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  • DSC  (58)
  • modeling  (50)
  • Springer  (107)
  • American Physical Society
  • Blackwell Publishers Ltd
  • 2000-2004  (107)
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  • Springer  (107)
  • American Physical Society
  • Blackwell Publishers Ltd
  • Springer-Verlag  (1)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Adsorption 6 (2000), S. 93-104 
    ISSN: 1572-8757
    Keywords: adsorption refrigerator ; transient operation ; activated carbon ; methanol ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption refrigerators are a particular type of refrigerator in which compression is avoided, and in a sense replaced by adsorption. No mobile parts are needed; the energy input, instead of being mechanical, is thermal and is used to achieve desorption. Such machines have a cyclic operation, made of successive adsorption/evaporation and of desorption/condensation steps. The transient operation of adsorption refrigerators is a relatively recent subject of research. The modeling of the adsorber is the key point of such studies, because of the complex coupled heat and mass transfer phenomena that occur during the cycle. The present work therefore presents a study of an annular type adsorber which is intended to account for transient temperatures observed experimentally. The equipment in which the experiments were performed and which uses alcohol adsorption on activated carbon is briefly described, and its operating cycle described, along with typical experimental observations of pressure and temperature transients. A model of the adsorber unit is proposed which accounts for the coupling of adsorption and heat transfer, and describes mass-transfer in the annular adsorbent layer as a global diffusional mechanism with temperature dependent parameters. This model correctly predicts, qualitatively and semi-quantitatively, the observed trends of the temperature changes. Finally, various aspects of the performances are discussed.
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  • 2
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    Annals of operations research 94 (2000), S. 139-162 
    ISSN: 1572-9338
    Keywords: irrigated system ; modeling ; multi‐agent system ; simulation ; social networks ; coordination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Economics
    Notes: Abstract The viability of irrigated systems in the Senegal River Valley is being brought into question today due to their under‐utilization. We assume that their viability depends largely on the way their different components behave and interact. We therefore sought to examine in greater depth today's knowledge of the structure of these systems and activities performed within them. This led to the development of a multi‐agent system model, a kind of virtual irrigated system, with a special focus on rules in use for access to credit, water allocation and cropping season assessment as well as organization and coordination of farmers. The purpose of this paper is to show how this kind of tool is relevant to the study of irrigated systems' viability. As an example it is used to examine the influence of existing social networks on the viability of irrigated systems.
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  • 3
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    Journal of polymer research 7 (2000), S. 257-266 
    ISSN: 1572-8935
    Keywords: Poly(ether sulfone) ; Epoxy resin ; Physical aging ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The physical aging process of 4-4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with various molecular weights of poly(ether sulfone) (PES; Mn = 28,600, 10,600, and 6,137) was studied by DSC. For DGEBA/DDS system blended with a low MW PES-3 (Mn = 6,137), no phase separation of the polymer blend and only one enthalpic relaxation process due to physical aging was observed. Since the high MW PES-1 (Mn = 28,600) had a Tg close to that of fully cured DGEBA/DDS, the fully cured DGEBA/DDS/PES-1 blend had a broader glass transition than a neat DGEBA/DDS system. However, the DSC results showed two enthalpic relaxation processes due to the physical aging of PES-rich and cured epoxy-rich phases as the material was aged at 155 °C (30 °C below Tg). Since the Tgs of PES-1-rich and epoxy-rich phases overlapped with each other, the enthalpic relaxation processes corresponding to each phase coupled to each other in the earlier stage of physical aging. The medium MW PES-2 (Mn = 10,600) has a much lower Tg than that of fully cured DGEBA/DDS, two well separated Tgs were observed for the cured DGEBA/DDS/PES-2 blend, indicating the cured epoxy was immiscible with PES. Aging the polymer blend at 155 °C (24 °C below Tg1 of the PES-2-rich phase and 53 °C below Tg2 of the epoxy-rich phase) produced two well separated relaxation processes due to PES-2-rich and epoxy-rich phases. The experimental results suggested that aging the polymer blend at a suitable temperature would improve the phase separation between PES-1-rich and epoxy-rich phases.
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  • 4
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    International journal of flexible manufacturing systems 12 (2000), S. 145-163 
    ISSN: 1572-9370
    Keywords: inventory ; modeling ; postponement ; supply chain management
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper studies the impact of a reduction in hardware complexity on the supply-chain inventory against various customer on-time delivery alternatives and manufacturing environments. Different methods of reducing hardware complexity are proposed, and their impact on total supply-chain inventory and customer serviceability quantified. An analytical inventory optimization scheme taking into account multistage supply networks, product structure, forecast accuracy, lead-time variability, and supplier reliability is used to determine optimal inventory levels in a stochastic modeling environment. The analysis is based on a business case for an IBM midrange computer family consisting of more than 200 models and upgrades with hundreds of features. We investigate different hardware complexity reduction strategies, including low-usage feature reduction, low-volume feature reduction, and feature substitution, as well as quick response and postponement mechanisms. Our computational results show that, in a fabrication-fulfillment center environment, reducing hardware complexity results in significantly higher inventory savings than in an integrated manufacturing environment. The results presented in this paper were used to reduce hardware complexity in IBM's midrange computer division.
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  • 5
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    Topics in catalysis 13 (2000), S. 213-219 
    ISSN: 1572-9028
    Keywords: heterogeneous catalysis ; selectivity ; quantum chemistry ; modeling ; butadiene ; α–β unsaturated aldehydes ; enantioselectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Reaching high selectivities is an important concern for heterogeneous catalysis. Insights in the factors which control the reaction selectivity can be obtained from theoretical approaches, also a full computational description of the reaction is not yet possible, due to the great complexity of the molecules generally involved in fine chemical catalysis. Some theoritical works related to the interpretation of chemical selectivity are rewieved in this paper, with a focus on the various types of selectivity: chemoselectivity, regioselectivity and enantioselectivity.
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  • 6
    ISSN: 1572-9761
    Keywords: environmental change ; GIS ; landscape ecology ; modeling ; remote sensing ; riparian ; statistics ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Ecotones are inherent features of landscapes, transitional zones, and play more than one functional role in ecosystem dynamics. The delineation of ecotones and environmental boundaries is therefore an important step in land-use management planning. The delineation of ecotones depends on the phenomenon of interest and the statistical methods used as well as the associated spatial and temporal resolution of the data available. In the context of delineating wetland and riparian ecosystems, various data types (field data, remotely sensed data) can be used to delineate ecotones. Methodological issues related to their detection need to be addressed, however, so that their management and monitoring can yield useful information about their dynamics and functional roles in ecosystems. The aim of this paper is to review boundary detection methods. Because the most appropriate methods to detect and characterize boundaries depend of the spatial resolution and the measurement type of the data, a wide range of approaches are presented: GIS, remote sensing and statistical ones.
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  • 7
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    Journal of thermal analysis and calorimetry 59 (2000), S. 83-92 
    ISSN: 1572-8943
    Keywords: cationic and photoinitiated polymerization ; DSC ; interfacial mixing ; interpenetrating polymer network (IPN) ; glass transition temperature ; NMR ; quantitative thermal analysis of phases ; reactive epoxy and acrylate systems ; Tg broadening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study NMR and DSC are used to probe the structure, thermal characteristics and morphology of a network formed from a diepoxide/acrylate system. Separate chemistries are employed to polymerize the diepoxide and acrylate components. The cationic polymerization of the diepoxide exhibits excellent selectivity in producing a crosslinked polyether network without affecting the acrylate monomer. Subsequent photoinitiated free-radical polymerization of the acrylate produces a phase separated, semi-interpenetrating polymer network (SIPN).
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  • 8
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    Journal of thermal analysis and calorimetry 59 (2000), S. 93-100 
    ISSN: 1572-8943
    Keywords: catalyst ; cure kinetics ; DSC ; HTPB ; kinetic compensation effect ; urethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of theurethane-forming cure reaction of hydroxyl terminated polybutadiene (HTPB) with isophorone diisocyanate (IPDI) in presence of ferric tris (acetyl acetonate) (FeAA) catalyst was investigated using differential scanning calorimetry (DSC). The Arrhenius activation parameters, viz., activation energy E and pre-exponential factor A were evaluated using the non-isothermal integral Coats-Redfern equation. The cure reaction was catalysed by ferric acetyl acetonate (FeAA), as revealed from the decrease in reaction temperatures and the increase in rate constants; however, the computed activation energy did not show any correlation to the catalyst concentration. The values of E and A for the uncatalysed reaction at different heating rates showed interdependence through kinetic compensation (KC) effect. Using KC correction, E values were normalised for the value of A for the uncatalysed reaction under identical conditions. The normalised E values decreased exponentially with increase in concentration of FeAA, showing high propensity of the HTPB-IPDI system for catalysis.
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  • 9
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    Journal of thermal analysis and calorimetry 59 (2000), S. 157-168 
    ISSN: 1572-8943
    Keywords: cellulose acetate ; DSC ; glass transition ; melting ; polycaprolactone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cellulose acetate-based polycaprolactones (CAPCL's) were synthesized by the polymerization of ε-caprolactone which was initiated by non-substituted OH group in cellulose acetate. The CL/OH (mol mol−1) ratios of the CAPCL's were changed from 2 to 20. Thermal and viscoelastic properties of the CAPCL sheets were studied by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Glass transition, cold crystallization and melting were determined by DSC. Dynamic modules (E'), dynamic loss modules (E'') and tanδ were measured in a temperature range from −150 to 50°C by DMA. Apparent activation energy of a dispersion was calculated from the frequency dependency of E'' peak temperature. It was found that the main chain motion of both CA and PCL is observed in a CL/OH ratio from 0 to 10 mol mol−1. However, when CL/OH ratio exceeds 10 mol mol−1, the crystalline region which is rearranged by the PCL chain association is observed and only the main chain motion of PCL can be detected.
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  • 10
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    Journal of thermal analysis and calorimetry 59 (2000), S. 245-255 
    ISSN: 1572-8943
    Keywords: DSC ; metallocene ; polyethylenes ; SAXS ; synchrotron radiation ; thermal fractionation ; WAXD ; Ziegler-Natta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, the stepwise isothermal crystallization or thermal fractionation of Ziegler—Natta and metallocene based polyethylenes (ZN-PE and m-PE) with two kinds of branch lengths (ethyl and hexyl) and branch compositions were studied using simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The crystal long period and the invariant were determined by SAXS, and the variations of crystal unit cell parameters and the degree of crystallinity were determined by WAXD. The arithmetic mean length (Ln), the weightedmean length (Lw) and the broadness index (Lw/Ln) of the studied polyethylenes were previously determined by DSC. Results from these studies were interpreted using the model of branch exclusion, which affects the ability of the chain-reentry into the crystal phase. Multiple SAXS peaks and step-change in crystallinity change (WAXD) were seen during heating, which corresponded well with the crystal thickness distribution induced by stepwise crystallization. The effects of the heterogeneity of the 1-olefin branch length and the distribution on the crystal long period and the invariant as well as the degree of crystallinity were discussed.
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  • 11
    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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  • 12
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    Journal of thermal analysis and calorimetry 59 (2000), S. 497-508 
    ISSN: 1572-8943
    Keywords: Avrami equation ; crystallization ; dibenzylidene sorbitol ; DSC ; isothermal kinetics ; nucleating agents ; nucleation ; pine crystal ; polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of nucleating agents such as dibenzylidene sorbitol (DBS) (a derivative of sorbitol), pine crystal 1500, sodium and potassium benzoates in commercial grade isotactic polypropylene iPP are studied using differential scanning calorimetry (DSC). Isothermal crystallization kinetics of polypropylene to the alpha phase have been analyzed using Avrami's model. Results indicate that dibenzylidene sorbitol and pine crystal are very effective in increasing the crystallization temperature of the polymer and number of nuclei formed during crystallization.
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  • 13
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    Journal of thermal analysis and calorimetry 59 (2000), S. 559-570 
    ISSN: 1572-8943
    Keywords: adhesive ; composition analysis ; curing kinetics ; DMA ; DSC ; TGA ; thermal cure ; thermoplastic/thermoset blend
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC, TGA and DMA thermal analysis techniques are used to characterize a complex adhesive blend. The chemical and thermomechanical property development shown to follow a two-stage process. Beneficial synergy between these analysis tools is demonstrated in this study.
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  • 14
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    Journal of thermal analysis and calorimetry 59 (2000), S. 23-31 
    ISSN: 1572-8943
    Keywords: DSC ; fullerene ; glass transition ; star-like polystyrene ; segmental dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Segmental dynamics around Tg in the 4- and 6-arm fullerene (C60) core star-like polystyrenes with different preset arm lengths was studied by DSC as compared to that in the linear PS and PS/C60 blend. The ‘anomalies’ in glass transition behavior were found for the stars including both suppression and facilitation of segmental motion, and pronounced dynamic heterogeneity within a transition range. The results are interpreted in terms of breakdown of intermolecular cooperativity of segmental motions and PS-C60 interactions.
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  • 15
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    Journal of thermal analysis and calorimetry 59 (2000), S. 675-680 
    ISSN: 1572-8943
    Keywords: conducting polymer ; DSC ; kinetic analysis ; PPV ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The title polymer was obtained electrochemically by the reduction of 4,4'-bis(dibromomethyl)-2,2'-dimethoxybiphenyl under very smooth conditions. The DSC and TG/DTG curves registered at four different heating rates showed that the polymer is stable in air up to 150°C, where smooth degradation starts. Above 300°C, decomposition is fast and exothermic (ΔH= –323 J g–1) . The activation energy (116±4 kJ mol–1 ) was determined by Ozawa's method.
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  • 16
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    Journal of thermal analysis and calorimetry 59 (2000), S. 721-727 
    ISSN: 1572-8943
    Keywords: ageing ; annealing ; DSC ; polyaniline ; relaxation transition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermally treated films of polyaniline-emeraldine base (PANI-EB) cast from NMP solution were studied by using differential scanning calorimetry. Dependence of the thermodynamic parameters of the relaxation transitions on temperature and annealing period as well as the effect of the thermal history of the samples upon the crosslinking processes were investigated. For the first time DSC analysis of PANI-EB films after prolonged ageing was performed. It was found that relaxation transitions can be registered only for crosslinked PANI-EB. The crosslinking processes proceed both upon short-time heating of the polymer studied over80°C and during long-time storage at room temperature.
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  • 17
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    Journal of thermal analysis and calorimetry 59 (2000), S. 711-719 
    ISSN: 1572-8943
    Keywords: cure ; dicyandiamide ; DSC ; epoxy ; hermetic ; solvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The curing characteristics of adicyandiamide-cured epoxy system under the influence of solvents in a closed environment were studied by means of isothermal differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The DSC analyses revealed that the presence of solvent results in decreases in the curing exotherm, the initial curing rate, the glass transition temperature, the reaction rate and the reaction order of the epoxy resin. The greatest decreases were caused by the solvent with the highest boiling temperature. A change in temperature-dependent curing route due to the heat absorbed during solvent evaporation is responsible for the difference. The FTIR analyses confirmed that the composition of the cured resin is affected by the solvent, the curing temperature and the specimen configuration. As compared with those obtained from open systems, specimens produced in a closed environment have an enhanced curing exotherm, initial curing rate, glass transition temperature, reaction rate and reaction order because of the retention of volatile catalytic by-products.
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  • 18
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    Journal of thermal analysis and calorimetry 59 (2000), S. 837-846 
    ISSN: 1572-8943
    Keywords: DSC ; γ-irradiation ; laser Raman ; microelectrophoresis ; XRD ; zeta-potential ; zirconium hydroxide ; ZrO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Zirconium hydroxide particles produced by rapid precipitation at pH 10.4, 7 or 2 were subjected toγ-irradiation up to a final dose of 20 MGy. The effects of the γ-irradiation were examined by X-ray powder diffraction, laser Raman spectroscopy, differential scanning calorimetry and microelectrophoretic measurements. It was found that γ-irradiation had no influence on the behaviour of zirconium hydroxide during calcination and subsequent cooling. The results of microelectrophoretic measurements showed that γ-irradiation influences the surface properties of zirconium hydroxide as a function of the precipitation pH. Zirconium hydroxide precipitated at pH 2 proved to be the most susceptible to γ-irradiation, while the sameγ-irradiation had very little (if any) effect on the surface properties of zirconium hydroxide precipitated at pH 10.5. After γ-irradiation, the electrophoretic mobility of zirconium hydroxide precipitated at pH 2 was increased at both low and high pH, thereby indicating an increase in its adsorption capacity. The analogy observed between the pH-dependence of the effects of γ-irradiation on the electrokinetic behaviour of zirconium hydroxide and the influence of ball-milling on the thermal behaviour of zirconium hydroxide [8] suggested that the susceptibility of amorphous zirconium hydroxide increases with decrease of the precipitation pH.
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  • 19
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    Journal of thermal analysis and calorimetry 61 (2000), S. 607-614 
    ISSN: 1572-8943
    Keywords: composted materials ; DSC ; thermal characterization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was applied to the study of material composted from sawdust, used coffee, farmyard manure and the organic fraction of domestic solid waste. Composting trials were carried out in Morocco and samples were collected after different periods of composting. The results obtained provided evidence that sawdust substrate is not a suitable source for composting due to the high content of lignin; samples from used coffee are characterized by a degree of aromaticity that is lower and a functional group heterogeneity that is higher than those of organic wastes from manure and the organic fraction of domestic wastes. The latter organic waste substrates appear to be easily degraded and humified and to give DSC curves that at the end of composting are vary close to those of native soil humic acids.
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  • 20
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    Journal of thermal analysis and calorimetry 61 (2000), S. 711-718 
    ISSN: 1572-8943
    Keywords: DSC ; PEG ; T-CR-T
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified isoconversional method is applied to perform the kinetic analysis of non-isothermal processes. The solidification process of a polyethylene glycol with a mean molecular of 4000 (PEG 4000) was here analyzed. It was stated that the Avrami model provides a good description of the solidification process. Temperature-cooling rate-transformation diagrams were constructed and there was a good agreement between experimental data and the calculated T-CR-T curves. Moreover, morphological qualitative analysis has been performed by means of scanning electron microscopy.
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  • 21
    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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  • 22
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    Journal of thermal analysis and calorimetry 61 (2000), S. 771-778 
    ISSN: 1572-8943
    Keywords: burning rate ; DATH ; DSC ; TG ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition characteristics of1,7-diazido-2,4,6-trinitrazaheptane (DATH) and multi-component systems containing DATH were studied by using DSC, TG and DTG techniques. Three –NO2 groups in the DATH molecule break away first from the main chain when DATH is heated up to 200°C. Following this process, the azido groups and the residual molecule decompose rapidly to release a great deal of heat within a short time. In the multi-component systems, DATH undergoes a strong interaction with the binder of the double-base propellant and a weak interaction with RDX. The burning rates of the two propellants were determined by using a Crawford bomb. The results showed that the burning rate rises by about 19–66% when 23.5%DATH is substituted for RDX in a minimum smoke propellant. Meanwhile, the N2 level in the combustion gases is enhanced, which is valuable for a reduction of the signal level of the solid propellant.
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  • 23
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    Journal of thermal analysis and calorimetry 62 (2000), S. 51-62 
    ISSN: 1572-8943
    Keywords: DSC ; kinetic models ; protein denaturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract New approaches to the analysis of differential scanning calorimetry (DSC) data relating to proteins undergoing irreversible thermal denaturation have been demonstrated. The experimental approaches include obtaining a set of DSC curves at various scanning rates and protein concentrations, and also reheating experiments. The mathematical methods of analysis include construction of a linear anamorphosis and simultaneous fitting of a theoretical expression for the dependence of the excess heat capacity on temperature to a set of experimental DSC curves. Different kinetic models are discussed: the one-step irreversible model, the model including two consecutive irreversible steps, the Lumry and Eyring model with a fast equilibrating first step, and the whole kinetic Lumry and Eyring model.
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  • 24
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    Journal of thermal analysis and calorimetry 60 (2000), S. 117-121 
    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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  • 25
    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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  • 26
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    Journal of thermal analysis and calorimetry 60 (2000), S. 111-116 
    ISSN: 1572-8943
    Keywords: DMTA ; DSC ; HMDI ; mesogenic chain extender ; polyurethane
    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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  • 27
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    Journal of thermal analysis and calorimetry 60 (2000), S. 163-166 
    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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  • 28
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; physical aging ; TGDDM epoxy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The physical aging of a system containing tetraglycidyl-4-4′-diaminodiphenylmethane (TGDDM), with a multifunctional novolac glycidyl ether resin hardened by 4,4′-diaminodiphenylsulphone (DDS) has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Samples fully cured were aged at temperatures between 200 and 250°C, during periods of time from 1 to a maximum of 336 h. Furthermore, the dynamic mechanical relaxation behaviour annealed at temperature of 220°C, was studied, aging during 24 and 168 h. The effect of the enthalpy relaxation during DSC heating scan is shown by the presence of an endothermic peak whose position and intensity depends on the aging conditions, both temperature and time. DSC studies suggest that enthalpy relaxation increases gradually with aging time to a limiting value for each temperature where structural equilibrium is reached. DMA results show that the effect of aging is to cause chain stiffening and a decrease in the height of the peak value of the loss factor.
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  • 29
    ISSN: 1572-8943
    Keywords: 2-benzylamino-butanol ; DSC ; mandelic acid ; melting phase diagram ; optical resolution
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The optical resolution of racemic mandelic acid (I) by S-2-benzylamino-butanol (II) was performed in water, ethyl acetate, and water saturated ethyl acetate. It was found that the efficiency of the resolution is three times higher in water saturated ethyl acetate than in either water or ethyl acetate. The salt mixtures produced during the resolutions and the pure diastereoisomeric salts were analyzed by TG, DSC and X-ray powder diffraction measurements. The R-(-)-I×S-(+)-II salt has the higher melting point and heat of fusion value which indicates that this is the more stable salt. Though the general assumption is that diastereoisomeric salt pairs of successful optical resolutions form eutectic systems, the R-mandelic acid-S-2-benzylamino-butanol and the S-mandelic acid-S-2-benzylamino-butanol system was found to behave in a different way. Melting did not start at or near the estimated eutectic temperature. The difference can be explained either by miscibility in the solid phase (solid solution) or by a blocked interaction between the crystals of the two solid salts. This unusual behaviour of the salt pair should be responsible for the unusual difference in the efficiency of the resolutions performed in different solvents
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  • 30
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    Journal of thermal analysis and calorimetry 60 (2000), S. 535-539 
    ISSN: 1572-8943
    Keywords: DSC ; ferrite ; Mössbauer spectra ; TG ; thermal decomposition ; zinc ferriformate
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis of zinc hexa(formato)ferrate(III) decahydrate, Zn3 [Fe(HCOO)6]2 10H2O has been investigated up to 800°C in static air atmosphere employing TG, DSC, XRD, IR, ESR and Mössbauer spectroscopic techniques. After dehydration at 160°C, the anhydrous complex decomposes into α-Fe2 O3 and zinc carbonate in successive stages. Subsequently the cations remix to yield fine particles of zinc ferrite, ZnFe2 O4 , as a result of solid state reaction between α-Fe2 O3 and zinc carbonate at a temperature (600°C) much lower than for ceramic method.
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  • 31
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    Journal of thermal analysis and calorimetry 60 (2000), S. 595-604 
    ISSN: 1572-8943
    Keywords: crystal structure ; DSC ; oxides ; X-ray diffraction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of TiO2 prepared by hydrolysis method was presented. Thermodynamics and kinetics of anatase crystallization reaction were investigated. Differential method of kinetic data evaluation in non-isothermal conditions according toKissinger, Ozawa and Kazeev-Yerofeev was applied. Starting, crystallized and thermally treated powders were determined using X-ray powder diffraction analysis. The characteristic parameters (the activation energy, constant rate and formal kinetic order of reaction) of TiO2 formation were calculated using DSC data.
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  • 32
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    Journal of thermal analysis and calorimetry 60 (2000), S. 683-689 
    ISSN: 1572-8943
    Keywords: DSC ; heat capacity ; mixed oxide TiO2-RuO2 ; RuO2 ; TiO2
    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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  • 33
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    Journal of thermal analysis and calorimetry 60 (2000), S. 333-343 
    ISSN: 1572-8943
    Keywords: base line ; DSC ; kinetics ; modeling ; thermodynamics ; TMDSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.
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  • 34
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    Journal of thermal analysis and calorimetry 60 (2000), S. 357-369 
    ISSN: 1572-8943
    Keywords: blends of polyamides ; copolyamides ; crystallization ; DSC ; melting point ; structure
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The DSC method was used to obtain more information on changes of thermal properties connected with different comonomers bound in the (co)polymer chains. The copolyamides propered were block ones which were less crystalline and compatible with poly-ε-caprolactam. The results have confirmed the crystalline nature of polyamides and copolyamides.
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  • 35
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    Journal of thermal analysis and calorimetry 60 (2000), S. 345-355 
    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Some DSC calorimeters, such as the model DSC 111, built by the society Setaram, allow the user to set the temperature programming parameters. Usually default values furnished by the constructor are often used, but it is very interesting to study the thermal behaviour of the regulation of the calorimeter under different conditions and with different kinds of set point temperatures. For this research, we have developed in C language a set of software in order to demonstrate the behaviour of the (proportional integral derivative) PID controller of the DSC. It can help the user to choose correct values for P, I and D parameters according to the kind of experiment conducted. The software allows studies of extra parameters, such as the sampling rate of the computerized PID controller or the determination of filtering of the correction.
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  • 36
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    Journal of thermal analysis and calorimetry 60 (2000), S. 917-926 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; KDNBF ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract KDNBF (potassium 4,6-dinitrobenzofuroxan) has been used as a primer explosive in igniters and detonators for many years. Considerable information about the sensitivity of KDNBF to various stimuli, such as impact, friction, shock and electrostatic charge, is known. However, the thermal sensitivity of KDNBF has been relatively unexplored. Hence, there is very little information available concerning the fundamental thermal properties of KDNBF. Therefore, as part of an extensive thermal hazard assessment, DSC, TG, accelerating rate calorimetry (ARC) and heat flux calorimetry (HFC) measurements have been undertaken on KDNBF. The results demonstrate that KDNBF decomposes via a multi-step exothermic process directly from the solid state. The decomposition process does not appear to depend on the nature of the atmosphere, except in the final stage of the TG decomposition in air, where remaining carbonaceous material is converted to CO2. The first stage of the decomposition is sufficiently rapid that ignition occurs if too large a sample is used. Dynamic and isothermal methods were used to obtain the kinetic parameters and a range of activation energies were obtained, depending on the experimental conditions. The kinetic results have been analyzed in terms of various solid state decomposition models.
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  • 37
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    Journal of thermal analysis and calorimetry 61 (2000), S. 75-89 
    ISSN: 1572-8943
    Keywords: DSC ; Fourier transformation ; heat capacity ; sawtooth-modulation ; TMDSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The determination of heat capacity data with sawtooth-type, temperature-modulated differential scanning calorimetry is analyzed using the Mettler-Toledo 820 ADSC™temperature-modulated differential scanning calorimeter (TMDSC). Heat capacities were calculated via the amplitudes of the first and higher harmonics of the Fourier series of the heat flow and heating rates. At modulation periods lower than about 150 s, the heat capacity deviates increasingly to smaller values and requires a calibration as function of frequency. An earlier derived correction function which was applied to the sample temperature-controlled power compensation calorimeter enables an empirical correction down to modulation periods of about 20 s. The correction function is determined by analysis of the higher harmonics of the Fourier transform from a single measurement of sufficient long modulation period. The correction function reveals that the time constant of the instrument is about 5 s rad−1 when a standard aluminum pan is used. The influence of pan type and sample mass on the time constant is determined, the correction for the asymmetry of the system is described, and the effect of smoothing of the modulated heat flow rate data is discussed.
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  • 38
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    Journal of thermal analysis and calorimetry 61 (2000), S. 91-98 
    ISSN: 1572-8943
    Keywords: DSC ; heat flow calibration ; temperature calibration
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermoanalytical instruments are extensively used in R&D as well as in industrial quality control. A quantitative analysis of the data of a thermoanalytical measurement requires a careful calibration of the instrument. In differential scanning calorimetry (DSC) the quantities that have to be calibrated are the temperature and the heat flow. These two quantities are usually calibrated by evaluating melting or solid-solid transitions of some reference materials with well known transition enthalpies and temperatures. In this contribution we investigate temperature and heat flow calibration in the temperature range between −100 and 160°C. We included 9 different samples for the analysis and established some general rules for the calibration process. As a result we found that with a well calibrated instrument the heat flow can be measured with 90% confidence to about ± 3% accuracy in this temperature range. With respect to temperature calibration we find that accuracies of ±0.8°C (90% confidence) may be expected. These values represent general accuracy limitations of DSC’s due to varying heat transfer conditions within the samples.
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  • 39
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    Journal of thermal analysis and calorimetry 61 (2000), S. 363-368 
    ISSN: 1572-8943
    Keywords: DSC ; glycosylated ribonuclease ; thermodynamic stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermodynamic stability of pancreatic ribonuclease B (RNase B), which possesses identical protein structure of pancreatic ribonuclease A (RNase A), but differs by the presence of a carbohydrate chain attached to Asn 34, was studied by means of differential scanning calorimetry (DSC) at different pH conditions. The comparison between the two proteins has shown a little but significant stabilization of RNase B with respect to the unglycosylated one at pH values higher than 7.0. The thermodynamic analysis reveals the carbohydrate moiety to have a small stabilization effect of 3 kJ mol–1 at pH 8.0 and 63°C on the protein.
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  • 40
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    Journal of thermal analysis and calorimetry 61 (2000), S. 341-350 
    ISSN: 1572-8943
    Keywords: DSC ; polymorphism ; X-ray
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the hydrocarbon chain length in the formation of interdigitated and non-interdigitated bilayers in n -alkylammonium chlorides has been investigated for chain lengths varying between 8 and 14 carbon atoms. The formation of non-interdigitated bilayers during crystallization from solution is favoured for shorter chains whilst the interdigitated structure is predominant for larger chains. The thermodynamic parameters of the solid to solid phase transitions in the non-interdigitated samples depend on chain length showing the odd-even alternation that characterized homologous series in n -paraffins. The solid to liquid crystal phase transition temperatures and enthalpies show a linear dependence with the chain length.
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  • 41
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    Journal of thermal analysis and calorimetry 61 (2000), S. 369-376 
    ISSN: 1572-8943
    Keywords: diclofenac ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry was applied to the determination of diclofenac in three 'Voltaren' formulas. The pharmaceutical products (soluble tablets, suppositories and vials) were selected in order to show that calorimetric analysis is an easy technique to perform and can be competitive with other conventional methods. In the tablets diclofenac (DH) was determined, without any pre-treatment, from the area of the endothermic peak which occurs at about 180°C in the DSC curve obtained in N2 atmosphere. In the analysis of the suppositories and vials, nitrilotriacetic acid (NTA) was added to transform the diclofenac sodium salt (DS) into the thermally active form (DH). In both cases, it was necessary to eliminate the interference of excipient by cyclohexane extraction (suppositories) or by a multistep program for the DSC run (vials). The accuracy of the results and the simplicity of the procedure justify the important role of DSC in the analysis of these drugs and certainly of several other commercial products.
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  • 42
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    Journal of thermal analysis and calorimetry 61 (2000), S. 389-396 
    ISSN: 1572-8943
    Keywords: compost ; DSC ; organic matter ; TG ; thermal stability
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    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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  • 43
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    Journal of thermal analysis and calorimetry 61 (2000), S. 411-423 
    ISSN: 1572-8943
    Keywords: bread baking ; DSC ; starch gelatinization
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Starch gelatinization in wheat flour dough of various moisture contents was quantitatively evaluated by means of DSC. The experimental records were worked out in the form of excess heat capacity vs. T traces which were deconvoluted to single out the contribution of starch gelatinization from that of the decomposition of amylose-lipid complexes. The quantitative procedure used put into evidence that a third endothermic process would take place in the dough with a poor moisture content. DSC runs carried out with sealed pans (i.e., at constant moisture level) and open pans (from which some water was free to evaporate) allow simulation of two extreme conditions of a real baking process, namely that relevant to the central core and to superficial layer of a dough loaf, respectively. The extent of starch gelatinization occurred in these conditions was quantitatively assessed. These data were collected at various heating rates and used to define temperature-time-transformation(TTT) diagrams which are useful tools to predict the progress of baking for any given thermal history of the system.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 451-459 
    ISSN: 1572-8943
    Keywords: DSC ; gelatin films ; high angle X-ray
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    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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  • 45
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    Journal of thermal analysis and calorimetry 62 (2000), S. 797-807 
    ISSN: 1572-8943
    Keywords: dimenhydrinate ; DSC ; film coating ; HPMC ; thermal conductivity
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    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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  • 46
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    Journal of thermal analysis and calorimetry 61 (2000), S. 565-578 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; PK99 ; rigid amorphous fraction ; WAXD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the whole range between the glass transition temperature (T g) and the melting temperature (T m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy. The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer, and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques. The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions. Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does not relax at T g.
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    Journal of thermal analysis and calorimetry 59 (2000), S. 847-858 
    ISSN: 1572-8943
    Keywords: derivative thermogravimetry ; diffusion-induced stress ; modeling ; molybdenum ferrite ; oxidation kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract From a model for isothermal oxidation kinetics in nanosized ferrite spinels based on a diffusion-induced stress effect, the authors present a modeling of the DTG curves for the oxidation of Fe2+ and Mo3+ cations on octahedral sites of a molybdenum ferrite. This has been made by considering that the chemical diffusion coefficient is given by the relation $$\tilde D = D_o \exp \left( {\frac{{E'_{\text{a}} + pV_{\text{a}} }}{{RT}}} \right)$$ , when D o is a pre-exponential factor, E a ′ an activation energy and V a an activation energy induced by the oxidation.
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  • 48
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    Journal of thermal analysis and calorimetry 61 (2000), S. 731-743 
    ISSN: 1572-8943
    Keywords: DSC ; phase transition ; phospholipid ; phthalates ; plasticizers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Phthalic acid esters, and in particular bis-2-(ethylhexyl) phthalate, are common environmental contaminants with long-term toxic and carcinogenic effects that readily dissolve in lipid substances. DSC measurements of hydrated multilamellar dipalmitoyl phosphatidylcholine liposomes in the presence of different amounts of bis-2-(ethylhexyl) phthalate, dioctyl phthalate, dibutyl phthalate (DBP) and diethyl phthalate (DEP) were considered. The effects on the main transition temperature, ΔH, and the shape and width of the transition were studied. A decrease in Tm, without an accompanying decrease in ΔH,and increases in both the asymmetry and the width of the main transition peak were observed. In some cases, the calorimetric curve showed complex peak structures arising from the coexistence of various aggregates of different sizes. This was particularly evident in the liposomes with DEP and DBP contents ranging from 5.0 to 7.5% m/m. For all the considered model systems, the effects were noticeable even in the presence of small amounts of phthalates; in the presence of greater amounts, the overall structure of the bilayer was in some cases strongly modified, with the appearance of new different phases. Since the function of a membrane-associated protein is dependent on the lipid structure, phthalates could modify the function by modifying the membrane structure.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 805-818 
    ISSN: 1572-8943
    Keywords: aluminium ; ARC ; DSC ; kinetics ; nanometric size ; SDT ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of Alex, a nanosized Al powder, were determined using various techniques, including DSC, TG, simultaneous TG-DTA (SDT) and accelerating rate calorimetry (ARC). The results demonstrate that the specific heat capacities of nano and micron size Al powders are similar between 30 and 400°C. Dynamic and isothermal methods were used to determine the kinetic parameters for the oxidation reaction of Alex, which was detected at an onset temperature of 481°C. The results obtained were in good agreement with each other. From the ARC experiments, exotherms were detected near 340 and 260°C for experiments started at ambient pressure and at 0.72 MPa, respectively.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 177-186 
    ISSN: 1572-8943
    Keywords: binary phase diagram ; DSC ; enthalpic method ; eutectic composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We construct with a differential scanning calorimeter (DSC) a phase diagram for the ethylene carbonate (EC)-dimethyl carbonate (DMC) binary system for its liquid-solid phase equilibria. We determine the eutectic composition of the binary system using an enthalpic method that we devised based on the composition dependence of the enthalpy of solidus melting, with highly consistent results. We also discuss the merits and limitations of this enthalpic method.
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    Journal of thermal analysis and calorimetry 59 (2000), S. 999-1015 
    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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  • 52
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    Journal of thermal analysis and calorimetry 59 (2000), S. 1023-1027 
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; fibers ; polybenzimidazole ; secondary transitions
    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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    Journal of thermal analysis and calorimetry 61 (2000), S. 579-587 
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; modified epoxy-amine ; epoxy rubber system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this work the curing kinetics behaviour of a rubber modified epoxy amine system is investigated through calorimetric analysis. This study is part of a wider investigation on new epoxy formulations to be used as matrices of composite materials. The aim is to enhance both the processing behaviour and the mechanical properties of the matrix in order to obtain higher performance composites for more demanding applications. The epoxy system is blended with a high molecular mass rubber containing functional groups reactive towards the epoxies. The formation of a rubber/epoxy network can be achieved by means of a 'pre-reaction' between the epoxy monomers and the rubber functional groups, carried out in the presence of a suitable catalyst and before the resin is cured with the amino hardener. In this work the influence of both the rubber and the catalyst on the resin cure kinetics is analysed.
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    Journal of thermal analysis and calorimetry 63 (2000), S. 339-344 
    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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  • 55
    ISSN: 1572-9001
    Keywords: Dynamic NMR ; 15N NMR ; 13C NMR ; DSC ; tautomerism ; melting point
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The behavior of neat 3(5)-methylpyrazole has been studied at low temperatures by DSC and by NMR (13C and 15N). The main conclusion is that the supercooled liquid is a mixture of four trimers formed by 3-methyl and 5-methyl tautomers.
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    Plasma chemistry and plasma processing 20 (2000), S. 65-86 
    ISSN: 1572-8986
    Keywords: thermal plasma ; waste processing ; fly-ash vitrification ; optical emission spectroscopy ; volatilization ; lead ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Results are presented of optical emission spectroscopy (OES) application asa control tool to improve fly-ash plasma vitrification. A twin-torch plasmasystem has been used for the fly-ash processing, and a new OES method hasexamined metallic vapors above the melt. The method allows the study ofnonhomogeneous optically thin plasmas exhibiting a symmetry plane withoutsophisticated tomographic systems. The dc arc torches are mounted above acold crucible filled with a synthetic glass. The arc intensity is from200 to 400 Å. Argon is introduced into the torches along the cathodeand the anode, while argon, oxygen or hydrogen are injected through thelance between the torches. Local plasma temperatures above the melt havebeen evaluated using measured relative intensities of spectral lines ofthe plasma-forming gas. Metallic vapor concentration in the plasma isdeduced from the intensity ratio of the metal–gas spectral lines. Leadoxide has been used to study heavy-metal behavior at the fly-ash plasmavitrification. Distribution of the lead along the crucible surface,depending on the plasma-forming gas composition as well as the concentrationevolution with time, have been examined. The elemental analysis of theresultant glass has been measured by scanning electron microscopy (SEM)with energy-dispersive spectrometry (EDS). A predictive model has beenadapted to simulate the noncongruent vaporization of heavy metals from themelt. According to the data obtained, steep variations of the volatility ofthe elements depend strongly on reducing properties of gases controllingthe plasma composition near the melted surface. In addition, the melttemperature and the redox potential of the gas phase are found to be themost critical parameters.
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    Plasma chemistry and plasma processing 20 (2000), S. 521-553 
    ISSN: 1572-8986
    Keywords: thermal plasma ; transferred arc ; fumed silica ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The volatilization of quartz in a transferred arc plasma followed byquench and recondensation is a promising route to the production offumed silica. In this work, an existing model of a transferred arcwas modified and combined with a newly developed model of a moltensilica anode to predict the behavior of a transferred arc evaporatoras a function of current and plasma gas flow rate. The model predictstemperature, current, and flow fields in both the plasma and anode aswell as evaporation rates. Although quantitative agreement withexperimental results was not possible because of insufficient propertydata for silica at high temperature, the results were within an orderof magnitude of those measured experimentally. The model developed isuseful for the design and scaleup of this type of reactor.
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    Journal of materials synthesis and processing 8 (2000), S. 139-144 
    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.
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    Oxidation of metals 53 (2000), S. 49-75 
    ISSN: 1573-4889
    Keywords: FeCrAl ; α Al2O3 ; high-temperature resistance ; residual stresses ; thermal stresses ; X-ray diffraction ; relaxation ; modeling ; elasto-viscoplastic model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The stresses generated in alumina scales during different oxidation stepscontrol the protective character of such scales and their lifetime. Laboratoryand industrial Fe–Cr–Al alloys, differing by their impuritycontent and preparation, and for which the oxidation kinetics werepreviously characterized, were studied here to experimentally determine ortheoretically calculate the stress level in the alumina scales. Theexperiments were performed by X-ray diffraction (XRD) at room temperature,using the sin2psi method. The oxide-stress level wascorrelated with many parameters, such as the scale microstructure andmorphology, the nature of the substrate, the substrate and oxide thickness,the oxide grain size, the cooling rate, etc. A numerical elasto-viscoplasticmodel was developed to calculate the thermal stresses and to point out theeffect of the relaxation phenomena either during cooling or duringisothermal treatment after oxidation. The results obtained by theelasto-viscoplastic model are in good agreement with the experimental ones.
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    Journal of nondestructive evaluation 19 (2000), S. 43-54 
    ISSN: 1573-4862
    Keywords: Ultrasonic testing ; modeling ; anisotropy ; shear horizontal wave ; field profile ; electromagnetic acoustic transducer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Mathematics
    Notes: Abstract Based on the description of shear horizontal (SH) wave propagation in arbitrarily oriented transversely isotropic media, radiation characteristics of ultrasonic transducers for this wave type are determined. The radiated wavefields are obtained by point source superposition, making use of an analytical relationship for the wave propagation direction as a function of the spatial coordinates. Approximate formulae are given for the radiation characteristics of circular and rectangular transducers in the far-field, which are in a form similar to the isotropic material case. Focusing on transversely isotropic weld metal specimens and unidirectional composites, numerical evaluation is performed for normal-incidence probes as well as for electromagnetic acoustic transducers.
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    Journal of materials synthesis and processing 8 (2000), S. 73-85 
    ISSN: 1573-4870
    Keywords: Chemical vapor deposition (CVD) ; diamond films ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The evolution of grain size, grain-size distribution, morphological and crystallographic texture, surface roughness, and the contribution of various surface facets to the growth of polycrystalline diamond films is performed by carrying out a series of two-dimensional computer simulations. The films are assumed to grow from a set of randomly oriented, {100}- and {111}-faceted nuclei by the motion of their vertices (the points where the adjoining facets of the same or neighboring grains meet). The vertex velocities are found to be a function of the orientation and the growth rate of the adjoining facets. To quantify the latter, a {100} to {111} growth-rate parameter is used. The results show that the evolution of the grain size and its distribution, surface roughness, morphological and crystallographic texture, and the portion of the film grown from different surface facets are all mutually linked and governed by the magnitude of the growth-rate parameter. The latter can be controlled by the CVD processing conditions, such as the substrate temperature, reactor pressure, mole fraction of carbon-source gas (e.g., CH4, C2H2).
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  • 62
    ISSN: 1573-4943
    Keywords: Serum transferrin ; modeling ; accessible surface area ; surface charge ; molecular recognition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In order to rationalize the physicochemical properties of human serum-transferrin (STf) and the STf-receptor (TfR) recognition process, we have tried to predict the 3D structures of apo- and iron-loaded STf using a homology modeling technique to study the changes in the structural characteristics that take place upon the uptake of iron by STf in solution. The crystal structures of both forms for ovotransferrin were used as templates for the STf modeling. The modeled structure of STf gave a satisfactory interpretation for the typical physicochemical properties such that (1) STf has a negative electrophoretic mobility and its value increases with iron uptake, and (2) the radius of gyration Rg of Tf decreases with iron uptake. It was found that upon iron binding, interdomain closures take place with large movements of the NII and CII subdomains comprising the N- and C-lobes in STf through a hinge-bending motion, accompanied by the opening of the bridge region with a displacement of more than 15 Å. Moreover, in view of the findings from our capillary electrophoresis experiments that the electrostatic interactions significantly contribute to a specific binding of Fe2-STf with TfR, it is inferred that the connecting (bridge) and its neighboring region associated with a surface exposure of negative charge play an important role in the STf-receptor recognition process.
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  • 63
    ISSN: 1573-4978
    Keywords: chromatin ; DNA ; DSC ; thermal denaturation
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    Topics: Biology
    Notes: Abstract The thermal denaturation of calf thymus total chromatin and of fractions enriched in heterochromatin or euchromatin, has been investigated by differential scanning calorimetry and compared to that of calf thymus DNA and DNA-histone complexes. In our experimental conditions, chromatin melts in three thermal transitions: the main one, assigned to separation of the DNA double helix, occurs at 83 °C, while the other two occur at 63 °C and 74 °C. The data show that: (a) the transition enthalpy for denaturation of DNA in the total chromatin and in DNA-histone complexes is nearly the same as that of DNA in solution; (b) the transition at 63 °C is present in the thermogram of the heterocromatin enriched fraction, while it is completely absent in that of the euchromatin enriched one. The results suggest that this transition can be attributed to the higher order structures of heterochromatin.
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  • 64
    ISSN: 1871-4528
    Keywords: root-water uptake ; modeling ; SWACROP ; Ferralsols ; tropics ; Cuba ; Solanum tuberosum L.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The SWACROP root-water uptake function for potatoes was determined in the 1994–95 crop season on a Ferralsol in Havana province, west Cuba. The maximum pressure-heads under which water is optimally extracted by potato roots were very similar to the original Feddes function. Nevertheless, the anaerobiosis point and the wilting point pressure-head in both functions were not in agreement. However, the simulated values of soil water contents in the 0–40 cm soil depth by performing SWACROP runs in the 1995–96 potato crop season using both functions were very similar. The original Feddes function seems to be good enough for predicting soil water contents in the tropics and no specific other functions need to be developed for any particular soil or climate condition.
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    Biology and philosophy 15 (2000), S. 197-210 
    ISSN: 1572-8404
    Keywords: ecology ; Levins ; modeling ; provisionality ; sociality
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract This essay extends Levins' 1966 analysis of modelbuilding in ecology and evolutionary biology. Amodel, as the product of modeling, might bevalued according to its correspondence to reality. Yet Levins' emphasis on provisionality and changeredirects attention to the processes ofmodeling, through which scientists select and generatetheir problems, define their categories, collect theirdata, compare competing models, and present theirfindings. I identify several points where decisionsare required that are not determined by nature. Thisinvites examination of the social considerationsmodelers are reacting to at the “sites of sociality”.Modelers must weave “socio-ecological webs” so thatthe models can be seen to represent their subjectmatter at the same time as the modelers secure thesupport of colleagues, collaborators and institutions,and enjoin others to act upon their conclusions. Notonly do theory justification and theory generationmerge, but the joint project becomes simultaneouslyphilosophical and sociological.
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    Mathematical geology 32 (2000), S. 301-317 
    ISSN: 1573-8868
    Keywords: hydrogeology ; modeling ; atoll ; coral reef ; carbonate platform
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Mathematics
    Notes: Abstract Large-scale steady-state groundwater flow in atoll carbonate platforms results from temperature and salinity-induced density gradients. Atolls are built on top of a basaltic substrate that provides geothermal heating from beneath. Moreover, they are immersed in the tropical ocean where temperature decreases rapidly with depth. Groundwater circulation in these platforms has long been associated with the geothermal heat flux because it is capable of generating inward and upward flow of oceanic origin water by buoyancy effects. This study shows that hydraulic circulation occurs even in the absence of a geothermal flux because the combination of the cold subsurface ocean waters with the warm surface conditions is sufficient to maintain a convection cell within the carbonate platform. Using a one-dimensional analytical model, validated by more sophisticated two-dimensional simulations, we can investigate the interaction between these two driving forces. The flow rate inside the platform is, in fact, a function of the ratio of the geothermal flux to the temperature gradient in the ocean. It increases with the geothermal flux but decreases with the oceanic temperature gradient. This one-dimensional model also shows that taking salinity effects on density into account increases the flow rates transiting through the platform by a third.
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    Autonomous robots 8 (2000), S. 25-42 
    ISSN: 1573-7527
    Keywords: visual servoing ; robust control ; mobile robot ; vehicles ; modeling ; vision
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We have been interested in Automatic Guided Vehicles (AGV) for several years. In this paper, we synthesize controllers for AGV applications using monocular vision. In particular, we are interested in road following and direction change tasks, and in analyzing the influence of extrinsic camera parameter perturbations on vehicle behavior. We use the bicycle as the kinematic vehicle model, and we choose the position of the white band on the road as the sensor signal. We define an interaction between the camera, which is mounted inside the vehicle, and the white band detected in the image space. Using this kind of interaction, we present how to use a pole assignment technique to solve the servoing task. We show the simulation and experimental results (1/10 scale demonstrator) with and without perturbations. We then investigate the use of a robust controller to slow down the effect of perturbations on the behavior of the vehicle.
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    Natural resources research 9 (2000), S. 215-222 
    ISSN: 1573-8981
    Keywords: market ; electricity ; regression ; calibration ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract Hydro power schemes operating in a free electricity market seek to maximize profits by differing generation rates to take best advantage of fluctuating selling prices, subject to the constraints of keeping storage lakes within their operational bounds and avoiding spillage losses. Various computer algorithms can be used in place of manual scheme operation to aid this maximization process, so it is desirable to quantify any profit gained from a given algorithm. A standard approach involves applying the algorithm to a period of past river flow records to see how much additional scheme income might have been obtained. This process requires the use of a hydro power scheme model, which inevitably can only approximate operational details, so the anticipated income gains are likely to be biased estimates of actual income gained from implementation of the algorithm. In addition to preliminary algorithm evaluation, it is desirable that hydro scheme managers have methodology to confirm anticipated income gain. Such confirmation can be difficult because true income gains are typically in the order of a few percentage and may not be easily distinguishable from background noise. We develop an approach, which allows estimation of true income gain for the situation where a change is made from manual to computer control of hydro power scheme operations, or upgrading from one maximization algorithm to another. The method uses a regression model to describe the former period of scheme operation. Postimplementation residuals from the regression predictions then provide estimates of actual income gain. The method can be sensitive to small but consistent income gains. Also, there is no requirement to construct any hydro scheme simulation model so bias effects should be considerably reduced. The approach was developed in the context of evaluating an income-maximization algorithm applied to a small hydro power scheme in the Kaimai Ranges of New Zealand. However, the methodology seems sufficiently simple and general to be applicable, with modification, to other power schemes moving toward increasing income through operational changes.
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    Transport in porous media 41 (2000), S. 105-116 
    ISSN: 1573-1634
    Keywords: flow ; integration ; Gassmann ; acoustics ; reservoir ; characterization ; modeling ; simulation ; Newton–Raphson
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Integrated flow modeling is the combination of a traditional flow simulator with a petrophysical model. By combining a petrophysical model with a traditional flow model, it is possible to perform calculations that improve our ability to monitor fluid movement in porous media. This paper outlines the formulation of an integrated flow model IFLO and its multi-variable, Newton–Raphson IMPES solution procedure. The benefits of integrated flow modeling and the underlying principles involved in the integration of a flow model with a petrophysical model are presented. Results from the IFLO model are used to illustrate the principles.
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    Higher education 40 (2000), S. 231-242 
    ISSN: 1573-174X
    Keywords: achievement ; attendance ; modeling ; motivation ; problem-based learning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Nature of Science, Research, Systems of Higher Education, Museum Science
    Notes: Abstract Problem-based learning is a constructivist approach toprofessional education stressing the use of real lifeproblems in education. Several previous attempts tounderstand the intricacies of learning in theproblem-based context have led to a causal model,elements of which were tested in the present study.The focus of the investigation was on the students' motivation to committhemselves to studying in a problem-based healthsciences curriculum, expressed in term of levels ofattendance at tutorial meetings. Data were collectedregarding functioning of the tutorial group, tutorfunctioning, level of prior knowledge, quality of theinstructional problems, time spent on individualstudy, academic achievement and increased interest.These data were analyzed using a structural equationsmodeling approach. As hypothesized, commitment appears to bea potent determinant of achievement. In fact, itrepresents one of the strongest determinants oflearning in the model tested.
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  • 71
    ISSN: 1573-1634
    Keywords: NAPLs ; radon ; modeling ; monitoring ; partitioning ; tracer ; emanation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract The recently developed natural radon tracer method has potential as a rapid, low‐cost, nondestructive, and noninvasive method for quantifying NAPL contamination. In the subsurface, radon‐222 (radon) is produced by the decay of naturally occurring radium‐226 contained in the mineral fraction of aquifer solids. In groundwater radon occurs as a dissolved gas, with a half‐life of 3.83 days. In the absence of NAPL, the radon concentration in groundwater quickly reaches a maximum value that is determined by the mineral composition of the aquifer solids, which controls the rate of radon emanation. In the presence of NAPL, however, the radon concentration in the groundwater is substantially reduced due to the preferential partitioning of radon into the organic NAPL phase. A simple equilibrium model and supporting laboratory studies show the reduction in radon concentration can be quantitatively correlated with residual NAPL saturation. Thus, by measuring the spatial distribution in radon it may be possible to identify locations where residual NAPL is present and to quantify the NAPL saturation. When the basic processes of partitioning, radon emanation from the aquifer solids, and first‐order decay are incorporated into an advective/dispersive transport model, good agreement is obtained with the results of laboratory and field experiments. Model sensitivity analyses shows many factors can contribute to the radon concentration response, including the length of the NAPL zone, NAPL saturation, groundwater velocity, porosity, and radon emanation. Thus, care must be taken when applying the radon method to locate and quantify NAPL contamination in the subsurface.
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    Transport in porous media 41 (2000), S. 47-60 
    ISSN: 1573-1634
    Keywords: unsaturated flow ; peat ; filters ; septic ; modeling ; hydraulics ; soil moisture retention curve
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Peat is an alternative filter medium for the treatment of various waste streams including septic tank effluent. The water holding capacity and adsorption capacity of peat make it a favorable filter medium over sand or gravel which are commonly used as the filter medium for the drainage field of septic systems. This paper presents the results of a field study to evaluate the hydraulics of a peat filter used to treat the septic tank effluent from a public school west of Ottawa, Canada. An experimental box was placed within the filter during its construction to provide access to the vertical profile of the peat layer. The filter is periodically pulsed with septic tank effluent, which is distributed over the top of the filter and flows vertically through the peat. The filter was instrumented with tensiometers and transducers to monitor the pore water pressures in response to a pulse of septic tank effluent. An in-depth study of the hydraulics of the system was completed. The soil moisture retention curve and the hydraulic conductivity as a function of density were determined in laboratory experiments. A one-dimensional unsaturated flow model was used to predict the pressure response due to a pulse. A comparison of the field and model results illustrates the impact of the density variations, and the corresponding hydraulic conductivity variations, on the model predictions. The compaction of the peat is an important design consideration for the filter since it directly impacts the flow characteristics and the hydraulic retention time within the filter.
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    Water resources management 14 (2000), S. 257-283 
    ISSN: 1573-1650
    Keywords: decision-making ; ecosystem management ; ecosystem protection ; ecosystem restoration ; modeling ; sustainable development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Notes: Abstract Ecosystem Management (EM) is a new holistic approach to the management of natural resources. It integrates the scientificknowledge on ecological interrelationships and the complex socioeconomic and political frame of values, aiming at the long-term sustainability of a region, i.e., the ecosystem. Itincludes the human, biological and natural dimensions, and canregulate the internal structures and functions of the ecosystem,and the inputs and outputs from it, so that solutions to development and protection problems can be achieved and be socially well-accepted. It has been given attention since 1991,mainly in the U.S.A., where the existing legal framework formeda basis for EM. The former experience of programs based on the traditional methods of management, the goal of sustainable development stated by many governmental, public or private agencies, and the advent of scientific knowledge, permitted the development of a theoretical basis for EM. Today, a significant number of EM programs have been established and are in progressin the U.S.A. Here the concept, general principles and methodology of EM are reviewed, and the EM program in the Stateof Florida in the U.S.A. is presented, which is considered a successful case study. In addition, the examples of managementof two very important ecosystems in Northern Greece are critically presented for comparison, in order to evaluate if they have EM characteristics.
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    Water quality and ecosystem modeling 1 (2000), S. 193-222 
    ISSN: 1573-1669
    Keywords: Sediment transport ; modeling ; Upper Hudson River
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Two-dimensional, vertically-averaged hydrodynamic and sediment transport models were developed and applied as part of a PCB fate and transport modeling study of Thompson Island Pool (TIP), Upper Hudson River. Mechanistic formulations were used to simulate cohesive and non-cohesive suspended load transport; site-specific data were extensively used to determine model inputs. This modeling approach is compared and contrasted to non-mechanistic solids transport sub-models used in other contaminant fate studies. A minimum number of model parameters were adjusted to calibrate the sediment transport model using data collected during the 1994 spring flood. The model was validated during the 1997 spring flood and for a 22-year (1977–1998) period. Successful calibration and validation of the model showed that: (1) deposition and resuspension processes were realistically and accurately formulated in the model; (2) the model is an effective diagnostic tool for quantitatively evaluating net deposition and erosion from various areas of TIP; and (3) sediment transport results can be coupled with a PCB fate model with a high degree of confidence.
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    Water quality and ecosystem modeling 1 (2000), S. 271-309 
    ISSN: 1573-1669
    Keywords: zebra mussels ; modeling ; water quality ; Seneca River ; dissolved oxygen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The development, testing and application of a dynamic two-dimensional (longitudinal-vertical) mass balance model for dissolved oxygen (DO) and chlorophyll (Chl) for rivers is documented that for the first time accommodates both the oxygen demand and filtering effects of zebra mussels. The test system is a phytoplankton-rich section (∼ 15 km long) of the Seneca River, NY, that is believed to represent an upper bound of the impact of this exotic invader. Changes in common measures of water quality of the river brought about by the zebra mussel invasion are reviewed and related longitudinal patterns in DO, Chl, and Secchi disc transparency are documented. Model testing is supported by comprehensive measurements of DO, Chl, and various forcing conditions over a three-month period, and independent determinations of several model coefficients. Wide variations in the areal consumption rate of DO (ZOD; g·m−2·d−1) and filtering rate (m3·m−2·d−1) of zebra mussels, as determined through model calibration, occurred over the study period. Values of ZOD in areas with dense zebra mussel populations at times (e.g., 〉 50 g·m−2·d−1) were an order of magnitude greater than the sediment oxygen demand associated with organically enriched deposits. The value of determinations of these fluxes from model calibration procedures is evaluated within the context of the limitations of protocols presently available to support independent specification of these rates. Model analyses are conducted to evaluate the relative magnitude of source and sink processes for DO and Chl, the potential operation and implications of feedback from low DO levels on oxygen consumption by zebra mussels, and the sensitivity of model simulations to selected sources of uncertainty and variability. Model projections of oxygen resources of the river are presented in a probabilistic format in evaluating reductions in zebra mussel biomass that would be necessary to eliminate violations of standards and regain assimilative capacity.
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    European journal of plant pathology 106 (2000), S. 401-413 
    ISSN: 1573-8469
    Keywords: inoculum density–disease incidence ; biological control agents ; pathogen detection and quantification with molecular and serological techniques ; polymerase chain reaction ; marker and reporter genes ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Understanding the dynamics between a pathogen and a biocontrol agent (BCA) in soil or in an infection court such as the rhizosphere is crucial for predicting the success of biological control. This is especially true for biological control using the strategy of reduction of initial inoculum prior to infection. By studying the population density fluxes over time, one can observe how the BCA and pathogen influence each other's population and life cycles, and how the biological and physical environment influence this relationship. Methods for quantifying fungi and bacteria in soil, including classical (dilution plating, baiting, bioassays), immunological (ELISA, IFC, immunomagnetic) and molecular (DNA hybridization, PCR, marker and reporter genes) methods, are discussed and critiqued. Finally, the value of mathematical modeling of population dynamics as a means of providing important information about the tripartite relationship between the pathogen, BCA, and host plant is reviewed.
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    Journal of electroceramics 5 (2000), S. 153-182 
    ISSN: 1573-8663
    Keywords: modeling ; SOFC ; internal reforming ; cermet
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Approaches to models and computer simulations of conductivity, polarization resistance, and impedance of composite electrodes in solid oxide fuel cells (SOFC) are reviewed with respect to the more important experimental findings. The approaches are classified according to how they model the highly disordered structure of composite SOFC electrodes: As corrugated layers of electrode material covered by a thin film of electrolyte or vice versa (thin film model), as a random packing of particles (Monte Carlo calculations), or using a macroscopic, averaged description of the disordered electrode structure (macroscopic porous-electrode model). Thin film models appear to be useful rationalizations of some experimental measurements of polarization resistance, but in the stricter sense fail to predict a number of important electrode characteristics. The Monte Carlo method, on the other hand, apparently meets with most of the more prominent experimental results reported so far, although some issues concerning parameter choices, among other things, remain to be resolved. The macroscopic porous-electrode theory may serve as a useful simplification of the Monte Carlo method, but with a more limited scope. Modeling of composite electrodes for SOFC thus appears to have reached a level where it can be used for practical engineering applications. As an example of this, the rate of methane reforming at Ni-YSZ cermet anodes under current load is calculated using the framework of the macroscopic porous-electrode theory, modified to include non-linear kinetics and gas-phase diffusion. The reforming reaction is quite evenly distributed in the anode, and its overall rate is therefore strongly dependent on thickness. However, most of the electrochemical reaction is likely to occur in a region closer than 10 μm to the bulk electrolyte. For an anode thickness larger than this, the current-collector potential at a given current is by and large independent of thickness. The ratio between the rates of the reforming and the electrochemical reactions can therefore be balanced to a certain degree by optimizing thickness, without significant loss in cell power. In addition, cermet porosity, volume fraction of Ni and Ni-particle size, appears to have a moderate effect in controlling the rate balance, which will have to be manipulated within the constraints set by the requirement of percolation in the gas-phase and the Ni- and YSZ-networks.
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    Pharmaceutical research 17 (2000), S. 589-592 
    ISSN: 1573-904X
    Keywords: modeling ; stochastic ; Log-normal ; distributions ; pharmacodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To develop a mathematical model for therapeutic drugmonitoring and to assess the kinetic relationships between the intensity ofcorrective action and the approach of drug concentrations to targetvalues. Methods. A mathematical model that succinctly accounts for thecorrective actions and the variability inherent in the pharmacokineticswas used. Results. The validity of the variability term was tested usingexperimental data for steady state concentrations of the drug procainamide.The approach of the monitored process to the target value followedexponential kinetics and an analytical expression for dependence thevariance with time and various dosing parameters was derived. Thevariance of the drug concentration depends critically on a singlenon-dimensional parameter containing the rate constant for the therapeuticcorrective actions and a coefficient describing the variance rate. Whenthe rate constant for the therapeutic corrective actions was less thanthis critical value, the variance increased indefinitely. Conclusions. From a dosing standpoint, large variances in drugconcentrations are undesirable because some patients will be overdosedor underdosed. Since deterministic models cannot provide analyticalsolutions for the moments of drug concentration distribution functions,stochastic models can be used to provide useful insights into the designof therapeutic regimens.
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  • 79
    ISSN: 1573-904X
    Keywords: controlled release ; diffusion ; hydrophilic matrix ; hydroxypropyl methylcellulose (HPMC) ; modeling ; swelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aims of this study were (i) to elucidate the transport mechanisms involved in drug release from hydrophilic matrices; and (ii) to develop an improved mathematical model allowing quantitative predictions of the resulting release kinetics. Methods. Our previously presented model has been substantially modified, by adding: (i) inhomogeneous swelling; (ii) poorly water-soluble drugs; and (iii) high initial drug loadings. The validity of the improved model has been tested experimentally using hydroxypropyl methylcellulose (HPMC)-matrices, containing either a poorly or a freely water-soluble drug (theophylline or chlorpheniramine maleate) at various initial loadings in phosphate buffer pH 7.4 and 0.1 N HCl, respectively. Results. By overcoming the assumption of homogeneous swelling we show that the agreement between theory and experiment could be significantly improved. Among others, the model could describe quantitatively even the very complex effect on the resulting relative release rates (first slowing down, then accelerating drug release) observed when increasing the initial loading of poorly water-soluble drugs. Conclusions. The practical benefit of this work is an improved design model that can be used to predict accurately the required composition and dimensions of drug-loaded hydrophilic matrices in order to achieve desired release profiles, thus facilitating the development of new pharmaceutical products.
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  • 80
    ISSN: 1573-904X
    Keywords: glycyrrhizic acid ; modeling ; enterohepatic cycling ; PBPK ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To analyze the role of the kinetics of glycyrrhizic acid (GD) in its toxicity. A physiologically-based pharmacokinetic (PBPK) model that has been developed for humans. Methods. The kinetics of GD, which is absorbed as glycyrrhetic acid (GA), were described by a human PBPK model, which is based on a rat model. After rat to human extrapolation, the model was validated on plasma concentration data after ingestion of GA and GD solutions or licorice confectionery, and an additional data derived from the literature. Observed interindividual variability in kinetics was quantified by deriving an optimal set of parameters for each individual. Results. The a-priori defined model successfully forecasted GA kinetics in humans, which is characterized by a second absorption peak in the terminal elimination phase. This peak is subscribed to enterohepatic cycling of GA metabolites. The optimized model explained most of the interindividual variance, observed in the clinical study, and adequately described data from the literature. Conclusions. Preclinical information on GD kinetics could be incorporated in the human PBPK model. Model simulations demonstrate that especially in subjects with prolonged gastrointestinal residence times, GA may accumulate after repeated licorice consumption, thus increasing the health risk of this specific subgroup of individuals.
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  • 81
    ISSN: 1573-6873
    Keywords: neural networks ; modeling ; population density ; orientation tuning ; visual cortex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine , Physics
    Notes: Abstract We explore a computationally efficient method of simulating realistic networks of neurons introduced by Knight, Manin, and Sirovich (1996) in which integrate-and-fire neurons are grouped into large populations of similar neurons. For each population, we form a probability density that represents the distribution of neurons over all possible states. The populations are coupled via stochastic synapses in which the conductance of a neuron is modulated according to the firing rates of its presynaptic populations. The evolution equation for each of these probability densities is a partial differential-integral equation, which we solve numerically. Results obtained for several example networks are tested against conventional computations for groups of individual neurons. We apply this approach to modeling orientation tuning in the visual cortex. Our population density model is based on the recurrent feedback model of a hypercolumn in cat visual cortex of Somers et al. (1995). We simulate the response to oriented flashed bars. As in the Somers model, a weak orientation bias provided by feed-forward lateral geniculate input is transformed by intracortical circuitry into sharper orientation tuning that is independent of stimulus contrast. The population density approach appears to be a viable method for simulating large neural networks. Its computational efficiency overcomes some of the restrictions imposed by computation time in individual neuron simulations, allowing one to build more complex networks and to explore parameter space more easily. The method produces smooth rate functions with one pass of the stimulus and does not require signal averaging. At the same time, this model captures the dynamics of single-neuron activity that are missed in simple firing-rate models.
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    Analog integrated circuits and signal processing 25 (2000), S. 157-169 
    ISSN: 1573-1979
    Keywords: microwave measurements ; SOI technology ; small-signal parameters ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract SOI devices are frequently used nowadays in the RF and HF field. Design of complex SOI integrated circuits involves a prior detailed analog simulation, that can only be performed through accurate SOI active components models. We are interested here in linear operation modeling; we test new methods for small-signal parameters determination, suitable for a conventional MOSFET high-frequency model and somewhat inspired from methods applied to MESFET technology. In this paper, we deal mainly with extrinsic parameters, for which we obtain reliable estimation on a large frequency range. Our finally adopted extraction procedure takes closely into account the model topology, which reflects the device electrical behavior. We completely describe the procedure, from measurements to the extracted equivalent circuit simulation, without having to optimize parameters and with a straightforward extrinsic elements extraction.
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    Flow, turbulence and combustion 63 (2000), S. 1-21 
    ISSN: 1573-1987
    Keywords: turbulence ; RANS ; modeling ; length-scale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We derive an equation for the average length-scale in a turbulent flow from a simple physical model. This is a tensorial length-scale. We use as a model the evolution of a blob of turbulent kinetic energy under the influence of production, dissipation, and transport, as well as distortion by the mean motion. A single length-scale is defined which is biased toward the smallest of the scales in the various directions. Constants are estimated by consideration of homogeneous decay. Preliminary computations are carried out in a mixing layer and a two-dimensional jet, using the new length-scale equation and the equation for the turbulent kinetic energy. The results are compared with data and with the predictions of the classical k-epsilon equations; the new results are quite satisfactory. In particular, the plane jet/round jet anomaly is approximately resolved.
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    Mitigation and adaptation strategies for global change 5 (2000), S. 123-142 
    ISSN: 1573-1596
    Keywords: Kyoto Protocol ; GHG ; mitigation strategies ; economiccosts ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering , Geography
    Notes: Abstract The Kyoto Protocol requires the U.S.to reduce the rate of emissions of six greenhousegases (GHG) to 93% of their 1990 rate and to achievethis target by the 2008 to 2012 commitment period. This study assesses the magnitude of change needed inthe U.S. economy and, specifically, in the U.S. energysector, to achieve and maintain the target establishedby the Kyoto Protocol. A simple carbon (C)emissions-energy model is explained in this analysisusing four key variables. Current and future trendsin C emissions are explained by: the carbon/energy(C/E) ratio, Gross Domestic Product growth, energyprices and an energy trend variable. Potential GHGmitigation policy actions affect C emissionsindirectly by affecting at least one of these keyvariables. The analysis concludes that reducingfossil energy use in the U.S. to meet the Kyoto GHGemissions reduction target would be very costly. Technological progress that reduces C emissions wouldnot be fully sufficient without prematurely abandoningproductive capital equipment. Energy price increasesof about 14% per year, or declines in economic growthof almost 5% per year, could reduce energy demand andassociated C emissions enough to achieve the terms ofthe Kyoto Protocol.
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    Nutrient cycling in agroecosystems 58 (2000), S. 259-276 
    ISSN: 1573-0867
    Keywords: agroecosystem ; trace gas ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A computer simulation model was developed for predicting trace gas emissions from agricultural ecosystems. The denitrification-decomposition (DNDC) model consists of two components. The first component, consisting of the soil climate, crop growth, and decomposition submodels, predicts soil temperature, moisture, pH, Eh, and substrate concentration profiles based on ecological drivers (e.g., climate, soil, vegetation, and anthropogenic activity). The second component, consisting of the nitrification, denitrification, and fermentation submodels, predicts NH3, NO, N2O, and CH4 fluxes based on the soil environmental variables. Classical laws of physics, chemistry, or biology or empirical equations generated from laboratory observations were used in the model to parameterize each specific reaction. The entire model links trace gas emissions to basic ecological drivers. Through validation against data sets of NO, N2O, CH4, and NH3 emissions measured at four agricultural sites, the model showed its ability to capture patterns and magnitudes of trace gas emissions.
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    Irrigation and drainage systems 14 (2000), S. 281-299 
    ISSN: 1573-0654
    Keywords: drainage design ; modeling ; steady-state criteria ; subsurface drainage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This paper presents the results of modelsimulations to evaluate drainage designparameters for the Fourth Drainage Project(FDP), Punjab, Pakistan. The SWAP model wasapplied to compute the effects of landdrainage (12 combinations of drain depthand spacing) on soil moisture conditions inthe root zone and their effect on cropyield and soil salinization. For theconditions considered, the selection ofdrain depth is found to be more criticalthan that of drain spacing. Deeper drainsperform technically better in relation tocrop growth and soil salinization. Theoptimum drain depth for the multiplecropping system of the FDP-area was foundto be 2.2 m. This drain depth will producereasonably good crop yields at rather lowdrainage intensity while keeping the rootzone salinity within acceptable limits.This drainage design also maintained thegroundwater table depth below the root zonethroughout the growing season. The outcomeof this study reveals that the drainagedesign criteria applied for the FDP israther conservative with high drainageintensity. The FDP-area can effectively bedrained with a 25 percent lower drainageintensity (q drain/Δh)provided no operational or maintenanceconstraints are present. However, the finaldecision on the optimum combination ofdrain depth and drain spacing would requirea thorough economical analysis. Thenon-steady state approach proved successfulin analyzing the complex interactionsbetween irrigation and drainage components.It is a valuable tool to optimize thedesign of drainage systems against cropyields and soil salinization.
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    Earth, moon and planets 89 (2000), S. 135-160 
    ISSN: 1573-0794
    Keywords: C/1995 O1 (Hale-Bopp) ; 19P/Borrelly ; 46P/Wirtanen ; comets ; modeling ; nucleus ; observations ; rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract We review several techniques used to retrieve rotational parameters from observations. The spin period of a dozen of comets retrieved with these techniques are summarized. We describe how the spin period of comet Hale-Bopp (C/1995 O1) has been calculated with a high accuracy (11.30–11.34 h). Although several authors converged to a spin axis orientation at (α,δ) = (275 ± 15°, -55 ± 5°), detailed studies indicate that the dust jets morphology in 1996–1997 may be incompatible with this orientation. Comet 19P/Borrelly has been recently observed by the Deep Space 1 spacecraft. At the same time, its spin axis orientation and period have been determined by several authors to be respectively (α,δ) = (225 ± 15°, -10 ± 10°)and 26h. These two comets are likely to be in (or close to) a principal axis spin state. We discuss new modeling of the spin state of comet 46P/Wirtanen, the target of the Rosetta mission. The model involves a three-dimensional shape and thermal model, from which the torque of the non gravitational force is calculated at each time step. The moments of inertia are computed for each irregular shape. The results from numerical integrations show that this comet can remain in a principal axis spin state during more than 10 orbits if the spin period does not get above∼6 h. If the spin period increases, its nucleus gets rapidly into excited spin states. It shows that even small and very active short-period comets are not necessarily in non principal axis spin states. In the last section, the consequences of recent observations and modeling of the rotational parameters of comet nuclei are discussed, and unsolved problems are presented.
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  • 88
    ISSN: 1573-1839
    Keywords: virtual reality ; modeling ; constructionism ; astronomy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Natural Sciences in General , Technology
    Notes: Abstract In this manuscript we describe an introductory astronomy course for undergraduate students in which we moved from the large-lecture format to one in which students were immersed in a technologically-rich, inquiry-based, participatory learning environment. Specifically, undergraduate students used 3-D modeling tools to construct virtual reality models of the solar system, and in the process, build rich understandings of various astronomical phenomena. For this study, primarily naturalistic inquiry was used to gain a holistic view of this semester-long course. These data are presented as two case studies focusing on: (1) the role of the teacher in this participatory learning environment; (2) the particular dynamics that formed in each group; (3) the modeling process; (4) the resources used, specifically student-developed inscriptions; and (5) the role of technology and whether learning the technology interfered with learning astronomy. Results indicated that VR can be used effectively in regular undergraduate university courses as a tool through which students can develop rich understandings of various astronomical phenomena.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 551-564 
    ISSN: 1572-8943
    Keywords: amphiphile oligomers ; DSC ; thermo-reversible gelation ; water states
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Symmetrical block oligomers having in common terminal groups (A) consisting of polyoxyethylene (20) stearyl ether are materials of pharmaceutical and cosmetic interest. Phase properties of their aqueous systems and amounts of water typologies were determined by differential scanning calorimetry (DSC). The overall amount of water absorbed by each investigated oligomer was not significantly influenced by the type of central bridging block, whereas the amount of free water decreased with increasing oligomer concentration in the gel. A number of 60–70 moles of water was found to solvate the oligomer chain. The oligomers studied presented a thermo-reversible gelation with and precipitation under determined temperature conditions.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 719-730 
    ISSN: 1572-8943
    Keywords: DSC ; TSDC ; unsaturated polyester resin ; X-ray fluorescence spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This work reports on the curing kinetics of unsaturated polymer resins (UPRs) cured with styrene, studied by differential scanning calorimetry and Fourier transform infrared spectroscopy. The data lead to determination of the experimental conditions with which to obtain a fully cured material and open the way for study of the relaxation phenomena by means of thermally stimulated depolarization current analysis (TSDC). In relaxation studies on fully cured resins, the TSDC spectra revealed important overlapping of the main relaxation peak with an extra upper peak. The importance of this extra peak a priori prevents further analysis of the main relaxation. To identify the origins of this peak (space charge or other), the purity of the resin was checked by X-ray fluorescence spectroscopy. The use of UPR specimens with different compositions (in terms of the resin/activator/initiator ratio) demonstrated that the bulk of the impurities Cl, K, Ca, Sr, Zr and Ba are due to the promoter. Decoupling of the mixed peaks (α-relaxation and extra) revealed that the a peak is independent of the proportion of the promoter in the resin and that the extra peak is principally due to the presence of these impurities.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 889-896 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; Fe40Ni40P14B6 glassy alloy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this paper a DSC study is reported of the behavior of Fe40Ni40P14B6 alloy produced by rapid quenching. The experimental results show that relaxation phenomena can be studied directly from the DSC curves. From these experiments, the spread of the E c values in the literature is attributed to differences in the quenching rates and the presence of variable number of quenched-in nuclei. It is also shown that the microstructure (number and size of crystals) of the non-isothermally devitrified metallic alloy changes with the heating rate; this is a consequence of the shift of crystallization temperatures and, therefore, of the change of the ratio of nucleation and crystal growth rates.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 163-171 
    ISSN: 1572-8943
    Keywords: alkylcyclohexanes ; binary phase diagrams ; DSC ; metastable solutions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was used to construct phase diagrams of binary mixtures of alkylcyclohexanes and to characterize metastable phases formed in the binary mixtures. The experimentally measured liquidus curves were compared to the liquidus curves calculated using ideal solution theory. The measured phase diagrams of pentadecylcyclohexane/nonadecylcyclohexane and octadecylcyclohexane/nonadecylcyclohexane binary mixtures are consistent with theoretical phase diagrams constructed based on the assumption that these mixtures form eutectic systems. It was also observed that a metastable phase formed in some binary mixtures of pentadecylcyclohexane/nonadecylcyclohexane under fast cooling conditions. It is hypothesized that this metastable phase recrystallizes into the eutectic phase upon heating.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 715-719 
    ISSN: 1572-8943
    Keywords: computer simulation ; DSC ; non-isothermal crystallization kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The applicability of the kinetic analysis of data obtained by non-isothermal differential scanning calorimetry (DSC) is discussed. The Johnson-Mehl-Avrami (JMA) model was used for the computer simulation of DSC traces subsequently analysed by common methods of kinetic analysis of non-isothermal data. For the temperature-independent kinetic exponent n of the JMA equation, the kinetic analysis was shown to provide correct results, e.g. a correct kinetic model and apparent activation energy. On the other hand, for the temperature-dependent kinetic exponent, there is a great possibility of erroneous determination of the correct kinetic model and apparent activation energy, especially at higher heating rates. Since the temperature dependence of n cannot be determined on the basis of non-isothermal DSC experiments, conclusions must be drawn with appropriate caution.
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    Journal of thermal analysis and calorimetry 63 (2000), S. 397-413 
    ISSN: 1572-8943
    Keywords: Cu–5 at%Zn ; DSC ; F.C.C. (Face Centered Cubic) ; kinetics ; short-range-order ; solute-vacancy complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value of 89.5±0.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 25-33 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; thermal decomposition ; 2,4,6-trinitrotoluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An autocatalytic model involving the limited solubility of volatile catalytic products was applied to the thermal decomposition of 2,4,6-trinitrotoluene. The critical supersaturation of the thermal decomposition products with the catalytic properties was higher at a low heating rate. Decrease of the sample mass led to an increased critical supersaturation of the decomposition products. This is probably a result of the greater contribution of products adsorption on the aluminium pan surface. It is presumed that the differences observed in the rate constant are connected with the uncontrolled critical supersaturation of the volatile thermal decomposition products.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 45-52 
    ISSN: 1572-8943
    Keywords: compatibilization ; DMTA ; DSC ; polyamide 6/thermoplastic polyurethane blends
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Blends obtained from polyamide 6 and a thermoplastic polyurethane compatibilized by diblock copolyurethaneamides were investigated by means of DMTA and DSC. The blends were prepared by compounding in a Brabender mixer. The compatibilizer affected the glass transition temperature of the amorphous phase of the blends. The non-isothermal crystallization temperature of the polyamide phase was lowered in the presence of the polyurethane and the copolyurethaneamide.
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    Photosynthesis research 66 (2000), S. 199-224 
    ISSN: 1573-5079
    Keywords: C4 photosynthesis ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A computer model comprising light reactions in PS II and PS I, electron-proton transport reactions in mesophyll and bundle sheath chloroplasts, all enzymatic reactions and most of the known regulatory functions of NADP-ME type C4 photosynthesis has been developed as a system of differential budget equations for intermediate compounds. Rate-equations were designed on principles of multisubstrate-multiproduct enzyme kinetics. Some of the 275 constants needed (ΔG0′ and K m values) were available from literature and others (V m) were estimated from reported rates and pool sizes. The model provided good simulations for rates of photosynthesis and pool sizes of intermediates under varying light, CO2 and O2. A basic novelty of the model is coupling of NADPH production via NADP-ME with ATP production and regulation of the C3 cycle in bundle sheath chloroplasts. The functional range of the ATP/NADPH ratio in bundle sheath chloroplasts extends from 1.5 to 2.1, being energetically most efficient around 2. In the presence of such stoichiometry, the CO2 concentrating function can be explained on the basis of two processes: (a) extra ATP consumption for starch and protein synthesis in bundle sheath leads to a faster NADPH and CO2 import compared with CO2 fixation in bundle sheath, and (b) the residual photorespiratory activity consumes RuBP by oxygenation, NADPH and ATP and causes the imported CO2 to accumulate in bundle sheath cells. As a wider application, the model may be used for predicting results of genetic engineering of plants.
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    Plant growth regulation 31 (2000), S. 1-16 
    ISSN: 1573-5087
    Keywords: apple ; application methods ; caustic sprays ; economics ; flowering ; growth regulators ; Malus xdomestics Borkh. ; modeling ; photosynthesis ; review
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The history of fruit thinning is reviewed, beginning with hand removalof fruits, the effects upon subsequent flowering, and current attemptsto develop mechanical methods of fruit removal. Early experiments withcaustic compounds and growth regulators and their subsequent developmentas commercial practices are discussed, as well as the modes of action ofgrowth regulators. Brief reviews of methods of application, factorsaffecting response, modeling to improve efficiency, and the economicvalue of thinning to the grower are also included.
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    Journal of aquatic ecosystem stress and recovery 8 (2000), S. 39-51 
    ISSN: 1573-5141
    Keywords: broad spectrum analysis ; contaminants ; distribution ; fate ; metals ; modeling ; persistent organic pollutants ; pulp-mill effluents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Northern river ecosystems worldwide are under increasing environmental stress from degrading developments that influence water quality and associated ecological integrity. In particular, contaminant-related threats to these systems are rising from enhanced industrial and municipal effluent discharges along with elevated non-point source inputs related to land-use activities such as forestry, agriculture, mining and long-range atmospheric transport. In this regard, the contaminants program of the Northern River Basins Study (NRBS) in western Canada identified key contaminant sources to the Athabasca, Slave and Peace river basins (particularly related to pulp-mill developments) and assessed their environmental fate and distribution in water and sediments. The study also developed and employed new analytical approaches and generated improved models to predict contaminant transport and fate in the aquatic environment and related food webs. Consequently the study focused on those contaminant families identified in characterization studies as arising from key point- and non-point sources within the basins or as being of greatest toxicological significance. These included resin acids, polychlorinated dioxins and furans, polychlorinated biphenyls, chlorinated phenolics, polyaromatic hydrocarbons and selected heavy metals such as mercury. Low or non-detectable concentrations of a number of contaminant groups were found in the ambient water phase including chlorinated phenolics, some chlorinated dioxins and furans and some resin acids. For both suspended and depositional sediments, significant declines were observed over the study period for the major chlorinated contaminant groups tested, correlating directly with the implementation of improved effluent treatment in many of the pulp mills located in the basins. In general, the environmental levels of chlorinated organic and metal contaminants in water or sediments were low and within Canadian health or environmental guidelines. It is hoped that the approaches used and lessons learned from the NRBS will be of use to others assessing contaminant and multiple stressor issues in other large river ecosystems.
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    ISSN: 1573-2959
    Keywords: modeling ; New York City ; risk assessment ; watershed monitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The International Life SciencesInstitute (ILSI) Risk Science Institute (RSI) convenedan expert panel of scientists to developrecommendations for a comprehensive monitoring programfor the Croton and Catskill/Delaware watersheds, whichprovide drinking water to New York City's residents. This effort was conducted as part of efforts topreserve and enhance the quality of New York City'sreservoir system through a watershed protectionprogram. The panel developed recommendations for astrategic framework on which to construct a monitoringprogram. As part of this activity, the paneldetermined whether existing monitoring activities weredeficient and, where activities were deficient, thepanel developed recommendations for additionalinformation that should be collected.The panel recommended the development and use of anintegrated approach to watershed monitoring, whichdraws on modeling, risk-based planning and analysis,statistical sampling and design, and basic compliancemonitoring. The approach should be designed toprovide an assessment of natural and anthropogenicsources of stress to the system as well as anassessment of water quality trends in response tostresses acting in concert, both over the long termand over the five-year New York City Memorandum ofAgreement (MOA) assessment time frame. It should alsoprovide an assessment of the human health andenvironmental risks posed by a variety of stressors,and the impact of management actions implemented toameliorate stressors.
    Type of Medium: Electronic Resource
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