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  • 1
    ISSN: 0935-9648
    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
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Clinical studies were conducted by gas chromatography mass spectrometry selected ion monitoring of urinary dicarboxylic acids as dicyclohexyl esters. The dicyclohexyl esters of the dicarboxylic acids give characteristic electron impact mass spectra suitable for selected ion monitoring. The mass spectra exhibit a prominent acid + 1H ion and an (acid + 1H)- H2O ion for use as quantitating and confirming ions. The cyclohexyl esters are stable for days at room temperature and have excellent chromatographic properties. Dicarboxylic acid quantitation is performed within one hour using only 50 μl of unpurified urine. A rapid method specifically for methylmalonic acid quantitation is described which has assisted physicians in the diagnosis of pernicious anemia and methylmalonic aciduria. This procedure is applicable for screening urinary organic acids for detection of inborn errors of metabolism. The detection of a child with elevated medium length dicarboxylic acids in the terminal urine specimen is reported. This condition, previously described as an inborn error, is attributed to a terminal event. Finally, an increase in urinary succinic acid paralleling putrescine levels is described during a response to cancer chemotherapy.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 42 (1991), S. 75-83 
    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: Polyimide (PI) is an insulating polymer that is finding increased use in the semiconductor industry as an intermetal dielectric, passivation coating, and planarization layer. It has a low dielectric constant (3.5 at audio frequencies) and can be processed at temperatures below 450°C. These features make PI attractive to the integrated circuit industry. One disadvantage of this material is that, like most polymers, it is hygroscopic. Moisture can lead to such reliability problems in integrated circuits as increased insulator conductivity, loss of adhesion, and corrosion. It is important to quantify the moisture uptake in polyimide so that the reliability implications of its use can be fully understood. In this study, the steady-state moisture uptake of the model PI pyromellitic dianhydride-oxydianiline (PMDA-ODA) is reported. The moisture uptake is measured using a Cahn 1000 Microbalance with a 1-μg resolution. The samples are prepared by spin-coating one or more layers of the precursor polyamic acid onto 2-in silicon substrates. The moisture uptake in these polymers is found to be linearly related to ambient relative humidity, and the maximum moisture uptake by weight is 3.2%. The moisture uptake in PI is also shown to be a bulk absorption rather than a surface adsorption phenomenon.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 46 (1992), S. 271-280 
    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: We are investigating the bulk and interfacial chemistry of polyimide (PI) exposed to heat and relative humidity (RH) stress (85°C/85% RH) over long periods to understand the long-term reliability aspects of PI for microelectronic applications. The PI surface chemistry and the PI-Si interface chemistry was followed with electron spectroscopy for chemical analysis (ESCA). For exposure times greater than 550 h, the PI surface exhibits significant changes in emission structure and atomic concentration. The PI-Si interface indicates little change in the PI chemistry when compared to control samples. The water-contact angle at the PI surface shows no statistically significant change as a function of exposure time. Bulk and surface chemistry were followed with Fourier transform infrared spectroscopy (FTIR) in a grazing incidence reflection configuration. There were measurable differences in FTIR spectra between aged and control samples only for the case of very thin PI layers. These results suggest that for exposure times of less than 1100 h, chemical changes in PI occur primarily at the PI-air interface for samples 1 μm thick and greater. These changes represent a possible rearrangement of the imide structure and may be a form of deimidization of the polymer, but the final state is not polyamic acid. The PI surface chemistry changes observed with ESCA are reversible upon reheating to the cure temperature.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2223-2231 
    ISSN: 0887-624X
    Keywords: poly(arylene vinylene) ; poly(1,4-phenylene vinylene) ; poly(para-phenylene vinylene) ; para-xylylene ; 1,4-benzoquinodimethane ; radical polymerization ; conducting polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular weights were studied by gel permeation chromatography of derivatized poly(α-tetrahydrothiophenio para-xylylene) chloride produced by aqueous or methanolic base-induced polymerization of 1,4-bis(tetrahydrothiopheniomethyl) benzene dichloride, both with and without a variety of added polymerization inhibiting agents. Efficient radical scavenging agents such as 2,2,6,6-tetramethylpiperidinoxyl and hydrogen atom donor 2,4,6-tri-tert-butylaniline reduced the degree of polymerization of the reactive α-(tetrahydrothiophenium chloride)-para-xylylene intermediate produced in this chemistry, and in some cases completely suppressed formation of high polymer. These two traps did not affect the equilibrium production of the para-xylylene by UV-Vis spectral analysis; hence they must affect the subsequent polymerization chain propagation steps in the mechanism. Electron spin resonance studies of polymerization in the presence of 0.00025 equiv of TEMPO showed disappearance of the spin label, a result consistent with a radical scavenging process. The results suggest that production of high molecular weight poly(α-tetrahydrothiophenio para-xylylene) chloride proceeds through a radical chain propagation sequence. © 1992 John Wiley & Sons, Inc.
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  • 6
    ISSN: 0887-624X
    Keywords: para-xylylenes ; 1,4-benzoquinodimethanes ; conducting polymers ; poly(arylene vinylene)s ; poly(phenylene vinylene)s ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: para-Xylylenes are generated by treatment of various 1,4-bis(dialkylsulfoniomethyl)arene dihalides with base in water, methanol, and aqueous acetonitrile, as shown by UV-Vis spectroscopy. This procedure allows the monitoring of the transient xylylene monomers that yield polyelectrolyte precursor polymers for poly(arylene vinylene)s, formed by variations of the chemistry developed originally by Wessling and co-workers. Alkoxy, alkyl, and halogen ring substituents on the sulfonium salt precursors do not greatly affect the ability to generate and observe the growth and decay of steady-state concentrations of the para-xylylene intermediates. Use of strong resonance-acceptor substituents - such as cyano or nitro - on the ring reduces production of a strong para-xylylene absorption, possibly due to reluctance of the ylides initially formed from the bis-sulfonium salts to eliminate to the xylylenes. By variation of UV-Vis conditions, it was found that use of 20% aqueous acetonitrile rather than water allowed formation of low to modest molecular weight polyelectrolytes in cyano-substituted cases (Mw = 8000-37,000). Use of UV-Vis test experiments should be useful for screening of bis sulfonium salt precursors that may be expected to give high molecular weight polyelectrolytes - in cases where para-xylylene formation is easy - as well as for finding reaction conditions that will optimize polymer formation. © 1992 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 587-602 
    ISSN: 0887-624X
    Keywords: plasma polymerization ; methyl methacrylate ; in situ FTIR/ATR diagnostic ; in situ FTIR plasma diagnostic ; analysis of variance ; regression analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate (MMA) plasmas and plasma-polymerized methyl methacrylate (PPMMA) films were studied in situ with FTIR and FTIR/ATR (attenuated total reflection) in an r.f. capacitively coupled glow discharge. A statistically designed experiment was conducted by varying the r.f. power, process pressure, and MMA flow rate. MMA plasma fragments were identified from the gas-phase FTIR measurements. They include the intermediate species such as dimethylketene, formaldehyde, allene, and propene; small hydrocarbons such as acetylene, methane, and ethylene; and oxygenates such as carbon dioxide, carbon monoxide, and methanol. Statistical analysis techniques (correlation analysis, analysis of variance and regression analysis) were used on both gas and film data. Gas-phase reaction mechanisms are proposed, and the relationship between the gas and film data is investigated to understand the film deposition chemistry. The deposition rate is positively correlated to the relative concentrations of MMA fragments which are identified as the major film precursors in the deposition process. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 587-602, 1998
    Additional Material: 11 Ill.
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  • 8
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-soluble, random copolymers containing L-glutamine and either N5-(3-hydroxypropyl)-L-glutamine or N5-(4-hydroxybutyl)-L-glutamine were synthesized, fractionated, and characterized. The thermally induced helix-coil transitions of these copolymers were studied in water. A short-range interaction theory was used to deduce the Zimm-Bragg parameters σ and s for the helix-coil transition in poly(L-glutamine) in water from an analysis of the melting curves of the copolymers in the manner described in earlier papers. The computed values of s indicate that L-glutamine is helix-indifferent at low temperature and a helix-destabilizing residue at high temperature in water. At all temperatures in the range of 0-70°C, the glutamine residue promotes helix-coil boundaries since the computed value of σ is large.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 57 (1995), S. 939-951 
    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 interactive computer simulation of the steady-state melt spinning of poly(ethylene terephthalate) was developed based upon a combination of physical laws and empirical relationships. The simulation incorporates crystallization effects which makes it valid for a wide range of take-up speeds. Modifications to the conventional threadline that allow judicious control over the threadline dynamics were modeled and included in the simulation for exploration of the effects of these perturbations. The modifications include quenching and on-line zone heating. The simulation was verified using experimental measurements of threadline diameter, velocity, and temperature at 3000, 4000, 5000, and 6000 m/min take-up. Off-line measurements of crystallinity and birefringence were also compared with the values calculated by the simulation at these speeds. © 1995 John Wiley & Sons, Inc.
    Additional Material: 20 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 30 (1990), S. 193-196 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: The effect of solvent evaporation on spun-on polymer thickness is investigated. Film thickness is shown to be proportional to spin speed raised to the negative of a constant, b. This constant is specifically considered. Of particular interest is the short initial period during spin coating signified by a rapid increase in solution viscosity, but where solvent diffusion in solution is not yet significant. Many previous theories have suggested the existence of a single value for b dependent only upon environment and spin coating system. Here, a single polymer dissolved in five pure solvents is examined. The polymer is Thermid IP-600 (National Starch and Chemical Co.), an isoimide precursor. The solvents considered are n-methyl-2-pyrrolidinone, dimethyl sulfoxide, dimethyl formamide, ethylene glycol dimethyl ether, and 2-methoxyethyl ether. Spin Speed ranges from 0.6 to 7.0 kRPM and spin time is held at 15 s. It is shown that b varies from 0.97 for n-methyl-2-pyrrolidinone to 0.57 for 2-tncthoxycthyl ether. An empirical relation describing the behavior of b for this particular polymer and spin conditions used is b = [(MW)s(Pvap)s]/[(MW)n(Pvap)n]-0.1, where (MW)s and (MW)n are the molecular weights of the solvent and of n-butyl acetate, respectively and where (PVaP)s and (Pvap)n are the vapor pressure of the pure solvent and the vapor pressure of n-butyl acetate, respectively.
    Additional Material: 2 Ill.
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