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  • kinetics  (77)
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  • Springer  (126)
  • 2000-2004  (126)
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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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    Adsorption 6 (2000), S. 137-147 
    ISSN: 1572-8757
    Keywords: adsorption ; kinetics ; linear driving force model ; process design
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Linear Driving Force (LDF) model for gas adsorption kinetics is frequently and successfully used for analysis of adsorption column dynamic data and for adsorptive process designs because it is simple, analytic, and physically consistent. Yet, there is a substantial difference in the characteristics of isothermal batch uptake curves on adsorbent particles by the LDF and the more rigorous Fickian Diffusion (FD) model. It is demonstrated by using simple model systems that the characteristics of the adsorption kinetics at the single pore or the adsorbent particle level are lost in (a) evaluating overall uptake on a heterogeneous porous solid, (b) calculating breakthrough curves from a packed adsorbent column, and (c) establishing the efficiency of separation by an adsorptive process due to repeated averaging of the base kinetic property. That is why the LDF model works in practice.
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  • 3
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; kinetics ; ruthenium catalysts ; promotional effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of NH3 synthesis over carbon-based ruthenium catalysts promoted with barium or alkali was studied. Both the ammonia partial pressure dependencies of the reaction rates (T = 400°C, p = 63 bar, H2 : N2 = 3 : 1) and the pressure variations of the activity (T = 370°C, p= 4–63 bar, H2 : NN2 = 3 : 1) were found to be different for Ba and for the alkali (K, Cs). Ba–Ru/C proved to be more sensitive to the NH3 content and to the total pressure. The rate of synthesis over the alkali-promoted catalysts is, in turn, much stronger influenced by the ruthenium dispersion. TOFs of NH3 synthesis for the promoted samples at 370°C and 4 bar (Ba 0.085 1/s, Cs 0.05 1/s, K 0.035 1/s) are significantly higher than that for the Ru(0001) basal plane (0.0085 1/s results from the literature data at 370°C, 2 bar). The most active Ru/C samples (Ba or Cs) exceed significantly the fused iron catalyst, especially at high conversions.
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  • 4
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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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  • 5
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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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  • 6
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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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  • 7
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    Topics in catalysis 11-12 (2000), S. 327-333 
    ISSN: 1572-9028
    Keywords: hydrodenitrogenation ; toluidine ; methylcyclohexylamine ; kinetics ; nickel-promoted molybdenum sulphide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The hydrodenitrogenation (HDN) of o-toluidine and its reaction intermediates was studied over a NiMo/γ-Al2O3 catalyst. The kinetics of the HDN of methylcyclohexylamine and of the hydrogenation of cyclohexene were also studied. Hydrogenation of o-toluidine alone produces methylcyclohexene and methylcyclohexane. When a sufficient quantity of cyclohexene is added during the HDN of toluidine, methylcyclohexylamine, the first intermediate in the hydrogenation of toluidine, becomes detectable. Because of its strong adsorption constant and high rate constant for reacting further to methylcyclohexene and methylcyclohexane, methylcyclohexylamine is not observed in the HDN of toluidine. Adding cyclohexene decreases the adsorption of methylcyclohexylamine, thus enabling its detection. The rate and adsorption constants of methylcyclohexylamine and cyclohexene in the HDN of methylcyclohexylamine were calculated by fitting the kinetic data to a Langmuir–Hinshelwood equation. A two-site model was used to describe the surface reactions, with one site for the methylcyclohexylamine reactions and the other for the cyclohexene reaction.
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  • 8
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    Adsorption 6 (2000), S. 349-357 
    ISSN: 1572-8757
    Keywords: sulfadiazene ; adsorption ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10−3 mol cm−3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl−, SO2− 4 and PO3− 4 (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.
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  • 9
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    Catalysis letters 64 (2000), S. 65-75 
    ISSN: 1572-879X
    Keywords: NO reduction ; CH3OH ; La2O3 ; methyl nitrite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Nitric oxide (NO) reduction by methanol was studied over La2O3 in the presence and absence of oxygen. In the absence of O2, CH3OH reduced NO to both N2O and N2, with selectivity to dinitrogen formation decreasing from around 85% at 623 K to 50–70% at 723 K. With 1% O2 in the feed, rates were 4–8 times higher, but the selectivity to N2 dropped from 50% at 623 K to 10% at 723 K. The specific activities with La2O3 for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of 35 μmol NO/s m2 was obtained whereas that for methanol was 600 μmol NO/s m2. The Arrhenius plots were linear under differential reaction conditions, and the apparent activation energy was consistently near 14 kcal/mol with CH3OH. Linear partial pressure dependencies based on a power rate law were obtained and showed a near‐zero order in CH3OH and a near‐first order in H2. In the absence of O2, a Langmuir–Hinshelwood type model assuming a surface reaction between adsorbed CH3OH and adsorbed NO as the slow step satisfactorily fitted the data, and the model invoking two types of sites provided the best fit and gave thermodynamically consistent rate constants. In the presence of O2 a homogeneous gas‐phase reaction between O2, NO, and CH3OH occurred to yield methyl nitrite. This reaction converted more than 30% of the methanol at 300 K and continued to occur up to temperatures where methanol was fully oxidized. Quantitative kinetic studies of the heterogeneous reaction with O2 present were significantly complicated by this homogeneous reaction.
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  • 10
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    Catalysis letters 69 (2000), S. 103-107 
    ISSN: 1572-879X
    Keywords: dicyclopentadiene ; Wacker oxidation ; Pd(AcO)2 ; benzoquinone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of dicyclopentadiene catalyzed by palladium(II) acetate and benzoquinone in the presence of perchloric acid was studied. Tricyclodecenone in high selectivity (85–98%) at a conversion of dicyclopentadiene up to 76% was obtained. The kinetic model assumed the significant inhibition complexation between dicyclopentadiene and tricyclodecenone with the catalytic species.
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  • 11
    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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  • 12
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    Journal of thermal analysis and calorimetry 59 (2000), S. 633-642 
    ISSN: 1572-8943
    Keywords: cadmium ; dialkyldithiocarbamate ; kinetics ; thermal decomposition ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition kinetics of the solid complexes Cd(S2 CNR2 )2 , where R =C2 H5 , n -C3 H7 , n -C4 H9 or iso -C4 H9 , was studied by using isothermal and non-isothermal thermogravimetry. The superimposed TG/DTG/DSC curves revealed that thermal decomposition reactions occur in the liquid phase. The kinetic model that best fitted the experimental isothermal TG data was the one-dimensional phase-boundary reaction-controlled process R1 . The thermal analysis data suggested the thermal stability sequence Cd(S2 CNBun 2 )2 〉Cd(S2 CNPrn 2 )2 〉Cd(S2 CNBui 2 )2 〉Cd(S2 CNEt2 )2 , which accords with the sequence of stability of the apparent activation energies.
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  • 13
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    Journal of thermal analysis and calorimetry 59 (2000), S. 807-814 
    ISSN: 1572-8943
    Keywords: facial and meridional Co(III) complexes ; kinetics ; thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal properties of facial and meridional uns-cis-[Co(eddp)gly]0.5H2O complexes were investigated by means of DSC and TG techniques. It wasshown that the processes of thermal decomposition of these complexes are multi-stepdegradation processes, which can also be well separated into individual steps, depending onthe molecular symmetry. Thus, the process of thermal degradation of the meridional isomerof the above complex consists of 4 well-separated steps in the temperature interval from 100to 500°C. The corresponding kinetic and thermodynamic parameters of this process weredetermined, and a possible mechanism is discussed.
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  • 14
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    Journal of thermal analysis and calorimetry 61 (2000), S. 955-965 
    ISSN: 1572-8943
    Keywords: kinetics ; metal complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetry (TG) and differential thermal analysis (DTA) were performed on the complexes with general formula (M(DEBT)n (where M =Fe, Co, Ni, Cu or Ru; n =2, or 3 and DEBT=N,N-diethyl-N'-benzoylthiourea). Derivative thermogravimetric (DTG) curves were also recorded in order to obtain decomposition data on the complexes. The complexes of Fe(III), Co(II), Ni(II), Cu(II) and Ru(III) displayed two- or three-stage decomposition patterns when heated in a dynamic nitrogen atmosphere. Mass loss considerations relating to the decomposition stages indicated the conversion of the complexes to the sulfides or to the corresponding metal alone (Cu, Ru, NiS, CoS or FeS). Mathematical analysis of the TG and DTG data showed that the order of reaction varied between 0.395 and 0.973. Kinetic parameters such as the decomposition energy, the entropy of activation and the pre-exponential factor are reported.
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  • 15
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    Journal of thermal analysis and calorimetry 62 (2000), S. 429-433 
    ISSN: 1572-8943
    Keywords: adsorption ; fast measurement ; gravimetry ; kinetics ; sorption ; kw6
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Jäntti introduced a method to reduce the time required for the stepwise measurement of adsorption isotherms. After each pressure change he measured the adsorbed mass three times and calculated its equilibrium value at the new pressure. In the present paper, we discuss the applicability of this method in a broader scope without starting from a given combination of sorptive and adsorbent and the influence of measuring inaccuracies. The method is applied to detect whether the adsorption process is based on more than one adsorption mechanism or not.
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  • 16
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    Journal of thermal analysis and calorimetry 63 (2000), S. 375-386 
    ISSN: 1572-8943
    Keywords: activation energy ; ammonium perchlorate ; decompositon ; isothermal ; kinetics ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the thermal decomposition of ammonium perchlorate at temperatures between 215 and 260°C is studied, in this work, by measuring the sample mass loss as a function of time applying the isothermal thermogravimetric method. From the maximum decomposition rate – temperature dependence two different decomposition stages, corresponding to two different structural phases of ammonium perchlorate, are identified. For the first region (215–235°C), corresponding to the orthorhombic phase, the mean value of the activation energy of 146.3 kJ mol–1, and the pre-exponential factor of 3.43⋅1014 min–1 are obtained, whereas for the second region (240–260°C), corresponding to the cubic phase, the mean value of the activation energy of153.3 kJ mol–1, and the pre-exponential factor of 4.11⋅1014 min–1 are obtained.
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  • 17
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    Journal of thermal analysis and calorimetry 60 (2000), S. 35-43 
    ISSN: 1572-8943
    Keywords: kinetics ; 10-methylacridinium halides ; thermodynamics ; thermogravimetric investigations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 10-Methylacridinium chloride, bromide and iodide were prepared in crystalline forms (the first two salts as monohydrates) and subjected to thermogravimetric investigations. Decomposition of the compounds is initially accompanied by the liberation of water (in case of monohydrates), halomethanes and acridine molecules. As decomposition proceeds, side reactions occur which are reflected in a complex pattern of thermogravimetric curves. TG traces corresponding to the initial decomposition stage were used to determine the kinetic characteristics of the thermal dissociation of the salts. MNDO/d, AM1 and PM3 methods were employed independently to examine reaction pathways and to predict thermodynamic and kinetic barriers for the thermal decomposition of the compounds. These data were subsequently supplemented with theoretically determined crystal lattice energies, which enabled the relevant characteristics for the decomposition of crystalline phases to be predicted. The theoretically predicted characteristics are qualitatively comparable with those originating from thermogravimetric investigations, which allows one to believe that both are valid.
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  • 18
    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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  • 19
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    Journal of thermal analysis and calorimetry 60 (2000), S. 247-255 
    ISSN: 1572-8943
    Keywords: desulfuration ; gas atmosphere ; kinetics ; thermal decomposition ; titanium dioxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The studies were devoted to determination of the effect of gas atmosphere and its pressure on the second step of decomposition of hydrated titanium dioxide (HTD) promoted by sulfate groups. It has been found that thermal decomposition of HTD at temperatures above 300°C consists of a number of processes such as dehydroxylation, desulfuration, recrystallization and sintering of solid grains, photochemical processes (if the decomposition proceeds in the presence of light) and adsorption of gas phase components (in the presence of air or SO2). Kinetic parameters characterizing this step of decomposition have been determined for processes carried out in vacuum and in argon or air atmospheres (at a pressure of 13.33hPa). The kinetic curves of decomposition carried out in the presence of gases capable of being adsorbed on the surface of partly dehydrated HTD are featured by local extrema due to simultaneous processes of decomposition and adsorption of gas components.
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  • 20
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    Journal of thermal analysis and calorimetry 60 (2000), S. 9-15 
    ISSN: 1572-8943
    Keywords: coordination compounds ; kinetics ; thermal dissociation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Physicalo-chemical importance of the quantitative study of kineticliability of coordination compounds in thermal dissociation processes is considered. Muchattention is given to the proof of the physicalo-chemical meaning and validity of kineticparameters calculated from thermoanalytical data. Experimental data (thermal dissociation ofcoordination compounds and clathrates with such a matrix) are discussed.
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  • 21
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    Journal of thermal analysis and calorimetry 60 (2000), S. 401-407 
    ISSN: 1572-8943
    Keywords: cross-linking ; isothermal crystallization ; kinetics ; modification ; polypropylene ; silica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of addition of silica on the parameters of isothermal crystallization of polypropylene has been investigated. It was found that the covering of the silica surface by a layer of low-density polyethylene leads to a deactivation of the filler regarding the positive effect on the polypropylene crystallization rate parameters. Cross-linking of the surface polyethylene layer results in a stronger attachment of the modifying polymer to the filler surface and the deactivation effect of the silica surface modification is more pronounced.
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  • 22
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    Journal of thermal analysis and calorimetry 60 (2000), S. 541-547 
    ISSN: 1572-8943
    Keywords: Cr(II) ; chromium trioxide ; kinetics ; reduction ; thermal analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of CrO3 on heating up to 600°C in dynamic atmospheres of air, N2 and H2 was examined by thermogravimetry (TG), differential thermal analysis (DTA), IR spectroscopy and diffuse reflectance spectroscopy (DRS). The results revealed three major thermal events, depending to different extents on the surrounding atmosphere: (i) melting of CrO3 near 215°C (independent of the atmosphere), (ii) decomposition into Cr2(CrO4)3 at 340–360°C (insignificantly dependent), and (iii) decomposition of the chromate into Cr2O3 at 415–490°C (significantly dependent). The decomposition CrO3 → Cr2(CrO4)3 is largely thermal and involves exothermic deoxygenation and polymerization reactions, whereas the decomposition Cr2(CrO4)3 → Cr2O3 involves endothermic reductive deoxygenation reactions in air (or N2) which are greatly accelerated and rendered exothermic in the presence of H2. TG measurements as a function of heating rate (2–50°C min−1) demonstrated the acceleratory role of H2, which extended to the formation of Cr(II) species. This could sustain a mechanism whereby H2 molecules are considered to chemisorb dissociatively, and then spillover to induce the reduction. DTA measurements as a function of the heating rate (2–50°C min−1) helped in the derivation of non-isothermal kinetic parameters strongly supportive of the mechanism envisaged.
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  • 23
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    Journal of thermal analysis and calorimetry 60 (2000), S. 667-674 
    ISSN: 1572-8943
    Keywords: accommodation function ; crystal growth ; glass-ceramics ; kinetics ; number of nuclei ; thermal history
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic modeling of the crystal growth from pre-existing nuclei was reexamined to obtain a fundamental information about the controlled crystallization of glasses during formation of advanced inorganic glass-ceramics. Methods of kinetic analysis were reviewed by taking account of thermal history of the sample within the temperature range of nucleation. An accommodation function depending on the thermal history was introduced in the kinetic equation. The role of the accommodation function was reinvestigated when determining the activation energy from a series of kinetic curves. The kinetic description of the crystal growth in the samples with different thermal history was generalized by extrapolating the rate behavior to infinite temperature.
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  • 24
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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
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.
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  • 25
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    Journal of thermal analysis and calorimetry 60 (2000), S. 759-778 
    ISSN: 1572-8943
    Keywords: decomposition temperature ; error sources ; gas-flow and vapor control ; kinetics ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The well-known divergence between the present ‘state of the art’ of thermogravimetry and industrial requirements is discussed. Sources of errors are analyzed and the optimization of measuring conditions is discussed regarding the problems associated with static and dynamic (flow) atmospheres, and interactions between materials and gases or vapors. Recommendations for gas-flow control systems and vapor sources are given. Thermal stability and the kinetics of gas-evolving, reversible, thermal decompositions of solids are discussed. The scope of TG-derived kinetics for practical use is examined. Some new characteristic points of TG curves are proposed and defined, e.g. ‘procedure-independent decomposition temperature’ and ‘augmented decomposition temperature’ (obtained at pseudo-equilibrium conditions).
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  • 26
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    Journal of thermal analysis and calorimetry 60 (2000), S. 879-886 
    ISSN: 1572-8943
    Keywords: driving force ; kinetics ; rate equation ; reversible reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper outlines the different ways of taking the distance from thermodynamic equilibrium into account in kinetic studies based on thermoanalytical experiments. The three main approaches are: (i) avoiding or neglecting the effect of the reverse reaction, (ii) describing the influence of distance from equilibrium on apparent kinetic parameters, and (iii) incorporating a driving force factor in the rate equation. Finally, the contradiction of the microscopic nature of the processes and the macroscopic character of the usual rate equation are briefly discussed.
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  • 27
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    Journal of thermal analysis and calorimetry 60 (2000), S. 943-954 
    ISSN: 1572-8943
    Keywords: CRTA ; kinetics ; self-generated atmospheric conditions ; synthetic malachite ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic behavior of the thermal decomposition of synthetic malachite was investigated by means of CRTA under different conditions of reduced pressure, flowing gases and quasi-isobaric atmospheres. The thermal decomposition was found to proceed at lower temperatures under the influence of the self-generated gases, CO2 and H2O. From a viewpoint of chemical equilibrium, the normal and opposite effects on the overall kinetics were observed for the self-generated CO2 and H2O, respectively. The complexity of the present reaction is also reflected by the variations of the apparent kinetic parameters which depend on the applied and self-generated atmospheric conditions. The practical usefulness of CRTA when applied to a complicated thermal decomposition is discussed as exemplified by the kinetic approaches to the present reaction.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 151-156 
    ISSN: 1572-8943
    Keywords: complexes ; kinetics ; TG-DTA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of a few lanthanide complexes of the type ML3(I) [M=Eu,Gd; HL=4,4,4-trifluoro- 1-(2-napthyl)-1,3-butanedione and EuL30.5dmm dmm=2,6-dimethylmorpholine(II)], has been investigated. From thermogravimetric(TG) curves, the decomposition pattern of the compounds has been analysed on the basis of mass loss data. The order and activation energy of the thermal decomposition reactions have been elucidated. From differential thermal analysis (DTA) studies, the heat of reaction and rate of thermal decomposition reaction have been enumerated.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 239-242 
    ISSN: 1572-8943
    Keywords: kinetics ; Mannich compounds ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors present data concerning the evaluation of kinetic parameters of the decomposition of a Mannich compound by using the classical method of constant heating rate thermal analysis and the new one of controlled rate thermal analysis (CRTA). The data processed using the CRTA method allow to obtain more reliable kinetic parameters according to the proposed reaction mechanism.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 437-450 
    ISSN: 1572-8943
    Keywords: crystallization ; EPDM ; kinetics ; morphology ; PP ; rubber
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the incorporation of an amorphous immiscible polymer (ethylene-propylene-diene- terpolymer) on the PP crystallization kinetics and thermodynamics is investigated by thermal analysis. The results of the investigation have shown that EPDM acts as a nucleant agent. A marked decrease of the half time of PP crystallization, τ1/2 , as well as a sensible increase of the overall crystallization rate, K n , has been observed in the presence of EPDM. Moreover, at any crystallization temperature, a minimum of τ1/2 , is obtained at 25% EPDM content in the blend. The Avrami model has been successfully applied to describe the crystallization kinetics of the blend. The kinetic curves obtained under non-isothermal conditions confirm the results obtained under isothermal conditions and demonstrate the nucleant action of the EPDM phase on the PP crystallization.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 721-727 
    ISSN: 1572-8943
    Keywords: kinetics ; metal exchange ; thermaldehydration ; zeolite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Zeolite-4A is a hydrated aluminosilicate which becomes more hydrated when exchanged with transition metals. In this work, the dehydration kinetics of cobalt, nickel and copper(II)-exchanged zeolite-4A were studied by means of TG and DTA over the temperature range from 20 to 500°C, and the numbers of water molecules in the metal-exchanged zeolite samples were calculated. It was observed that, as the ionic radius of the hydrated metal increased, the number of water molecules also increased. The loss of water from the zeolite samples generally occurred in the temperature range 100–300°C and was manifested in the DTA graphs by an extended endothermic effect. The DTA curves demonstrated that the peak position shifted towards lower temperatures as the metal concentration increased or, in other words, the water of hydration increased. The kinetic parameters (order of reaction and activation energy) were calculated via the Coats and Redfern method. The process of dehydration was found to follow first-order kinetics.
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  • 32
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    Journal of thermal analysis and calorimetry 63 (2000), S. 359-374 
    ISSN: 1572-8943
    Keywords: KEKAM equation ; kinetics ; thermal dissociation of solids
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Relationships have been established between the average conversion degree and the dissociation time for polydisperse granular material, taking its grain size distribution into account. It has been checked in which cases the kinetic curves obtained by a numerical solution can be described in terms of KEKAM equation.
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  • 33
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    Keywords: isoconversional methods ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An analysis is presented of the consequences of the use of a one term equation containing apparent activation parameters, instead of the true rate equation to describe two successive decomposition reactions undergone by a solid compound. It is demonstrated that the apparent activation energy, obtained by means of isoconversional differential and integral methods, varies with the conversion degree for a relatively narrow temperature range and with temperature at a given value of the conversion degree. The activation energy values obtained with the isoconversional differential method are higher than the corresponding values obtained with the isoconversional integral method.
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  • 34
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    Journal of thermal analysis and calorimetry 59 (2000), S. 869-875 
    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; plumbo-jarosite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An investigation was carried out on the kinetics of thermal decomposition of plumbo-jarosite. The kinetic models of dissociation of the compounds in the ore were identified. The results of the kinetic studies and the mechanism of the process are discussed. The thermal decomposition of plumbo-jarosite occurs in three stages: the first up to 763, the second up to 1023 and the third up to 1223 K, the corresponding activation energy values being 62.2, 60.3 and 98.0 kJ mol–1 , respectively.
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    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
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    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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  • 36
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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
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    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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  • 37
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    Journal of thermal analysis and calorimetry 61 (2000), S. 861-871 
    ISSN: 1572-8943
    Keywords: DAGN ; kinetics ; mechanism and IR spectroscopy ; TAGN ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Diaminoguanidine nitrate (DAGN) and triaminoguanidine nitrate (TAGN),potential energetic materials in emerging propulsion technology with high mass impetus at low isochoric flame temperature have been studied as regards kinetics and mechanism of thermal decomposition using thermogravimetry (TG), differential thermal analysis (DTA),infrared spectroscopy (IR) and hot stage microscopy. Kinetics of thermolysis has been followed by isothermal TG and IR. For the initial stage of thermolysis of DAGN the best linearity with a correlation coefficient of 0.9976 was obtained for the Avrami-Erofe'evequation, n=2, by isothermal TG. The activation energy was found to be 130 kJ mol–1 and logA=11.4. The initial stage of thermolysis of TAGN also obeyed the Avrami-Erofe'ev equation, n=2, with a correlation coefficient of 0.9975by isothermal TG and the kinetic parameters are E=160.0 kJ mol–1 and logA=16.0. High temperature IR spectra showed exquisite preferential loss in intensity of the NH2, NH, N–N stretching and CNN bending. Spectroscopic and other results favour deamination reaction involving the rupture of the N–N bond as the primary step in the thermal decomposition.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 979-984 
    ISSN: 1572-8943
    Keywords: kinetics ; nucleation-growth
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The author presents some applications of the fractal geometry in the kinetics of heterogeneous decomposition of solids.
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  • 39
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    Journal of thermal analysis and calorimetry 59 (2000), S. 935-942 
    ISSN: 1572-8943
    Keywords: CoSO46H2O ; kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetry (TG-DTG), and differential thermal analysis (DTA) were used in the study of the kinetics of decomposition of cobalt sulphate hexahydrate under an air atmosphere. The kinetics of the particular stages of CoSO4 6H2 O decomposition were evaluated from the dynamic mass loss data. The values of the kinetic parameters for each stage of the thermal decomposition were calculated from the α(T) data by using the integral method, applying the Coats-Redfern approximation.
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  • 40
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    Journal of thermal analysis and calorimetry 62 (2000), S. 681-685 
    ISSN: 1572-8943
    Keywords: coal-burning additive ; combustion ; graphite ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The catalytic and accelerating effects of three coal-burning additives (CBA) on the burning of graphite were studied with the help of thermogravimetric (TG) analysis. The kinetic study on the catalytic oxidation of the graphite doped with CBA was carried out and the results were presented. The results show that the CBA can change the carbon oxidation/combustion course by catalytic action and change the activation energy, thus improving the combustion efficiency.
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  • 41
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    Journal of thermal analysis and calorimetry 63 (2000), S. 457-463 
    ISSN: 1572-8943
    Keywords: isoconversional methods ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract It is demonstrated that, if the activation energy depends on the degree of conversion, its values obtained by isoconversional differential and integral methods are different.
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  • 42
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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
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    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
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    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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  • 44
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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
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    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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  • 46
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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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  • 47
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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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    Journal of materials synthesis and processing 8 (2000), S. 271-277 
    ISSN: 1573-4870
    Keywords: Comminution ; kinetics ; mechanical alloying ; phase transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract It has been shown that structural evolution occurring in powder mixtures subjected to mechanical treatment by milling follow well-defined conversion trends as a function of milling time. Sigmoidal curves were observed in the case of the mechanical alloying of transition metal mixtures, whereas a simpler kinetic course with a progressively decreasing transformation rate was found to characterize the disordering process of intermetallic equilibrium compounds by mechanical milling. Under the stipulation that collisions are the dominant energy transfer events, a kinetic model is developed to relate the observed macrokinetic features to the discrete powder fractions, which transform at each impact. Because of its intrinsic qualities, the milling process was regarded as discrete processing. A statistical approach was followed to work out a set of differential equations, solutions of which provide a sound description of the transformation kinetics in terms of conventional rate expressions. The model allows one to reproduce the different kinetic behaviors by means of a single, unifying mathematical formalism. Furthermore, quantifying the structural evolution rate by suitable kinetic constants permits the exploration of the reactive behavior of a system treated under different milling regimes or to compare, on an absolute basis, different systems processed under similar conditions.
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    Oxidation of metals 53 (2000), S. 351-360 
    ISSN: 1573-4889
    Keywords: Co-base superalloy ; high-temperature oxidation ; kinetics ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of the Co-base superalloy DZ40M was studied in air at900–1100°C for times of up to 2000 hr. The results indicated thatthis alloy can grow a protective oxide scale at 900 and 1000°C duringisothermal oxidation, but not at 1100°C because of serious cracking andspalling of the oxide scales. Moreover, an internal-precipitate zone formedin the subsurface region of the alloy at all temperatures and times. Theprecipitates were rich in Cr in the vicinity of the alloy–scaleinterface and rich in Al deep in the alloy. The internal-precipitatemorphology changed from a granular to needlelike shape with increasingoxidation temperature.
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  • 50
    ISSN: 1573-4943
    Keywords: Aluminum ; yeast hexokinase ; preferential interactions ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The aluminum and yeast hexokinase interaction was studied. Structural changes were correlated with variations in protein functionality. Results show two different behaviors: At low metal concentrations preferential adsorption of metal (and water exclusion) induces aggregate formation. No significant changes in the protein structure occur, but there is a continuous loss of activity (from the first concentration). At large salt concentrations a monomerization process and a conformational change in the secondary structure as well as in the three-dimensional structure take place. This change reduces the percentage of α-helix conformation, gives thermal stability to the protein, and allows the exposure of some tryptophan residue and hydrophobic regions. The protein inhibition increases. Conformational change and monomerization may allow access of the metal to the substrate site, mainly the ATP site. The inhibition in any case is of mixed type with a competitive component.
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  • 51
    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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  • 52
    ISSN: 1573-4943
    Keywords: Creatine kinase ; human ; expression ; brain ; muscle ; purification ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We report the expression of the human muscle (CK-MM) and brain (CK-BB) creatine kinases in Escherichia coli. The proteins have been purified to apparent homogeneity and several of their physical and kinetic properties investigated. In the process, we have conclusively verified the correct DNA sequence of the genes encoding the respective isozymes, and determined the correct primary structure and mass of the gene products. Alignment of the primary sequences of these two enzymes shows 81% sequence identity with each other, and no obvious gross structural differences. However, Western blot analyses demonstrated the general lack of antigenic cross-reactivity between these isozymes. Preliminary kinetic analyses show the K m and k cat values for the creatine and MgATP substrates are similar to values reported for other isozymes from various tissues and organisms. The human muscle and brain CKs do not, however, exhibit the synergism of substrate binding that is observed, for example, in rabbit muscle creatine kinase.
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  • 53
    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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    Russian chemical bulletin 49 (2000), S. 1974-1976 
    ISSN: 1573-9171
    Keywords: ammonium dinitramide ; thermal decomposition ; kinetics ; stabilization ; isotope composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of accumulation of the main products of thermal decomposition of ammonium dinitramide in the melt was investigated. The isotope composition of nitrogen-containing gases evolved by the decomposition of 15NH4N(NO2)2 and NH4 15N(NO2)2 was found. Easily oxidized salts, amines, amides, iodides, and other compounds soluble in the melt interfere with the liquid-phase decomposition of ammonium dinitramide.
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  • 55
    ISSN: 1573-9171
    Keywords: 2-alkylthiopropenals ; Diels–Alder reaction ; kinetics ; reaction mechanism ; 2,5-dialkylthio-3,4-dihydro-2H-pyran-2-carbaldehyde ; IR spectroscopy ; ab initio calculations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of 2-alkylthiopropenals cyclodimerization was studied in the temperature range from -7 to +42 °C in heptane and at 20 °C in various solvents. The rate constants for cyclodimerization of 2-alkylthiopropenals are four orders of magnitude higher than those for dimerization of the oxygen-containing analogs, 2-alkoxypropenals, and are independent of the solvent polarity and substituent steric constant. The activation parameters for 2-butylthiopropenal cyclodimerization were estimated. The distribution of electron density in the 2-methoxy- and 2-methylthiopropenals molecules was calculated by the ab initio method. From comparison of the HOMO and LUMO energies for these aldehydes it was concluded that the ratio between the cyclodimerization rates for 2-alkylthio-, 2-ethoxypropenals, and propenal is determined by the HOMO–LUMO gap.
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  • 56
    ISSN: 1608-3245
    Keywords: DNA ; kinetics ; oligonucleotide derivatives ; photomodification ; sensitization
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    Topics: Biology
    Notes: Abstract Quantitative characteristics of thermodynamic and kinetic cooperativity arising in the process of photomodification of a single-stranded DNA fragment with binary systems of oligonucleotide conjugates forming an active site on the target were studied. Oligonucleotides of the binary system were complementary to adjacent segments of the DNA target, and contained arylazide (X) and perylene (S) residues covalently attached to their terminal phosphates. Upon irradiation at the perylene absorption wavelength, the target was modified by the arylazide residue, which was activated owing to the contiguity with the sensitizing perylene group in the tandem complex. Basing on the kinetic data, the constants of association of both derivatives of oligonucleotides with the target were determined: K x = 1.13 · 106 M–1, K s = 1.49 · 104 M–1. It was determined that association of both oligonucleotides with the target proceeded with a positive cooperativity characterized by parameter α = 45. The kinetic cooperativity parameter β was found to be approximately equal to 200; this characterized the acceleration of target modification in complex with the binary reagent versus that in the absence of sensitizer.
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  • 57
    ISSN: 1608-3407
    Keywords: Dunaliella salina ; lactate dehydrogenase ; kinetics ; glycerol synthesis
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    Topics: Biology
    Notes: Abstract The dependence of the catalytic properties of lactate dehydrogenase (LDH, EC 1.1.1.27) from a halophilic alga Dunaliella salina, a glycophilic alga Chlamydomonas reinhardtii, and from porcine muscle on glycerol concentration, medium pH, and temperature was investigated. Several chemical properties of the enzyme from D. salina differentiated it from the LDH preparation obtained from C. reinhardtii and any homologous enzymes of plant, animal, and bacterial origin. (1) V max of pyruvate reduction manifested low sensitivity to the major intracellular osmolyte, glycerol. (2) The affinity of LDH for its coenzyme NADH dropped in the physiological pH region of 6–8. Above pH 8, NADH virtually did not bind to LDH, while the enzyme affinity for pyruvate did not change considerably. (3) The enzyme thermostability was extremely low: LDH was completely inactivated at room temperature within 30 min. The optimum temperature for pyruvate reduction (32°C) was considerably lower than with the enzyme preparations from C. reinhardtii (52°C) and porcine muscle (61°C). (4) NADH greatly stabilized LDH: the ratio of LDH inactivation constants in the absence of the coenzyme and after NADH addition at the optimum temperature in the preparation from D. salina exceeded the corresponding indices of LDH preparations from C. reinhardtii twelve times and from porcine muscle eight times. The authors believe that these LDH properties match the specific metabolism of D. salina which is set at rapid glycerol synthesis under hyperosmotic stress conditions. The increase of cytoplasmic pH value produced in D. salina by the hyperosmotic shock can switch off the terminal reaction of the glycolytic pathway and thus provide for the most efficient utilization of NADH in the cycle of glycerol synthesis. As LDH is destabilized in the absence of NADH, this reaction is also switched off. In the course of alga adaptation to the hyperosmotic shock, glycerol accumulation and the neutralization of intracellular pH stabilize LDH, thus creating the conditions for restoring the complete glycolytic cycle.
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    Journal of applied phycology 12 (2000), S. 45-52 
    ISSN: 1573-5176
    Keywords: ichtyotoxicity ; macroalgae ; marine algae ; México ; seaweed ; toxic extracts ; toxicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Seventy-three species of macroalgae from the Mexican Pacific, Atlantic and Caribbean coast were screened for ichtyotoxic activity. Ethanolic, acetonic and aqueous extracts were prepared and tested against the fish Carassius auratus. The extracts were classified on the basis of their effects as: toxic if the fish died in two hours or less; moderately toxic, if the organism behaved abnormally but death did notoccur, and non-toxic if the fish did not display any change. 79% species were ichtyotoxic to some degree. Extracts of 39 species were toxic, with at least one extract with lethal effects, 19 were moderately toxic and 15 species were non-toxic. Only the extracts ofDictyota bartayresiana, Dictyota cervicornis,Lobophora variegata, Bryothamnion triquetrum and Laurencia obtusa were toxic in all three solvents. The acetone and ethanol extracts were more active, and therefore are more suitable for extraction of toxic substances.
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  • 59
    ISSN: 1573-4986
    Keywords: β-glycosidase ; temperature dependence ; kinetics ; glucose ; transglycosylation ; (Thermus thermophilus)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A β-glycosidase of a thermophile, Thermus thermophilus, belonging to the glycoside hydrolase family 1, was cloned and overexpressed in Escherichia coli. The purified enzyme (Ttβgly) has a broad substrate specificity towards β-D-glucoside, β-D-galactoside and β-D-fucoside derivatives. The thermostability of Ttβgly was exploited to study its kinetic properties within the range 25–80[emsp4 ]°C. Whatever the temperature, except around 60[emsp4 ]°C, the enzyme displayed non-Michaelian kinetic behavior. Ttβgly was inhibited by high concentrations of substrate below 60[emsp4 ]°C and was activated by high concentrations of substrate above 60[emsp4 ]°C. The apparent kinetic parameters (k cat and K m ) were calculated at different temperatures. Both k cat and K m increased with an increase in temperature, but up to 75[emsp4 ]°C the values of k cat increased much more rapidly than the values of K m . The observed kinetics might be due to a combination of factors including inhibition by excess substrate and stimulation due to transglycosylation reactions. Our results show that the substrate could act not only as a glycosyl donor but also as a glycosyl acceptor. In addition, when the glucose was added to reaction mixtures, inhibition or activation was observed depending on both substrate concentration and temperature. A reaction model is proposed to explain the kinetic behavior of Ttβgly. The scheme integrates the inhibition observed at high concentrations of substrate and the activation due to transglycosylation reactions implicating the existence of a transfer subsite.
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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
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    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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  • 66
    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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    Journal of applied spectroscopy 67 (2000), S. 981-989 
    ISSN: 1573-8647
    Keywords: nonlinear regime of stimulated Raman scattering ; fluctuation ; Stokes radiation ; kinetics ; spectrum ; distribution function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Statistical properties of the Raman scattering of an intense step pulse are investigated by numerical solution of the equations of a semi-classical theory with assignment of a random Gaussian distribution of the initial polarization over the sample. The probability density functions of the intensity, energy, delay time, and width of a Stokes pulse and also of the position, height, and width of the spectral peaks of the first incidental Stokes component with the preservation of the phase memory of scattering centers are calculated. The influence of collisional dephasing on the fluctuation of these characteristics is considered.
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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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    Powder metallurgy and metal ceramics 39 (2000), S. 540-544 
    ISSN: 1573-9066
    Keywords: compaction ; facing ; cumulative charge ; powder ; composite ; heterogeneous structure ; particle ; kinetics ; surface ; die ; model ; xeroradiogram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An experimental and numerical (finite element method) study is carried out for the effect of forming scheme on property distribution for cumulative charge facings made from composite heterogeneous powder material. An experimental procedure is developed for studying powder particle flow kinetics. It is shown that use of composite punches and partition of the moulded material into a number of sub-divisions with their successive compaction achieves a more uniform density distribution for an article. It is demonstrated how the direction of the force of friction on the die walls during compaction affects the compaction of articles with faces that are not perpendicular to the direction of the pressing. The results obtained make it possible to select the optimum compaction regime taking account of production features connected with powder material composition as well as service characteristics.
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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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    Pharmaceutical research 17 (2000), S. 701-706 
    ISSN: 1573-904X
    Keywords: vapor sorption ; molar heat of adsorption ; kinetics ; isothermal microcalorimetry ; recrystallization ; hydration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. In this study, instrumentation for measuring vapor sorptionenthalpies and sorption uptakes simultaneously with an isothermalmicrocalorimeter is introduced. Various pharmaceutical modelsubstances undergoing phase transitions when exposed to humid conditions(25°C), were employed to evaluate the usefulness and sensitivity ofthe constructed experimental method. Methods. The sample is placed in the sample vessel of a RH cell andthe moisture content of the air flow is controlled. From the RH cellthe air flow is conducted into a subsequent perfusion cell in which asaturated salt solution has been loaded. The RH cell and perfusioncells are positioned in the sample sides of two twin calorimetric units.Depending on the moisture content in the outlet flow leaving thepreceding RH cell, the heat flow signal from the subsequent perfusioncell will vary. By means of blank measurement with identical settings,the rate of water sorption can be calculated and, by integration, theamount of sorbed water is obtained. Results. Amorphous lactose and cefadroxil undergo recrystallizationwhen the moisture level in the surroundings exceeds the thresholdvalues specific to each compound. During the sorption phase, heat isevolved fairly linearly as a function of consumed moisture, and alsoafter the recrystallization, the heats indicate linear behavior. The heatvalues for the desorption phase of amorphous lactose and the adsorptionof crystalline lactose coincide. With the different anhydrous forms oftheophylline, the hydration takes place more rapidly in the metastableform I, and generally, the process is more energetic in form I. In allcases, the gravimetric results agree with the water sorption uptakescalculated from the calorimetric data. Conclusions. The technique introduced offers a rapid and sensitivemethod to gain new insights into the transitions in which vapors areinvolved. In addition, different kinds of surfaces with various energeticscan now be studied more closely.
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  • 77
    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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  • 78
    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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  • 79
    ISSN: 1573-515X
    Keywords: gaseous ; kinetics ; mercury ; methods ; speciation ; waters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Mercury evasion from water is commonly modeled using measurements of dissolved gaseous mercury (DGM). We developed a method using a recently available automated field-ready mercury vapor analyzer to rapidly measure the concentrations of DGM in surface waters. We summarize here results of laboratory tests of the method, field intercomparisons with a manual method, and selected data from recent sampling campaigns in Florida and Michigan. The method uses the 1.5 lpm flow of a Tekran® Model 2537A mercury analyzer to purge and analyze discrete water samples, generating near real time (5-min) data on DGM in samples and blanks. Application of the Tekran allowed for detailed analysis of DGM removal kinetics and short-term diel studies characterizing the influence of sunlight and precipitation on DGM production in surface waters. Gas removal kinetics for dozens of samples indicates a first-order rate constant, and supports a 20-min. purge time for surface water samples from Florida (40-min for Michigan samples). Blanks are measured during a second such purge. Our results indicate that DGMs determined by both automated and manual methods are generally comparable, and that DGM in Florida samples is unstable during storage (loss rate constant ∼0.1--0.2 h-1), probably due to oxidation. This suggests that rapid in-field analysis is preferred to storage with delayed analysis. Our data indicate that DGM at the Florida site is influenced by inputs of reactive Hg in rainwater, and by production of surface DGM during photoreduction of oxidized Hg in the water column.
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  • 80
    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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    Genetica 108 (2000), S. 229-237 
    ISSN: 1573-6857
    Keywords: autoregulation ; dimerization ; kinetics ; post-transcriptional regulation ; transposable elements (TEs)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Kinetic modeling of the self-regulatory mechanisms of transposable elements (TEs) involving interactions of one or a few gene products makes predictions that are often at odds with observed results. In particular, explanations of TE autorepression at high copy number that invoke a decrease in number of active monomers through dimerization, amyloidization, and protein-mRNA binding to create an inactive state are not supported by analysis of the corresponding kinetic models. This is also true for similar mRNA–mRNA binding models. Self-repression in marineras well as other TEs can, however, be explained by a host-independent model in which inactive dimers compete with monomers for TE binding sites at the ends of the element. This model would also allow heterodimer poisoning to down-regulate transposition in the presence of divergent nonautonomous elements, since nondivergent monomers would be required at both TE ends for transposition.
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  • 82
    ISSN: 1573-6881
    Keywords: Permeability transition ; ADP/ATP translocase ; kinetics ; adenosine diphosphate ; carboxya tractyloside ; bongkekic acid ; mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract Low levels of ADP binding at the ADP/ATP translocase caused inhibition of the Ca2+-inducedpermeability transition of the mitochondrial inner membrane, when measured using the shrinkage assay on mitochondria, which have already undergone a transition. Inhibition was preventedby carboxyatractyloside, but potentiated by bongkrekic acid, which increased the affinity forinhibition by ADP. This suggests that inhibition was related to the conformation of thetranslocase. Ca2+ addition was calculated to remove most of the free ADP. Ca2+ added after ADPinduced a slow decay of the inhibition, which probably reflected the dissociation of ADP fromthe translocator. We conclude that the probability of forming a permeability transition pore(PTP) is much greater when the translocase is in the CAT conformation than in the BKAconformation, and, in the absence of CAT and BKA, the translocator is shifted between theBKA and CAT conformations by ADP binding and removal, even in deenergized mitochondria with no nucleotide gradients.
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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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  • 84
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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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  • 85
    ISSN: 1573-2614
    Keywords: Neuromuscular relaxants ; rocuronium ; kinetics ; distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine
    Notes: Abstract Objective.To determine the relationship between the rate ofrocuronium injection and the onset time of neuromuscular block. Methods.After intravenous induction, 60 female patients (ASA I–II) wereassigned randomly into 3 groups for rocuronium administration within1–15, 15–30 or 30–60 seconds. Acceleromyography of the thumbwas performed using train-of-four (TOF) stimulation. Times to 50% and 90%twitch depression of the first twitch of the TOF stimulation (T1) wererecorded. Results.Injection time significantly influences time to 50%relaxation, but not time to 90% relaxation. Body mass index is negativelycorrelated with time to 50% and 90% relaxation. Conclusions.Weconclude that rate of injection influences only the initial phase ofdevelopment of the block and that slower injection times do not significantlyaffect time to 90% relaxation at the adductor pollicis muscle.
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  • 86
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    Journal of clinical monitoring and computing 16 (2000), S. 351-360 
    ISSN: 1573-2614
    Keywords: carbon dioxide ; oxygen ; kinetics ; non-steady state ; cardiac output ; PEEP ; pulmonary embolism ; pulmonary gas exchange monitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine
    Notes: Abstract Traditionally, the study of CO2 and O2 kinetics in the body has been mostly confined to equilibrium conditions. However, the peri-anesthesia period and the critical care arena often involve conditions of non-steady state. The detection and explanation of CO2 kinetics during non-steady state pathophysiology have required the development of new methodologies, including the CO2 expirogram, average alveolar expired PCO2, and CO2 volume exhaled per breath. Several clinically relevant examples of non-steady state CO2 kinetics perturbations are examined, including abrupt decrease in cardiac output, application of positive end-expiratory pressure during mechanical ventilation, and occurrence of pulmonary embolism. The lesser known area of non-steady state O2 kinetics is introduced, including the measurement of pulmonary O2 uptake per breath. Future directions include the study of the respiratory quotient per breath, where the anaerobic threshold during anesthesia is identified by increasing respiratory quotient.
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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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  • 90
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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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    Water resources management 14 (2000), S. 417-434 
    ISSN: 1573-1650
    Keywords: adsorption ; feldspar ; industrial effluent ; pollution control ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Notes: Abstract Feldspar, among many natural substances such as termitemount-clay, saw-dust, kaolinite and dolomite, offers asignificant removal ability for sulfate, phosphate, and coloredsubstances. Optimization of experimental parameters such assolution pH and flow rate reveals, that the maximum efficiency forremoval of phosphate, sulfate, and colored substances is about42, 52, and 73% respectively. X-ray diffraction, adsorptionisotherm and recovery studies suggest, that the removal processof anions occurs via ion exchange in conjunction with surfaceadsorption. Furthermore, reaction rate studies indicate thatthe removal of the selected pollutants by feldspar follows first-order kinetics. Although the percent removal, under the optimized conditions, is higher for laboratory prepared solutions, efficiency is a little less for industrial effluentsdue to interferent effects.
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  • 92
    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 62 (2000), S. 353-363 
    ISSN: 1572-8943
    Keywords: controlled environment ; high-T c superconductors ; kinetics ; microgravimetric investigations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Many properties of oxide superconductors depend on the oxygen concentration and its distribution in the samples. The microgravimetric method is very useful to study of oxide superconductors, as it allows investigations in vacuum and controlled environments in classical applications: thermogravimetric analysis for the study of solid-state reactions, determinations of oxygen contents in redox reactions and the combined measurement of mass and additional parameters, e.g. evolved gas analysis etc. Single-phase samples of high-temperature superconductors were synthesized from stoichiometric mixtures of high-purity oxides and carbonates. Appropriate amounts of the precursor powders were homogenized manually or by a mechanical ball mill and subsequently calcined at temperatures in the 800 to 950°C range with intermediate grinding to ensure homogenous reaction. The lattice parameters of all preparations were controlled, in both initial and final experiments, by the X-ray powder method (CuKα radiation), using a Stadi P (Stoe) diffractometer with a position-sensitive detector. It is well known that temperature and mass can be measured with an accuracy higher by orders of magnitude than it is still possible for the thermoanalyst to determine the transformation temperatures or the mass changes due to overlapping partial reactions. Applications of Cahn microbalance to study of high-temperature superconductors are presented.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 747-755 
    ISSN: 1572-8943
    Keywords: benzoic acid ; europium complex ; kinetics ; non-isothermal ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition of Eu2(BA)6(bipy)2 (BA=C2H5N– 2, benzoate; bipy=C10H8N2, 2,2'-bipyridine)and its kinetics were studied under the non-isothermal condition by TG-DTG, IR and SEM methods. The kinetic parameters were obtained from analysis of the TG-DTG curves by the Achar method, the Madhusudanan-Krishnan-Ninan (MKN) method, the Ozawa method and the Kissinger method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as: dα/dt=Aexp(–E/RT)3(1–α)2/3.
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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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    Structural chemistry 11 (2000), S. 341-346 
    ISSN: 1572-9001
    Keywords: Positronium chemistry ; kinetics ; spin-exchange reactions ; high- and low-spin 3d complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Continuing in our work on the correlations between the rate constants, k CR, of the ortho into para-positronium conversion reactions, CR, promoted by complexes of various 3d ions and the metal electron delocalization β caused by the ligands, the relationship between the parameters of the correlation lines pertinent to highand low-spin complexes of CrII, MnII, and CoII ions was ascertained. Moreover, it was experimentally verified, for the first time, that the statistical probability of the CR promoted by paramagnetic compounds with S = 1/2 is three times larger than that of the CR caused by compounds with S 〉 1/2.
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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.
    Type of Medium: Electronic Resource
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    Electronic Resource
    Electronic Resource
    Springer
    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.
    Type of Medium: Electronic Resource
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