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  • kinetics  (286)
  • Modelling
  • Springer  (340)
  • GeoForschungsZentrum Potsdam  (2)
  • Cell Press
  • 2005-2009  (5)
  • 1995-1999  (337)
  • 1950-1954
  • 1
    Publication Date: 2017-04-04
    Description: Ground deformation occurring on the southern flank of Mt Etna volcano during the JulyAugust 2001 eruption was monitored by GPS measurements along an EW profile crossing the fissure system. This profile was measured eight times during the eruption, using the 'stop and go' semi-kinematic technique. Horizontal and vertical displacements between GPS surveys are reported for each station. The most significant event is a deformation episode occurring during the first week of the eruption, between 2527 July. Displacements were measured on benchmarks close to the eruptive fissure and the tensile 1989 fracture. Data inversions for measured displacements were performed using the Okada model. The model shows the narrowing of the 2001 dyke accompanied by a dextral dislocation along an east-dipping fault, parallel to the 1989 fracture.
    Description: Published
    Description: 336-341
    Description: partially_open
    Keywords: GPS ; Ground deformation ; Modelling ; Volcano monitoring ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.03. Geodesy::04.03.09. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
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    Bulletin of engineering geology and the environment 57 (1999), S. 311-318 
    ISSN: 1435-9537
    Keywords: Mots clés Sédimentation ; Consolidation ; Vase ; Modélisation ; Key words Sedimentation ; Consolidation ; Mud ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Description / Table of Contents: Abstract  Nowadays numerical models tend to replace physical models for the study of sediment transport processes in fluvial or marine environments. The variability of both the materials and the environments make the processes complex in areas of major economic importance such as estuaries. The representativeness of current models depends much on the evaluation of the material which is deposited and/or re-suspended, hence the modelling of the deposit and consolidation phenomena. The paper proposes a unidimensional analysis of the sedimentation-consolidation process based on a continuous action and taking account of the complexity of the sedimentary materials. The distinction between sedimentation (the fall of isolated grains in a fluid medium) and consolidation (compression of a solid deposit by evacuation of pore water) is difficult to determine in the case of muds. In muds, particles frequently interact (for example in flocculation and deflocculation) although the grains remain separated by a film of water at a microscopic scale. In the 1980s and 1990s, several authors attempted to unify the two phenomena. This paper reviews the most significant works on sedimentation and consolidation and discusses their limitations, noting that there is always a boundary between the two processes. The model proposed in this paper assumes a continuity of the sedimentation-consolidation process which remains compatible with previous theories. It is based on wide assumptions, postulating the effective stress can be time dependent and the infiltration velocity is not necessarily governed by Darcy's law. A system of equations is derived which are valid for a polyphasic medium (solid, liquid, gas) and where the solid phase can be composed of isolated grains and aggregates. State equations, equations of mass conservation and equations of mechanical equilibrium are completed by laws derived from the experimental approaches described in this paper or from those of other authors. The model allows the introduction of various shapes of constitutive laws, incorporating time in the effective stress function (taking account of creep phenomena) and a filtration velocity which does not follow Darcy's law (notably for the very low hydraulic gradients). This new model is applicable to a great number of sedimentation and/or consolidation cases, e.g. – Under water sedimentation-consolidation cyclic   load (swell, tide, etc.). – Consolidation of mud in ground deposits. – Consolidation of soft clay layers. The model has been validated by means of the sedimentation-consolidation simulation tests as undertaken by Been (1981). Despite the use of simple constitutive laws, the model gives a theoretical evolution of density profiles which is very similar to the experimental one for the same initial conditions. This model of the transition between sedimentation and consolidation has a wide field of application, including civil engineering, medicine, the food industry, chemical engineering and ecology.
    Notes: Résumé L'étude de la sédimentation et de la consolidation des sédiments cohésifs présente un grand intérêt scientifique par son aspect interdisciplinaire, à la frontière hydraulique-géotechnique et en raison de l'importance de ses applications à la gestion des zones cotières. Nous proposons d'associer les points de vue hydraulique et géotechnique en vue d'établir un modèle continu du processus de sédimentation-consolidation basé sur les équations de conservation de deux phases compressibles. Ce modèle, général et évolutif, permet d'envisager la prise en compte de phénomènes négligés jusqu'alors: fluage, floculation, écoulements non-darciens, ... Il constitue donc un élément fondamental pour une modélisation globale et précise de la dynamique sédimentaire en estuaire.
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  • 3
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    Bulletin of engineering geology and the environment 58 (1999), S. 45-59 
    ISSN: 1435-9537
    Keywords: Mots clés Tunnel ; Alpes ; Contraintes in situ ; Mesures de contraintes ; Méthode HTPF ; Modélisation ; Key words Tunnel ; Alps ; In-situ stresses ; Stress measurements ; HTPF method ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Description / Table of Contents: Abstract  The 52 km running tunnel of the proposed Lyon–Turin railway link will be excavated through different geological formations across the Franco-Italian Alps. The overburden of most of the route is greater than 1000 m, and it reaches 2500 m in the Ambin Massif, a regular micaschistic dome. As part of the reconnaissance program for this project, stress measurements using the HTPF (Hydraulic Testing on Pre-existing Fractures) method have been carried out in 13 deep boreholes, which provides a unique opportunity to better understand the regional stress field. After a presentation of the HTPF method and of its possible interpretation methods, the paper presents and discusses the results obtained. The influences of topography and tectonics are highlighted with the support of numerical modelling with the Finite Difference Method (FLAC code). Despite a great scatter of information on stress values and directions, three main stress regimes can be distinguished in three different geological-topographical contexts. The first one is found near the Arc valley, which is the main topographic feature in the area: the vertical stresses are greater than the weight of overburden and the horizontal stresses are highly anisotropic, σh being approximately perpendicular to the valley. This suggests a strong topographic influence of the Arc valley, especially for those measurements closest to its axis. Two other regimes have been encountered in the Ambin Massif. On the one hand, in the heart of the massif, under two small valleys, horizontal stresses are anisotropic with σh parallel and σh perpendicular to the valleys; but curiously vertical stresses are nearly 20% lower than the weight of overburden and are in both cases the minor principal stresses. On the other hand, under its Italian border and in a slope situation, the measured states of stress are those classically obtained in soils: vertical stresses are equal to the weight of overburden and horizontal stresses are nearly isotropic, equal to the half of the vertical ones. In order to better understand these measurements and their relation to the regional state of stress, a series of numerical calculations of increasing complexity were undertaken. They all take into consideration the effects of both the simplified topography and, in a parametrical manner, the tectonic stresses. The results are consistent with most of the global trends presented above, and particularly for the first and third stress regimes. For the second one, however, in the heart of the Ambin Massif, modelling gives only a first qualitative explanation for the low measured vertical stresses.
    Notes: Résumé Dans le cadre de la conception d'un futur grand tunnel à travers les Alpes, des mesures de contraintes naturelles ont été faites dans 13 forages profonds, dans des contextes géologiques et topographiques variés. L'article en propose une analyse critique en insistant sur l'influence des méthodes d'interprétation employées, et s'appuie pour les interpréter sur des modélisations simplifiées prenant en compte la topographie et la tectonique. Malgré la dispersion des résultats, trois grands types d'états de contraintes se dégagent. A proximité de la vallée de l'Arc, les contraintes horizontales sont fortement anisotropes, orientées suivant la vallée et les contraintes verticales sont fortes, ce qui traduit un effet topographique classique. Sous deux vallons du massif d'Ambin, les contraintes horizontales sont anisotropes et supérieures aux verticales. Enfin, sous la retombée orientale de ce massif, on trouve plutôt un état de contraintes de "type K0". Tous ces résultats sont en bonne concordance avec les modélisations présentées, à l'exception des faibles contraintes verticales du massif d'Ambin.
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  • 4
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    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Keywords: cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
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  • 5
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    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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  • 6
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    Adsorption 1 (1995), S. 133-151 
    ISSN: 1572-8757
    Keywords: PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.
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  • 7
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    Adsorption 2 (1996), S. 265-277 
    ISSN: 1572-8757
    Keywords: frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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  • 8
    ISSN: 1572-8757
    Keywords: characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
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  • 9
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 10
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    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Keywords: dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
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  • 11
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    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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  • 12
    ISSN: 1572-882X
    Keywords: accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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  • 13
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    Journal of solution chemistry 27 (1998), S. 1123-1138 
    ISSN: 1572-8927
    Keywords: Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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  • 14
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    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Keywords: paper ; degradation ; ageing ; kinetics ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
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  • 15
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    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Keywords: aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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  • 16
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    Journal of inorganic and organometallic polymers and materials 8 (1998), S. 111-117 
    ISSN: 1572-8870
    Keywords: Organosiloxane ; kinetics ; poly(phenylmethylsiloxane) ; catalyst ; anionic ; ring-opening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is well known that the rate of polymerization for an anionic mechanism is dependent on the ability of the bulk material or solvent system to disassociate the ion pair at the propagating chain end. In the anionic ring-opening polymerization of cyclic organosiloxanes in particular, the larger and softer the counter ion, the more rapidly the reaction proceeds. A recently developed phosphazene initiator system provides a large, soft counter ion relative to other traditional initiators used for the polymerization of poly(dimethylsiloxane) (PDMS). This novel initiator system was used in this investigation for the ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane (P4) and the reaction kinetics under bulk and solution conditions were investigated. The new initiator system showed a dramatic increase in the rate of polymerization over the conventional potassium hydroxide-catalyzed system. Furthermore, this initiator was sufficiently reactive to be useful for the ring-opening polymerization of P4 at 293 K.
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  • 17
    ISSN: 1572-8900
    Keywords: Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 18
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    Topics in catalysis 5 (1998), S. 133-147 
    ISSN: 1572-9028
    Keywords: NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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  • 19
    ISSN: 1572-9028
    Keywords: nonlinear temperature behavior ; Eyring plot ; modified Eyring plot ; selectivity ; selection process ; enantioselectivity ; selection level ; isoinversion principle ; isoinversion temperature ; inversion temperature ; kinetics ; catalysis ; asymmetric hydrogenation ; dihydroxylation ; cocyclization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.
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  • 20
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 21
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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  • 22
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 23
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 24
    ISSN: 1572-8773
    Keywords: aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Based on kinetic evidence, it has been shown for the first time that the mode of binding of aromatic donor molecules is similar in horseradish peroxidase and lactoperoxidase; also that the nature of the heme plays an important role in the reaction with hydrogen peroxide, and has no effect on the reaction of the intermediate compound II with aromatic substrates.
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    Catalysis letters 31 (1995), S. 431-438 
    ISSN: 1572-879X
    Keywords: partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.
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  • 26
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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    Catalysis letters 55 (1998), S. 73-77 
    ISSN: 1572-879X
    Keywords: enantioselectivity ; hydrogenation of ethyl pyruvate ; Pt/alumina catalyst ; solvent effects ; kinetics ; solvent polarity
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of solvent on the kinetics of enantioselective hydrogenation of ethyl pyruvate by Pt/Al2O3/dihydrocinchonidine is reported. In a non‐polar solvent, toluene, the reaction is approximately zero order in substrate at constant hydrogen pressure, while under the same conditions and at the same substrate concentration, in the polar solvents ethanol and propylene carbonate the reaction shows a first‐order substrate concentration dependence. Fits to a Michaelis–Menten rate expression show that these differences are the expression of the relative magnitudes of the adsorption term in the rate expression, which in turn reflects the influence of the solvent on the adsorption–desorption processes which take place at the catalyst surface.
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  • 29
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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    Biology and fertility of soils 22 (1996), S. 171-178 
    ISSN: 1432-0789
    Keywords: Aporrectodea nocturna ; Dispersal ; Cast production ; Modelling ; Earthworms ; Soil moisture ; Microbial biomass ; Prealpine meadow
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Field and laboratory experiments were carried out to describe the effects of Aporrectodea nocturna on soil characteristics in a pre-alpine meadow and to support the development of a model of cast production. In the prealpine meadow, increased cast production, first observed about 20 years ago around a newly planted hedge, was recorded to a distance of maximal 170 m from the hedge. Numbers of A. nocturna between 130 and 165 m from the hedge decreased from 164 to 16 individuals m-2. In the same area cast production steadily decreased from about 1.5 kg m-2 week-1 to nil, the plant community structure changed and the microbial biomass decreased, but the root biomass and the moisture content did not change. Laboratory experiments demonstrated that high cast production was not a specific feature of the A. nocturna population nor of the soil in the meadow. Diapause of A. nocturna was terminated in the laboratory during September. A model of cast production potential by the earthworm A. nocturna was established using laboratory determinations of the relationships with body weight, temperature, and water potential. The model was shown to predict cast production in the field given the assumption that the water potential was 0 MPa. According to the model, 81% of surface cast production was by juveniles, and 19% by adults of A. nocturna.
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  • 31
    ISSN: 1432-0789
    Keywords: Key words Soil organic carbon ; Geographical Information Systems ; Modelling ; Carbon sequestration ; Hungarian soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  Soil organic matter (SOM) represents a major pool of carbon within the biosphere. It is estimated at about 1400 Pg globally, which is roughly twice that in atmospheric CO2. The soil can act as both a source and a sink for carbon and nutrients. Changes in agricultural land use and climate can lead to changes in the amount of carbon held in soils, thus, affecting the fluxes of CO2 to and from the atmosphere. Some agricultural management practices will lead to a net sequestration of carbon in the soil. Regional estimates of the carbon sequestration potential of these practices are crucial if policy makers are to plan future land uses to reduce national CO2 emissions. In Europe, carbon sequestration potential has previously been estimated using data from the Global Change and Terrestrial Ecosystems Soil Organic Matter Network (GCTE SOMNET). Linear relationships between management practices and yearly changes in soil organic carbon were developed and used to estimate changes in the total carbon stock of European soils. To refine these semi-quantitative estimates, the local soil type, meteorological conditions and land use must also be taken into account. To this end, we have modified the Rothamsted Carbon Model, so that it can be used in a predictive manner, with SOMNET data. The data is then adjusted for local conditions using Geographical Information Systems databases. In this paper, we describe how these developments can be used to estimate carbon sequestration at the regional level using a dynamic simulation model linked to spatially explicit data. Some calculations of the potential effects of afforestation on soil carbon stocks in Central Hungary provide a simple example of the system in use.
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    Biology and fertility of soils 27 (1998), S. 263-266 
    ISSN: 1432-0789
    Keywords: Key words Soil organic matter ; Climate change ; Modelling ; Sensitivity analysis ; Feedback
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    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  The nonlinear model of the carbon cycle in soils (NAMSOM) was used to analyze the sensitivity of soil organic matter levels to variations in carbon turnover parameters. We were able to predict the sensitivity of soil organic matter levels to variations of climate-dependent carbon turnover parameters, which allowed us to compare the sensitivity of soil organic matter levels to net primary productivity of plant communities and plant debris decomposition rate constants across the range of soils in the European part of Russia. The results indicate that meadow steppes show the lowest sensitivity to variations of these parameters. In passing from meadow steppes to the northern taiga and to semideserts, the sensitivity increases. In general, soil organic matter levels of boreal forest ecosystems are about 2–3 times more sensitive to input and decomposition of plant debris than to decomposition of humus. In subboreal grassland ecosystems the sensitivity to humus decomposition increases and becomes closer to the degree of sensitivity shown by soil organic matter levels to variations of productivity and decomposition of plant debris. The proposed method may be useful for predicting the response of ecosystems to climatic change.
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  • 33
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    Biology and fertility of soils 22 (1996), S. 171-178 
    ISSN: 1432-0789
    Keywords: Key wordsAporrectodea nocturna ; Dispersal ; Cast production ; Modelling ; Earthworms ; Soil moisture ; Microbial biomass ; Prealpine meadow
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    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Field and laboratory experiments were carried out to describe the effects of Aporrectodea nocturna on soil characteristics in a pre-alpine meadow and to support the development of a model of cast production. In the pre-alpine meadow, increased cast production, first observed about 20 years ago around a newly planted hedge, was recorded to a distance of maximal 170 m from the hedge. Numbers of A. nocturna between 130 and 165 m from the hedge decreased from 164 to 16 individuals m–2. In the same area cast production steadily decreased from about 1.5 kg m–2 week–1 to nil, the plant community structure changed and the microbial biomass decreased, but the root biomass and the moisture content did not change. Laboratory experiments demonstrated that high cast production was not a specific feature of the A. nocturna population nor of the soil in the meadow. Diapause of A. nocturna was terminated in the laboratory during September. A model of cast production potential by the earthworm A. nocturna was established using laboratory determinations of the relationships with body weight, temperature, and water potential. The model was shown to predict cast production in the field given the assumption that the water potential was 0 MPa. According to the model, 81% of surface cast production was by juveniles, and 19% by adults of A. nocturna.
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  • 34
    ISSN: 1432-0789
    Keywords: Key words Carbon evolution ; Decomposition ; Modelling ; Temperature coefficient (Q10) ; Temperature effects
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    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  The literature was reviewed regarding laboratory incubation studies where C mineralization was measured. Experiments were selected in which the same substrate was incubated at least at two different temperatures and where time-series were available with at least four measurements for each substrate and temperature. A first-order one-component model and a parallel first-order two-component model were fitted to the CO2–C evolution data in each experiment using a least-squares procedure. After normalising for a reference temperature, the temperature coefficient (Q 10 ) function and three other temperature response functions were fitted to the estimated rate constants. The two-component model could describe the dynamics of the 25 experiments much more adequately than the one-component model (higher R2, adjusted for the number of parameters), even when the rate constants for both were assumed to be equally affected by temperature. The goodness-of-fit did not differ between the temperature response models, but was affected by the choice of the reference temperature. For the whole data set, a Q 10 of 2 was found to be adequate for describing the temperature dependence of decomposition in the intermediate temperature range (about 5–35  °C). However, for individual experiments, Q 10 values deviated greatly from 2. At least at temperatures below 5  °C, functions not based on Q 10 are probably more adequate. However, due to the paucity of data from low-temperature incubations, this conclusion is only tentative, and more experimental work is called for.
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    Formal aspects of computing 9 (1997), S. 409-424 
    ISSN: 1433-299X
    Keywords: Distributed algorithms ; Modelling ; Correctness ; Petri nets ; Verification techniques ; Temporal logic
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    Topics: Computer Science
    Notes: Abstract A technique to model and to verify distributed algorithms is suggested. This technique (based on Petri nets) reduces the modelling and analysis effort to a reasonable level. The paper outlines the technique using the example of a typical network algorithm, theecho algorithm.
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    The international journal of advanced manufacturing technology 13 (1997), S. 214-226 
    ISSN: 1433-3015
    Keywords: Design ; Flexible production systems ; Functional analysis ; Modelling ; Performance analysis ; Petri nets
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The aim of this work is to present an approach, which allows the reproduction of a flexible production system behaviour during production operations and gives feedback about its efficiency, in order to validate the system's specifications. The modelling and analysis of flexible production systems are investigated for both functional and performance objectives. The paper focuses particularly on the modelling and analysis of production systems using a new proposed temporised Petri net tool and demonstrates how the model obtained suits the tasks well by producing a higher accuracy system description. An analysis methodology based on both structural and reachability-like approaches, is also presented to derive the behaviour characteristics of the modelled systems in terms of their functionality and performance. From validation data analysis the user can obtain useful suggestions regarding layout configuration and strategies of resource management and can be guided throughout the whole production system design phase. An application example is given.
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    The international journal of advanced manufacturing technology 11 (1996), S. 258-266 
    ISSN: 1433-3015
    Keywords: Cellular automaton ; Flexible manufacturing systems ; Modelling
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this paper, we propose a high-level state-based dependency description and structuring formalism for flexible manufacturing systems (FMS). This extended cellular automaton model (ECAM) is designed to capture the behaviour and performance of a large complex concurrent system in an easier and more concise way than is possible with other contemporary FMS models. Concurrency problems of FMS can be clearly identified by the model. The model is defined mathematically as a quintuple by adapting the cellular automaton. A set of graphical symbols is also defined to represent the states of the model. The proposed model can serve as a formal specification and documentation tool for an FMS. It can also provide a basis for modelling important characteristics of FMS which includes conflict resolution, dependencies and starvation of resources. In real applications, it can serve as a conceptual model in the FMS design process. Based on this model a prototype system has been developed to generate a set of executable grammar rules. With appropriate extensions, the system can be used as simulation and performance analysis tools.
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    The international journal of advanced manufacturing technology 11 (1996), S. 449-461 
    ISSN: 1433-3015
    Keywords: Knowledge-based system ; Modal-cutting ; Modelling
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper looks into a new area for knowledge-based system application, that of manufacturing modelling. The objective is to develop a knowledge-based manufacturing modelling system that can be used to build company-specific “as-is” and “to-be” IDEF0 models, and can therefore greatly reduce the turnaround time and effort involved in IDEF0 modelling of manufacturing systems, which can be time-consuming if done manually or even with the aid of a commercially available software package like DESIGN/IDEF™. This is especially so when the systems being modelled are large and complex. Besides, there is also the inconsistency problem associated with conventional IDEF0 modelling systems owing to the terms and terminologies in IDEF0 not being precisely defined, and hence being subject to individual interpretations. In this paper, a knowledge-based IDEF0 modelling system that can not only automate the tiresome and time-consuming process of manufacturing modelling but can also eliminate the inconsistency problem is proposed. The paper explains the knowledge-based approach to automated generation of IDEF0 models, and also identifies the kinds of domain knowledge that are required for the construction of the knowledge-based manufacturing modelling system.
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    The international journal of advanced manufacturing technology 14 (1998), S. 369-375 
    ISSN: 1433-3015
    Keywords: Evaluation ; Manufacturing Strategy ; Modelling
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Practising engineers frequently seek to understand what the effects of various manufacturing strategies will be on the performance of their production facilities. In this situation a computer model can help to provide insight and form predictions about future manufacturing system performance. Various types of modelling methods exist and each provide models that have distinct characteristics. This paper presents a review of popular modelling techniques and, based on the results of a structured experimental study, summarises their capabilities to support the evaluation of manufacturing strategies.
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    Neural computing & applications 7 (1998), S. 107-114 
    ISSN: 1433-3058
    Keywords: Crossflow filtration ; Learning algorithm ; Modelling ; Multilayer neural networks ; Simplex
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    Topics: Computer Science , Mathematics
    Notes: Abstract A learning algorithm based on the modified Simplex method is proposed for training multilayer neural networks. This algorithm is tested for neural modelling of experimental results obtained during cross-flow filtration tests. The Simplex method is compared to standard back-propagation. Simpler to implement, Simplex has allowed us to achieve better results over four different databases with lower calculation times. The Simplex algorithm is therefore of interest compared to the classical learning techniques for simple neural structures.
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    International journal of earth sciences 85 (1996), S. 58-64 
    ISSN: 1437-3262
    Keywords: Aperiodicity ; Buckling ; Evolution ; Modelling ; Spatial chaos
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    Topics: Geosciences
    Notes: Abstract Naturally occurring fold systems are typically irregular. Although such systems may sometimes be approximated by a periodic geometry, in reality they are commonly aperiodic. Ord (1994) has proposed that naturally occurring fold systems may display spatial chaos in their geometry. Previous work has indicated that linear theories for the formation of fold systems, such as those developed by Biot (1965), result in strictly periodic geometries. In this paper the development of spatially chaotic geometries is explored for a thin compressed elastic layer embedded in a viscoelastic medium which shows elastic softening. In particular, it is shown that spatially localized forms of buckling can develop and the evolution of these systems in the time domain is presented. A nonlinear partial differential equation, fourth order in a spatial variable and first order in time, is found to govern the evolution. A related nonlinear fourth-order ordinary differential equation governs an initial elastic phase of folding. The latter equation belongs to a class with spatially chaotic solutions. The paper reviews the implications of localization in the geological framework, and draws some tentative conclusions about the development of spatial chaos. Crudely arrived-at, yet plausible, evolutionary time plots under the constraint of constant applied end displacement are presented. Emphasis throughout is on phenomenology, rather than underlying mathematics or numerics.
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    International journal of earth sciences 88 (1999), S. 190-200 
    ISSN: 1437-3262
    Keywords: Key words Himalaya ; Syntaxes ; Folding ; Modelling ; Intermontane basins ; Pakistan
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  We describe the eastern and western Himalayan syntaxes, which are large-scale antiforms situated at geodynamically similar locations and the metamorphic evolution of which is coeval in the India–Asia collisional history. To understand the mechanical plausibility of the structural interpretation, we present two-dimensional finite-element modelling of lithospheric folding. The models reveal the coeval development of adjacent synformal basins, analogous to the Peshawar and Kashmir basins on both sides of the western syntaxis. Similarities between geological data and calculated models indicate that lithospheric buckling is a basic response to large-scale continental shortening and an efficient mountain building process.
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  • 43
    ISSN: 1436-5073
    Keywords: kinetics ; rates ; integrating ratemeter ; optimization ; first-order
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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    Meccanica 31 (1996), S. 163-176 
    ISSN: 1572-9648
    Keywords: Modelling ; Audio-frequency vibrations ; Envelope ; Hilbert transform ; Vibrations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Scopo di questo articolo è quello di fornire un panorama critico delle tecniche che si sono o si stanno attualmente sviluppando per lo studio delle vibrazioni nel campo delle alte frequenze e per problemi di accoppiamento acustico-strutturale. Vengono, in particolare, messe in evidenza similitudini e differenze tra i vari metodi esaminati. Successivamente viene descritto in dettaglio un modello, chimato inviluppo complesso di spostamento, che appare molto promettente e ricco di sviluppi futuri. Vengono infine presentati alcuni risultati per evidenziare il diverso contenuto informativo delle soluzioni ottenute con le varie tecniche analizzate.
    Notes: Abstract The aim of this paper is to review the main techniques used to provide a significant solution to high frequency vibrations and/or structural-acoustic coupling. The characteristics of the different approaches are illustrated, focusing similarities and differences among them. A detailed description of the complex envelope displacement analysis is then presented, because of the promising developments of this approach. Finally some results are shown and discussed to emphasize the informative character of the different solutions.
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    Nutrient cycling in agroecosystems 51 (1998), S. 209-215 
    ISSN: 1573-0867
    Keywords: Desorption ; kinetics ; microbial transformation ; phosphate ; soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The improvement of P management in agriculture and environment requires a good understanding of residual effect of applied P in soils. The specific adsorption of P on variable charge minerals has been considered as the major mechanism that leads to a very low utilization of P fertilizer by crops within a growing season in Chinese red soils. Soil incubation and isotope tracing analysis were carried out to examine the transformation kinetics and potential availability of added specifically sorbed 32P in two pH contrasting light textured soils. The 32P recovered by 0.5 M NaHCO3 extraction and microbial biomass-P measurement from the added specifically sorbed 32P in the soils was well described by a first-order reaction and a Langmuir-type kinetic model, with correlation coefficients (R) being, on average, 0.938 and 0.959, respectively. The half-life (t1/2, from the first-order model) of the four tested mineral-P complexes ranged from 29 to 47 d in the acid sandy soil and 33 to 105 d in the neutral silty soil. Goethite-P was the most stable among the four tested mineral-P complexes. The potential availability of the mineral complex P (q m , in percent of total 32P added) obtained from the Langmuir equation ranged from 43.7 to 90.9% for the four mineral-P complexes, and decreased in the order: Al oxide-P (90.9%) 〉 montmorillonite-P (86.2%) 〉 kaolinite-P (77.5%) 〉 goethite-P (60.2%) in the acid sandy soil, whereas the order was Al oxide-P (89.3%) 〉 kaolinite-P (86.2%) 〉 montmorillonite-P (82.6%) 〉 goethite-P (43.7%) in the neutral silty soil. Based on the release rate and potential availability, kaolinite-P and Al oxide-P could be important sources for residual effect of applied P in variable-charge soils. The goethite-P has the lowest release rate and potential availability among the mineral-P complexes, implying that iron oxides may be the most important variable-charge mineral responsible for P fixation in the Chinese red soils.
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    Journal of statistical physics 95 (1999), S. 23-43 
    ISSN: 1572-9613
    Keywords: model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
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  • 47
    ISSN: 1572-9729
    Keywords: bioavailability ; builders ; detergents ; kinetics ; mineralization ; sewage sludge ; soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Tetradecenyl succinic acid (TSA) is the major component of a detergent builder (C12-C14 alkenyl succinic acid), which is inherently biodegradable. 14C-TSA was dosed as a component of sewage sludge into a soil with a history of sludge amendment at final added concentrations of 1.5 and 30 mg (kg soil)-1. In addition, it was dosed to the soil in an aqueous solution to a final added concentration of 30 mg (kg soil)-1. Dose and form were found to have a pronouced effect on the mineralization kinetics. When dosed in a realistic form and concentration (i.e. 1.5 mg (kg soil)-1 as a component of sludge), TSA was mineralized at its highest rate and to its greatest extent, and the mineralization half-life was 2.4 days. When dosed at 30 mg (kg soil)-1 as a component of sludge, mineralization began immediately, and the half-life was 23 days. In contrast, when dosed at this concentration in aqueous solution, the onset of mineralization was preceded by a 13 day lag period and the mineralization half-life was 69 days. Primary biodegradation and mineralization rates of TSA were very similar. Approximately, half the radioactivity was evolved as 14CO2, while the remaining radioactivity became non-extractable, having presumably been incorporated into biomass or natural soil organic matter (humics). This study demonstrated that TSA is effectively removed from sludge-amended soils as a result of biodegradation. Furthermore, it showed the effect that dose form and concentration have on the biodegradation kinetics and the importance of dosing a chemical not only at a relevant concentration but also in the environmental form in which it enters the soil environment.
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  • 48
    ISSN: 1572-9729
    Keywords: bacteria ; degradation ; denitrification ; kinetics ; stoichiometry ; toluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Batch experiments were carried out to investigate the stoichiometry and kinetics of microbial degradation of toluene under denitrifying conditions. The inoculum originated from a mixture of sludges from sewage treatment plants with alternating nitrification and denitrification. The culture was able to degrade toluene under anaerobic conditions in the presence of nitrate, nitrite, nitric oxide, or nitrous oxide. No degradation occurred in the absence of Noxides. The culture was also able to use oxygen, but ferric iron could not be used as an electron acceptor. In experiments with14C-labeled toluene, 34%±8% of the carbon was incorporated into the biomass, while 53%±10% was recovered as14CO2, and 6%±2% remained in the medium as nonvolatile water soluble products. The average consumption of nitrate in experiments, where all the reduced nitrate was recovered as nitrite, was 1.3±0.2 mg of nitrate-N per mg of toluene. This nitrate reduction accounted for 70% of the electrons donated during the oxidation of toluene. When nitrate was reduced to nitrogen gas, the consumption was 0.7±0.2 mg per mg of toluene, accounting for 97% of the donated electrons. Since the ammonia concentration decreased during degradation, dissimilatory reduction of nitrate to ammonia was not the reductive process. The degradation of toluene was modelled by classical Monod kinetics. The maximum specific rate of degradation, k, was estimated to be 0.71 mg toluene per mg of protein per hour, and the Monod saturation constant, K s , to be 0.2 mg toluene/l. The maximum specific growth rate, μ max , was estimated to be 0.1 per hour, and the yield coefficient, Y, was 0.14 mg protein per mg toluene.
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    Biodegradation 7 (1996), S. 73-81 
    ISSN: 1572-9729
    Keywords: diesel oil ; biodegradation ; CSTR ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In batch culture diesel oil was degraded rapidly, with a maximum growth rate (for a consortium of microorganisms) of 0.55 h-1. The corresponding yield Y SX was 0.1 Cmol/Cmol. In a continuous stirred tank reactor the maximum dilution rate was about 0.25 h-1, with a yield of 0.3 Cmol/Cmol. With a residence time of 1 day 82% of the influent oil was degraded. In the batch reactor, of the mixture of linear and branched alkanes the linear alkanes were degraded fastest and with the highest yield. Only after most of the linear alkanes had disappeared were the branched alkanes consumed. In a CSTR a large part of the branched alkanes was not degraded.
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  • 50
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    Journal of molecular modeling 2 (1996), S. 362-369 
    ISSN: 0948-5023
    Keywords: Opioid Receptors ; Morphine ; Modelling ; G-Protein Coupled Receptors ; Bacteriorhodopsin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Opioid receptors (OPRs) are important agents in the centeral nervous system (CNS) function. These receptors belong to “G-Protein Coupled Receptors (GPCRs)” which have structural similarity with the BACTERIORHODOPSIN (bR). Because of receptor location in the membrane, three dimensional (3D) structure of GPCRs are unknown. The Computer-Aided Receptor Modelling on the basis of amino acid sequence, accompanied by the experimental results is a useful method to understanding the structure and mechanism of these receptors. In this study we tried to modell three types of Human Opioid Receptors; Mu, Kappa and Delta. We applied several methods to predict secondary structure (such as Hydropathicity Plot) of opioid receptors and also determined the possible regions of transmembrane helices (TMHs). Results were confirmed by inclusion of other human GPCRs sequence in multiple alignment methods. Then similarity between these receptors and bR were calculated on the basis of parameters such as Mutation Matrix and Secondary Structure Scale. After calculation and refinment of geometric coordinates of atoms located in helices by computerized mutation method (on the basis of 3D structure of bR, as a template) these data were corrected and optimized using Molecular Mechanics Calculations (AMBER Force Field). We used Morphin, Naloxone, Ethylketazocine (EKC) and SKF-10047 as general/specific ligand for these receptors. We optimized conformation of ligands by Quantum Mechanical Semiemprical Calculations (MOPAC). In final step we tried to dock ligands into the receptor cavity with attention to Mutagenesis Data and Structure-Activity Relationships (SAR) information. Our results show that in Delat receptors ‘ASP-96′ in TMH-II is important to binding of agonists and antagonists. In Mu receptors charged amino acid residues in TMH-II (ASP-116), TMH-III (ASP-149) and TMH-VI (HIS-299) interact with agonists. In Kappa receptors TMH-VI (GLU-297) and TMH-II (ASP-106) play a major role in interaction with antagonists. All of the mentioned residues are located in or near the inner cavity of receptors. With attention to results we suggest that other sites of receptors (such as loops and terminals) may be interact with ligands.
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  • 51
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    Environmental geology 39 (1999), S. 1-19 
    ISSN: 1432-0495
    Keywords: Key words Pyrite ; Oxidation ; Waste rock ; Leachate ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  A field survey and modelling of the oxidation and carbonate buffering reactions inside the alum-shale-containing waste rock dumps located in Maardu, Estonia, was accomplished. In the slope areas, the shale has been altered at high temperatures due to the spontaneous combustion and the pyritic acidity has been eliminated through migration of SOx gases out from the dump. In the central parts of the waste rock plateaus, low temperature pyrite oxidation fronts develop towards the dump depth and towards the centres of individual shale lumps. The main secondary phases precipitating in the weathering profile are gypsum, ferric oxyhydroxide, K-jarosite and smectite. The respective field data made it possible to calibrate the two-stage oxygen diffusion model and the characteristic pyrite oxidation rate 0.06–0.08 mol of pyrite reacted per kg of available water (pyrox/H2O value) was estimated to describe the first tens of years of dump performance. The model is capable to compare different shale disposal strategies that are illustrated with two case scenarios. The buffering of sulphuric acid by Mg-calcite appears to be an incongruent reaction with gypsum precipitating that leads to the build-up of the high Mg/Ca ratio in the leachate. Application of the Mg/Ca method estimates the pyrox/H2O value in the range of 0.05–0.14 mol/kg.
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  • 52
    ISSN: 1432-0495
    Keywords: Key words Pyrite oxidation ; Acid mine drainage ; Tailings ; landfill ; Sealing ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  Annually, an amount of approximately 13 million cubic meters of hard-coal tailings must be disposed of in the German Ruhr Valley. Besides the waste of land in a densily populated region, the disposal of the pyrite-bearing material under atmospheric conditions may lead to the formation of acid mine drainage (AMD). Therefore, alternative disposal opportunities are of increasing importance, one of which being the use of tailings under water-saturated conditions, such as in backfilling of abandoned gravel pits or in the construction of waterways. In this case, the oxidation of pyrite, and hence the formation of AMD, is controlled by the amount of oxygen dissolved in the pore water of tailings deposited under water. In case the advective percolation of water is suppressed by sufficient compaction of the tailings, oxygen transport can be reduced to diffusive processes, which are limited by the diffusive flux of dissolved oxygen in equilibrium with the atmospheric pO2. Calculations of the duration of pyrite oxidation based on laboratory experiments have shown that the reduction of oxygen is mainly controlled by the content of organic substance rather than the pyrite content, a fact that is supported by results from oxidation experiments with nitrate. A "worst case" study has lead to the result that the complete oxidation of a 1.5-m layer of hard-coal tailings deposited under water-saturated conditions would take as much as several hundred thousand years.
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  • 53
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    Pure and applied geophysics 147 (1996), S. 367-375 
    ISSN: 1420-9136
    Keywords: Induced seismicity ; kinetics ; rock fracture ; rockburst ; earthquake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Powerful seismic events, such as earthquakes and rockbursts, are caused by the accumulation of energy in rocks and loss of rock mass stability. Usually methods of their forecasting are based on the registration of anomalous behavior of geophysical fields. However an efficiency of this approach is low. The present paper proposes a kinetic approach to the description of rock fracture process, which can be used for the forecasting of seismic events and an investigation of structure and energy distributions in rock. 3-D and 1-D kinetic equations describing a process of cluster formation in rock were obtained. The equations are invariant to deformation conditions and to the scale level of events. They showed a good agreement with the results of field observations and laboratory experiments. It was also shown that these equations well describe the processes of earthquake, rockburst and rock sample failure preparation. Catalogues of rockbursts in mines were analyzed with the use of the kinetic equations to find out evidence of induced seismic events. The proposed approach makes it possible to reveal trends in rock behavior and thus predict the rock failure at different scale levels.
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  • 54
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    Trees 12 (1998), S. 385-394 
    ISSN: 0931-1890
    Keywords: Key words Wind Damage ; Tree Movement ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A mathematical, computer-based, dynamic sway model of a Sitka spruce (Picea sitchensis) tree was developed and tested against measurements of the movement of a tree within a forest. The model tree was divided into segments each with a stiffness, mass and damping parameter. Equations were formulated to describe the response of every segment which together form a system of coupled differential equations. These were solved with the aid of matrices and from the resulting modes, the transfer function of the tree was found and used to calculate the movement of the tree in the wind. Comparison of the modelled movement of a tree in response to the measured wind speed above a forest canopy gave good agreement with the measured movement of the top of the tree but less satisfactory agreement close to the base. The comparison also pointed to the complexity of tree response to the wind and inadequacies in the model. In particular, the branches need to be treated as coupled cantilevers attached to the stem rather than simply as masses lumped together.
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  • 55
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    Bulletin of volcanology 59 (1998), S. 311-326 
    ISSN: 1432-0819
    Keywords: Key words Mt. Etna ; Microgravity ; Magma sources ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  Results are presented from 11 microgravity surveys on Mt. Etna between 1987 and 1993, a period including the major 1989 and 1991–1993 flank eruptions and subordinate 1990 activity. Measurements were made with LaCoste and Romberg D-62 and D-157 gravity meters along a network around the volcano between 1000 and 1900 m a.s.l. and, since 1992, a N–S summit profile. Gravity changes of as much as 200 μGal were observed at scales from the size of the summit region to that of the volcano. None was associated with significant changes in ground elevation. The data show an increase in gravity for 2 years before the 1989 eruption. The increase is attributed to the accumulation of magma (0.25–1.7×109 m3) in an elongate zone, oriented NNW–SSE, between 2.5 and 6 km below sea level. Part of this magma was injected into the volcanic pile to supply the 1989 and 1990 eruptions. It also probably fed the start of the 1991–1993 eruption, since this event was not preceded by significant gravity changes. A large gravity increase (up to 140 μGal) detected across the volcano between June and September 1992 is consistent with the arrival in the accumulation zone of 0.32–2.2×109 m3 of new magma, thus favoring continued flank effusion until 1993. A large gravity decrease (200 μGal) in the summit region marked the closing stages of the 1991–1993 event and is associated with magma drainage from the upper levels of Etna's central feeding system.
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  • 56
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    Bulletin of volcanology 60 (1999), S. 412-424 
    ISSN: 1432-0819
    Keywords: Key words Alkali basalt ; Segregation veins ; Trace element geochemistry ; Differentiation ; Modelling ; Volatiles ; Penghu Islands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract An approximately 20-m-thick alkali basalt flow on the Penghu Islands contains ∼20 cm thick, horizontally continuous (〉50 m), vesicular layers separated by ∼1.5 m of massive basalt in its upper 8.5 m. The three layers contain ocelli-like "vesicles" filled with nepheline and igneous carbonate. They are coarse grained and enriched in incompatible elements relative to the massive basalt with which they form sharp contacts. These vesicular layers (segregation veins) formed when residual liquid in the underlying crystal mush was forced (gas filter pressing) or siphoned into three thermally induced horizontal cracks that opened successively in the advancing crystal mush of the flow's upper crust. Most vesicular layer trace elements can be modelled by residual melt extraction after 25–40% fractional crystallization of massive basalt underlying each layer. Sulphur, Cl, As, Zn, Pb, K, Na, Rb, and Sr show large concentration changes between the top, middle, and bottom layers, with each vesicular and underlying massive basalt forming a chemically distinct "pair." The large changes between layers are difficult to account for by crystal fractionation alone, because other incompatible elements (e.g., La, Sm, Yb, Zr, Nb) and the major elements change little. The association of these elements (S, Cl, etc.) with "fluids" in various geologic environments suggests that volatiles influenced differentiation, perhaps by moving alkali, alkaline earth, and chalcophile elements as magma-dissolved volatile complexes. Volatiles may have also led to large grain sizes in the segregation veins by lowering melt viscosities and raising diffusion rates. The chemical variability between layers indicates that a convection and concentration mechanism acted within the flow. The specific process cannot be determined, but different rates of vesicle plume rise (through the flow) and/or accumulation in the upper crust's crystal mush might account for the chemical pairing and extreme variations in Cl, S, As, and C. This study emphasizes the importance of sampling vesicular rocks in flows. It also suggests that volatiles play important physical and chemical roles in rapidly differentiating mafic magmas in processes decoupled from crystal fractionation.
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  • 57
    ISSN: 1432-1254
    Keywords: Key words Meteorology ; Turbulence ; Modelling ; Spray drift ; Wind
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    Topics: Geography , Physics
    Notes: Abstract  An insight into the nature of prevailing meteorological conditions and the manner in which they interact with spraying parameters is an important prerequisite in the analysis of the dynamics of agrochemical sprays. Usually, when these sprays are projected from hydraulic nozzles, their initial velocity is greater than that of the ambient wind speed. The flowfield therefore experiences changes in speed and direction which are felt upstream as well as downstream of the spray droplets. The pattern of the droplet flow, i.e. the shape of the streamlines marking typical trajectories, will be determined by a balance of viscous forces related to wind speed, inertial forces resulting from the acceleration of the airstream and pressure forces which can be viewed in terms of the drag forces exerted on the spray droplets themselves. At a certain distance in the ensuing motion, when the initial velocity of the spray droplets has decreased sufficiently for there to be no acceleration, their trajectories will be controlled entirely by the random effects of turbulence. These two transport processes in the atmosphere can be modelled mathematically using computers. This paper presents a model that considers the velocity of spray droplets to consist of a ballistic velocity component superimposed by a random-walk velocity component. The model is used to study the influence of meteorological and spraying parameters on the three-dimensional dynamics of spray droplets projected in specified directions in neutral and unstable weather conditions. The ballistic and random-walk velocity components are scaled by factors of (1–ξ) and ξ respectively, where ξ is the ratio of the sedimentation velocity and the relative velocity between the spray droplets and the surrounding airstream. This ratio increases progressively as the initial velocity of the spray droplet decreases with air resistance and attains a maximum when the sedimentation velocity has been reached. As soon as this occurs, the random-walk process predominates. The computed effects of the release height of spray droplets, atmospheric turbulence intensity, evaporation, drop size spectrum, wind velocity and wind direction on the transport process have been studied and an analysis of spray drift is provided.
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  • 58
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    Informatik-Spektrum 20 (1997), S. 328-334 
    ISSN: 1432-122X
    Keywords: Schlüsselwörter  Informatik-Curriculum ; Objektorientierung ; Modellierung ; Entwurf ; Entwurfsmuster ; Key words  Computer science Curriculum ; Object orientedness ; Modelling ; Design ; Design patterns ; Computing Reviews Classification  D.1.5 ; K.3.0
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Description / Table of Contents: Summary   The service oriented economy challenges the software engineer in today’s industry. Some experience from daily work points to deficiencies of the computer science education with respect to these challenges. However, they also hint at measures to repair theses deficiencies. The arguments illustrate, that focussing the education on object technology not only fulfills an immediate request of today’s industry but also opens further opportunities for improvement. We argue to emphasize communication, modelling, design and design patterns over languages.
    Notes: Zusammenfassung   Die Dienstleistungsgesellschaft stellt hohe Anforderungen an einen Software-Ingenieur1 in heutigen Industrieprojekten. Punktuelle Erfahrungen aus der Praxis zeigen Defizite der Ausbildung bezüglich dieser Anforderungen auf, geben aber auch Hinweise zur Behebung dieser Defizite. Dabei wird deutlich, daß eine Konzentration der Ausbildung auf Objektorientierung nicht nur einen Bedarf der Industrie per se erfüllt, sondern zusätzliche Chancen für eine Verbesserung der Ausbildung bietet. Wichtiger sind Ausbildungsschwerpunkte auf Kommunikation, Modellierung, Entwurf und Entwurfsmuster als auf bestimmten Programmiersprachen.
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    International journal of biometeorology 42 (1999), S. 146-152 
    ISSN: 1432-1254
    Keywords: Key words Landscape ecology ; Area-wide management ; Modelling ; Interpolation ; Kriging ; Regression ; Climate change
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography , Physics
    Notes: Abstract  We simulated male gypsy moth flight phenology for the location of 1371 weather stations east of 100° W longitude and north of 35° N latitude in North America. The output of these simulations, based on average weather conditions from 1961 to 1990, was submitted to two map-interpolation methods: multiple regression and universal kriging. Multiple regression was found to be as accurate as universal kriging and demands less computing power. A map of the date of peak male gypsy moth flight was generated by universal kriging. This map itself constitutes a useful pest-management planning tool; in addition, the map delineates the potential range of the gypsy moth based on its seasonality at the northern edge of its current distribution in eastern North America. The simulation and map-interpolation methods described in this paper thus constitute an interesting approach to the study and monitoring of the ecological impacts of climate change and shifts in land-use patterns at the sub-continental level.
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  • 60
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    European journal of clinical pharmacology 52 (1997), S. 505-506 
    ISSN: 1432-1041
    Keywords: Key words Ibuprofen; effervescent tablets ; kinetics ; bioavailability
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    Topics: Chemistry and Pharmacology , Medicine
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  • 61
    ISSN: 1432-1041
    Keywords: Key words Diphemanil methylsulphate ; Neonate; antimuscarinic agent ; kinetics
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    Topics: Chemistry and Pharmacology , Medicine
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  • 62
    ISSN: 1432-072X
    Keywords: Key words Auxostat ; Batch culture ; Chemostat ; Continuous culture ; Fermentation control ; Inhibition ; kinetics ; Nutristat ; On-line measurement ; Pentachlorophenol ; Pollutant ; Sphingomonas ; Steady-state conditions ; Toxicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A bacterium degrading pentachlorophenol (PCP) as the only source of carbon and energy was grown in a “nutristat”, i.e., a continuous culture with on-line measurement and control of the substrate concentration. We improved the PCP nutristat by incorporation of a personal computer with a proportional integral derivative (PID) algorithm for controlling the medium feed pump. The controlled value deviated from the average (set-point) value by 1% maximally. In the PCP nutristat (30°C), the steady-state dilution rate, and hence, specific growth rate, showed a maximum value of 0.142 ± 0.004 h–1 at set-point PCP concentrations between 37 and 168 μM. At PCP concentrations above 168 μM, the steady-state growth rate decreased because of inhibition. The growth yield coefficient was not seriously affected by the PCP concentration, suggesting that uncoupling was not the inhibitory mechanism. It was concluded that the PCP nutristat is very useful for establishing steady-state conditions that maintain growth-inhibitory PCP concentrations and high cell concentrations, conditions for which the chemostat is not suitable.
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  • 63
    ISSN: 1432-1327
    Keywords: Key words Flavocytochrome b2 ; Cytochrome c ; Electron transfer ; Modelling ; site-directed mutagenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  Saccharomyces cerevisiae flavocytochrome b 2 couples the oxidation of L-lactate to the reduction of cytochrome c. The second-order rate constant for cytochrome c reduction by flavocytochrome b 2 depends on the rate of complex formation and is sensitive to ionic strength. Mutations in the heme domain of flavocytochrome b 2 (Glu63→Lys, Asp72→Lys and the double mutation Glu63→Lys:Asp72→Lys) have significant effects on the reaction with cytochrome c, implicating these residues in complex formation. This kinetic information has been used to guide molecular modelling studies, which are consistent with there being no one single best-configuration. Rather, there is a set of possible complexes in which the docking-face of cytochrome c can approach flavocytochrome b 2 in a variety of orientations. Four cytochromes c can be accommodated on the flavocytochrome b 2 tetramer, with each cytochrome c forming interactions with only one flavocytochrome b 2 subunit. All the models involve residues 72 and 63 on flavocytochrome b 2 but in addition predict that Glu237 may also be important for complex formation. These acidic residues interact with the basic residues 13, 27 and 79 on cytochrome c. Through this triangle of interactions runs a possible σ-tunnelling pathway for electron transfer. This pathway starts with the imidazole ring of His66 (a ligand to the heme-iron of flavocytochrome b 2) and ends with the ring of Pro68, which is in van der Waals contact with the cytochrome c heme. In total, the edge-to-edge "through space" distance from the imidazole ring of His66 to the C3C pyrrole ring of cytochrome c is 13.1 Å.
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    Sciences of soils 3 (1998), S. 11-22 
    ISSN: 1432-9492
    Keywords: Glucose ; Glucose ; Decomposition kinetics ; Modelling ; Microbial soil biomass ; CO2 ; 14C
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Decomposition rates of the [2-14C]-glucose and [2-14C]-glycine in four different soils of the long-term field trial of Moscow were investigated in a 3-months laboratory experiment in which 14CO2 respiration was measured. A model with three decomposition components and two distribution parameters was developed and validated with the data of the experiment. The decay rate constants of free [2-14C]-glucose (4–32 day-1) were slower than those of [2-14C]-glycine (16–44 day-1). The calculated use efficiency for microbial biosynthesis of the second carbon atom was 47% for glucose and 31% for glycine. The potential half-life of labelled carbon in the microbial soil biomass ranged from 0.6 to 4.4 days, depending on the soil type and the initial amount of added substrate. The calculated total utilisation of carbon by the soil biomass from glycine was about 2–5 times lower than that of glucose. The modelled 14C incorporation into the microbial soil biomass reached its maximum on the first day of the incubation experiment and did not exceed 22% of the 14C input. Both of the investigated substances decomposed most rapidly in the soil samples from sites that have not being fertilised with organic or mineral fertilisers during an 81-years period.
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    Theoretical chemistry accounts 101 (1999), S. 2-8 
    ISSN: 1432-2234
    Keywords: Key words: Hydrophobic core ; Solvent accessibility ; Hydrophobicity ; Folding ; Modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract. The positions of a given fold always occupied by strong hydrophobic amino acids (V, I, L, F, M, Y, W), which we call “topohydrophobic positions”, were detected and their properties demonstrated within 153 non-redundant families of homologous domains, through 3D structural alignments. Sets of divergent sequences possessing at least four to five members appear to be as informative as larger sets, provided that their mean pairwise sequence identity is low. Amino acids in topohydrophobic positions exhibit several interesting features: they are much more buried than their equivalents in non-topohydrophobic positions, their side chains are far less dispersed; and they often constitute a lattice of close contacts in the inner core of globular domains. In most cases, each regular secondary structure possesses one to three topohydrophobic positions, which cluster in the domain core. Moreover, using sensitive alignment processes such as hydrophobic cluster analysis (HCA), it is possible to identify topohydrophobic positions from only a small set of divergent sequences. Amino acids in topohydrophobic positions, which can be identified directly from sequences, constitute key markers of protein folds, define long-range structural constraints, which, together with secondary structure predictions, limit the number of possible conformations for a given fold.
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  • 66
    ISSN: 1432-2234
    Keywords: Key words: Model peptides ; Monolayers ; Penetration depth ; Modelling
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    Topics: Chemistry and Pharmacology
    Notes: Abstract. Molecular modelling calculations based on experimental data obtained in solution and in small unilamellar vesicles are used to study interactions between amphiphilic basic peptides and membranes. The behaviour of such peptides during the initial and final stages of the adsorption process is our primary interest. Primary sequences of 20 amino acid residues were designed with equal numbers of basic lysines and hydrophobic leucines in order to get an amphipathic α helix. First, in solution, aggregates with an increasing number (up to nine) of helical monomers were built up and the hydrophobic solvent accessible surface per monomer was analysed on energy minimised structures. This showed that aggregates with 5–8 of monomers should be equally probable, in reasonable accordance with experimental data. In addition, models of membranes with 21 dimyristoyl-phosphatidylcholine lipids were constructed; amphiphilic peptides were merged into these assemblies with their axes parallel to the monolayer surface and the whole lipid/peptide complex was submitted to a few steps of simulated annealing and further energy minimisation techniques in order to equilibrate alkyl chains in the vicinity of the peptide. These simulations yield an estimation of the penetration depth for the peptide in the monolayer of ∼3.2 Å, whereas experimental approaches to this question were not productive. The modification in the peptide net electrical charge by interchanging Leu in Lys residues in such systems is also examined: for low-charged peptides the penetration depth increases.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Keywords: bone cement ; DSC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Keywords: compensation effect ; DSC ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 569-575 
    ISSN: 1572-8943
    Keywords: Bi2O3 ; CaCO3 decomposition ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Former studies concerning the formation of the compounds in the pseudobinary systems of Bi2O3-MO type (M =Ca, Sr, Ca+Sr) have shown that the reaction which occurs with the highest rate is that between Bi2O3 and CaO. In the present work CaCO3 was used as CaO source. We carried out an investigation of the thermal decomposition of CaCO3 in the presence of Bi2O3 in comparison with the decomposition of pure CaCO3. The presence of Bi2O3 exerts a complex influence on the CaCO3 decomposition acting on the nucleation as well as on the diffusion of CO2. The decomposition of the samples with low Bi2O3 content follows the mechanism of a contracting sphere. A change from surface nucleation to bulk nucleation is recorded for higher amounts of Bi2O3.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1437-1450 
    ISSN: 1572-8943
    Keywords: browning ; crystallization ; glass transition ; kinetics ; milk powder ; water
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An exotherm, observed in differential scanning calorimetry (DSC) scans of amorphous food materials above their glass transition temperature,T g, may occur due to sugar crystallization, nonenzymatic browning, or both. In the present study, this exothermal phenomenon in initially anhydrous skim milk and lactose-hydrolyzed skim milk was considered to occur due to browning during isothermal holding at various temperatures above the initialT g. The nonenzymatic, Maillard browning reaction produces water that in amorphous foods, may plasticize the material and reduceT g. The assumption was that quantification of formation of water from theT g depression, which should not be observed as a result of crystallization under anhydrous conditions, can be used to determine kinetics of the nonenzymatic browning reaction. The formation of water was found to be substantial, and the amount formed could be quantified from theT g measured after isothermal treatment at various temperatures using DSC. The rate of water formation followed zero-order kinetics, and its temperature dependence well aboveT g was Arrhenius-type. Although water plasticization of the material occurred during the reaction, and there was a dynamic change in the temperature differenceT−T g, the browning reaction was probably diffusioncontrolled in anhydrous skim milk in the vicinity of theT g of lactose. This could be observed from a significant increase in activation energy. The kinetics and temperature dependence of the Maillard reaction in skim milk and lactose-hydrolyzed skim milk were of similar type well above the initialT g. The difference in temperature dependence in theT g region of lactose, but above that of lactose-hydrolyzed skim milk, became significant, as the rate in skim milk, but not in lactose-hydrolyzed skim milk, became diffusion-controlled. The results showed that rates of diffusion-controlled reactions may follow the Williams-Landel-Ferry (WLF) equation, as kinetic restrictions become apparent within amorphous materials in reactions exhibiting high rates at the same temperature under non-diffusion-controlled conditions.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 917-923 
    ISSN: 1572-8943
    Keywords: copper compound ; coupled technique ; kinetics ; macrocyclic complex ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition process of the complex [Cu(NBOCTB)][Cu(NO3)4] H2O has been studied by TG and DTG technique, and possible intermediates of the thermal decomposition have also been conjectured from the TG and DTG curves. The results suggest that the decomposition of the complex involves five steps: The non-isothermal kinetics of steps 1, 2 and 3 have been studied by means of the Achar and Coats-Redfern method based on TG and DTG curves. Step 1 is a ‘Coring and Growth’ mechanism (n= 1), its kinetic equation may be expressed as: dα/dt=Ae−E/RT(1−α). Steps 2 and 3 are both ‘two order chemical reaction’ mechanisms, their kinetic equations can be expressed as: dα/dt=Ae−E/RT(1−α)2.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 87-94 
    ISSN: 1572-8943
    Keywords: kinetics ; poly(di-propyl itaconates) ; polymer structure ; thermal degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Non-isothermal thermogravimetry was performed in a dynamic nitrogen atmosphere, on a series of poly(di-n-propyl itaconates) (PDnPI) and poly(di-iso-propyl itaconates) (PDiPI) which had been prepared in the presence of various amounts of the chain transfer agentn-dodecyl mercaptan (DDM). Differential thermogravimetry (DTG) showed that both polymers degraded in two stages. The DTG curve of PDnPI had a large first peak followed by a smaller shoulder, whereas the DTG curve of PDiPI was composed of two peaks of almost equal heights. The addition of DDM during the polymerisations in both cases resulted in a similar decrease in the relative area of the first peak.
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  • 73
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    Journal of thermal analysis and calorimetry 49 (1997), S. 183-191 
    ISSN: 1572-8943
    Keywords: kinetics ; thermooxidative degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of non-isothermal kinetic analysis of the thermooxidative degradation in air and oxygen of an unsaturated polyester resin are presented. It has been shown that the thermooxidative degradation in oxygen occurs at lower temperatures than the thermooxidative degradation in air. The kinetic parameters of the thermooxidative degradation depend on the heating rate and the oxygen pressure. Two straight lines of InAvs. E (A is the preexponential factor andE is the activation energy), characteristic for the compensation effect, have been obtained for the thermooxidative degradation in air and in oxygen respectively. The difference between the intercepts of these straight lines can be explained by dependence of the pre-exponential factor on the oxygen pressure.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 857-862 
    ISSN: 1572-8943
    Keywords: analytical methods ; kinetics ; powder milk ; temperature
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This work present comparative results on powder milk storage quality, obtained from analytical methods. Protein content was determined conventional (Kjeldahl) and colorimetric with biuret reagent at 540 nm and integral quality by thermogravimetric and biological methods. A method was developed for the protein separation of powder milk. Powder milk was submitted to degradation processes at 45, 60 and 80°C for 20 days. The results indicated that protein content values were inconsistent if determinations by Kjeldahl and colorimetric methods and biological tests were compared. There is evidence of thermal decomposition of powder milk as detected by biological and thermogravimetric methods.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 937-941 
    ISSN: 1572-8943
    Keywords: kinetics ; mebendazole ; quality control ; technology
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A study was made of the thermal behavior of the starting materials, their mixtures and the resulting mebendazole tablets. The thermal curves were obtained with a Shimadzu thermobalance, model TGA-50, using an air flow of 50 mL min−1 and a heating rate of 10°C min−1 in the temperature interval 30–900°C. The reaction constant velocities for the mebendazole salt and tablets were determined isothermally, using the Arrhenius expression. The thermal stability of mebendazole tablets is lower than that of the mebendazole salt, due to the presence of starch and lactose in the composition. Analysis of the data reveals that thermogravimetry is a powerful tool in pharmaceutical technology and quality control.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1081-1091 
    ISSN: 1572-8943
    Keywords: kinetics ; thermal degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic study of thermal degradation takes into account the validity of the Arrhenius equation. From TG data, the activation energy,E a and pre-exponential factor,A, are evaluated. These results are interpreted by using the ‘kinetic compensation effect’ as basis. A linear correlation between In(A) andE a is obtained in all cases studied. However, in a plot of the logarithm of the rate constant as a function of reciprocal temperature for the same series of reactions, the thermal oxidative degradations of Nylon-6 and PVC display a point of concurrence and one isokinetic temperature, whereas those of HIPS and PC do not. Therefore, in the thermal oxidative degradations of Nylon-6 and PVC a ‘true’ compensation effect occurs, which could be related to the bulk properties of metal oxides, such as different valence states, whereas for other polymers it displays only an ‘apparent’ compensation effect. This means that degradation is largely independent of the bulk properties of oxides, but may be related to the distribution of different kinds of active links in the polymer surface having different activation energies.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 343-348 
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; crude oil ; differential scanning calorimetry ; kinetics ; thermogravimetric analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A weighted mean activation energy method was applied to describe the reactivity and combustibility of crude oils via simultaneous TG/DTG. Thermal experiments were conducted with a non-isothermal method at a heating rate of 10
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    Journal of thermal analysis and calorimetry 48 (1997), S. 385-401 
    ISSN: 1572-8943
    Keywords: dehydration and decomposition ; kinetics ; Fe(III) chloride
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100–200
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    Journal of thermal analysis and calorimetry 48 (1997), S. 413-425 
    ISSN: 1572-8943
    Keywords: alcoholic fermentation ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The control of alcoholic fermentation is necessary to obtain a quality wine. The overall dynamic and phenomenological modelling already applied to the simulation of this type of reaction enables us to suggest, in this study, a simple model (of which two variants), are relatively satisfactory. The first variant does not take into account the variation of the ambient temperature; the model translates exactly the first phase of the experimental curve or the moment when highest temperatures are measured. The relaxation phase is less well described because of influence of variation of the ambient temperature is relatively important. The second one considers the system depending on the ambient temperature, the model is correct for the relaxation phase too (the reaction temperature decreases, it nears the ambient temperature). The advantage of this model: It permits one to determine the reaction enthalpy and the kinetic parameters.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 623-634 
    ISSN: 1572-8943
    Keywords: bismalleimide/carbon fiber composite ; DMA ; kinetics ; TSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The correlation between structure/microstructure and thermomechanical properties has been investigated by the Thermally Stimulated Creep (TSC) technique in a high performance thermostable thermoset matrix composite. The high resolving power of this technique allows us to analyse the α retardation mode. The kinetics of molecular movements liberated at the glass transition has been investigated by the technique of fractional loading: the analysis of each elementary process gives the real compliance and the retardation time as a function of temperature. The values of the activation parameters show the existence of a compensation phenomenon which characterizes the microstructure. It also gives access to the loss compliance of the composite material as a function of temperature and frequency. The predictive calculation of loss compliance has been validated by the results obtained by dynamic mechanical analysis (DMA).
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    Journal of thermal analysis and calorimetry 48 (1997), S. 769-782 
    ISSN: 1572-8943
    Keywords: kinetics ; non-linear optimization ; reactor time constants ; software ; time constants of sensors
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    Topics: Chemistry and Pharmacology
    Notes: Abstract All temperature sensors have a finitely time constant. The influence of the sensor time constant gts on the results of kinetic evaluation is demonstrated at four reaction types. The ignorance of the sensor indolence gives incorrect activation parameters. Therefore the determination of Τs is necessary. For the estimation of parameters the nonlinear evaluation program TA-kin was used. With its help it is possible to find the real parameters, also when Τs=32 s, if the real Τs-value was entered.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1517-1525 
    ISSN: 1572-8943
    Keywords: β-cyclodextrin ; cinnamyl alcohol ; kinetics ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of β-cyclodextrin-cinnamyl alcohol inclusion complex (β-CD·C9H10·8H2O) was investigated using TG and DSC. The mass loss took place in three stages: the dehydration occurred between 50–120°C; the dissociation of β-CD·C9H10O occurred in the range of 210–260°C; and the decomposition of β-CD began at 280°C. The dissociation of β-CD·C9H10O was studied by means of thermogravimetry, and the results showed: the dissociation of β-CD·C9H10O was dominated by a two-dimensional diffusion process (D2). The activation energyE was 161.2 kJ mol−1, the pre-exponential factorA was 4.5×1013 min−1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the interesting of studies focussed on the energy binding cyclodextrin and the guest molecule. In this paper, β-cyclodextrin-cinnamyl alcohol inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show: the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of Van der Waals interaction.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1553-1564 
    ISSN: 1572-8943
    Keywords: deconvolution ; differential scanning calorimetry ; feedforward neural networks ; kinetics ; signal filtering ; simulations ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Feedforward neural networks have been used for kinetic parameters determination and signal filtering in differential scanning calorimetry. The proper learning function was chosen and the network topology was optimized, using an empiric procedure. The learning process was achieved using simulated thermoanalytical curves. The resilient-propagation algorithm have led to the best minimization of the error computed over all the patterns. Relative errors on the thermodynamic and kinetic parameters were evaluated and compared to those obtained with the usual thermal analysis methods (single scan methods). The errors are much lower, especially in presence of noisy signals. Then, our program was adapted to simulate thermal effects with known thermodynamic and kinetic parameters, generated electrically, using a PC computer and an electronic interface on the serial port. These thermal effects have been generated by using an inconel thread.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1467-1475 
    ISSN: 1572-8943
    Keywords: CRTA ; DSC ; kinetics ; synthetic brochantite ; TG-DTA ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction pathway of the thermal decomposition of synthetic brochantite, Cu4(OH)6SO4, to copper(II) oxide was investigated through the detailed kinetic characterization of the thermal dehydration and desulferation processes. The dehydration process was characterized by dividing into two overlapped kinetic processes with a possible formation of an intermediate compound, Cu4O(OH)4SO4. The dehydrated sample, Cu4O3SO4, was found first to be amorphous by means of XRD, followed by the crystallization to a mixture of CuO and CuO-CuSO4 at around 776 K. The specific surface area and the crystallization behaviour of the amorphous dehydrated compound depend largely on the dehydration conditions. The thermal desulferation process is influenced by the gross diffusion of the gaseous product SO3, which is governed by the advancement of the overall reaction interface from the top surface of the sample particle assemblage to the bottom.
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    Journal of thermal analysis and calorimetry 50 (1997), S. 455-462 
    ISSN: 1572-8943
    Keywords: kinetics ; statistical analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A statistical technique based on the Wilcockson criterion is suggested for estimation of the reproducibility of thermoanalytical experiments. Reduction of the whole physicochemical process to a quasi-one-stage process is described.
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    Journal of thermal analysis and calorimetry 50 (1997), S. 425-430 
    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors present the results concerning the thermal behaviour of three polynuclear coordination compounds of Nd(III) and Co(II) or Fe(III) with triptophan. For the dehydration steps the values of the non-isothermal kinetic parameters have been determined.
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    Journal of thermal analysis and calorimetry 52 (1998), S. 569-579 
    ISSN: 1572-8943
    Keywords: bromomethylated polysulfone ; carboxylated polysulfone ; kinetics ; polysulfone ; thermoxidative decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic aspects of the first step of thermoxidative decomposition, under dynamic conditions of heating, of some polysulfones have been studied. The dependence of the kinetic parameters on the heating rate and conversion degree has been established. The compensation effect and conversion function have also been discussed. Polysulfone decomposes by the breaking of the main chain, a process involving very high activation energy. Chemically modified polysulfones show the first step of thermoxidative decomposition at relatively low temperatures. This step corresponds to the elimination of functional side - groups for the bromomethylated polysulfone while in the case of the carboxylated polysolfone, the loss of the carboxyl group is probably accompanied by a crosslinking reaction.
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    Journal of thermal analysis and calorimetry 53 (1998), S. 397-410 
    ISSN: 1572-8943
    Keywords: barium oxalate ; kinetics ; non-isothermal thermogravimetry ; stepwise isothermal analysis ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal decomposition of BaC2O4·0.5H2O in air was studied by a combination of stepwise isothermal analysis (SIA) and non-isothermal thermogravimetry. The results from both techniques show that the crystal water is released in one step and that anhydrous barium oxalate is decomposed in one step, while BaCO3 decomposes in three steps to BaO, forming two intermediate compounds with the formulas of BaCO3·(BaO)2 and (BaCO3)0.5·(BaO)2.5. Reaction mechanism analyses using the data from SIA measurements show that the controlling mechanism for all the five decomposition steps in isothermal conditions is a two-dimensional phase-boundary controlled process. Kinetic parameters are obtained for the five decomposition steps from the non-isothermal thermogravimetric data.
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    Journal of thermal analysis and calorimetry 54 (1998), S. 695-704 
    ISSN: 1572-8943
    Keywords: activation energy ; decomposition ; kinetics ; modulated temperature ; thermogravimetry ; volatilization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another. Results obtained are in agreement with those obtained by other kinetic methods.
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  • 91
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    Keywords: β-cyclodextrin ; ethyl benzoate ; inclusion complex ; kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of β-cyclodextrin·ethyl benzoate·6H2O(β-CD·C6H5COOC2H5·6H2O) was investigated by TG and DSC. The mass loss takes place in three stages: the dehydration occurs at 50-120°C; the dissociation of β-CD·C6H5COOC2H5occurs at 200-260°C; the decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C6H5COOC2H5in a dry nitrogen flow was studied by means of thermogravimetry both at constant temperature and linearly increasing temperature. The results show that the dissociation of β-CD·C6H5COOC2H5is dominated by a three-dimensional diffusion process (D3). The activation energy E is 116.19 kJ mol-1and the pre-exponential factor A 6.5358·109min-1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the studies focus on the energy of binding between cyclodextrin and the guest molecule. In this paper, the β-cyclodextrin·ethyl benzoate inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show that the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of van der Waals interaction.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 233-241 
    ISSN: 1572-8943
    Keywords: cadmium(II) atom ; kinetics ; non-isothermal decomposition ; Schiff-base compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal C81H78N12O6Cd3 was synthesized and its structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system space group P21/n with cell parameters, a=15.959(4) Å, b=26.222(3) Å, c=25.907(6) Å, β=101.60(2)°. The non-isothermal kinetics of the crystal was studied by use of non-isothermal TG and DTG curves. The kinetic parameters were analyzed by means of integral and differential methods, and mechanism functions of the thermal decomposition reaction for its second step were proposed. The kinetic equation of thermal decomposition is expressed as: dα/dt=Aexp(-E/RT)1.5(1-α)4/3[1/(1-α)1/3-1]−1. The average values of E(kJ mol−1) and lnA/s−1 are 339.25, 43.95, respectively.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 301-309 
    ISSN: 1572-8943
    Keywords: dehydroxylation ; goethite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies EA of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol−1 for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of EA are in a good agreement with those given for goethite in literature. The EA values are linearly related with the chemically bound excess H2O/OH− in the crystal lattice that is apparently influenced by Al substitution.
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  • 95
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    Journal of thermal analysis and calorimetry 55 (1999), S. 841-849 
    ISSN: 1572-8943
    Keywords: cobalt(II)-dothiepin ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The complexes of cobalt(II) with dothiepin (DOT) hydrochloride have been studied for kinetics of thermal degradation by thermogravimetric analysis (TG) and derivative thermogravimetric studies (DTG) in a static nitrogen atmosphere at a heating rate of 10° C min−1. A general mechanism of thermal decomposition is advanced involving dehydration and decomposition process for both organic and inorganic ligands. The thermal degradation reactions were found to proceed in three steps having an activation energy in the range 6.75–170 kJ mol−1. Thermal decomposition kinetics parameters were computed on the basis of thermal decomposition data.
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  • 96
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    Journal of thermal analysis and calorimetry 56 (1999), S. 297-303 
    ISSN: 1572-8943
    Keywords: β-zeolite ; coke ; cumene ; kinetics ; regeneration ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An accurate description of coke burn off is obtained from a catalyst based on β-zeolite and used for benzene alkylation with propylene giving cumene by using the thermogravimetric technique. A simple empirical kinetic model was successfully applied to interpolate the data of thermogravimetric analysis performed on samples after partial burn off. Different temperatures, partial pressures of oxygen and gas flow rates were the variables studied in order to calculate the apparent rates and the activation energy for the coke oxidation reaction and to outline the best conditions for the industrial regeneration procedure of our proprietary catalyst PBE-1 for cumene synthesis. Combining the unusually long lifetime per reaction cycle with the optimized regeneration procedure leads to an outstanding overall catalyst life.
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  • 97
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    Journal of thermal analysis and calorimetry 56 (1999), S. 953-958 
    ISSN: 1572-8943
    Keywords: differential scanning calorimeter ; kinetics ; oil shale ; pyrolysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this research, non-isothermal pyrolysis behavior and kinetics of three oil shales were studied by thermal analysis methods. All the thermal effects were endothermic and no exothermic region was observed in DSC curves. When oil shales are heated in nitrogen atmosphere in TG/DTG, two different mechanisms causing loss of mass were observed. The region between ambient temperature and 500 K was distillation. The second mechanism was visbreaking and cracking and it was observed between the region 500 and 800 K. Kinetic parameters of all the samples are determined by Coats and Redfern method and the results are discussed with regard to their accuracy and the ease of interpretation.
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  • 98
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1461-1473 
    ISSN: 1572-8943
    Keywords: CaCO3 ; densification ; kinetics ; Li2CO3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pressureless sintering of CaCO3 was carried out, with Li2CO3 (from 0.5 to 8 wt%) as an additive, under different pressures of CO2. Densification occurs between 600 and 700°C. Sintering above the eutectic temperature (T〉662°C) leads to the decomposition of calcium carbonate and the materials become expanded. At 620° under 1 kPa of CO2, a relative density of 96% is reached. Li2CO3 enhances the densification process and grain growth of calcium carbonate. CO2 pressure slows down densification and grain growth kinetics. These results are explained by the influence of carbonate and calcium ion vacancies on the sintering mechanisms.
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  • 99
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    Journal of thermal analysis and calorimetry 58 (1999), S. 383-391 
    ISSN: 1572-8943
    Keywords: 1-aminopyrene (apyr) ; N-(2-pyridylmethylene)-1-pyrenylamine (pmpa) ; kinetics ; palladium(II)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1−aminopyrene and pmpa=N−(2−pyridylmethylene)−1−pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, Šesták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.
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  • 100
    ISSN: 1572-8943
    Keywords: first order autocatalytic reaction ; HNNC ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation $$\frac{{{\text{d}}y}} {{dt}} = - 10^{16.4} \exp \left( { - \frac{{210380}} {{RT}}} \right)y - 10^{16.7} \exp \left( { - \frac{{171205}} {{RT}}} \right)y(1 - y)$$ and that for the latter 50% mass-loss of HNNC described by the reaction equations $$\frac{{dy}} {{dy}} = - 10^{16.3} \exp \left( { - \frac{{169483}} {{RT}}} \right)y\quad (n = 1)$$ and $$\frac{{dy}} {{dt}} = - 10^{16.8} \exp \left( { - \frac{{165597}} {{RT}}} \right)y^{2.61} \quad (n \ne 1)$$
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