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  • Chemistry  (23)
  • Inorganic Chemistry
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  • 1993  (23)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 27 (1993), S. X 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Materialwissenschaft und Werkstofftechnik 24 (1993), S. 86-90 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Ziel der Untersuchungen war die Analyse der Schichtwachstumsprozesse bei der plasmaunterstützten CVD-Abscheidung (PACVD) von Titannitridschichten auf Stählen im Niedertemperaturbereich ≤ 500°C.Im Vordergrund standen werkstoffkundliche Untersuchungen der verschiedenen Schichtwachstumsstadien, die sich als Funktion der Beschichtungsdauer ergeben. Die Herstellung der Schichten erfolgte in einer Puls-Plasma-CVD-Anlage. Um den gesamten Wachstumsprozeß vom Beginn der Abscheidung bis zum Wachstum geschlossener Schichten zu untersuchen, wurden die Proben bei konstanten Abscheidungsbedingungen jeweils unterschiedlich lange dem Reaktionsgasfluß ausgesetzt. Der Abbruch des Beschichtungsprozesses für die entsprechende Probe nach einer festgelegten Beschichtungszeit wurde durch die Verwendung eines Probenwechslers gewährleistet.Die Bildung der TiN-Schichten wurde an Proben aus dem Schnellarbeitsstahl S 6-5-2 (DIN 1.3343) im vergüteten Zustand untersucht. Es wurde festgestellt, daß bei diesem Substratwerkstoff zwei Oberflächenqualitäten mit unterschiedlich guten Anlagerungsbedingungen für, während der Vorbehandlung entstehende, adhäsive Verbindungen vorliegen. Die Bildung von Keimen und das Wachstum von Agglomeraten wird wesentlich durch diese Sorptionsschichten beeinflußt. Die Zahl der gebildeten Agglomerate ist bei Proben, die einer Vorbehandlung im Plasma ausgesetzt wurden, um den Faktor 10 größer als bei Proben, die während dieser Vorbehandlung abgedeckt waren. Es wurden neue Modellvorstellungen für die Entstehung und das Wachstum von Schichten entwickelt.
    Additional Material: 15 Ill.
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  • 3
    ISSN: 0935-6304
    Keywords: Coupled LC-GC-MS ; Aqueous sample ; s-Triazine Herbicides ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid chromatographic (LC) type trace enrichment is coupled online with capillary gas chromatography (GC) with mass spectrometric (MS) detection for the analysis of aqueous samples. A volume of 1-10 ml of an aqueous sample is preconcentrated on a trace-enrichment column packed with a polymeric stationary phase. After cleanup with HPLC-grade water the precolumn is dried with nitrogen and subsequently desorbed with ethyl acetate. A fraction of 60 μl is introduced on-line into a diphenyltetramethyldisilazane-deactivated retention gap under partially concurrent solvent evaporation conditions and using an early solvent vapor exit. The analytes are separated and detected by means of GC-MS. The potential of the LC-GC-MS system for monitoring organic pollutants in river and drinking water is studied. Target analysis is carried out with atrazine and simazine as model compounds; the detection limits achieved under full-scan and multiple ion detection conditions are 30 pg and 5 pg, respectively. Identification of unknown compounds (non-target analysis), is demonstrated using a river water sample spiked with 168 pollutants varying in polarity and volatility.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 16 (1993), S. 459-463 
    ISSN: 0935-6304
    Keywords: LC-GC ; Aqueous samples ; Large volume injection ; PTV injector ; Solid-phase extraction ; Thermal desorption ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A system is described that allows the introduction of large volumes of water samples in capillary GC. Water elimination is carried out in the solvent split mode in a PTV injector with a packed liner. Two ways of separating water and analytes, i.e. evaporative and non-evaporative (solid-phase extraction), are compared. Sampling in the solid-phase extraction mode is favorable both in terms of recovery as well as with regard to sampling time. Quantitative recovery is obtained for priority pollutants ranging in volatility from dimethyl-phenol to phenanthrene. Losses occur for more volatile compounds, but even for these compounds the repeatability of the recoveries remains acceptable. With the system described here, water samples up to at least 1 ml of water can be directly analyzed. The detection limits are in the sub-ppb range.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 44 (1993), S. 402-409 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: CORIS™: Corrosion data baseIn this paper the main component of the CORIS system, the corrosion database, is presented. The database contains corrosion facts for metallic materials with respect to all important corrosion parameters. E/R-Models (Entity-Relationship-models) were used for structuring the corrosion knowledge, and the functionality of the system is described in detail from the conceptual and the practical point of view. The system offers the possibility to enter own corrosion data as well as to evaluate stored data. The graphical interactive user interface was designed for simple use.
    Notes: In der vorliegenden Arbeit wird die Kernkomponente des Systems CORIS, die Korrosionsdatenbank, vorgestellt. In ihr sind Korrosionsfakten unter Berücksichtigung aller relevanten Parameter abgelegt. Es wird die dem System zugrunde liegende Korrosionsstruktur mit Hilfe von E/R-Modellen (Entity-Relationship-Modelle) erläutert und ein detaillierter Einblick in die Funktionalität und das Erscheinungsbild gegeben. Das System bietet dem Anwender die Möglichkeit, sowohl eigene Korrosionserfahrungen abzulegen als auch unter Eingabe von Suchbedingungen vorhandenes Wissen zu recherchieren. Die graphisch interaktive Benutzeroberfläche ist auch für ungeübte DV-Nutzer leicht zu bedienen.
    Additional Material: 12 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 206 (1993), S. 97-110 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Ablation von Triazenpolymeren durch Exzimerlaserpulse mit einer Welenlänge von 308 nm wird als Funktion der auf der Oberfläche deponierten Energiedichte untersucht. Um PMMA, welches als Homopolymeres keine Absorption bei 308 nm aufweist, für die Ablation bei dieser Wellenlänge zu sensitivieren, wird ein PMMA-Copolymeres synthetisiert, in welchem ein Anteil von 0.3 mol-% der Seitengruppen die Triazengruppe enthält. An diesem Material beabachtet man Abtragtiefen von bis zu ≈ 30μm pro Puls; das Ablationsverhalten des Copolymeren ist in dieser Hinsicht vergleichbar mit demjenigen von PMMA, welches durch Lösen niedermolekularer Triazenverbindungen physikalisch dotiert wird.Als Alternative zur Copolymerisation werden durch eine Polykondensationsreaktion Triazen-Hauptkettenpolymere mit einer bzw. zwei Triazengruppen pro Wiederholungseinheit synthetisiert (Polymere TP 1 bzw. TP 2). Während die Bestrahlung von TP 1 in unbefriedigenden Ablationsprofilen mit geneigten Kraterwänden resultiert, erhält man bei TP 2 gut definierte kreisförmige Profile mit scharfen Kanten, senkrechten Wänden und ebenen Böden der Ablationskrater. Ein Vergleich des Ablationsverhaltens von TP 2 bei 248 und 308 nm zeigt eine höhere Effizienz der Einstrahlung bei der größeren Wellenlänge: Der Grenzwert der Abtragtiefe pro Plus für hohe Laser-Energiedichten beträgt 1 μm bei 248 nm, im Vergleich zu 3 μm bei 308 nm. Diese Wellenlängenabhängigkeit wird auf dem Mechanismus der Ablation im vorliegenden System zurückgeführt: Der bei der Photolyse der Triazene freigesetzte Stickstoff wirkt als ‘Treibgas’ für die Ablation. Als Konsequenz wird im Bereich der eingesetzten Laser-Energiedichten bereits beim ersten Plus Abtragung von Material beobachtet, d. h. es sind keine Inkubationspulse erforderlich.
    Notes: The excimer laser-induced ablation of triazene polymers at a wavelength of 308 nm has been investigated as a function of laser fluence deposited on the surface in one or several pulses. PMMA, which as a homopolymer can not be ablated at 308 nm, has been sensitized for ablation at this wavelength by synthesizing a copolymer in which 0.3 mol-% of the side chains contain the triazene functional groups. The high ablated depths per pulse achieved in this manner are similar to the ones observed upon physical doping of PMMA with monomeric triazene compounds. In an alternative approach, the triazene functional group is introduced once (polymer TP 1) or twice (TP 2) into each repeating unit of the polymer backbone by a polycondensation reaction. Irradiation of TP 1 gives rise to ill-defined ablation profiles with sloping wall. In contrast, clean circular ablation profiles are obtained with polymer TP 2, which are characterized by circular contours, steep edges, and flat bottoms of the ablated craters. The origins of these differences are investigated. A comparative study of excimer laser ablation of TP 2 at 248 and 308 nm shows that the latter wavelength is more effective; the plateau value of the ablated depth per pulse corresponds to ≈ 1 μm at 248 nm and ≈ 3 μm at 308 nm. This dependence is attributed to the photolysis behaviour of the triazene compounds: nitrogen released upon photolytic bond cleavage acts as a driving gas which promotes the ablation. As a consequence, no ‘incubation pulses’ are required for triazene polymer ablation in the investigated fluence range.
    Additional Material: 8 Ill.
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  • 7
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymere, die bei einer spezifischen Wellenlänge nicht absorbieren, können durch Dotierung mit geringen Konzentrationen geeigneter Verbindungen für die laserinduzierte Oberflächenmodifizierung und -ablation sensitiviert werden. In der vorliegenden Untersuchung fand diese Methode bei der Ablation von PMMA mit XeCl*-Excimerlaserstrahlung von 308 nm Anwendung. Als Ablationspromotoren wurden mehrere substituierte Phenyl- und Diphenyltriazene, zwei Pentazadiene sowie eine Hexazadienverbindung in Konzentrationen von 1, 2 und 5 Gew.-% eingesetzt. Diese Substanzen setzen bei ihrer photochemischen Zersetzung Stickstoff frie. Das Ablationsverhalten des PMMA hängt von dessen Molekulargewicht in der Form ab, daß ein höheres Molekulargewicht zu geringeren Abtragtiefen pro Puls führt. Die mit den verschiedenen Promotoren erreidchten äAtzraten sind mit deren photophysikalischen und photochemischen Eigenschaften in Lösung (z.B. dem Absorptionsquerschnitt und der Quantenausbeute bei der Photolyse) korreliert. Oberhalb einer charakteristischen Mindestkonzentration des Additivs verläuft die Abtragtiefe annähernd umgekehrt proportional zu dessen Konzentration. Im Bereich niedrigen Laserenergieflusses hängt die Abtragtiefe pro Puls logarithmisch vom Energiefluß ab und ist proportional zur Quantenausbeute bei der Photolyse in Lösung. Für die Grenzätzrate bei hohem Energiefluß wurde keine Korrelation zum Absorptionsquerschnitt in Lösung beobachtet.
    Notes: Polymers which are not absorbing at the wavelength of irradiation may be sensitized by doping with low concentrations of suitable compounds for laser-induced surface modification and ablation. In the present study this approach is applied to the ablation of PMMA by 308 nm irradiation (XeCl* excimer laser). Substituted phenyltriazene and diphenyltriazene compounds, two pentazadienes and a hexazadiene are tested as ablation promoters in concentrations of 1, 2, and 5 wt.-%, respectively. From all of these compounds, nitrogen is released upon photochemical decomposition.A significant influence of the PMMA molecular weight on the ablation characteristics is found: higher molecular weights result in lower ablated depths per pulse. The etch rates achieved for the various dopants are correlated with the photophysical and photochemical parameters (i. e., absorption cross section and photolysis quantum yield) in solution. Above a characteristic minimum concentration of the additive, the ablated depth is approximately inversely proportional to the dopant concentration. In the regime of low laser fluence, the ablated depth per pulse scales with the logarithm of fluence, and is proportional to the quantum yield of photolysis in solution. For the limiting etch rate at high fluence, no correlation with the solution absorption cross section was found.
    Additional Material: 14 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 33 (1993), S. 659-664 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen bonding between N-t-butoxycarbonylproline N′-methylamide and phenol derivatives (pKa = 10.20-7.75) are investigated by ir and Fourier transform ir spectrometry. The thermodynamic parameters determined in carbon tetrachloride solution show that the complexes are of medium strength, the stability constants at 298 K range from 80 to 1530 L mol-1, and the enthalpies of complex formation range from - 30 to -34 kJ mol-1. The study of the ir spectra in the νOH, νNH, and νc=o regions shows that complex formation occurs at the oxygen atom of the amide carbonyl. Hydrogen-bond formation at this site strengthens the intramolecular hydrogen bond of the seven-membered ring. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 9
    ISSN: 1040-7685
    Keywords: solid phase extraction ; thermal desorption ; on-line ; aqueous samples ; gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A module for combined solid-phase extraction and thermal desorption (SPETD) was incorporated into a system for automated GC analysis. Solid-phase extraction of analytes from water could be carried out after injection of an aqueous sample of 100 μL either by a loop using the carrier gas for sample introduction or manually with a syringe. After drying of the stationary phase by the carrier gas at a high flow rate, thermal desorption could be carried out at temperatures up to 300-350°C. Suitable packing materials for the liner in the SPETD module, i.e., materials which efficiently trap the organic compounds from an aqueous solution and are sufficiently thermostable, include Tenax and carbon-based phases, as well as a silylated alkylmodified silica. With the latter, however, the problem of efficient drying after sorption still must be solved. Each phase has its own application range which, from among the analytes which are trapped during sorption, is determined at the volatile end by losses occurring during drying by helium purging, and at the nonvolatile end by losses due to incomplete release during thermal desorption. From this study (using n-alkanes, chlorobenzenes, and chlorophenols as test solutes), it appears that the Tenax phases, Tenax-TA and Tenax-GR, have the widest application range; essentially quantitative recoveries were obtained for C10 through C26 n-alkanes. The carbon-based phases appear to be useful for relatively volatile compounds, i.e., up to C19 n-alkanes. Each phase gave good recoveries for two test mixtures containing chlorobenzenes and chlorophenols dissolved in 100 μL of water at the 10 ppb level.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid chromatography/thermospray mass spectrometry (LC/TSP MS) has been used for the determination of vitamin D3 and some of its metabolites, i.e. 1α(OH) vitamin D3, 25(OH) vitamin D3, 1α,25(OH)2 vitamin D3 and 24,25(OH)2 vitamin D3, using positive and negative ion detection. Using these two modes positional isomers can be identified. Detection in the negative ion mode was preferred because of the slightly higher sensitivity. The limits of detection, using multiple ion detection, are 50-100 nM (6-12 pmol injected). On-line post-column derivatization based on [4 + 2] cyclo-addition (Diels-Alder reaction) proceeds within 1 min at room temperature. If this step is included in LC/TSP MS, the detection limits of the analytes can be improved 7-70-fold depending on the analyte tested. The best results (detection limits down to 1 nM, i.e. 0.12 pmol injected) are obtained with discharge ionization in the negative ion mode.
    Additional Material: 8 Ill.
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