC from sedimentary diatom assemblages using weighted averaging (WA) and weighted averaging partial least squares (WA-PLS) regression. Relationships between diatoms and mean July air temperature were independent of lake-water pH, TOC, alkalinity and maximum depth. The results demonstrated that diatoms in lake sediments can provide useful and independent quantitative information for estimating past changes in mean July air temperature (R2 jack = 0.62, RMSEP = 0.86 °C; R2 and root mean squared error of prediction (RMSEP) based on jack-knifing), pH (R2 jack = 0.61, RMSEP = 0.30) and TOC (R2 jack = 0.49, RMSEP = 1.33 mg l-1). The paper focuses mainly on the relationship between diatom community composition and mean July air temperature, but the relationships to pH and TOC are also discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008128014721
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  • 12
    Electronic Resource
    Electronic Resource
    A first estimate of organic carbon storage in Holocene lake sediments in Alberta, Canada (2000)
    Springer
    Journal of paleolimnology 24 (2000), S. 395-400 
    Details
    ISSN: 1573-0417
    Keywords: carbon storage ; lake sediment ; Holocene ; Canada ; climate change ; organic matter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract This paper reports a first estimate of the Holocene lake sediment carbon pool in Alberta, Canada. The organic matter content of lake sediment does not appear to depend strongly on lake size or other limnological parameters, allowing a simple first estimate in which we assume all Alberta lake sediment to have the same organic matter content. Alberta lake sediments sequester about 15 g C m-2 yr-1, for a provincial total of 0.23 Tg C yr-1, or 2.3 Pg C over the Holocene. Alberta lakes may represent as much as 1/1700 of total global, annual permanent carbon sequestration.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008103605817
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  • 13
    Electronic Resource
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    Using a Crop/Soil Simulation Model and GIS Techniques to Assess Methane Emissions from Rice Fields in Asia. III. Databases (2000)
    Springer
    Nutrient cycling in agroecosystems 58 (2000), S. 179-199 
    Details
    ISSN: 1573-0867
    Keywords: climate change ; databases ; GIS ; methane ; rice ; soils ; weather
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract As part of a series of papers describing the use of a simulation model to extrapolate experimental measurements of methane (CH4) emissions from rice fields in Asia and to evaluate the large-scale effect of various mitigation strategies, the collation and derivation of the spatial databases used are described. Daily weather data, including solar radiation, minimum and maximum temperatures, and rainfall were collated from 46 weather stations from the five countries in the study, namely China, India, Indonesia, Philippines, and Thailand. Quantitative soil data relevant to the input requirements of the model were derived by combining data from the World Inventory of Soil Emissions (WISE) database, the ISIS database, and the FAO Digital Soil Map of the World (FAO-DSMW). These data included soil pH; organic carbon content; sand, silt, and clay fractions; and iron content for top and subsoil layers, and average values of bulk density and available water capacity for the whole profile. Data on the areas allocated to irrigated, rainfed, upland, and deepwater rice at the province or district level were derived from the Huke & Huke (1997) database developed at IRRI. Using a geographical information system (GIS), a series of georeferenced data sets on climate, soils, and land use were derived for each country, at the province or district level. A summary of the soil-related derived databases is presented and their applicationn for use in global change modeling discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009898720354
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  • 14
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    Structure and Morphology of a Polyether/Polyacrylate Semi-interpenetrating Polymer Network (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 83-92 
    Details
    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).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010123610324
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  • 15
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    A DSC Study on Cure Kinetics of HTPB-IPDI Urethane Reaction (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 93-100 
    Details
    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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    URL: http://dx.doi.org/10.1023/A:1010127727162
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  • 16
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    The Effect of Side Chain Association on Thermal and Viscoelastic Properties: Cellulose acetate based polycaprolactones (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 157-168 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010140129888
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  • 17
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    Structural Development During Thermal Fractionation of Polyethylenes (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 245-255 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010100432613
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  • 18
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    Applications of Successive Self-Nucleation and Annealing (SSA) to Polymer Characterization (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 451-470 
    Details
    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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    Nucleating Agents in Polypropylene (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 497-508 
    Details
    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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    URL: http://dx.doi.org/10.1023/A:1010197609840
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    Thermal Analysis Characterization of a Commercial Thermoplastic/Thermoset Adhesive (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 559-570 
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    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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    URL: http://dx.doi.org/10.1023/A:1010166230313
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    Anomalies of Glass Transition: Manifestation in fullerene core polystyrene stars (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 23-31 
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    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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    URL: http://dx.doi.org/10.1023/A:1010163307598
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    Kinetic Analysis of the Decomposition of Chelates of Di-alkyldithiocarbamate of Cd(II) (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 633-642 
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    ISSN: 1572-8943
    Keywords: cadmium ; dialkyldithiocarbamate ; kinetics ; thermal decomposition ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition kinetics of the solid complexes Cd(S2 CNR2 )2 , where R =C2 H5 , n -C3 H7 , n -C4 H9 or iso -C4 H9 , was studied by using isothermal and non-isothermal thermogravimetry. The superimposed TG/DTG/DSC curves revealed that thermal decomposition reactions occur in the liquid phase. The kinetic model that best fitted the experimental isothermal TG data was the one-dimensional phase-boundary reaction-controlled process R1 . The thermal analysis data suggested the thermal stability sequence Cd(S2 CNBun 2 )2 〉Cd(S2 CNPrn 2 )2 〉Cd(S2 CNBui 2 )2 〉Cd(S2 CNEt2 )2 , which accords with the sequence of stability of the apparent activation energies.
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    Synthesis And Kinetic Analysis of Poly(2,2'-dymethoxy-4,4'-biphenylenevinylene. A novel conducting polymer (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 675-680 
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    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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    URL: http://dx.doi.org/10.1023/A:1010133116243
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    Relaxation Transitions in Thermally Treated Polyaniline Films (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 721-727 
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    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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    URL: http://dx.doi.org/10.1023/A:1010141418060
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    DSC and FTIR Analyses of The Curing Behavior of Epoxy/dicy/solvent Systems on Hermetic Specimens (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 711-719 
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    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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    Kinetic and Thermodynamic Studies of Facial and Meridional uns-cis-[Co(eddp)gly] Complexes (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 807-814 
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    ISSN: 1572-8943
    Keywords: facial and meridional Co(III) complexes ; kinetics ; thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal properties of facial and meridional uns-cis-[Co(eddp)gly]0.5H2O complexes were investigated by means of DSC and TG techniques. It wasshown that the processes of thermal decomposition of these complexes are multi-stepdegradation processes, which can also be well separated into individual steps, depending onthe molecular symmetry. Thus, the process of thermal degradation of the meridional isomerof the above complex consists of 4 well-separated steps in the temperature interval from 100to 500°C. The corresponding kinetic and thermodynamic parameters of this process weredetermined, and a possible mechanism is discussed.
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    The Effects of γ-Irradiation on the Electrokinetic and Thermal Behaviour of Zirconium Hydroxide (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 837-846 
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    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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    Differential Scanning Calorimetric Analysis of Composted Materials From Different Sources (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 607-614 
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    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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    URL: http://dx.doi.org/10.1023/A:1010146207459
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    Thermal Analysis of a Polyethylene Glycol (PEG 4000): T-CR-T Diagram Construction (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 711-718 
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    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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    URL: http://dx.doi.org/10.1023/A:1010120424573
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    Thermoanalytical Study of O,O'-Dibenzoyl-(2R,3R)-Tartaric Acid Supramolecular Compounds. Part I. Investigation of compounds with water, achiral alcohols and phenols (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 745-755 
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    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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    Thermal Decomposition Characteristics of 1,7-Diazido-2,4,6-trinitrazaheptane and its Application in Propellants (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 771-778 
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    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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    Thermal Decomposition Kinetics of Some Metal Complexes of N,N-diethyl-n '-benzoylthiourea (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 955-965 
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    ISSN: 1572-8943
    Keywords: kinetics ; metal complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetry (TG) and differential thermal analysis (DTA) were performed on the complexes with general formula (M(DEBT)n (where M =Fe, Co, Ni, Cu or Ru; n =2, or 3 and DEBT=N,N-diethyl-N'-benzoylthiourea). Derivative thermogravimetric (DTG) curves were also recorded in order to obtain decomposition data on the complexes. The complexes of Fe(III), Co(II), Ni(II), Cu(II) and Ru(III) displayed two- or three-stage decomposition patterns when heated in a dynamic nitrogen atmosphere. Mass loss considerations relating to the decomposition stages indicated the conversion of the complexes to the sulfides or to the corresponding metal alone (Cu, Ru, NiS, CoS or FeS). Mathematical analysis of the TG and DTG data showed that the order of reaction varied between 0.395 and 0.973. Kinetic parameters such as the decomposition energy, the entropy of activation and the pre-exponential factor are reported.
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    Analysis of DSC Data Relating to Proteins Undergoing Irreversible Thermal Denaturation (2000)
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 51-62 
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    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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    Fast Gas Adsorption Measurements For Complicated Adsorption Mechanisms (2000)
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 429-433 
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    ISSN: 1572-8943
    Keywords: adsorption ; fast measurement ; gravimetry ; kinetics ; sorption ; kw6
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Jäntti introduced a method to reduce the time required for the stepwise measurement of adsorption isotherms. After each pressure change he measured the adsorbed mass three times and calculated its equilibrium value at the new pressure. In the present paper, we discuss the applicability of this method in a broader scope without starting from a given combination of sorptive and adsorbent and the influence of measuring inaccuracies. The method is applied to detect whether the adsorption process is based on more than one adsorption mechanism or not.
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    Study of Thermal Decomposition Kinetics of Low-temperature Reaction of Ammonium Perchlorate by Isothermal TG (2000)
    Springer
    Journal of thermal analysis and calorimetry 63 (2000), S. 375-386 
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    ISSN: 1572-8943
    Keywords: activation energy ; ammonium perchlorate ; decompositon ; isothermal ; kinetics ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the thermal decomposition of ammonium perchlorate at temperatures between 215 and 260°C is studied, in this work, by measuring the sample mass loss as a function of time applying the isothermal thermogravimetric method. From the maximum decomposition rate – temperature dependence two different decomposition stages, corresponding to two different structural phases of ammonium perchlorate, are identified. For the first region (215–235°C), corresponding to the orthorhombic phase, the mean value of the activation energy of 146.3 kJ mol–1, and the pre-exponential factor of 3.43⋅1014 min–1 are obtained, whereas for the second region (240–260°C), corresponding to the cubic phase, the mean value of the activation energy of153.3 kJ mol–1, and the pre-exponential factor of 4.11⋅1014 min–1 are obtained.
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    Theoretical and Experimental Investigations of The Decomposition of 10-methylacridinium Halides (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 35-43 
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    ISSN: 1572-8943
    Keywords: kinetics ; 10-methylacridinium halides ; thermodynamics ; thermogravimetric investigations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 10-Methylacridinium chloride, bromide and iodide were prepared in crystalline forms (the first two salts as monohydrates) and subjected to thermogravimetric investigations. Decomposition of the compounds is initially accompanied by the liberation of water (in case of monohydrates), halomethanes and acridine molecules. As decomposition proceeds, side reactions occur which are reflected in a complex pattern of thermogravimetric curves. TG traces corresponding to the initial decomposition stage were used to determine the kinetic characteristics of the thermal dissociation of the salts. MNDO/d, AM1 and PM3 methods were employed independently to examine reaction pathways and to predict thermodynamic and kinetic barriers for the thermal decomposition of the compounds. These data were subsequently supplemented with theoretically determined crystal lattice energies, which enabled the relevant characteristics for the decomposition of crystalline phases to be predicted. The theoretically predicted characteristics are qualitatively comparable with those originating from thermogravimetric investigations, which allows one to believe that both are valid.
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    DSC Studies on Melting and Crystallization of Polyamide 6/Biopol Blends (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 117-121 
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    ISSN: 1572-8943
    Keywords: biopol/polyamide 6 blends ; DSC
    Source: Springer Online Journal Archives 1860-2000
    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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    Thermal Decomposition of Triazine Herbicides. I. 1,2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropionitrile (cyanazine) (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 103-110 
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    ISSN: 1572-8943
    Keywords: cyanazine ; DSC ; kinetics ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    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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    Properties of Polyurethanes Based on Mesogenic Diol and 4,4'-methylenebis(cyclohexyl Isocyanate) (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 111-116 
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    ISSN: 1572-8943
    Keywords: DMTA ; DSC ; HMDI ; mesogenic chain extender ; polyurethane
    Source: Springer Online Journal Archives 1860-2000
    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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    Calorimetric and Thermal Investigation of Metal Derivatives of 6-aminopicolinic Acid (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 163-166 
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    ISSN: 1572-8943
    Keywords: comparison ; decomposition ; DSC ; enthalpy
    Source: Springer Online Journal Archives 1860-2000
    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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    Influence of Gas Atmosphere on Removal of Sulphate Groups From Titanium Oxide (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 247-255 
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    ISSN: 1572-8943
    Keywords: desulfuration ; gas atmosphere ; kinetics ; thermal decomposition ; titanium dioxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The studies were devoted to determination of the effect of gas atmosphere and its pressure on the second step of decomposition of hydrated titanium dioxide (HTD) promoted by sulfate groups. It has been found that thermal decomposition of HTD at temperatures above 300°C consists of a number of processes such as dehydroxylation, desulfuration, recrystallization and sintering of solid grains, photochemical processes (if the decomposition proceeds in the presence of light) and adsorption of gas phase components (in the presence of air or SO2). Kinetic parameters characterizing this step of decomposition have been determined for processes carried out in vacuum and in argon or air atmospheres (at a pressure of 13.33hPa). The kinetic curves of decomposition carried out in the presence of gases capable of being adsorbed on the surface of partly dehydrated HTD are featured by local extrema due to simultaneous processes of decomposition and adsorption of gas components.
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    Solid State Coordination Chemistry. The quantitative thermoanalytical study of thermal dissociation reactions (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 9-15 
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    ISSN: 1572-8943
    Keywords: coordination compounds ; kinetics ; thermal dissociation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Physicalo-chemical importance of the quantitative study of kineticliability of coordination compounds in thermal dissociation processes is considered. Muchattention is given to the proof of the physicalo-chemical meaning and validity of kineticparameters calculated from thermoanalytical data. Experimental data (thermal dissociation ofcoordination compounds and clathrates with such a matrix) are discussed.
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    The Effect of Cross-linked Polyethylene As a Surface Modifier on Crystallization of Polypropylene (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 401-407 
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    ISSN: 1572-8943
    Keywords: cross-linking ; isothermal crystallization ; kinetics ; modification ; polypropylene ; silica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of addition of silica on the parameters of isothermal crystallization of polypropylene has been investigated. It was found that the covering of the silica surface by a layer of low-density polyethylene leads to a deactivation of the filler regarding the positive effect on the polypropylene crystallization rate parameters. Cross-linking of the surface polyethylene layer results in a stronger attachment of the modifying polymer to the filler surface and the deactivation effect of the silica surface modification is more pronounced.
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    Physical Aging of a Tetrafunctional/phenol Novolac Epoxy Mixture Cured with Diamine. DSC and DMA measurements (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 391-399 
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    ISSN: 1572-8943
    Keywords: DMA ; DSC ; physical aging ; TGDDM epoxy
    Source: Springer Online Journal Archives 1860-2000
    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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    Mechanism of Optical Resolutions Via Diastereoisomeric Salt Formation. Part 6 Thermoanalytical investigation of the optical resolution of racemic mandelic acid with S-(+)-2-benzylamino-butanol (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 409-415 
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    ISSN: 1572-8943
    Keywords: 2-benzylamino-butanol ; DSC ; mandelic acid ; melting phase diagram ; optical resolution
    Source: Springer Online Journal Archives 1860-2000
    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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    Physico-chemical Studies on Zinc Hexa(formato)ferrate(III) Decahydrate (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 535-539 
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    ISSN: 1572-8943
    Keywords: DSC ; ferrite ; Mössbauer spectra ; TG ; thermal decomposition ; zinc ferriformate
    Source: Springer Online Journal Archives 1860-2000
    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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    Formation of Cr(II) Species in the H2/CrO3 System. Parameter control (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 541-547 
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    ISSN: 1572-8943
    Keywords: Cr(II) ; chromium trioxide ; kinetics ; reduction ; thermal analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of CrO3 on heating up to 600°C in dynamic atmospheres of air, N2 and H2 was examined by thermogravimetry (TG), differential thermal analysis (DTA), IR spectroscopy and diffuse reflectance spectroscopy (DRS). The results revealed three major thermal events, depending to different extents on the surrounding atmosphere: (i) melting of CrO3 near 215°C (independent of the atmosphere), (ii) decomposition into Cr2(CrO4)3 at 340–360°C (insignificantly dependent), and (iii) decomposition of the chromate into Cr2O3 at 415–490°C (significantly dependent). The decomposition CrO3 → Cr2(CrO4)3 is largely thermal and involves exothermic deoxygenation and polymerization reactions, whereas the decomposition Cr2(CrO4)3 → Cr2O3 involves endothermic reductive deoxygenation reactions in air (or N2) which are greatly accelerated and rendered exothermic in the presence of H2. TG measurements as a function of heating rate (2–50°C min−1) demonstrated the acceleratory role of H2, which extended to the formation of Cr(II) species. This could sustain a mechanism whereby H2 molecules are considered to chemisorb dissociatively, and then spillover to induce the reduction. DTA measurements as a function of the heating rate (2–50°C min−1) helped in the derivation of non-isothermal kinetic parameters strongly supportive of the mechanism envisaged.
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    Evaluation of Kinetic Data for Crystallization of Tio2 Prepared by Hydrolysis Method (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 595-604 
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    ISSN: 1572-8943
    Keywords: crystal structure ; DSC ; oxides ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    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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    Kinetic Modeling of Advanced Inorganic Glass-ceramics Formation by Crystal Growth From Pre-existing Nuclei (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 667-674 
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    ISSN: 1572-8943
    Keywords: accommodation function ; crystal growth ; glass-ceramics ; kinetics ; number of nuclei ; thermal history
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic modeling of the crystal growth from pre-existing nuclei was reexamined to obtain a fundamental information about the controlled crystallization of glasses during formation of advanced inorganic glass-ceramics. Methods of kinetic analysis were reviewed by taking account of thermal history of the sample within the temperature range of nucleation. An accommodation function depending on the thermal history was introduced in the kinetic equation. The role of the accommodation function was reinvestigated when determining the activation energy from a series of kinetic curves. The kinetic description of the crystal growth in the samples with different thermal history was generalized by extrapolating the rate behavior to infinite temperature.
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    Anomalies in Heat Capacity Measurements of RuO2-TiO2 System (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 683-689 
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    ISSN: 1572-8943
    Keywords: DSC ; heat capacity ; mixed oxide TiO2-RuO2 ; RuO2 ; TiO2
    Source: Springer Online Journal Archives 1860-2000
    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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    Temperature Modulated DSC. Theoretical interpretation (2000)
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    Journal of thermal analysis and calorimetry 60 (2000), S. 333-343 
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    ISSN: 1572-8943
    Keywords: base line ; DSC ; kinetics ; modeling ; thermodynamics ; TMDSC
    Source: Springer Online Journal Archives 1860-2000
    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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    The DSC Study of PA 6, Polyamides and Copolyamides (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 357-369 
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    ISSN: 1572-8943
    Keywords: blends of polyamides ; copolyamides ; crystallization ; DSC ; melting point ; structure
    Source: Springer Online Journal Archives 1860-2000
    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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    A New Software to Show The Behaviour of The PID Controller. Part II. Influence of the setting parameters of DSCs (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 345-355 
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    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
    Source: Springer Online Journal Archives 1860-2000
    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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    Practical Thermogravimetry (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 759-778 
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    ISSN: 1572-8943
    Keywords: decomposition temperature ; error sources ; gas-flow and vapor control ; kinetics ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The well-known divergence between the present ‘state of the art’ of thermogravimetry and industrial requirements is discussed. Sources of errors are analyzed and the optimization of measuring conditions is discussed regarding the problems associated with static and dynamic (flow) atmospheres, and interactions between materials and gases or vapors. Recommendations for gas-flow control systems and vapor sources are given. Thermal stability and the kinetics of gas-evolving, reversible, thermal decompositions of solids are discussed. The scope of TG-derived kinetics for practical use is examined. Some new characteristic points of TG curves are proposed and defined, e.g. ‘procedure-independent decomposition temperature’ and ‘augmented decomposition temperature’ (obtained at pseudo-equilibrium conditions).
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    The Thermodynamic Driving Force in the Kinetic Evaluation of Thermoanalytical Curves (2000)
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    Journal of thermal analysis and calorimetry 60 (2000), S. 879-886 
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    ISSN: 1572-8943
    Keywords: driving force ; kinetics ; rate equation ; reversible reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper outlines the different ways of taking the distance from thermodynamic equilibrium into account in kinetic studies based on thermoanalytical experiments. The three main approaches are: (i) avoiding or neglecting the effect of the reverse reaction, (ii) describing the influence of distance from equilibrium on apparent kinetic parameters, and (iii) incorporating a driving force factor in the rate equation. Finally, the contradiction of the microscopic nature of the processes and the macroscopic character of the usual rate equation are briefly discussed.
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    Kinetic Studies of the Thermal Decomposition of KDNBF, a Primer for Explosives (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 917-926 
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    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; KDNBF ; TG
    Source: Springer Online Journal Archives 1860-2000
    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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    Kinetic Analysis of the Thermal Decomposition of Synthetic Malachite by CRTA (2000)
    Springer
    Journal of thermal analysis and calorimetry 60 (2000), S. 943-954 
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    ISSN: 1572-8943
    Keywords: CRTA ; kinetics ; self-generated atmospheric conditions ; synthetic malachite ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic behavior of the thermal decomposition of synthetic malachite was investigated by means of CRTA under different conditions of reduced pressure, flowing gases and quasi-isobaric atmospheres. The thermal decomposition was found to proceed at lower temperatures under the influence of the self-generated gases, CO2 and H2O. From a viewpoint of chemical equilibrium, the normal and opposite effects on the overall kinetics were observed for the self-generated CO2 and H2O, respectively. The complexity of the present reaction is also reflected by the variations of the apparent kinetic parameters which depend on the applied and self-generated atmospheric conditions. The practical usefulness of CRTA when applied to a complicated thermal decomposition is discussed as exemplified by the kinetic approaches to the present reaction.
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    Heat Capacity Measurements Using Temperature-modulated Heat Flux DSC with Close Control of the Heater Temperature (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 75-89 
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    ISSN: 1572-8943
    Keywords: DSC ; Fourier transformation ; heat capacity ; sawtooth-modulation ; TMDSC
    Source: Springer Online Journal Archives 1860-2000
    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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    Temperature and Heat Flow Calibration of A DSC-instrument in the Temperature Range Between −100 and 160°C (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 91-98 
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    ISSN: 1572-8943
    Keywords: DSC ; heat flow calibration ; temperature calibration
    Source: Springer Online Journal Archives 1860-2000
    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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    Thermal Studies on Some Lanthanide Complexes (2000)
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    Journal of thermal analysis and calorimetry 61 (2000), S. 151-156 
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    ISSN: 1572-8943
    Keywords: complexes ; kinetics ; TG-DTA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of a few lanthanide complexes of the type ML3(I) [M=Eu,Gd; HL=4,4,4-trifluoro- 1-(2-napthyl)-1,3-butanedione and EuL30.5dmm dmm=2,6-dimethylmorpholine(II)], has been investigated. From thermogravimetric(TG) curves, the decomposition pattern of the compounds has been analysed on the basis of mass loss data. The order and activation energy of the thermal decomposition reactions have been elucidated. From differential thermal analysis (DTA) studies, the heat of reaction and rate of thermal decomposition reaction have been enumerated.
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    Non-isothermal Kinetic Study of the Heterogeneous Thermal Decomposition of a Mannich Compound (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 239-242 
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    ISSN: 1572-8943
    Keywords: kinetics ; Mannich compounds ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors present data concerning the evaluation of kinetic parameters of the decomposition of a Mannich compound by using the classical method of constant heating rate thermal analysis and the new one of controlled rate thermal analysis (CRTA). The data processed using the CRTA method allow to obtain more reliable kinetic parameters according to the proposed reaction mechanism.
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    Thermodynamic Stability of Ribonuclease B (2000)
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    Journal of thermal analysis and calorimetry 61 (2000), S. 363-368 
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    ISSN: 1572-8943
    Keywords: DSC ; glycosylated ribonuclease ; thermodynamic stability
    Source: Springer Online Journal Archives 1860-2000
    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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    DSC and X-ray Diffraction Study of Polymorphism in n-Alkylammonium Chlorides (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 341-350 
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    ISSN: 1572-8943
    Keywords: DSC ; polymorphism ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    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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    DSC in the Chemical Analysis of Drugs. Determination of diclofenac in pharmaceutical formulations (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 369-376 
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    ISSN: 1572-8943
    Keywords: diclofenac ; DSC
    Source: Springer Online Journal Archives 1860-2000
    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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    Thermal Methods of Organic Matter Maturation Monitoring During a Composting Process (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 389-396 
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    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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    Polypropylene Crystallization in an Ethylene-propylene-diene Rubber Matrix (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 437-450 
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    ISSN: 1572-8943
    Keywords: crystallization ; EPDM ; kinetics ; morphology ; PP ; rubber
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the incorporation of an amorphous immiscible polymer (ethylene-propylene-diene- terpolymer) on the PP crystallization kinetics and thermodynamics is investigated by thermal analysis. The results of the investigation have shown that EPDM acts as a nucleant agent. A marked decrease of the half time of PP crystallization, τ1/2 , as well as a sensible increase of the overall crystallization rate, K n , has been observed in the presence of EPDM. Moreover, at any crystallization temperature, a minimum of τ1/2 , is obtained at 25% EPDM content in the blend. The Avrami model has been successfully applied to describe the crystallization kinetics of the blend. The kinetic curves obtained under non-isothermal conditions confirm the results obtained under isothermal conditions and demonstrate the nucleant action of the EPDM phase on the PP crystallization.
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    Starch Gelatinization Kinetics in Bread Dough. DSC investigations on 'simulated' baking processes (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 411-423 
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    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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    Structural and Mechanical Properties of Crosslinked Drawn Gelatin Films (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 451-459 
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    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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    TG and DTA Study of the Thermal Dehydration of Metal-exchanged Zeolite-4A Samples (2000)
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 721-727 
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    ISSN: 1572-8943
    Keywords: kinetics ; metal exchange ; thermaldehydration ; zeolite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Zeolite-4A is a hydrated aluminosilicate which becomes more hydrated when exchanged with transition metals. In this work, the dehydration kinetics of cobalt, nickel and copper(II)-exchanged zeolite-4A were studied by means of TG and DTA over the temperature range from 20 to 500°C, and the numbers of water molecules in the metal-exchanged zeolite samples were calculated. It was observed that, as the ionic radius of the hydrated metal increased, the number of water molecules also increased. The loss of water from the zeolite samples generally occurred in the temperature range 100–300°C and was manifested in the DTA graphs by an extended endothermic effect. The DTA curves demonstrated that the peak position shifted towards lower temperatures as the metal concentration increased or, in other words, the water of hydration increased. The kinetic parameters (order of reaction and activation energy) were calculated via the Coats and Redfern method. The process of dehydration was found to follow first-order kinetics.
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    Surface Treatment of Dimenhydrinate Crystals (2000)
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 797-807 
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    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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    Kinetic Equations for Thermal Dissociation Processes. Part I. KEKAM equation (2000)
    Springer
    Journal of thermal analysis and calorimetry 63 (2000), S. 359-374 
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    ISSN: 1572-8943
    Keywords: KEKAM equation ; kinetics ; thermal dissociation of solids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Relationships have been established between the average conversion degree and the dissociation time for polydisperse granular material, taking its grain size distribution into account. It has been checked in which cases the kinetic curves obtained by a numerical solution can be described in terms of KEKAM equation.
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    Critical Analysis of the Isoconversional Methods for Evaluating the Activation Energy. II. The activation energy obtained from isothermal data corresponding to two successive reactions (2000)
    Springer
    Journal of thermal analysis and calorimetry 63 (2000), S. 465-469 
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    ISSN: 1572-8943
    Keywords: isoconversional methods ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An analysis is presented of the consequences of the use of a one term equation containing apparent activation parameters, instead of the true rate equation to describe two successive decomposition reactions undergone by a solid compound. It is demonstrated that the apparent activation energy, obtained by means of isoconversional differential and integral methods, varies with the conversion degree for a relatively narrow temperature range and with temperature at a given value of the conversion degree. The activation energy values obtained with the isoconversional differential method are higher than the corresponding values obtained with the isoconversional integral method.
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    Study of the Crystallization of an Aromatic Poly-ether-ketone (PK99) by Calorimetric and X-ray Analysis (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 565-578 
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    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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    Kinetics of Thermal Decomposition of Plumbo-jarosite (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 869-875 
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    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; plumbo-jarosite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An investigation was carried out on the kinetics of thermal decomposition of plumbo-jarosite. The kinetic models of dissociation of the compounds in the ore were identified. The results of the kinetic studies and the mechanism of the process are discussed. The thermal decomposition of plumbo-jarosite occurs in three stages: the first up to 763, the second up to 1023 and the third up to 1223 K, the corresponding activation energy values being 62.2, 60.3 and 98.0 kJ mol–1 , respectively.
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    DSC Study on the Interaction Between Bis-2-(Ethylhexyl) Phthalate and Other o-phthalic Acid Esters and Dipalmitoyl Phosphatidylcholine Liposomes (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 731-743 
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    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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    Thermal Characterization of Passivated Nanometer Size Aluminium Powders (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 805-818 
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    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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    Thermal and Spectroscopic Studies on the Decomposition of Some Aminoguanidine Nitrates (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 861-871 
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    ISSN: 1572-8943
    Keywords: DAGN ; kinetics ; mechanism and IR spectroscopy ; TAGN ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Diaminoguanidine nitrate (DAGN) and triaminoguanidine nitrate (TAGN),potential energetic materials in emerging propulsion technology with high mass impetus at low isochoric flame temperature have been studied as regards kinetics and mechanism of thermal decomposition using thermogravimetry (TG), differential thermal analysis (DTA),infrared spectroscopy (IR) and hot stage microscopy. Kinetics of thermolysis has been followed by isothermal TG and IR. For the initial stage of thermolysis of DAGN the best linearity with a correlation coefficient of 0.9976 was obtained for the Avrami-Erofe'evequation, n=2, by isothermal TG. The activation energy was found to be 130 kJ mol–1 and logA=11.4. The initial stage of thermolysis of TAGN also obeyed the Avrami-Erofe'ev equation, n=2, with a correlation coefficient of 0.9975by isothermal TG and the kinetic parameters are E=160.0 kJ mol–1 and logA=16.0. High temperature IR spectra showed exquisite preferential loss in intensity of the NH2, NH, N–N stretching and CNN bending. Spectroscopic and other results favour deamination reaction involving the rupture of the N–N bond as the primary step in the thermal decomposition.
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    Fractal Approach in the Kinetics of Solid-Gas Decompositions. Part II (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 979-984 
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    ISSN: 1572-8943
    Keywords: kinetics ; nucleation-growth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The author presents some applications of the fractal geometry in the kinetics of heterogeneous decomposition of solids.
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    Phase Diagram of EC–DMC Binary System and Enthalpic Determination of Its Eutectic Composition (2000)
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 177-186 
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    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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    A New Software to Show the Behaviour of the PID Controller. Influence of the setting parameters of DSCs. Part I (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 999-1015 
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    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
    Source: Springer Online Journal Archives 1860-2000
    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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    Thermal Measurements on Poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] Fibers (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 1023-1027 
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    ISSN: 1572-8943
    Keywords: DMA ; DSC ; fibers ; polybenzimidazole ; secondary transitions
    Source: Springer Online Journal Archives 1860-2000
    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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    Cure Kinetics of a Tetrafunctional Rubber Modified Epoxy-amine System (2000)
    Springer
    Journal of thermal analysis and calorimetry 61 (2000), S. 579-587 
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    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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    Study of The Mechanism and Kinetic Parameters of The Thermal Decomposition of Cobalt Sulphate Hexahydrate (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 935-942 
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    ISSN: 1572-8943
    Keywords: CoSO46H2O ; kinetics ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetry (TG-DTG), and differential thermal analysis (DTA) were used in the study of the kinetics of decomposition of cobalt sulphate hexahydrate under an air atmosphere. The kinetics of the particular stages of CoSO4 6H2 O decomposition were evaluated from the dynamic mass loss data. The values of the kinetic parameters for each stage of the thermal decomposition were calculated from the α(T) data by using the integral method, applying the Coats-Redfern approximation.
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    Kinetic Study of the Accelerating Effect of Coal-burning Additives on the Combustion of Graphite (2000)
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 681-685 
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    ISSN: 1572-8943
    Keywords: coal-burning additive ; combustion ; graphite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The catalytic and accelerating effects of three coal-burning additives (CBA) on the burning of graphite were studied with the help of thermogravimetric (TG) analysis. The kinetic study on the catalytic oxidation of the graphite doped with CBA was carried out and the results were presented. The results show that the CBA can change the carbon oxidation/combustion course by catalytic action and change the activation energy, thus improving the combustion efficiency.
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    D-xylose Derivative Liquid Crystals (2000)
    Springer
    Journal of thermal analysis and calorimetry 63 (2000), S. 339-344 
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    ISSN: 1572-8943
    Keywords: amphiphile ; DSC ; D-xylose ; derivatives ; lyotropy ; thermotropy
    Source: Springer Online Journal Archives 1860-2000
    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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    Critical Analysis of the Isoconversional Methods for Evaluating the Activation Energy. I. Theoretical background (2000)
    Springer
    Journal of thermal analysis and calorimetry 63 (2000), S. 457-463 
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    ISSN: 1572-8943
    Keywords: isoconversional methods ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is demonstrated that, if the activation energy depends on the degree of conversion, its values obtained by isoconversional differential and integral methods are different.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010148611036
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    Some Considerations about the Structure of 3(5)-Methylpyrazole (2000)
    Springer
    Structural chemistry 11 (2000), S. 77-83 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009276524564
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  • 88
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    Modeling of the Phase Transformation Induced by Ball Milling in Anatase TiO2 (2000)
    Springer
    Journal of materials synthesis and processing 8 (2000), S. 139-144 
    Details
    ISSN: 1573-4870
    Keywords: TiO2 ; phase transformations ; mechanical alloying ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A high-pressure and high-temperature phase of TiO2 : TiO2 II is formed transiently during room-temperature high-energy ball milling of anatase TiO2 : TiO2 anatase → TiO2 II → TiO2 rutile. Rutile is the only phase present after prolonged ball milling. The present paper focuses on the influences of physical and chemical processing conditions on the transformation kinetics. The effects of two milling parameters on the kinetics of phase transformation of anatase TiO2 were investigated: the nature of milling tools and the powder-to-ball weight ratio R. Granulometric characterizations and TEM observations have demonstrated that the transformation of TiO2 anatase into TiO2 II occurs without fracturing of particles and that TiO2 II nanograins form at the surface of anatase particles. The parameter R affects only the transformation rate. For a given R, the transformation rate is the largest with alumina grinding tools, intermediate with zirconia tools, and the smallest with steel tools. The parameters involved in current models of the mechanical alloying process do not suffice to explain the differences in transformation rates observed here. A parameter, which takes into account the influence of the mechanical properties of grinding materials, is considered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1011351807629
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  • 89
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    Relating Single-Impact Events to Macrokinetic Features in Mechanical Alloying Processes (2000)
    Springer
    Journal of materials synthesis and processing 8 (2000), S. 271-277 
    Details
    ISSN: 1573-4870
    Keywords: Comminution ; kinetics ; mechanical alloying ; phase transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract It has been shown that structural evolution occurring in powder mixtures subjected to mechanical treatment by milling follow well-defined conversion trends as a function of milling time. Sigmoidal curves were observed in the case of the mechanical alloying of transition metal mixtures, whereas a simpler kinetic course with a progressively decreasing transformation rate was found to characterize the disordering process of intermetallic equilibrium compounds by mechanical milling. Under the stipulation that collisions are the dominant energy transfer events, a kinetic model is developed to relate the observed macrokinetic features to the discrete powder fractions, which transform at each impact. Because of its intrinsic qualities, the milling process was regarded as discrete processing. A statistical approach was followed to work out a set of differential equations, solutions of which provide a sound description of the transformation kinetics in terms of conventional rate expressions. The model allows one to reproduce the different kinetic behaviors by means of a single, unifying mathematical formalism. Furthermore, quantifying the structural evolution rate by suitable kinetic constants permits the exploration of the reactive behavior of a system treated under different milling regimes or to compare, on an absolute basis, different systems processed under similar conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1011382008963
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  • 90
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    High-Temperature Oxidation Behavior of the Co-Base Superalloy DZ40M in Air (2000)
    Springer
    Oxidation of metals 53 (2000), S. 351-360 
    Details
    ISSN: 1573-4889
    Keywords: Co-base superalloy ; high-temperature oxidation ; kinetics ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of the Co-base superalloy DZ40M was studied in air at900–1100°C for times of up to 2000 hr. The results indicated thatthis alloy can grow a protective oxide scale at 900 and 1000°C duringisothermal oxidation, but not at 1100°C because of serious cracking andspalling of the oxide scales. Moreover, an internal-precipitate zone formedin the subsurface region of the alloy at all temperatures and times. Theprecipitates were rich in Cr in the vicinity of the alloy–scaleinterface and rich in Al deep in the alloy. The internal-precipitatemorphology changed from a granular to needlelike shape with increasingoxidation temperature.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004597405809
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  • 91
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    Global climate change and regional sustainable development: the case of Mackenzie Basin in Canada (2000)
    Springer
    Integrated assessment 1 (2000), S. 21-36 
    Details
    ISSN: 1573-1545
    Keywords: integrated assessment ; climate change ; regional sustainability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Cohen et al. [16] suggest that in order to explore ways to bring climate change (CC) and sustainable development (SD) research together, it is necessary to develop more heuristic tools that can involve resource users and other stakeholders. In this respect, this paper focuses on methodological development in research to study climate change impacts and regional sustainable development (RSD). It starts with an introduction of an integrated land assessment framework (ILAF) which is part of the integrated phase of the Mackenzie Basin Impact Study (MBIS) in Canada. The paper then provides some articulation on how the integrated approach was applied in the Mackenzie Basin to show implications of climate change for RSD.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019167412598
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  • 92
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    Models at the interface between science and society: impacts and options (2000)
    Springer
    Integrated assessment 1 (2000), S. 267-280 
    Details
    ISSN: 1573-1545
    Keywords: participatory integrated assessment ; climate change ; low energy society
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Within the CLEAR project a new approach to integrated assessment modelling has been developed for the participatory integrated assessment of regional climate change involving citizens' focus groups. The climate change decision problem was structured by focusing separately on climate impacts and mitigation options. The attempt was made to link the different scales of the problem from the individual to the global level. The abstract topic of climate change was related to options on the level of a citizen's individual lifestyle. The option of a low energy society was emphasised in order to embed the climate change decision problem in a wider range of societal concerns. Special emphasis was given to the characterisation and communication of uncertainties. The chosen approach allows different kinds of uncertainties in one framework to be addressed. The paper concludes with a summary of the experience made, and recommendations for the use of models in participatory integrated assessments.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018927120883
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    Natural climate variability and climate change in the North-Atlantic European region; chance for surprise? (2000)
    Springer
    Integrated assessment 1 (2000), S. 301-306 
    Details
    ISSN: 1573-1545
    Keywords: CLEAR ; natural climate variability ; climate change ; atmosphere ; ocean
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Long-term variability in the North Atlantic Oscillation (NAO) and the Atlantic thermohaline ocean circulation (THC) are both shaping the European climate on time scales of decades and longer. Possible linear and non-linear changes in the characteristics of these natural climate modes due to global warming are an important source of uncertainty in long-term regional projections of future climate changes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018908027243
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    Assessing alpine plant vulnerability to climate change: a modeling perspective (2000)
    Springer
    Integrated assessment 1 (2000), S. 307-320 
    Details
    ISSN: 1573-1545
    Keywords: climate change ; ecological impact assessment ; alpine and subalpine belts ; plant distribution ; statistical modeling ; local scale ; GIS ; GLM ; Swiss Alps
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The potential ecological impact of ongoing climate change has been much discussed. High mountain ecosystems were identified early on as potentially very sensitive areas. Scenarios of upward species movement and vegetation shift are commonly discussed in the literature. Mountains being characteristically conic in shape, impact scenarios usually assume that a smaller surface area will be available as species move up. However, as the frequency distribution of additional physiographic factors (e.g., slope angle) changes with increasing elevation (e.g., with few gentle slopes available at higher elevation), species migrating upslope may encounter increasingly unsuitable conditions. As a result, many species could suffer severe reduction of their habitat surface, which could in turn affect patterns of biodiversity. In this paper, results from static plant distribution modeling are used to derive climate change impact scenarios in a high mountain environment. Models are adjusted with presence/absence of species. Environmental predictors used are: annual mean air temperature, slope, indices of topographic position, geology, rock cover, modeled permafrost and several indices of solar radiation and snow cover duration. Potential Habitat Distribution maps were drawn for 62 higher plant species, from which three separate climate change impact scenarios were derived. These scenarios show a great range of response, depending on the species and the degree of warming. Alpine species would be at greatest risk of local extinction, whereas species with a large elevation range would run the lowest risk. Limitations of the models and scenarios are further discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018912114948
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    Analysis of Aluminum—Yeast Hexokinase Interaction: Modifications on Protein Structure and Functionality (2000)
    Springer
    The protein journal 19 (2000), S. 199-208 
    Details
    ISSN: 1573-4943
    Keywords: Aluminum ; yeast hexokinase ; preferential interactions ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The aluminum and yeast hexokinase interaction was studied. Structural changes were correlated with variations in protein functionality. Results show two different behaviors: At low metal concentrations preferential adsorption of metal (and water exclusion) induces aggregate formation. No significant changes in the protein structure occur, but there is a continuous loss of activity (from the first concentration). At large salt concentrations a monomerization process and a conformational change in the secondary structure as well as in the three-dimensional structure take place. This change reduces the percentage of α-helix conformation, gives thermal stability to the protein, and allows the exposure of some tryptophan residue and hydrophobic regions. The protein inhibition increases. Conformational change and monomerization may allow access of the metal to the substrate site, mainly the ATP site. The inhibition in any case is of mixed type with a competitive component.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007055719926
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    A Comparative Study of Human Muscle and Brain Creatine Kinases Expressed in Escherichia coli (2000)
    Springer
    The protein journal 19 (2000), S. 59-66 
    Details
    ISSN: 1573-4943
    Keywords: Creatine kinase ; human ; expression ; brain ; muscle ; purification ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We report the expression of the human muscle (CK-MM) and brain (CK-BB) creatine kinases in Escherichia coli. The proteins have been purified to apparent homogeneity and several of their physical and kinetic properties investigated. In the process, we have conclusively verified the correct DNA sequence of the genes encoding the respective isozymes, and determined the correct primary structure and mass of the gene products. Alignment of the primary sequences of these two enzymes shows 81% sequence identity with each other, and no obvious gross structural differences. However, Western blot analyses demonstrated the general lack of antigenic cross-reactivity between these isozymes. Preliminary kinetic analyses show the K m and k cat values for the creatine and MgATP substrates are similar to values reported for other isozymes from various tissues and organisms. The human muscle and brain CKs do not, however, exhibit the synergism of substrate binding that is observed, for example, in rabbit muscle creatine kinase.
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    URL: http://dx.doi.org/10.1023/A:1007047026691
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  • 97
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    Differential scanning calorimetry of chromatin at different levels of condensation (2000)
    Springer
    Molecular biology reports 27 (2000), S. 175-180 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007237930301
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  • 98
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    Stabilization of ammonium dinitramide in the liquid phase (2000)
    Springer
    Russian chemical bulletin 49 (2000), S. 1974-1976 
    Details
    ISSN: 1573-9171
    Keywords: ammonium dinitramide ; thermal decomposition ; kinetics ; stabilization ; isotope composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of accumulation of the main products of thermal decomposition of ammonium dinitramide in the melt was investigated. The isotope composition of nitrogen-containing gases evolved by the decomposition of 15NH4N(NO2)2 and NH4 15N(NO2)2 was found. Easily oxidized salts, amines, amides, iodides, and other compounds soluble in the melt interfere with the liquid-phase decomposition of ammonium dinitramide.
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    URL: http://dx.doi.org/10.1023/A:1009555405171
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    The kinetics and mechanism of cyclodimerization of alkylthiopropenals (2000)
    Springer
    Russian chemical bulletin 49 (2000), S. 1977-1980 
    Details
    ISSN: 1573-9171
    Keywords: 2-alkylthiopropenals ; Diels–Alder reaction ; kinetics ; reaction mechanism ; 2,5-dialkylthio-3,4-dihydro-2H-pyran-2-carbaldehyde ; IR spectroscopy ; ab initio calculations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of 2-alkylthiopropenals cyclodimerization was studied in the temperature range from -7 to +42 °C in heptane and at 20 °C in various solvents. The rate constants for cyclodimerization of 2-alkylthiopropenals are four orders of magnitude higher than those for dimerization of the oxygen-containing analogs, 2-alkoxypropenals, and are independent of the solvent polarity and substituent steric constant. The activation parameters for 2-butylthiopropenal cyclodimerization were estimated. The distribution of electron density in the 2-methoxy- and 2-methylthiopropenals molecules was calculated by the ab initio method. From comparison of the HOMO and LUMO energies for these aldehydes it was concluded that the ratio between the cyclodimerization rates for 2-alkylthio-, 2-ethoxypropenals, and propenal is determined by the HOMO–LUMO gap.
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    URL: http://dx.doi.org/10.1023/A:1009507522009
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  • 100
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    Cooperative Interactions in Photosensitized Modification of DNA with Oligonucleotide-derived Binary Reagents (2000)
    Springer
    Molecular biology 34 (2000), S. 814-822 
    Details
    ISSN: 1608-3245
    Keywords: DNA ; kinetics ; oligonucleotide derivatives ; photomodification ; sensitization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Quantitative characteristics of thermodynamic and kinetic cooperativity arising in the process of photomodification of a single-stranded DNA fragment with binary systems of oligonucleotide conjugates forming an active site on the target were studied. Oligonucleotides of the binary system were complementary to adjacent segments of the DNA target, and contained arylazide (X) and perylene (S) residues covalently attached to their terminal phosphates. Upon irradiation at the perylene absorption wavelength, the target was modified by the arylazide residue, which was activated owing to the contiguity with the sensitizing perylene group in the tandem complex. Basing on the kinetic data, the constants of association of both derivatives of oligonucleotides with the target were determined: K x = 1.13 · 106 M–1, K s = 1.49 · 104 M–1. It was determined that association of both oligonucleotides with the target proceeded with a positive cooperativity characterized by parameter α = 45. The kinetic cooperativity parameter β was found to be approximately equal to 200; this characterized the acceleration of target modification in complex with the binary reagent versus that in the absence of sensitizer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026619607955
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