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  • Chemistry  (40)
  • GEOPHYSICS  (9)
  • METEOROLOGY AND CLIMATOLOGY
  • Meteorology and Climatology
  • 1995-1999  (36)
  • 1970-1974  (17)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 15 (1971), S. 811-828 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An attempt has been made to rationalize the variables in the preparation procedure of Loeb-Sourirajan-type reverse-osmosis membranes. The quaternary phase diagram of the system cellulose acetate-acetone-formamide-water was determined and has proved a useful tool in the discussion of membrane structures and properties. A mechanism based on differences in the precipitation rate of the polymer during the membrane formation process has been suggested to explain the observed asymmetry in the membrane structure. The porosity of the membrane has been ascribed to the relative rates of water entering and solvent leaving the cast film. The effects of the casting solution composition, the evaporation time, the wash bath temperature, and the annealing procedure have been studied. X-Ray diffraction and electron microscopy were used to supplement flux and retention data of membranes made from a cellulose acetate-formamide-acetone casting solution.
    Additional Material: 14 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 14 (1970), S. 1197-1214 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Batch and flow recirculation cells were used to study the properties of high-flux ultrafiltration membranes with different macromolecular solutions. At low pressures, solutions of completely retained macromolecular solutes have a flux which is approximately the same as the flux of pure solvent. At higher pressures, the solution flux levels off. The flux, at the leveling-off period, is approximately inversely proportional to the solution concentration. In this plateau region the flux increases with temperature and agitation of the solution but decreases with time. These results are explained by the formation of a gel layer on the membrane surface during the filtration of macromolecular solutions. In ultrafiltration, in contrast to dialysis and GPC, a linear polymer penetrates the selective barrier more readily than does a globular protein of the same molecular weight. The difference may arise from the liquid shear stresses within the barrier medium due to the movement of fluid relative to the pore walls, which is large only in ultrafiltration. Also, retention of polymers was found to decrease with pressure and to increase with agitation of the solution.
    Additional Material: 13 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 633-642 
    ISSN: 0887-624X
    Keywords: free radicals ; grafting ; kinetics ; methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of grafting a basic monomer, 2-(dimethylamino)-ethyl methacrylate (DMAEMA) to hydrocarbon substrates have been investigated. These systems were chosen as models for the grafting of a homopolymerizable monomer to polyolefins such as polyethylene. The reactions with squalane and n-eicosane were initiated by an organic peroxide, 2,5-dimethyl 2,5 dit-butylperoxy)-3-hexyne; grafting yields become significant at high reaction temperatures and low monomer concentrations. In squalane, the order of reaction with respect to monomer increased from about 1.1 for 0.22-0.44M DMAEMA to almost 2 at 0.69M DMAEMA; the order with respect to initiator was 0.56. The overall activation energy in the 130-160°C temperature range was, however, surprisingly low, 42±5 kJ mol-1. When analytical data were used to separate the overall rate into those for grafting and homopolymerization, different kinetic paths were observed for the competing reactions. These results are interpreted in terms of two different mechanisms; intramolecular chain transfer plays an important role in grafting, while depropagation becomes a major factor in homopolymerization at temperatures above 150°C. © 1995 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3517-3525 
    ISSN: 0887-624X
    Keywords: peroxide ; vinylsilane ; grafting ; polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The peroxide-initiated grafting of vinyltrimethoxysilane (VTMS) onto dodecane has been examined as a model for grafting onto polyethylene. At 160°C, 2% v/v VTMS and 0.08% v/v initiator, the monomer was grafted onto dodecane with a 59% conversion and an average of 2.37 VTMS grafts per dodecane. These values were obtained by separation of the grafted material through reduced pressure distillation then characterization with FTIR and NMR spectroscopy, mass spectrometry, and gel permeation chromatography. NMR studies strongly indicate that the multiple grafts consist predominantly of multiple single grafts rather than homopolymer grafts. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3517-3525, 1997
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1573-1582 
    ISSN: 0887-624X
    Keywords: amic acid ; secondary amine ; maleic anhydride ; melt reaction kinetics ; model compounds ; polymer-bound functional groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study examines the legitimacy of using the reaction kinetics of low molecular weight model compounds in solution to predict the chemical kinetics of polymer-bound species in a homogeneous melt. The reaction under study takes place between an aliphatic secondary amine, diisooctadecylamine (DiOA), and a 5-membered anhydride ring, saturated maleic anhydride (MA), forming an amic acid product. The MA species was present as a pendant graft on either a model compound, dodecane-g-(maleic anhydride) (dodecane-g-MA), or a polymer chain, linear low-density polyethylene-g-(maleic anhydride) (LLDPE-g-MA). Pseudo-second-order kinetics of the anhydride consumption are followed by infrared spectroscopy, either in situ in dodecane solution or by scanning frozen film samples taken from a linear low-density polyethylene melt. It was found that the LLDPE-g-MA/DiOA system reacted at a slightly slower rate than the dodecane-g-MA/DiOA system in the low-viscosity solution at 140°C. In the melt, the dodecane-g-MA/DiOA system experienced a small decrease in the overall reaction rate compared to the same reaction carried out in dodecane. However, the LLDPE-g-MA/DiOA system underwent a 65% decrease in the observed second-order rate constant on going from a solution to the melt. To explain these phenomena, the effects of diffusion, miscibility, and chain entanglements in the melt are examined here. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1573-1582, 1998
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1108-1115 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A lab-scale nonflowing reactor was built to study chemical vapor deposition reactions. Mass spectrometry is used to follow reaction pathways and to determine instantaneous reaction rates throughout film growth. In each experiment, the kinetic rate dependence on concentration for a wide range of concentrations is observed as reactants convert to products. This method of obtaining kinetic data is efficient in terms of sample loading, gas usage, and time, since over 200 instantaneous rate/composition pairs can be determined from one 30-min deposition. Because the rate is determined from gas-mass balance, rather than film-thickness measurements, an unlimited number of rate studies can be made on one sample. As a test case, the SiH4 reduction of WF6, used to deposit tungsten during integrated-circuit production, was investigated in the 0.64-L nonflowing laboratory reactor. Gas compositions were measured 2 mm from the growing surface, throughout time, with a mass spectrometer equipped with a capillary sampling tube. Tungsten was deposited on the 95°C surface, and SiHF3 was the primary silicon fluoride reaction product for most tested conditions. A multiple-regression analysis of 1,975 instantaneous composition/rate pairs gives orders of 1.22 in silane, 0.27 in hydrogen, and -2.17 in WF6. The ratio of SiF4 to SiHF3 stays low and constant until the gas becomes silane-rich. The evolution of the instantaneous rate over time implies that a minimal level of thermal activation of the reactive gases is necessary for the deposition to be surface-rate-limited. Preliminary heat-transfer models of the wire substrate imply that heat transfer to the gas phase is in the Knudsen regime.
    Additional Material: 10 Ill.
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  • 7
    ISSN: 0899-0042
    Keywords: microbial chiral inversion ; 2-phenylpropionic acid ; kinetic isotope effect ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous investigations have described the development of nongrowing suspension of Verticillium lecanii as a microbial model of the mammalian chiral inversion of the 2-arylpropionic acids (2-APAs). Mechanistic studies in mammals have shown that inversion involves loss of the α-methine proton but retention of the original atoms at the β-methyl position, and a mechanism has been proposed involving enzymatic epimerisation of acyl-CoA thioester derivatives of the substrate. Inversion of the 2-APAs by V. lecanii exhibits extensive intersubstrate variation in the presence, rate, extent, and direction of inversion, which are different from those observed in mammalian systems, possibly indicating differences in the mechanism of inversion between mammalian and microbial cells. This study involved the investigation of proton/deuterium exchange by 1H-nuclear magnetic resonance following incubation of deuterated derivatives of 2-phenylpropionic acid (2-PPA), a model compound, in cell suspensions of V. lecanii and incubation of undeuterated 2-PPA in cell suspensions containing D2O. The results indicated that the inversion of 2-PPA by V. lecanii also involved exchange of the α-methine proton but complete retention on the original atoms at the β-methyl position. No kinetic deuterium isotope effect was observed, indicating that loss of the α-methine proton is not the rate-limiting step of the inversion process. This suggests that the observed differences between microbial and mammalian systems probably involve the stereoselective acyl-CoA thioester formation step and not the subsequent epimerisation of the resultant diastereomers. Chirality 9:254-260, 1997. © 1997 Wiley-Liss, Inc.
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  • 8
    ISSN: 0899-0042
    Keywords: stereoselective synthesis ; carboxyibuprofen diastereoisomers ; circular dichroism ; chiral LC separation ; ibuprofen ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic resolution of the four stereoisomers of carboxyibuprofen, a major metabolite of ibuprofen in man, was achieved using a Chiralpak AD chiral stationary phase (CSP) (J.T. Baker, Milton, Keynes, UK). The elution order of the stereoisomers was determined to be 2′S,2R; 2′R,2R; 2′R,2S; 2′S,2S by a combination of stereoselective synthesis of diastereoisomeric mixtures and analysis of the two diastereoisomers isolated from human urine following the administration of (S)-ibuprofen. The individual stereoisomers were isolated by semipreparative chiral phase chromatography and characterized by circular dichroism spectroscopy. Chirality 9:75-87, 1997. © 1997 Wiley-Liss, Inc.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 17 (1971), S. 1006-1008 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: No. Abstract.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 18 (1972), S. 734-738 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bass' feedback controller design technique is extended to distributed parameter systems and its use is illustrated for a parabolic system with boundary control.The development of the design technique rests on a conjecture concerning the necessary and sufficient conditions for the asymptotic stability of linear time invariant partial differential equations. It is shown through a study of the discretized analog of a distributed system that the most likely candidate for a Lyapunov functional general enough to yield the necessary and sufficient conditions for asymptotic stability is a double integral with a symmetric kernel.
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