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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of superconductivity and novel magnetism 10 (1997), S. 645-647 
    ISSN: 1557-1947
    Keywords: EuBaSrCu3O7−δ superconductor ; Ca doping ; orthorhombicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract The effect of Ca doping in EuBaSrCu3O7−δ has been investigated by X-ray diffraction, ac susceptibility, and electrical resistivity measurements. X-Ray diffraction analyses of the samples showed that up to 30 at.% Ca can be substituted for Sr in EuBaSrCu3O7−δ, which has orthorhombic symmetry. The orthorhombicity decreases with increase inx, in EuBaSr1−xCax Cu3O7−δ, the material becoming tetragonal atx=0.2. Ac susceptibility and dc electrical resistivity measurements as function of temperature from 10 to 300 K showed that the superconducting transition temperatureT c decreases monotonically from 84 to 75K as the Ca concentrationx increases from 0.0 to 0.3 The decrease inT c can be attributed to the structural change taking place in EuBaSrCu3O7 as a consequence of replacement of Sr by Ca.
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  • 2
    ISSN: 1557-1947
    Keywords: Superconductivity ; research opportunities ; state of the art
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract This report surveys the considerable progress made over the last five years—such as the marketing of superconducting quantum interference devices (SQUIDs), cellular wireless filter systems, and high current leads—and assesses needs and opportunities in the areas of fundamental science, materials development, thin film and device applications, and wire and bulk applications. It examines the challenges facing high-temperature superconductivity: from the need to understand the mechanism of high-temperature superconductivity and the unusual “normal” state to the need for new instrumentation for material characterization. Advances in thin film and bulk materials are reviewed, and obstacles impeding the commercialization of HTS materials are examined.
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  • 3
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    Journal of superconductivity and novel magnetism 10 (1997), S. 649-655 
    ISSN: 1557-1947
    Keywords: Single crystal of Bi2Sr2CaCu2O8 ; high-resolution electron microscopy ; low-temperature electron diffraction ; lattice anomaly
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract High-resolution electron microscopy of a Bi2Sr2CaCu2O8 (Bi2212) single crystal prepared by the floating zone method shows that the single crystal is of high quality; there is no intergrowth faulting in the layered structure along thec-axis. Low-temperature selected area diffraction and convergent beam electron diffraction (CBED) studies of this high-quality single crystal show that there is no detectable change for both the point group symmetry of the basic structure and the modulated structure from room temperature to about 15 K. However, a lattice anomaly around 215 K was suggested by measuring the temperature dependence of the ratio between the cross-point distances of the HOLZ lines in high-index CBED patterns. The presence of the lattice anomaly was further confirmed by low-temperature X-ray diffraction.
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  • 4
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    Journal of superconductivity and novel magnetism 10 (1997), S. 623-643 
    ISSN: 1557-1947
    Keywords: Superconductivity ; crystal field ; rare earth ; relaxation ; gap symmetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract Neutron spectroscopy is a powerful tool to determine unambiguously the crystal-field (CF) potential in rare-earth (R) based high-T c superconducting materials. This technique provides detailed information on the electronic ground state of the R ions which is important to understand the thermodynamic magnetic properties as well as the observed coexistence between superconductivity and long-range magnetic ordering of the R ion sublattice at low temperatures. Moreover, the decay of the antiferromagnetic state of the parent compound as well as the evolution of the superconducting state upon doping can be directly and quantitatively monitored. It is found that the observed CF spectra separate into different local components whose spectral weights distinctly depend on the doping level, i.e., there is clear experimental evidence for cluster formation. The onset of superconductivity can be shown to result from percolation which means that the superconductivity is an inhomogeneous materials property. Since the linewidths of CF transitions directly probe the static electronic susceptibility, we discuss temperature-dependent experiments of the relaxation rate of CF excitations in both optimally doped and underdoped regimes. It is shown that there is clear evidence for the opening of an electronic gap in the normal state of underdoped superconductors. Furthermore, the relaxation behavior appears to be extremely dependent upon the energy at which the static susceptibility is being probed. The main observed features can be reproduced by considering a strongly anisotropic gap function.
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  • 5
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    Journal of superconductivity and novel magnetism 10 (1997), S. 663-668 
    ISSN: 1557-1947
    Keywords: Thermal diffusivity ; acoustic plasmons ; cobalt substitution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract The thermal diffusivity κ(T) of the cobalt-substituted sintered YBCO system, YBa2Cu3−x Co x O7∮δ (x=0.0, 0.1), has been measured to, investigate, effects of atomic substitution and charge carrier concentration on the thermal diffusion processes. The thermal diffusivity was measured in the temperature range 35–300 K, using the transient-plane-source technique. The results show that, belowT c , the κ(T) values of the doped (x=0.1), samples are lower than the corresponding values for the undoped (x=0.0) samples. This may be due to the difference in the free-charge carrier concentrations of the two samples. A decoupling between the conducting Cu−O planes as a result, of Co-doping in the chain sites may contribute to additional decrease in the thermal diffusivity of the doped sample. An attempt was made to explain the rise in the thermal diffusivity belowT c by adopting a recent theoretical model based on the existence of weakly damped collective electron excitations of Bose type, with acoustic dispersion relation, (acoustic plasmons) inside the superconducting gap.
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  • 6
    ISSN: 1557-1947
    Keywords: High-T c superconductors ; order parameter ; Josephson junctions ; Josephson critical current ; pair symmetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract An intrinsic gap depression at the superconductor-insulator interface due to the very short value of the coherence length in high-T c superconductors [HTS] is considered in the framework of a mixed (s+id)-wave pair symmetry for the order parameter ranging from pures to pured-wave. This gap depression acts as the main physical agent causing the relevant reduction ofI c (T)R n (T) values with respect to BCS expectations in HTS SIS Josephson junctions. Good agreement with various experimental data is obtained with both pures-wave and pured-wave symmetries of the order parameter, but with amounts of gap depression depending on the pair symmetry adopted. Regardless of the apir symmetry considered, these results prove the importance of the surface order-parameter depression in the correct interpretation of theI c (T)R n (T) data in HTS SIS junctions. In the case of a planar YBCO-based junction the use of the de Gennes condition allowed us to tentatively obtain an upper limit for the amount ofd-wave present in the gap of YBCO.
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  • 7
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    Journal of superconductivity and novel magnetism 10 (1997), S. 669-672 
    ISSN: 1557-1947
    Keywords: Equation of state ; bulk modulus ; cohesive energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract In the present paper the expression of cohesive energy and the bulk modulus as a function of volume are formulated for high-T c copper oxide superconductors. The model employed consists of long-range electrostatic Coulomb interaction and short-range overlap repulsion. The short-range overlap potential is considered in the Born-Landé inverse power form. The model, parameters of the Born-Landé model are calculated from the equilibrium condition and data of bulk modulus at room temperature. The computed values of pressure derivatives of bulk modulus atP=0 and the values of bulk modulus are found to be in very close agreement with experimental values for high-T c copper oxide and their nonsuperconducting parent compounds. It is also found that the quantity ΔU/U(V o) of these compounds increases with increasing hydrostistic pressure.
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  • 8
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    Journal of superconductivity and novel magnetism 10 (1997), S. 673-675 
    ISSN: 1557-1947
    Keywords: Cuprates ; van Hove singularity ; pseudo-gap
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract Several experimental features in the normal state of cuprates have been interpreted using a “pseudogap”. We show that these results may be explained by the band structure of the CuO2 planes in the metallic region, which exhibits, saddle points (van Hove singularities).
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  • 9
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    Polymer bulletin 36 (1996), S. 745-752 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Acrylamide/itaconic acid (AAm/IA) hydrogels prepared by irradiating with γ radiation were used in experiments on the adsorption of some cationic dyes such as basic red 9 (BR 9), basic green 4 (BG 4), cresyl violet (CV), and basic blue 20 (BB 20). Adsorption of the cationic dyes onto AAm/IA hydrogels is studied by batch adsorption technique. In the experiments of the adsorption, Langmiur type adsorption in the Giles classification system was found. Monolayer coverages for AAm/IA hydrogel-dye systems were calculated by using B point method. Adsorption studies indicated that monolayer coverages of AAm/IA hydrogel by these dyes were increased with following order; BB 20〉CV〉BR9〉BG 4.
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  • 10
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Styrene was polymerized using combined systems of diphenylzinc, Ph2Zn, and metallocene compounds activated by methylaluminoxane, MAO. From the various metallocenes employed bis (indenyl) zirconium dichloride, Ind2ZrCl2, [isopropyl (cyclopentadienyl) (1-fluorenyl)] zirconiumdichloride, i-Pr (Flu) (Cp) ZrCl2, and bis (cyclopentadienyl) titanium dichloride, Cp2TiCl2, produced the larger amounts of polymer. Ph2Zn-Cp2TiCl2-MAO system gave polystyrene, PSt, whose DSC analysis indicated a major endotherm peak at 256°C. A butanone insoluble fraction of the polymer was separated from the crude PSt. The proportion of insoluble polymer depends on the metallocene employed and on the conversion to polymer.
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  • 11
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    Polymer bulletin 37 (1996), S. 29-33 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Polymerization of propylene was carried out at 0°C in the presence of methyl methacrylate(MMA) or ethyl benzoate(EB) using rac-Et(Ind)2ZrMe2 or rac-Me2Si(Ind)2ZrMe2/Ph3CB(C6F5)4 as catalyst, which resulted in highly isotactic poly(propylene) with [mmmm]〉98%, Tm=160–161°C and very few 1,3- or 2,1 regioirregular units. With the use of an achiral zirconocene Cp2ZrMe2, a polymer with Tm=139°C was resulted as well. Base on these experimental fact that the zirconocene can form a C1-symmetrical complex with a Lewis base.
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  • 12
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    Polymer bulletin 37 (1996), S. 21-28 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary By using γ-butyrolactone (γ-BL) as the reaction media, highly active catalysts--light rare earth chloride-epoxidy-γ--BL-for the solution polymerization of ε-caprolactone, have been obtained for the first time. With these catalyst, PCL with molecular weight as his as 40x104(Mv) can be prepared at 60°C for 1.5 hr. The amount of epoxide in catalyst solution, catalyst aging temperature and time affect the catalyst activity significantly. The mechanism study shows that in γ-BL, the weakening of Ln-Cl bonds by the donation of coordinated γ-BL with Ln3+ and the homogenous effect promote the reaction between light rare earth chloride and epoxide. The produced rare earth alkoxide initiates CL polymerization via a ‘coordination-insertion’ mechanism with Acyl-oxygen bond cleavage.
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  • 13
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Triethoxysilane groups were covalently attached onto the surface of ethylene-vinyl alcohol (EVOH) copolymer film via a urethane linkage through reaction between the hydroxyl groups in EVOH and 3-isocyanatopropyltriethoxysilane in the presence of dibutyltin dilaurate as catalyst. This reaction was confirmed by ATR-IR and XPS analysis. XPS results also indicated that this reaction was not surface sensitive and the modified layer was at least 40 Å in depth. The modified film samples were further reacted with tetramethoxysilane (TMOS) for partial hydrolysis and condensation and XPS results showed a significant increase in the contents of oxygen and silicone on the surface which confirmed the above reaction.
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  • 14
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    Polymer bulletin 37 (1996), S. 59-65 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The title monomer was synthesized from the corresponding aldehyde via a Wittig reaction. The monomer was polymerized using free radical initiation and its high field 1H- and 13C-NMR spectra were recorded. When analyzed in terms of stereochemistry the spectra showed poly(6-vinyl-1,4-benzodioxane) is an atactic polymer when synthesized via free radical initiation.
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  • 15
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A resin containing 4-vinylpyridine and 2-acrylamidoglycolic acid was synthesized by radical polymerization with subsequent crosslinking by N,N′-methylene-bis-acrylamide. The resin was characterized by elemental analyses and FT-IR spectroscopy. The ability of this resin as well as both crosslinked homopolymers to bind Cu(II), Fe(II), Fe(III) and U(VI) was studied at different pHs depending on the metal ion. From pH=2 U(VI) was sorbed above 96% from an aqueous solution of 1.0 g/L. A dual sorption mechanism to U(VI) depending on the pH is suggested. The elution of the metal ions from the loaded resins was assayed with H2SO4 and Na2CO3.
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  • 16
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    Polymer bulletin 37 (1996), S. 199-206 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The photopolymerization of four analogous monomers: 2,2′-thiobisethanol diacrylate and its dimethacrylate plus 2,2′-oxybisethanol diacrylate and its dimethacrylate has been studied by isothermal differential scanning calorimetry (DSC) over a range of incident light intensities. The results obtained prove that the sulfide group accelerates polymerization both in the presence and absence of oxygen and enhances the conversion. The light intensity exponents for each monomer were determined and the mechanism of termination was discussed. The intensity exponents of sulfur-containing monomers are lower than their corresponding oxygen analogues, pointing to a greater participation of the bimolecular termination during their polymerization.
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  • 17
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Photoinitiated methyl methacrylate-ethylene glycol dimethacrylate (MMA/EGDM) copolymerization has been investigated in toluene at a monomer concentration of 35 w/v %. Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (DPTPO) was used as a photoinitiator at 0.3 wt% concentration. Monomer conversions and the size distribution of the polymer molecules were measured as a function of the reaction time up to the onset of macrogelation. Compared to the photoinitiators benzoin or benzoin derivatives, gelation process proceeds at much higher rates in the presence of DPTPO. The size distribution curves obtained by size-exclusion chromatography (SEC) change from monomodal to bimodal distributions as the polymerization proceeds. Strongly bimodal SEC curves were obtained in the close vicinity of the gel point. This finding confirms the coagulation type gelation mechanism of compact primary particles. It also indicates that the present gelation theories cannot describe the structure dependent kinetics of free-radical crosslinking copolymerization.
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  • 18
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary FT-Raman spectroscopy of commercial amorphous and crystalline nylon 6–12 filaments subjected to various γ-radiation doses are presented. The results show that a difference exists in the interaction of γ-radiation with these polyamides, depending on the crystallinity which can be evaluated by measuring the CH-stretching/CH-bending Raman band intensity ratio as a function of applied γ-dose.
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  • 19
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Solid-state 13C NMR spectroscopy involving magic angle spinning (MAS) techniques with and without cross-polarization was employed for interaction studies in natural rubber (NR)/EVA and NR/mercapto-modified EVA (EVASH) blends. From arrayed of variable contact time spectra, the proton T1ϱ values were determined at short contact times to analyze the EVA or EVASH domains and longer contact times to investigate the interactions in the NR domains. Substantial changes have been observed when dicumyl peroxide was employed as curing agent in NR/EVASH and NR/EVA/EVASH blends.
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  • 20
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    Polymer bulletin 37 (1996), S. 229-235 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Thermogravimetric analysis (TGA) has been shown to be a useful technique to determine the content of starch and other components that are usually present in blends of starch with synthetic polymers. However, some of these blends are composed of elements with an important superposition in their temperature degradation range. In these cases interpretation of the TGA results becomes quite difficult and usually important errors are committed in the determination of blend composition. We present here a method to improve the accuracy of the interpretation of TGA data. The analysis was developed to study blends containing starch, an ethylene-vinyl alcohol copolymer, and water plus glycerin as plasticizers. Using this procedure it is possible to predict blend composition with an error less than 3%, even when there is an appreciable superposition between the temperature degradation range of starch and poly(ethylene-co-vinyl alcohol). As the proposed method of analysis is quite general it may be extended to be used with other types of blends that give thermograms with similar characteristics to those described in this paper.
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  • 21
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The synthesis of polysulfone-polydimethylsiloxane (PSU-PDMS)linear block copolymers has been carried out in solution by condensation of chloro-terminated bisphenol A, diphenylsulfone and α, ω-di (hydrogensilyl)-polydimethylsiloxane with Si−C bond. 1H-NMR spectra of the block copolymers allow the estimation of siloxane and polysulfone ratio. The molecular weight of the polysulfone and polysiloxane oligomers and the block copolymers was determined by GPC. Thermogravimetric analysis indicates a thermal stability of block copolymers up to 400°C and allows estimation of the process activation energy. Microphase separation of the block copolymers was observed by differential scanning calorimetry (DSC).
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  • 22
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Aim of this work was to study the effectiveness of a novel oxazoline-functionalized polypropylene as a compatibilizer for PP/PBT and PP/PA6 blends. This polypropylene-based compatibilizer mixes well with the polypropylene and is capable of reacting with the carboxylic and amine end groups of PBT and PA6. Significant improvements in blend toughness were achieved without reduction in strength and stiffness. These effects were related to stabilized morphology of finely dispersed minor phase well attached to the matrix. The enhanced interfacial interactions between the two phases, in particular at high PBT content were evidenced by increased melt viscosity.
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  • 23
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    Polymer bulletin 37 (1996), S. 361-367 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The polyamides with aromatic rings in the main chain were synthesized by the solution polymerization of 4,4′-diphenylmethane diisocyanate and aliphatic dicarboxylic acid in the presence of catalyst. The thermal properties and the miscibility behaviours with polyamide-6,6 of these aromatic polyamides were studied. The aromatic polyamides synthesized with one kind of dicarboxylic acid had typical thermal properties of crystalline polymers, whereas those synthesized with the mixtures of dicarboxylic acids were not easily crystallized. The observed miscibility behaviours showed some differences from those predicted by binary interaction model.
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  • 24
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    Polymer bulletin 37 (1996), S. 369-376 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A series of aryl-aliphatic polyamides, copoly(4,4′-diaminobenzanilide-adipamide/2,6-naphthalamide)s, with feed mole ratios of adipic acid/2,6-naphthalene dicarboxylic acid of 1/9, 3/7, and 5/5 were synthesized. A new family of molecular composites based on the synthesized aryl-aliphatic polyamides and nylon 6 has been discovered. The molecular composites were found to have at least partial miscibility between aryl-aliphatic polyamides and nylon 6. Well-defined aryl-aliphatic polyamide microfibrils a few nanometers in diameter were observed in the molecular composites. 10 wt% aryl-aliphatic polyamide clearly promoted the toughness of nylon 6.
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  • 25
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    Polymer bulletin 37 (1996), S. 377-383 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A new type of coordination polyurethane was prepared by incorporating the transition metal ions into the pyridine containing thermoplastic polyurethane films. Then the metal ions dispersed in the polyurethane matrix were reduced by controlling the exposure of the metal sites to NaBH4 under mild condition. The reduction of the polyurethane metal complex films resulted in the production of amorphous ultrafine metal powders. The size of these powders was controlled by the content of the metal ions and the polarity of the polymer matrix. A polar polymer backbone and lower metal ion concentration favored to achieve a smaller particle. It was also found that the polymer chains prohibited the excessive aggregation of the metal atoms and have protective effect on the final metal powders.
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  • 26
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Crack-tip deformation has been investigated in pre-cracked samples of core-shell rubber particle modified epoxy resins with different degrees of crosslinking. Light cross linking resulted in cavitation of the modifier, the formation of croids and extensive crack-tip yielding, whereas these deformation mechanisms were suppressed at room T in highly crosslinked specimens. A zone of particle debonding was observed in these latter at high T, but this appeared detrimental to the toughness. Indeed it was possible to increase the toughness in this case by oxygen plasma treatment of the modifier particles.
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  • 27
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary An initiator for living free radical polymerization may be prepared by trapping the benzylic ethylbenzene radical with the stable 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) radical. The adduct, 2,2,6,6-tetramethyl-1-(1-phenethyloxy)piperidine (TMPEP), smoothly undergoes thermal fragmentation at temperatures approaching 140° C to afford an active carbon radical capable of initiating polymerization and a passive mediating nitroxyl radical to reversibly cap and preserve the propagating polymer chain.
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  • 28
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Association processes of D-fructose dehydrogenase (FDH) onto surfaces of liposomes which were composed of N-(5-dimethylamino-1-naphthalenesulfonyl)-L-α-dimyristoylphosphatidylethanolamide and L-α-dimyristoylphosphatidylcholine or L-α-dimyristoylphosphatidylglycerol (1:9) were investigated by the fluorescence stopped-flow technique. The association processes were divided into two relaxation processes: the faster process whose apparent rate constant monotonously increased with the concentration of FDH, and the slower process whose rate constant showed a saturation behavior. Taking the number of binding sites on the liposome surface into consideration, the corrected association rate constant of the faster process was 4.4% of the theoretical value for a binary collision, probably due to a disadvantageous surface-searching and dehydration processes on the liposome and protein surfaces. The Arrhenius plots of the rate constants both for the faster and slower steps showed a discontinuous change around the gel to liquid-crystal phase transition temperature of the liposomes. Strong influences of deformability of liposomes, and state of hydrating water molecules around polar heads, on the rate of association processes were suggested.
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  • 29
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    Polymer bulletin 37 (1996), S. 423-428 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Copolymers with 2-aceto-1,3-phenanthrenylene units in the chain have been directly prepared by Ru catalyzed step-growth copolymerization of 2-acetyl phenanthrene and α,ω-dienes such as 1,3-divinyltetramethyldisiloxane. Copolymers which incorporate 2-aceto-1,3-phenanthrenylene units possess higher TgS and increased thermal stability compared to analogous copolymers which have 2-aceto-5-phenyl-1,3-phenylene(biphenyl) or 2-aceto-1,3-phenylene units. Fluorescence spectra of these copolymers have been obtained.
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  • 30
    ISSN: 1436-2449
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    Notes: Summary A new methodology is described for the synthesis of reactive polymers bearing triphenylphosphine dichloride groups by the use of triphosgene. These materials show high reactivity for the room temperature conversion of benzyl alcohol to benzyl chloride. In one hour, yields higher than 90% were achieved using reactive copolymers with up to 25 w% divinylbenzene (DVB). The functional groups can be easily and efficiently regenerated using 1.0 mol of triphosgene for every 2.6 moles of phosphine in the polymer. Preliminary results showed up to 40% conversion of benzyl alcohol in column reactions using regenerated polymers at 5 to 10 min contact times.
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  • 31
    ISSN: 1436-2449
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The biosynthesis of poly (β-hydroxybutyrate) (PHB) byBacillus circulans was carried out through cultivation in nutrient broth in a single step. $$\overline {\text{M}} {\text{v}}$$ of polymer fractions soluble in chloroform were close to 2 x 105. IR,1H and13C NMR spectra of the isolated PHB were in agreement with the assumed structure of this poly-β-hydroxyester. NMR spectroscopy pointed out a high percentage of isotactic polymer, while differential scanning calorimetry showed that the PHB was crystalline.
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  • 32
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    Polymer bulletin 37 (1996), S. 437-442 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Graft copolymers of polyacrylonitrile (PAN) and poly(ethylene oxide) (PEO) were synthesized by radical copolymerization of acrylonitrile and methacrylate-headed poly(ethylene oxide) macromonomer. The macromonomer was prepared by reaction of methacryloyl chloride with PEO. The effects of solution concentration, initiator concentration and acrylonitrile/macromonomer molar ratio on the conversion, molecular weight and PEO branch content in the graft copolymer were studied. The graft copolymers were characterized by GPC, FTIR,13C-NMR and Kjeldhal method.
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  • 33
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    Polymer bulletin 37 (1996), S. 457-462 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The title vinyl thiophene monomer was synthesized by dehydration of the corresponding secondary alcohol. Free radical initiated copolymerizations with methyl methacrylate, styrene or isobutyl methacrylate were performed and the copolymer compositions were used in the calculation of reactivity ratios. The data was analyzed via a nonlinear least squares error-in-variables method. The 2,5-dimethyl-3-vinylthiophene was shown to have equal or slightly less reactivity than each of the monomers chosen as comonomers.
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  • 34
    ISSN: 1436-2449
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    Notes: Summary Alkylation of the methylene bridged tetrahydropyrimidine derivatives by chloromethylstyrene produces the bridged bis(4-vinylbenzyl)-1,4,5,6,-tetrahydropyrimidinium salts in high yields. Similar procedures are used to prepare 2-imidazolinium derivatives. The quaternary salts which support functional side groups of potential biomedical interest are characterized by means of spectroscopic methods. These monomers are readily polymerized free radically in solution of dimethyl formamide at moderate temperatures. The soluble and insoluble polymers containing 2-imidazolinium and 1,4,5,6-tetrahydropyrimidinium salts were found to exhibit antibacterial activites againstEscherichia coli.
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  • 35
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    Polymer bulletin 37 (1996), S. 463-468 
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The parent polymer, poly(allylamine) as ligand polymer was employed to synthesize polychelates of heavy metal ions. The functional poly(allylamine) and its Ni(II), Co(II) and Cu(II) metal chelates were characterized by elemental analysis, FT-IR spectroscopy, TGA, and SEM. For the polychelates magnetic and conductivimetry studies were also carried out.
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  • 36
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    Polymer bulletin 37 (1996), S. 475-482 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A new chemically amplified polymeric imaging system based on polymers containingt-butylmalonate pendant groups has been demonstrated. Both the homopolymer of di-t-butyl (vinylbenzyl)benzylmalonate and its copolymer with styrene have been tested in coatings containing a photoacid generator. Imaging experiments confirm that the materials have very high sensitivities when exposed to UV radiation near 250nm.
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  • 37
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    Notes: Summary New pseudoaffinity chromatography supports were prepared and characterized from poly(sucrose acrylate) crosslinked with MDI or TDI and Cibacron Blue dye as ligand. Blue gels were useful in the retention of albumin and the results are reported.
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  • 38
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    Notes: Summary Copolymers of ethylene and 1-hexexe, 1-octene and 4-methyl-1-pentene were obtained using Et[In]2ZrCl2/MAO catalyst at various pressures. The increase of 1-hexene and 1-octene concentration in the feed increases catalyst activity(g/nZr.h.bar) and productivity(g/nZr.h). For 4-methyl-1-pentene the activity is independent on comonomer concentration. Increasing the ethylene pressure the productivity of the copolymerization increases and the activity shows a weak decay. Characterization of the copolymer shows that at higher pressure the cristallinity of the copolymers is higher due to lower comonomer incorporation. There is a good linear correlation of cristallinity with comonomer concentration in the feed for 1-hexene and 1-octene at a fixed pressure, but not for 4-methyl-1-pentene.
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  • 39
    ISSN: 1436-2449
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The present work deals with copolymerization of styrene (STY) and methyl methacrylate (MMA) catalysed by nickel acetylacetonate - Ni(acac) 2 , employing methylaluminoxane (MAO) as cocatalyst. This catalyst system presented low catalyst activities for STY homopolymerization and very high activities for MMA. It seems that the catalyst system based on Ni(acac) 2 /MAO is effective for the copolymerization of MMA and STY to give block copolymer but it also produced polystyrene and poly(methyl methacrylate) homopolymers. The polymers were characterized by 13 C NMR, GPC and FTIR. The polystyrene homopolymer was identified by IR and NMR analyses of the cyclohexane soluble fraction. The presence of absorption bands correspondent to carbonyl group and aromatic ring was observed in the IR spectrum of the acetic acid soluble part. This result is a clue that STY-MMA copolymer with low molecular weight was produced. The high molecular weight copolymer (acetic acid insoluble fraction) was also characterized by IR analysis which indicated the presence of characteristic absorption bands of carbonyl group and aromatic ring. These results were confirmed by 13 C NMR analysis.
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  • 40
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    Polymer bulletin 40 (1998), S. 555-562 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Four narrow-distribution samples of sodium hyaluronate with weight-average molecular weights M w of 3.8 × 103 to 1.1 × 104 in 0.02 and 0.1 M aqueous NaCl at 25°C have been studied by small-angle X-ray scattering. Data for their z-average radii of gyration 〈S2〉z 1/2 and particle scattering functions P(θ), together with previous 〈S2〉z data from light scattering for high molecular weights, are compared with relevant theories for the wormlike chain with or without excluded volume, using the parameters estimated previously from intrinsic viscosity ([η]) data. It is shown that for M w lower than 1.1 × 104, 〈S2〉z, P(θ), and [η] of the polysaccharide in the aqueous salts are all consistently explained by this model without excluded volume.
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  • 41
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    Notes: Summary Three new side chain liquid crystalline polythiiranes were prepared with new substituants on the mesogenic groups. Their thermotropic liquid crystalline behaviour was studied by the usual techniques (DSC, X-ray diffraction and polarized optical microscopy). Unlike the polyoxiranes described in the literature, the size of the terminal group has no influence on the nature of the mesophases of polythiiranes ; only slight changes of the transition temperatures were observed. In this series of polymers, a phase, denoted X, appeared at temperatures below the smectic E phase, and could not be identified by usual characterization techniques. An isothermal kinetic study for the smectic E / X phase transition resulted in an Avrami exponent close to 1, suggesting a one-dimensional ordering occurred during the transformation from the smectic phase. This result, combined with other observations, helped us to assign the X phase to the crystalline phase.
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    Polymer bulletin 40 (1998), S. 583-590 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Hybrid materials from Polyvinyl chloride (PVC) and titania were prepared using sol-gel technique. In-situ generation of titania network in the PVC matrix was carried out by introducing required amounts of tetrapropylorthotitanate (TPOT) followed by hydrolysis/condensation of TPOT in the matrix. Homogeneous and semi-transparent films were obtained by casting and solvent evaporation. Mechanical properties of these films up to 15 wt. % titania contents were studied. The results showed an increase in the Young's modulus, length at rupture and toughness of the unplasticised PVC. However, the tensile strength and stress at break point decreased with the addition of titania contents. Thermal stability of the material was studied using dehydrochlorination (DHCl) technique and thermogravimetric analysis. The PVC samples with small amount of titania were found to be more stable as compared with the pure PVC.
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  • 43
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    Notes: SUMMARY The sorption characteristics of benzene and cyclohexane vapours in the poly(urethane-urea) (PUU) with well defined structure were measured using an improved version of the Mc Bain's microbalance. The diffusion coefficients were calculated for the different vapour activities from the kinetics of solvent uptake, i.e. the sorption isotherms over time. Sorption and diffusion coefficients measured, showed a strong dependence of the applied vapour activity. The obtained transport parameters were discussed with regard to the polymer structure. Based on the sorption and diffusion data, the pervaporation performance of the PUU-based membrane in separation of the benzene/cyclohexane mixtures was predicted and compared with the experimental pervaporation characteristic.
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  • 44
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    Notes: Summary The polymerization of styrene with catalysts based on Ni(acac)2 supported on SiO2 and Al2O3 was investigated. Using catalysts based on MAO supported on silica, a highly isotactic polystyrene was obtained. Nevertheless, the Al2O3-supported catalyst can promote isospecific polymerization activated by common. alkyl aluminum compounds even by any prior support treatment with MAO.
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  • 45
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    Polymer bulletin 40 (1998), S. 701-706 
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A novel polymer having β,β-triketone unit in the main chain was prepared by polycondensation of triethylene glycol bis(p-butoxycarbonylphenyl) ether (1) with triethylene glycol bis(p-acetylacetophenyl) ether (4). The obtained polymer was soluble in CHCl3, DMF, and DMSO. The structure of the polymer was confirmed by 1H-NMR. Insoluble brownish yellow copper (II) chelate was obtained by adding a methanol solution of copper (II) acetate to a chloroform solution of the polymer. The IR analysis and the measurement of copper content by iodometric titration showed the quantitative formation of binuclear copper (II) complex.
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  • 46
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    Polymer bulletin 40 (1998), S. 715-720 
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    Notes: Summary Synthesis and polymerization behavior of 1-trimethylsiloxy- or 1-triphenylsiloxy-silacyclobutane derivatives were studied. These monomers gave polymers with reasonably high molecular weight by platinum catalyst like platinum 1,3-divinyl-1,1,3,3-tetramethyldisfloxane complex. Side-chain smectic, liquid crystalline polymer was obtained from 1-methyl-1-[3-{(4-cyanobiphenyl-4'-yl)oxy}propyl]dimethylsiloxysilacyclobutane. In the polymerization by butyllithium or phenyllithium, monomers corresponding to the amounts of the initiator were consumed, but no polymers were formed. Apparently, elimination of the trimethylsiloxy or triphenylsiloxy group occurred in the nucleophilic attack of the initiator or propagating species on the silicon atom of the monomer.
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  • 47
    ISSN: 1436-2449
    Keywords: (Keywords: lanthanocene; methylaluminoxane; polymerization; butadiene; isoprene; styrene.)
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The polymerization of butadiene(Bd), isoprene(Ip) and styrene(St) has been examined using the six catalyst systems composed of lanthanocene, (C5H9Cp)2NdCl(I), (C5H9Cp)2SmCl(II), (MeCp)2Sm OAr'(III), (Ind)2NdCl(IV), Me2Si(Ind)2NdCl(V) and (Flu)2NdCl(VI), and methylaluminoxane(MAO) respectively. All of them can be used to form the polyisoprene with molecular weights of 1 to 10 thousand and cis-1,4-unit contents of 41 to 47%. (I), (II) and (III) of them can be also used to form the polybutadiene with molecular weights of 10 to 20 thousand and cis-1,4-unit contents of 62 to 78%. In addition, the catalysts from (II) to (V) are still active for St polymerization and (II) of them gives a syndio -rich random polystyrene. It is noteworthy that (II) and (III) are active for homopolymerization of Bd, Ip and St in the same polymerization condition.
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    Polymer bulletin 40 (1998), S. 741-747 
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary In this work, a series of 2,3-O-methylcellulose (MC) with different DS value were prepared. Its phase transition behavior in aqueous solution was studied in terms of DS value, concentration and molecular weight. The the following conclusions were obtained. (1) All the 2,3-O-MC samples show no sol-gel transition in aqueous solution despite the molecular weight. (2) No phase separation was observed for the 2,3-O-MCs with a DS value lower than 1.0, even when the temperature was raised to 95°C. (3) The precipitation temperature is surprisingly different between 2,3-O-MCs. and other MCs possessing comparable total DS value. (4) The precipitation temperature of 2,3-O-MCs depends on the molecular weight rather than on the concentration.
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  • 49
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    Notes: Summary Ultrahigh molecular weight polyacrylamides (PAAM) were obtained by plasma-induced polymerization in water solutions. The influenceof monomer concentration, sealing pressure, initiation time and post polymerization period on polymer yield and molecular weight were investigated. The viscosity and “screen factor” measurements, as well as the thermally stimulated depolarization currents spectroscopic data of the synthesized polymers, indicate good properties as efficient viscosity modifiers in displacement of fluids for enhance oil recovery (EOR).
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  • 50
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary In this report, the relaxation behavior of amorphous poly(ethylene terephthalate) (PET) in global chain orientation but nearly random segmental orientation (GOLR) state is studied by infrared dichroism, optical birefringence and hot shrinkage measurements at temperatures below or up PET's glass transition temperature, Tg. The results indicate that the difference in the relaxing rate between global chains and segments is at least in ∼ 102 times order above PET's Tg (∼ 84°C), with a rough approximation; while the sudden decrease of small Δn of the sample (∼ 10−4) upon being treated at about 85 ∼ 90°C, implies us that the small Δn is closely related with the orientation of global chains.
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    Polymer bulletin 41 (1998), S. 129-130 
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  • 52
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    Notes: Summary New biomedical polyurethanes and a polyurethane urea based on Ε-caprolactone and 1,4-butanediisocyanate have been developed. On degradation, only non-toxic products are produced. The polyurethane urea with poly(Ε-caprolactone) soft segments and butanediisocyanate/butanediamine hard segments shows a high tensile strength, a high modulus and a high resistance to tearing but as a result of the strong interactions between the solvent and the polymer processing is difficult. When butanediamine is replaced by butanediol in the chain extension step, a processible polyurethane is obtained but the polymer lacks the desired mechanical properties for biomedical applications. By chain extending with a longer urethane diol block, a processible polymer was obtained with mechanical properties comparable to the polyurethane urea. This polyurethane has been made porous and can be used as a meniscal prosthesis.
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  • 53
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    Notes: Summary Catalytic 1,3-butadiene polymerization systems can be obtained with the new complex [NbO(C16H11O6 −)(C2O4 2−)] as a catalyst. When the catalysis occurs in a homogeneous medium (toluene as a solvent) in conjunction with AlEt2Cl, cis-1,4-polybutadiene is obtained. A remarkable inversion of stereoselectivity has been observed when the catalysis is carried out in a two phase system with the molten salt AlCl3.1-methyl-3-n-butyl-imidazolium chloride (MBIC) as a solvent and AlEt2Cl as a cocatalyst, giving the trans 1,4-polybutadiene.
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  • 54
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    Notes: Summary Highly branched aliphatic molecules have been used for the first time as tethers in the preparation of polymeric chiral stationary phases. Attachment of a specifically designed chiral selector to organic porous polymer beads through a branched linker substantially increases the enantioselectivity compared to that of the equivalent separation medium with a traditional linear tether.
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  • 55
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    Notes: Summary The EPR spectra of composite dextran and carboxymethyldextran gels were studied in order to identify the functional groups involved in copper(II) complexation depending on pH. The porous structure resulting from crosslinking of polymer chains of dextran, via epichlorohydrin, forces the immobilization of Cu2+ ions surrounded by different oxygen groups of the polymer gel matrix. The different polynuclear structures are postulated to be formed depending on the type of polysaccharide derivatives. The results indicate that carboxyl and deprotonated hydroxyl groups participate in the complex formation.
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  • 56
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    Notes: Summary Individual polystyrene (PS) and polyacrylonitrile (PAN) solutions in N,N-dimethylformamide (DMF) were studied by electronic absorption spectroscopy. Upon increasing the polymer concentration in the PS-DMF binary system a bathochromic shift of the band at about 260 nm was found. This spectral effect could be explained by an association of PS phenyl groups and/or by a complex formation between DMF and PS. The UV spectrum of PAN in DMF solution was interpreted in terms of the variety of possible donor-acceptor complex formations. The specific intermolecular interactions in the investigated binary liquid systems were discussed on the basis of the spectral data.
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  • 57
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    Notes: Summary Measurement of swelling is used to estimate the extent of cross-linking of latex particles prepared by emulsion polymerization. In this paper we report swelling data as a function of solvent activity for two latexes: (1) a poly(butylacrylate) (PBA) latex, and (2) a poly(isodecylacrylate) latex. In the latter case comparison is made between the swelling behavior of fully cross-linked, i.e., networks without free polymer chains, and partially cross-linked latexes. It is demonstrated that the equilibrium swelling properties are only slightly affected by the presence of uncross-linked chains. Swelling gives reliable results for the cross-link density only if the latex does not contain free chains.
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  • 58
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    Notes: Summary A correlation between interface strength and data of acoustic emission measurements in particle filled polymer composites was found. The method allows the evaluation of the interface strength in situ in polymer composite specimens at uniaxial loading. The measurements have shown that the tailored interface with the monomolecular tethered polymer layers of various grafting density change the mechanism of microdefect formation.
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    Stochastic environmental research and risk assessment 10 (1996), S. 1-15 
    ISSN: 1436-3259
    Keywords: Spacings ; quantiles ; generalized Pareto distribution ; log-logistic distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract The maximum product of spacings (MPS) method is discussed from the standpoint of information theory. MPS parameter and quantile estimates for the generalized Pareto distribution and the two parameter log-logistic distribution are compared with the maximum likelihood(ML) and probability weighted moment (PWM) estimates.
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    Stochastic environmental research and risk assessment 10 (1996), S. 17-37 
    ISSN: 1436-3259
    Keywords: Diffusion ; network ; reservoir ; power law
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract A diffusion approximation for a network of continuous time reservoirs with power law release rules is examined. Under a mild assumption on the inflow processes, we show that for physically reasonable values of the power law constants, the system of processes converges to a multi-dimensional Gaussian diffusion process. We also illustrate how the limiting Gaussian process may be used to compute approximations to the original system of reservoirs. In addition, we study the quality of our approximations by comparing them to results obtained by simulations of the original watershed model. The simulations offer support for the use of the approximation developed here.
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    Stochastic environmental research and risk assessment 10 (1996), S. 39-63 
    ISSN: 1436-3259
    Keywords: Saturated flow ; rainfall ; groundwater monitoring
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    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract A numerical experiment of flow in variably saturated porous media was performed in order to evaluate the spatial and temporal distribution of the groundwater recharge at the phreatic surface for a shallow aquifer as a function of the input rainfall process and soil heterogeneity. The study focused on the groundwater recharge which resulted from the percolation of the excess rainfall for a 90-days period of an actual precipitation record. Groundwater recharge was defined as the water flux across the moving phreatic surface. The observed spatial non-uniformity of the groundwater recharge was caused by soil heterogeneity and is particularly pronounced during the stage of recharge peak (substantial percolation stage). During that stage the recharge is associated with preferential flow paths defined as soil zones of locally higher hydraulic conductivity. For the periods of low percolation intensity the groundwater recharge was exhibiting more uniform spatial characteristics. The temporal distribution of the recharge was found to be a function of the frequency and intensity of the rainfall events. Application of sampling design demonstrates the joint influence of the spatial and temporal recharge variability on the cost-effective monitoring of groundwater potentiometric surfaces.
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    Stochastic environmental research and risk assessment 10 (1996), S. 65-85 
    ISSN: 1436-3259
    Keywords: Streamflow ; drought ; tree-ring data ; renewal model ; geometric variables
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    Notes: Abstract It is shown that runs of low-flow annual streamflow in a coastal semiarid basin of Central California can be adequately modelled by renewal theory. For example, runs of below-median annual streamflows are shown to follow a geometric distribution. The elapsed time between runs of below-median streamflow are geometrically distributed also. The sum of these two independently distributed geometric time variables defines the renewal time elapsing between the initiation of a low-flow run and the next one. The probability distribution of the renewal time is then derived from first principles, ultimately leading to the distribution of the number of low-flow runs in a specified time period, the expected number of low-flow runs, the risk of drought, and other important probabilistic indicators of low-flow. The authors argue that if one identifies drought threat with the occurrence of multiyear low-flow runs, as it is done by water supply managers in the study area, then our renewal model provides a number of interesting results concerning drought threat in areas historically subject to inclement, dry, climate. A 430-year long annual streamflow time series reconstructed by tree-ring analysis serves as the basis for testing our renewal model of low-flow sequences.
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    Stochastic environmental research and risk assessment 10 (1996), S. 87-106 
    ISSN: 1436-3259
    Keywords: Climate change ; daily precipitation modelling ; generalized linear models ; iteratively reweighted least squares ; spline functions
    Source: Springer Online Journal Archives 1860-2000
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    Notes: Abstract The precipitation amounts on wet days at De Bilt (the Netherlands) are linked to temperature and surface air pressure through advanced regression techniques. Temperature is chosen as a covariate to use the model for generating synthetic time series of daily precipitation in a CO2 induced warmer climate. The precipitation-temperature dependence can partly be ascribed to the phenomenon that warmer air can contain more moisture. Spline functions are introduced to reproduce the non-monotonous change of the mean daily precipitation amount with temperature. Because the model is non-linear and the variance of the errors depends on the expected response, an iteratively reweighted least-squares technique is needed to estimate the regression coefficients. A representative rainfall sequence for the situation of a systematic temperature rise is obtained by multiplying the precipitation amounts in the observed record with a temperature dependent factor based on a fitted regression model. For a temperature change of 3°C (reasonable guess for a doubled CO2 climate according to the present-day general circulation models) this results in an increase in the annual average amount of 9% (20% in winter and 4% in summer). An extended model with both temperature and surface air pressure is presented which makes it possible to study the additional effects of a potential systematic change in surface air pressure on precipitation.
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  • 64
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    Stochastic environmental research and risk assessment 10 (1996), S. 107-126 
    ISSN: 1436-3259
    Keywords: Gaussian process ; spatial correlation ; anisotropy ; Fourier transform ; Gauss-Newton ; ECM ; measurement error ; signal extraction ; irregular data
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    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract This paper is concerned with developing computational methods and approximations for maximum likelihood estimation and minimum mean square error smoothing of irregularly observed two-dimensional stationary spatial processes. The approximations are based on various Fourier expansions of the covariance function of the spatial process, expressed in terms of the inverse discrete Fourier transform of the spectral density function of the underlying spatial process. We assume that the underlying spatial process is governed by elliptic stochastic partial differential equations (SPDE's) driven by a Gaussian white noise process. SPDE's have often been used to model the underlying physical phenomenon and the elliptic SPDE's are generally associated with steady-state problems. A central problem in estimation of underlying model parameters is to identify the covariance function of the process. The cumbersome exact analytical calculation of the covariance function by inverting the spectral density function of the process, has commonly been used in the literature. The present work develops various Fourier approximations for the covariance function of the underlying process which are in easily computable form and allow easy application of Newton-type algorithms for maximum likelihood estimation of the model parameters. This work also develops an iterative search algorithm which combines the Gauss-Newton algorithm and a type of generalized expectation-maximization (EM) algorithm, namely expectation-conditional maximization (ECM) algorithm, for maximum likelihood estimation of the parameters. We analyze the accuracy of the covariance function approximations for the spatial autoregressive-moving average (ARMA) models analyzed in Vecchia (1988) and illustrate the performance of our iterative search algorithm in obtaining the maximum likelihood estimation of the model parameters on simulated and actual data.
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    Stochastic environmental research and risk assessment 10 (1996), S. 127-150 
    ISSN: 1436-3259
    Keywords: Rainfall estimation ; indicator cokriging ; rain gage measurements
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    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Indicator cokriging (Journel 1983) is examined as a tool for real-time estimation of rainfall from rain gage measurements. The approach proposed in this work obviates real-time estimation of real-time statistics of rainfall by using ensemble or climatological statistics exclusively, and reduces computational requirements attendant to indicator cokriging by employing only a few auxiliary cutoffs in estimation of conditional probabilities. Due to unavailability of suitable rain gage measurements, hourly radar rain fall data were used for both indicator covariance estimation and a comparative evaluation. Preliminary results suggest that the indicator cokriging approach is clearly superior to its ordinary kriging counterpart, whereas the indicator kriging approach is not. The improvement is most significant in estimation of light rainfall, but drops off significantly for heavy rainfall. The lack of predictability in spatial estimation of heavy rainfall is borne out in the integral scale of indicator correlation: peaking to its maximum for cutoffs near the median, indicator correlation scale becomes increasingly smaller for larger cutoffs of rainfall depth. A derived-distribution analysis, based on the assumption that radar rainfall is a linear sum of ground-truth and a random error, suggests that, at low cutoffs, indicator correlation scale of ground-truth can significantly differ from that of radar rainfall, and points toward inclusion of rainfall intermittency, for example, within the framework proposed in this work.
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    Stochastic environmental research and risk assessment 10 (1996), S. 151-161 
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    Stochastic environmental research and risk assessment 10 (1996), S. 163-166 
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    Stochastic environmental research and risk assessment 10 (1996), S. 187-207 
    ISSN: 1436-3259
    Keywords: log-Gumbel distribution ; flood frequency analysis ; quantile estimation ; confidence intervals
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    Notes: Abstract The log-Gumbel distribution is one of the extreme value distributions which has been widely used in flood frequency analysis. This distribution has been examined in this paper regarding quantile estimation and confidence intervals of quantiles. Specific estimation algorithms based on the methods of moments (MOM), probability weighted moments (PWM) and maximum likelihood (ML) are presented. The applicability of the estimation procedures and comparison among the methods have been illustrated based on an application example considering the flood data of the St. Mary's River.
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    Stochastic environmental research and risk assessment 10 (1996), S. 167-186 
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    Keywords: Reservoir stochastic theory ; reliability ; mean ; variance ; indicator function ; storage bounds ; nonlinear programming ; simulation
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    Notes: Abstract A new formulation is presented for the analysis of reservoir systems synthesizing concepts from the traditional stochastic theory of reservoir storage, moments analysis and reliability programming. The analysis is based on the development of the first and second moments for the stochastic storage state variable. These expressions include terms for the failure probabilities (probabilities of spill or deficit) and consider the storage bounds explicitly. Using this analysis, expected values of the storage state, variances of storage, optimal release policies and failure probabilities — useful information in the context of reservoir operations and design, can be obtained from a nonlinear programming solution. The solutions developed from studies of single reservoir operations on both an annual and monthly basis, compare favorably with those obtained from simulation. The presentation herein is directed to both traditional reservoir storage theorists who are interested in the design of a reservoir and modern reservoir analysts who are interested in the long term operation of reservoirs.
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    Stochastic environmental research and risk assessment 10 (1996), S. 209-229 
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    Keywords: Infiltration-advance equation ; water spreading ; cellular automata ; irrigation ; surface hydrology ; hydrodynamics ; stochastic processes
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    Notes: Abstract A technique has been developed for predicting the irregular advance pattern often observed as water spreads on the surface of the ground. The technique is a combination of stochastic sketching, potential theory, probability theory, and a mass balance equation in the form of an advance equation. The technique can be used on flat as well as sloping terrain and addresses any form of obstructions or constraints to the flow of the water. The stochastic sketching portion of the technique uses cellular automata with transition probability movement rules to sketch the dynamics of small volume water elements in the defined environment. Randomly selected small volume flow path segments are computed and plotted. The envelope of these segments defines the wetted area and the advance front. Several examples are presented showing the patterns produced for various situations.
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    Stochastic environmental research and risk assessment 10 (1996), S. 231-251 
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    Keywords: Stochastic ; multiphase ; three phase ; heterogeneity
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    Notes: Abstract The first paper (Chang et al., 1995b) of this two-part series described the stochastic analysis using spectral/perturbation approach to analyze steady state two-phase (water and oil) flow in a, liquid-unsaturated, three fluid-phase porous medium. In this paper, the results between the numerical simulations and closed-form expressions obtained using the perturbation approach are compared. We present the solution to the one-dimensional, steady-state oil and water flow equations. The stochastic input processes are the spatially correlated logk where k is the intrinsic permeability and the soil retention parameter, α. These solutions are subsequently used in the numerical simulations to estimate the statistical properties of the key output processes. The comparison between the results of the perturbation analysis and numerical simulations showed a good agreement between the two methods over a wide range of logk variability with three different combinations of input stochastic processes of logk and soil parameter α. The results clearly demonstrated the importance of considering the spatial variability of key subsurface properties under a variety of physical scenarios. The variability of both capillary pressure and saturation is affected by the type of input stochastic process used to represent the spatial variability. The results also demonstrated the applicability of perturbation theory in predicting the system variability and defining effective fluid properties through the ergodic assumption.
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    Stochastic environmental research and risk assessment 10 (1996), S. 295-317 
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    Keywords: Bayesion methods ; time series ; hydrology
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    Notes: Abstract A review of literature reveals the inadequacy of Intervention analysis and spectrum based methods to adequately quantify changes in hydrologic times series. A Bayesian method is used to investigate the statistical significance of observed changes in hydrologic times series and the results are reported herein. The Bayesian method is superior to the previous methods.
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    Stochastic environmental research and risk assessment 10 (1996), S. 253-278 
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    Keywords: Random fields ; stochastic processes ; fractals
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    Notes: Abstract This paper describes a new method for generating spatially-correlated random fields. Such fields are often encountered in hydrology and hydrogeology and in the earth sciences. The method is based on two observations: (i) spatially distributed attributes usually display a stationary correlation structure, and (ii) the screening effect of measurements leads to the sufficiency of a small search neighborhood when it comes to projecting measurements and data in space. The algorithm which was developed based on these principles is called HYDRO_GEN, and its features and properties are discussed in depth. HYDRO_GEN is found to be accurate and extremely fast. It is also versatile: it can simulate fields of different nature, starting from weakly stationary fields with a prescribed covariance and ending with fractal fields. The simulated fields can display statistical isotropy or anisotropy.
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    Stochastic environmental research and risk assessment 10 (1996), S. 279-294 
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    Keywords: Linear estimation ; interpolation ; kriging ; splines ; conditional
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    Notes: Abstract This work presents analytical expressions for the best estimate, conditional covariance function, and conditional realizations of a function from sparse observations. In contrast to the prevalent approach in kriging where the best estimates at every point are determined from the solution of a system of linear equations, the best-estimate function can be represented analytically in terms of basis functions, whose number depends on the observations. This approach is computationally superior when graphing a function estimate and is also valuable in understanding what the solution should look like. For example, one can immediately see that all “singularities” in the best-estimate function are at observation points.
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    Stochastic environmental research and risk assessment 10 (1996), S. 319-329 
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    Keywords: Particle tracking ; numerical methods ; random walks ; advection-dispersion equation ; stochastic processes
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    Notes: Abstract A formal statistical discussion of the origins of the random walk and its relation to the classic advection-dispersion equation is given. At issue is the common use of Gaussian distributed steps in producing the desired dispersive effects. Shown are alternative solutions to the basic Langevin equation describing mass displacements based on non-Gaussian, white increments. In particular, the results reveal that uniform or symmetric-triangular steps can be employed without loss of generality in accuracy of the solution (over all Peclet numbers) and may yield significant savings in the computational generation of the random deviates required in the Monte Carlo procedures of the random walk method.
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    Stochastic environmental research and risk assessment 10 (1996), S. 330-330 
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    Stochastic environmental research and risk assessment 11 (1997), S. 17-31 
    ISSN: 1436-3259
    Keywords: Bivariate density ; meta-Gaussian density ; normal quantile transform ; likelihood ratio dependence ; correlation coefficient
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    Notes: Abstract Convenient bivariate densities found in the literature are often unsuitable for modeling hydrologic variates. They either constrain the range of association between variates, or fix the form of the marginal distributions. The bivariate meta-Gaussian density is constructed by embedding the normal quantile transform of each variate into the Gaussian law. The density can represent a full range of association between variates and admits arbitrarily specified marginal distributions. Modeling and estimation can be decomposed into i) independent analyses of the marginal distributions, and ii) investigation of the dependence structure. Both statistical and judgmental estimation procedures are possible. Some comparisons to recent applications of bivariate densities in the hydrologic literature motivate and illustrate the model.
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    Stochastic environmental research and risk assessment 11 (1997), S. 33-50 
    ISSN: 1436-3259
    Keywords: Unit hydrograph ; uncertainty analysis ; linearly constrained Monte-Carlo simulation ; reliability analysis
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    Notes: Abstract Unit hydrographs (UHs), along with design rainfalls, are frequently used to determine the discharge hydrograph for design and evaluation of hydraulic structures. Due to the presence of various uncertainties in its derivation, the resulting UH is inevitably subject to uncertainty. Consequently, the performance of hydraulic structures under the design storm condition is uncertain. This paper integrates the linearly constrained Monte-Carlo simulation with the UH theory and routing techniques to evaluate the reliability of hydraulic structures. The linear constraint is considered because the water volume of each generated design direct runoff hydrograph should be equal to that of the design effective rainfall hyetograph or the water volume of each generated UH must be equal to one inch (or cm) over the watershed. For illustration, the proposed methodology is applied to evaluate the overtopping risk of a hypothetical flood detention reservoir downstream of Tong-Tou watershed in Taiwan.
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    Stochastic environmental research and risk assessment 11 (1997), S. 1-16 
    ISSN: 1436-3259
    Keywords: Nash cascade reservoir model ; rainfall-runoff ; EM algorithm ; filtering ; maximum likelihood estimation ; martingale estimating function
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    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Abstract: Linear continuous time stochastic Nash cascade conceptual models for runoff are developed. The runoff is modeled as a simple system of linear stochastic differential equations driven by white Gaussian and marked point process noises. In the case of d reservoirs, the outputs of these reservoirs form a d dimensional vector Markov process, of which only the dth coordinate process is observed, usually at a discrete sample of time points. The dth coordinate process is not Markovian. Thus runoff is a partially observed Markov process if it is modeled using the stochastic Nash cascade model. We consider how to estimate the parameters in such models. In principle, maximum likelihood estimation for the complete process parameters can be carried out directly or through some form of the EM (estimation and maximization) algorithm or variation thereof, applied to the observed process data. In this research we consider a direct approximate likelihood approach and a filtering approach to an algorithm of EM type, as developed in Thompson and Kaseke (1994). These two methods are applied to some real life runoff data from a catchment in Wales, England. We also consider a special case of the martingale estimating function approach on the runoff model in the presence of rainfall. Finally, some simulations of the runoff process are given based on the estimated parameters.
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    Stochastic environmental research and risk assessment 11 (1997), S. 173-192 
    ISSN: 1436-3259
    Keywords: Uncertainty analysis ; unit hydrograph ; regression analysis ; probabilistic point estimation methods
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    Notes: Abstract Hydrologic model parameters obtained from regional regression equations are subject to uncertainty. Consequently, hydrologic model outputs based on the stochastic parameters are random. This paper presents a systematic analysis of uncertainty associated with the two parameters, N and K, in Nash's IUH model from different regional regression equations. The uncertainty features associated with N and K are further incorporated to assess the uncertainty of the resulting IUH. Numerical results indicate that uncertainty of N and K from the regional regression equations are too significant to be ignored.
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    Stochastic environmental research and risk assessment 11 (1997), S. 145-171 
    ISSN: 1436-3259
    Keywords: Hydrologic regionalization ; unit hydrograph ; regression analysis ; multivariate regression ; seemingly unrelated regression ; validation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Hydrologic regionalization is a useful tool that allows for the transfer of hydrological information from gaged sites to ungaged sites. This study developed regional regression equations that relate the two parameters in Nash's IUH model to the basin characteristics for 42 major watersheds in Taiwan. In the process of developing the regional equations, different regression procedures including the conventional univariate regression, multivariate regression, and seemingly unrelated regression were used. Multivariate regression and seeming unrelated regression were applied because there exists a rather strong correlation between the Nash's IUH parameters. Furthermore, a validation study was conducted to examine the predictability of regional equations derived by different regression procedures. The study indicates that hydrologic regionalization involving several dependent variables should consider their correlations in the process of establishing the regional equations. The consideration of such correlation will enhance the predictability of resulting regional equations as compared with the ones from the conventional univariate regression procedure.
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    Stochastic environmental research and risk assessment 11 (1997), S. 193-210 
    ISSN: 1436-3259
    Keywords: Turbulence ; sediment ; fluvial ; river ; bursting process ; statistics
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    Notes: Abstract Entrainment of sediment particles from channel beds into the channel flow is influenced by the characteristics of the flow turbulence which produces stochastic shear stress fluctuations at the bed. Recent studies of the structure of turbulent flow has recognized the importance of bursting processes as important mechanisms for the transfer of momentum into the laminar boundary layer. Of these processes, the sweep event has been recognized as the most important bursting event for entrainment of sediment particles as it imposes forces in the direction of the flow resulting in movement of particles by rolling, sliding and occasionally saltating. Similarly, the ejection event has been recognized as important for sediment transport since these events maintain the sediment particles in suspension. In this study, the characteristics of bursting processes and, in particular, the sweep event were investigated in a flume with a rough bed. The instantaneous velocity fluctuations of the flow were measured in two-dimensions using a small electromagnetic velocity meter and the turbulent shear stresses were determined from these velocity fluctuations. It was found that the shear stress applied to the sediment particles on the bed resulting from sweep events depends on the magnitude of the turbulent shear stress and its probability distribution. A statistical analysis of the experimental data was undertaken and it was found necessary to apply a Box-Cox transformation to transform the data into a normally distributed sample. This enabled determination of the mean shear stress, angle of action and standard error of estimate for sweep and ejection events. These instantaneous shear stresses were found to be greater than the mean flow shear stress and for the sweep event to be approximately 40 percent greater near the channel bed. Results from this analysis suggest that the critical shear stress determined from Shield's diagram is not sufficient to predict the initiation of motion due to its use of the temporal mean shear stress. It is suggested that initiation of particle motion, but not continuous motion, can occur earlier than suggested by Shield's diagram due to the higher shear stresses imposed on the particles by the stochastic shear stresses resulting from turbulence within the flow.
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    Stochastic environmental research and risk assessment 11 (1997), S. 211-227 
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    Notes: Abstract The principle of maximum entropy (POME) was employed to derive a new method of parameter estimation for the 2-parameter generalized Pareto (GP2) distribution. Monte Carlo simulated data were used to evaluate this method and compare it with the methods of moments (MOM), probability weighted moments (PWM), and maximum likelihood estimation (MLE). The parameter estimates yielded by POME were comparable or better within certain ranges of sample size and coefficient of variation.
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    Stochastic environmental research and risk assessment 11 (1997), S. 523-547 
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    Notes: Abstract Kernel density estimators are useful building blocks for empirical statistical modeling of precipitation and other hydroclimatic variables. Data driven estimates of the marginal probability density function of these variables (which may have discrete or continuous arguments) provide a useful basis for Monte Carlo resampling and are also useful for posing and testing hypotheses (e.g bimodality) as to the frequency distributions of the variable. In this paper, some issues related to the selection and design of univariate kernel density estimators are reviewed. Some strategies for bandwidth and kernel selection are discussed in an applied context and recommendations for parameter selection are offered. This paper complements the nonparametric wet/dry spell resampling methodology presented in Lall et al. (1996).
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    Stochastic environmental research and risk assessment 11 (1997), S. 459-482 
    ISSN: 1436-3259
    Keywords: Karhunen-Loéve expansion ; Empirical Orthogonal Functions ; stochastic simulation ; gaussian fields ; analytical covariance functions ; eigenfunctions ; kriging
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    Notes: Abstract Simulation of multigaussian stochastic fields can be made after a Karhunen-Loéve expansion of a given covariance function. This method is also called simulation by Empirical Orthogonal Functions. The simulations are made by drawing stochastic coefficients from a random generator. These numbers are multiplied with eigenfunctions and eigenvalues derived from the predefined covariance model. The number of eigenfunctions necessary to reproduce the stochastic process within a predefined variance error, turns out to be a cardinal question. Some ordinary analytical covariance functions are used to evaluate how quickly the series of eigenfunctions can be truncated. This analysis demonstrates extremely quick convergence to 99.5% of total variance for the 2nd order exponential (‘gaussian’) covariance function, while the opposite is true for the 1st order exponential covariance function. Due to these convergence characteristics, the Karhunen-Loéve method is most suitable for simulating smooth fields with ‘gaussian’ shaped covariance functions. Practical applications of Karhunen-Loéve simulations can be improved by spatial interpolation of the eigenfunctions. In this paper, we suggest interpolation by kriging and limits for reproduction of the predefined covariance functions are evaluated.
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    Stochastic environmental research and risk assessment 12 (1998), S. 1-14 
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    Keywords: Key words: Exceedance probability ; trend ; stochastic variables ; non-stationarity
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    Notes: Abstract Studying the hypothetical case of a trend superimposed on a random stationary variable, we highlight the strong influence of possible non-stationarities on exceedance probability. After a general outline, the subject is analytically developed using the Gumbel distribution, emphasizing the quick increase of the exceedance probability over time in the presence of weak rising trends, and its sensitive underestimation where the non-stationarity goes unnoticed or is considered negligible. Finally the work is applied to hydrological series of rainfall and river flow.
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    Stochastic environmental research and risk assessment 12 (1998), S. 53-64 
    ISSN: 1436-3259
    Keywords: Key words: Risk ; clustering ; point process ; Poisson ; flood.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract: Since the introduction into flood risk analysis, the partial duration series method has gained increasing acceptance as an appealing alternative to the annual maximum series method. However, when the base flow is low, there is clustering in the flood peak or flow volume point process. In this case, the general stochastic point process model is not suitable to risk analysis. Therefore, two types of models for flood risk analysis are derived on the basis of clustering stochastic point process theory in this paper. The most remarkable characteristic of these models is that the flood risk is considered directly within the time domain. The acceptability of different models are also discussed with the combination of the flood peak counted process in twenty years at Yichang station on the Yangtze river. The result shows that the two kinds of models are suitable ones for flood risk analysis, which are more flexible compared with the traditional flood risk models derived on the basis of annual maximum series method or the general stochastic point process theory.
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  • 88
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    Stochastic environmental research and risk assessment 12 (1998), S. 33-52 
    ISSN: 1436-3259
    Keywords: Keywords: Streamflow ; simulation ; nonparametric
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract A new approach for streamflow simulation using nonparametric methods was described in a recent publication (Sharma et al. 1997). Use of nonparametric methods has the advantage that they avoid the issue of selecting a probability distribution and can represent nonlinear features, such as asymmetry and bimodality that hitherto were difficult to represent, in the probability structure of hydrologic variables such as streamflow and precipitation. The nonparametric method used was kernel density estimation, which requires the selection of bandwidth (smoothing) parameters. This study documents some of the tests that were conduced to evaluate the performance of bandwidth estimation methods for kernel density estimation. Issues related to selection of optimal smoothing parameters for kernel density estimation with small samples (200 or fewer data points) are examined. Both reference to a Gaussian density and data based specifications are applied to estimate bandwidths for samples from bivariate normal mixture densities. The three data based methods studied are Maximum Likelihood Cross Validation (MLCV), Least Square Cross Validation (LSCV) and Biased Cross Validation (BCV2). Modifications for estimating optimal local bandwidths using MLCV and LSCV are also examined. We found that the use of local bandwidths does not necessarily improve the density estimate with small samples. Of the global bandwidth estimators compared, we found that MLCV and LSCV are better because they show lower variability and higher accuracy while Biased Cross Validation suffers from multiple optimal bandwidths for samples from strongly bimodal densities. These results, of particular interest in stochastic hydrology where small samples are common, may have importance in other applications of nonparametric density estimation methods with similar sample sizes and distribution shapes.
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  • 89
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    Stochastic environmental research and risk assessment 12 (1998), S. 15-32 
    ISSN: 1436-3259
    Keywords: Key words: Kalman filtering ; groundwater modelling ; inverse methods ; uncertainty analysis ; state prediction ; parameter estimation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract The popularity of applying filtering theory in the environmental and hydrological sciences passed its first climax in the 1970s. Like so many other new mathematical methods it was simply the fashion at the time. The study of groundwater systems was not immune to this fashion, but neither was it by any means a prominent area of application. The spatial-temporal characteristics of groundwater flow are customarily described by analytical or, more frequently, numerical, physics-based models. Consequently, the state-space representations associated with filtering must be of a high order, with an immediately apparent computational over-burden. And therein lies part of the reason for the but modest interest there has been in applying Kalman filtering to groundwater systems, as reviewed critically in this paper. Filtering theory may be used to address a variety of problems, such as: state estimation and reconstruction, parameter estimation (including the study of uncertainty and its propagation), combined state-parameter estimation, input estimation, estimation of the variance-covariance properties of stochastic disturbances, the design of observation networks, and the analysis of parameter identifiability. A large proportion of previous studies has dealt with the problem of parameter estimation in one form or another. This may well not remain the focus of attention in the future. Instead, filtering theory may find wider application in the context of data assimilation, that is, in reconstructing fields of flow and the migration of sub-surface contaminant plumes from relatively sparse observations.
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  • 90
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    Stochastic environmental research and risk assessment 12 (1998), S. 65-82 
    ISSN: 1436-3259
    Keywords: Key words: Flood flow ; threshold ; generalized Pareto ; Poisson
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract This study uses the method of peaks over threshold (P.O.T.) to estimate the flood flow quantiles for a number of hydrometric stations in the province of New Brunswick, Canada. The peak values exceeding the base level (threshold), or `exceedances', are fitted by a generalized Pareto distribution. It is known that under the assumption of Poisson process arrival for flood exceedances, the P.O.T. model leads to a generalized extreme value distribution (GEV) for yearly maximum discharge values. The P.O.T. model can then be applied to calculate the quantiles X T corresponding to different return periods T, in years. A regionalization of floods in New Brunswick, which consists of dividing the province into `homogeneous regions', is performed using the method of the `region of influence'. The 100-year flood is subsequently estimated using a regionally estimated value of the shape parameter of the generalized Pareto distribution and a regression of the 100-year flood on the drainage area. The jackknife sampling method is then used to contrast the regional results with the values estimated at site. The variability of these results is presented in box-plot form.
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  • 91
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    Stochastic environmental research and risk assessment 12 (1998), S. 97-116 
    ISSN: 1436-3259
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract : The knowledge of the volume and duration of low-flow events in river channels is essential for water management and the design of hydraulics structures. In this study, both preceding characteristics, X 1 and X 2, are considered simultaneously via two types of bivariate distributions whose marginals are exponential. One of these bivariate distributions has been presented by Nagao and Kadoya (1971) and the other has been used by Singh and Singh (1991) to the study of rainfall intensity and rainfall depth. The results are applied to the low-flow series (“peaks-below-threshold”) of Lepreau River (station 01AQ001) in New Brunswick, Canada. These results show that the model that was successfully employed by Singh and Singh (1991) to study rainfall, presents certain difficulties when a very strong correlation, ρ, between the two random variables X 1 and X 2, exists. The model by Nagao and Kadoya (1971) seems to be more satisfactory for such situations, although this model seems also to be quite sensitive to variations in ρ.
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  • 92
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    Stochastic environmental research and risk assessment 12 (1998), S. 83-96 
    ISSN: 1436-3259
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Many natural porous geological rock formations, as well as engineered porous structures, have fractal properties, i.e., they are self-similar over several length scales. While there have been many experimental and theoretical studies on how to quantify a fractal porous medium and on how to determine its fractal dimension, the numerical generation of a fractal pore structure with predefined statistical and scaling properties is somewhat scarcer. In the present paper a new numerical method for generating a three-dimensional porous medium with any desired probability density function (PDF) and autocorrelation function (ACF) is presented. The well-known Turning Bands Method (TBM) is modified to generate three-dimensional synthetic isotropic and anisotropic porous media with a Gaussian PDF and exponential-decay ACF. Porous media with other PDF's and ACF's are constructed with a nonlinear, iterative PDF and ACF transformation, whereby the arbitrary PDF is converted to an equivalent Gaussian PDF which is then simulated with the classical TBM. Employing a new method for the estimation of the surface area for a given porosity, the fractal dimensions of the surface area of the synthetic porous media generated in this way are then measured by classical fractal perimeter/area relationships. Different 3D porous media are simulated by varying the porosity and the correlation structure of the random field. The performance of the simulations is evaluated by checking the ensemble statistics, the mean, variance and ACF of the simulated random field. For a porous medium with Gaussian PDF, an average fractal dimension of approximately 2.76 is obtained which is in the range of values of actually measured fractal dimensions of molecular surfaces. For a porous medium with a non-Gaussian quadratic PDF the calculated fractal dimension appears to be consistently higher and averages 2.82. The results also show that the fractal dimension is neither strongly dependent of the porosity nor of the degree of anisotropy assumed.
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  • 93
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    Stochastic environmental research and risk assessment 12 (1998), S. 117-140 
    ISSN: 1436-3259
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Transport of non-ergodic solute plumes by steady-state groundwater flow with a uniform mean velocity, μ, were simulated with Monte Carlo approach in a two-dimensional heterogeneous and statistically isotropic aquifer whose transmissivity, T, is log-normally distributed with an exponential covariance. The ensemble averages of the second spatial moments of the plume about its center of mass, 〈S i i (t)〉, and the plume centroid covariance, R i i (t) (i=1,2), were simulated for the variance of Y=log T, σ Y 2=0.1, 0.5 and 1.0 and line sources normal or parallel to μ of three dimensionless lengths, 1, 5, and 10. For σ Y 2=0.1, all simulated 〈S i i (t)〉−S i i (0) and R i i (t) agree well with the first-order theoretical values, where S i i (0) are the initial values of S i i (t). For σ Y 2=0.5 and 1.0 and the line sources normal to μ, the simulated longitudinal moments, 〈S 11(t)〉−S 11(0) and R 11(t), agree well with the first-order theoretical results but the simulated transverse moments 〈S 22(t)〉−S 22(0) and R 22(t) are significantly larger than the first-order values. For the same two larger values of σ Y 2 but the line sources parallel to μ, the simulated 〈S 11(t)〉−S 11(0) are larger than but the simulated R 11 are smaller than the first-order values, and both simulated 〈S 22(t)〉−S 22(0) and R 22(t) stay larger than the first-order values. For a fixed value of σ Y 2, the summations of 〈S i i (t)〉−S i i (0) and R i i , i.e., X i i (i=1,2), remain almost the same no matter what kind of source simulated. The simulated X 11 are in good agreement with the first-order theory but the simulated X 22 are significantly larger than the first-order values. The simulated X 22, however, are in excellent agreement with a previous modeling result and both of them are very close to the values derived using Corrsin's conjecture. It is found that the transverse moments may be significantly underestimated if less accurate hydraulic head solutions are used and that the decreasing of 〈S 22(t)〉−S 22(0) with time or a negative effective dispersivity, defined as , may happen in the case of a line source parallel to μ where σ Y 2 is small.
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    Stochastic environmental research and risk assessment 12 (1998), S. 141-154 
    ISSN: 1436-3259
    Keywords: Key words: Ground truth ; geostatistical techniques ; areal reduction factor ; Rainfall process ; linear relationship.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Geostatistical techniques are used to quantify the reference mean areal rainfall (ground truth) from sparse raingaugenetworks. Based on the EPSAT-Niger event cumulative rainfall, a linear relationship between the ground truth considered as the mean area rainfall estimated from the densely available raingauge network and the area rainfall estimated from sparse network are derived. Also, a linear relationship between the ground truth and point rainfall is established. As it was reported experimentally by some authors, the slope of these relationships is less than one. Based on the geostatistical framework, the slope and the ordinate at the origin can be estimated as a function of the spatial structure of the rainfall process. It is shown that the slope is smaller than one. For the special case of one gauge inside a fixed area or a Field Of View (FOV), an areal reduction factor is derived. It has a limit value which depends only on the size of the area and the spatial structure of the rainfall process. The relative variance error of estimating the FOV cumulative rainfall from point rainfall is also given.
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  • 95
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    Stochastic environmental research and risk assessment 12 (1998), S. 223-245 
    ISSN: 1436-3259
    Keywords: Key words: Stochastic differential equation ; spatial data ; irregularly sampled data ; parameter estimation.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract: A second order stochastic differential equation is used for modeling of water-table elevation. The data were sampled at the Borden Aquifer as a part of a tracer experiment. The purpose of the water-table data collection was to determine presence of a water flow. We argue that the water-table surface is a simple plane oscillating up and down in time according to an equation for a stochastic oscillator. We derive the model, estimate its parameters and provide arguments for goodness-of-fit of the model.
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  • 96
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    Stochastic environmental research and risk assessment 12 (1998), S. 267-283 
    ISSN: 1436-3259
    Keywords: Key words: Flood frequency analysis ; TCEV ; non-systematic information ; regional ; statistical gain.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract: Due to the social and economic implications, flood frequency analysis must be done with the highest precision. For this reason, the most suitable statistical model must be selected, and the maximum amount of information must be used. Floods in Mediterranean rivers can be produced by two different mechanisms, which forces the use of a non-traditional distribution like the TCEV. The information can be increased by using additional non-systematic data, or with a regional analysis, or both. Through the statistical gain concept, it has been shown that in most cases the use of additional non-systematic information can decrease the quantile estimation error in about 50%. In a regional analysis, the␣benefit of additional information in one station, is propagated to the rest of␣the␣stations with only a small decrease with respect to the at-site equivalent analysis.
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    Stochastic environmental research and risk assessment 12 (1998), S. 285-298 
    ISSN: 1436-3259
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract We present a geostatistically based inverse model for characterizing heterogeneity in parameters of unsaturated hydraulic conductivity for three-dimensional flow. Pressure and moisture content are related to perturbations in hydraulic parameters through cross-covariances, which are calculated to first-order. Sensitivities needed for covariance calculations are derived using the adjoint state sensitivity method. Approximations of the conditional mean parameter fields are then obtained from the cokriging estimator. Correlation between parameters and pressure – moisture content perturbations is seen to be strongly dependent on mean pressure or moisture content. High correlation between parameters and pressure data was obtained under saturated or near saturated flow conditions, providing accurate estimation of saturated hydraulic conductivity, while moisture content measurements provided accurate estimation of the pore size distribution parameter under unsaturated flow conditions.
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  • 98
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    Stochastic environmental research and risk assessment 12 (1998), S. 247-266 
    ISSN: 1436-3259
    Keywords: Key words: Stochastic control ; dynamic programming ; reservoir systems ; hydrologic forecasting ; hydropower ; feedback control ; autoregressive models.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract : As with all dynamic programming formulations, differential dynamic programming (DDP) successfully exploits the sequential decision structure of multi-reservoir optimization problems, overcomes difficulties with the nonconvexity of energy production functions for hydropower systems, and provides optimal feedback release policies. DDP is particularly well suited to optimizing large-scale multi-reservoir systems due to its relative insensitivity to state-space dimensionality. This advantage of DDP encourages expansion of the state vector to include additional multi-lag hydrologic information and/or future inflow forecasts in developing optimal reservoir release policies. Unfortunately, attempts at extending DDP to the stochastic case have not been entirely successful. A modified stochastic DDP algorithm is presented which overcomes difficulties in previous formulations. Application of the algorithm to a four-reservoir hydropower system demonstrates its capabilities as an efficient approach to solving stochastic multi-reservoir optimization problems. The algorithm is also applied to a single reservoir problem with inclusion of multi-lag hydrologic information in the state vector. Results provide evidence of significant benefits in direct inclusion of expanded hydrologic state information in optimal feedback release policies.
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  • 99
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    Stochastic environmental research and risk assessment 12 (1998), S. 299-316 
    ISSN: 1436-3259
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract This paper presents a geostatistical approach to multi-directional aquifer stimulation in order to better identify the transmissivity field. Hydraulic head measurements, taken at a few locations but under a number of different steady-state flow conditions, are used to estimate the transmissivity. Well installation is generally the most costly aspect of obtaining hydraulic head measurements. Therefore, it is advantageous to obtain as many informative measurements from each sampling location as possible. This can be achieved by hydraulically stimulating the aquifer through pumping, in order to set-up a variety of flow conditions. We illustrate the method by applying it to a synthetic aquifer. The simulations provide evidence that a few sampling locations may provide enough information to estimate the transmissivity field. Furthermore, the innovation of, or new information provided by, each measurement can be examined by looking at the corresponding spline and sensitivity matrix. Estimates from multi-directional stimulation are found to be clearly superior to estimates using data taken under one flow condition. We describe the geostatistical methodology for using data from multi-directional simulations and address computational issues.
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  • 100
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    Stochastic environmental research and risk assessment 9 (1995), S. 33-47 
    ISSN: 1436-3259
    Keywords: Hidden markov models ; maximum likelihood estimation ; EM algorithm ; martingale estimating function ; forward-backward algorithm ; Monte Carlo ; filtering ; Nash cascade model ; rainfall runoff modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract Many stochastic process models for environmental data sets assume a process of relatively simple structure which is in some sense partially observed. That is, there is an underlying process (Xn, n ≥ 0) or (Xt, t ≥ 0) for which the parameters are of interest and physically meaningful, and an observable process (Yn, n ≥ 0) or (Yt, t ≥ 0) which depends on the X process but not otherwise on those parameters. Examples are wide ranging: the Y process may be the X process with missing observations; the Y process may be the X process observed with a noise component; the X process might constitute a random environment for the Y process, as with hidden Markov models; the Y process might be a lower dimensional function or reduction of the X process. In principle, maximum likelihood estimation for the X process parameters can be carried out by some form of the EM algorithm applied to the Y process data. In the paper we review some current methods for exact and approximate maximum likelihood estimation. We illustrate some of the issues by considering how to estimate the parameters of a stochastic Nash cascade model for runoff. In the case of k reservoirs, the outputs of these reservoirs form a k dimensional vector Markov process, of which only the kth coordinate process is observed, usually at a discrete sample of time points.
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