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  • 1
    ISSN: 1432-0630
    Keywords: 42.65 ; 78.65
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The second-harmonic generation (SHG) in a layered system consisting of Ag-islands/SiO x spacer/Ag is investigated. The efficiency of this process depends strongly on the mass thickness d of the dielectric SiO x . An enhancement by a factor of 80 of the second harmonic (SH) of this system in comparison to the SH signal of an Ag-island film for p-polarized excitation and 50° angle of incidence was observed for a specific separation distance of 40 nm. We interpret this increase of the SH as being due to the strongly increased absorption at the fundamental frequency, caused by the excitation of localized surface plasmons and thin-film resonances in this layer structure. The theoretical description of the enhancement factor is in good agreement with the experimental results using stratified medium theory for modelling the thin-film system.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 50 (1993), S. 187-200 
    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: Air plasma treatment has been used to introduce polar functional groups onto polypropylene surfaces to enhance the adhesion of coatings and paints. Plasma exposure times as well as the reaction medium (ambient, technical, and moistured technical air) have been varied. Time-dependent changes subsequent to the plasma treatment are monitored by contact-angle measurements. After short plasma exposures, the polar component of the surface energy is observed to decrease, to reach a minimum after ≈ 40 min. This behavior is interpreted in terms of a rotation of the introduced surface hydroperoxide groups into the interior of the polymer. This undesired loss in surface functionalization can be avoided by (a) increasing the treatment time in dry air, (b) use of moistured air as the reaction medium, or (c) posttreatment of the plasma-treated parts by water immersion. A plasma exposure of 120 s in dry air, followed by posttreatment in an aqueous medium at room temperature for 2-5 min, results in reproducible values of the surface energy σ, with polarities (σpolar/σtotal) close to the desired value of ≈ 50%. © 1993 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 3
    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.
    Type of Medium: Electronic Resource
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  • 4
    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.
    Type of Medium: Electronic Resource
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  • 5
    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: Polydiaryldiazosulfide wurden durch Grenzflächenpolykondensation aus aromatischen Bisdiazoniumionen und Benzol-1,3-dithiol erhalten. Auf diese Weise wurden Molekulargewichte Mn von 3400 bis 11700 erreicht (GPC).Die neue Polymerklasse zeichnet sich durch hohe Photolabilität und relativ geringe Thermostabilität aus. Mittels UV-Spektroskopie wurde die Photolyse von Modellver-bindungen und Polymeren verfolgt, wobei in nahezu allen Fällen ein Zerfall 1. Ordnung beobachtet wurde. Der photochemische Kettenabbau konnte durch GPC-Untersuchungen verfolgt werden. Die thermische Stabilität der polymeren Diazosulfide wurde durch DSC-Messungen untersucht.
    Notes: Poly(diaryl diazosulfide)s were synthesized from aromatic bisdiazonium ions and benzene-1,3-dithiol via interfacial polycondensation. Number-average molecular weights Mn in the range of 3400 to 11700 were determined by gel permeation chromatography (GPC).The new polymer class is distinguished by high photosensitivity and low thermostability. First order kinetics during photolysis of nearly all polymers and model compounds under investigation was observed by means of UV spectroscopy. Polymer degradation upon irradiation was verified by GPC measurements. Thermal decay was followed by differential scanning calorimetry (DSC).
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 30 (1992), S. 1178-1185 
    ISSN: 0749-1581
    Keywords: 1-Aryl-3,3-dialkyltriazenes ; 1H NMR ; Hindered rotation ; Thermal decomposition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Aryl-3,3-dialkyltriazenes have been synthesized by coupling the corresponding diazonium salts of substituted aniline derivatives with dialkylamines. The thermostability of these compounds was investigated by differential scanning calorimetry; activation energies of 240-280 kJ mol-1 were determined for the thermal decomposition. The hindered rotation of the dialkylamino group was studied by 1H NMR exchange measurements. Both experiments are interpreted in terms of an involvement of a 1,3-dipolar structure of the —N=N—N— functional group. The influence of substituents, both on the aromatic ring and at the amino group, on the kinetic and activation parameters is investigated; results are analysed on the basis of mesomeric and steric effects on the dipolar charge distribution in the molecule.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 435-441 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The groove binding dye Hoechst 33258 was investigated both in aqueous solution and in the adsorbed form on silver colloids and island films. Fourier transform Raman, resonance Raman and surface enhanced resonance Raman spectra were used together with the results of a normal coordinate analysis for a comprehensive assignment of the rich vibrational spectrum. Relative band intensities in the SERRS spectra indicate that the molecule is adsorbed with its long axis oriented along the silver surface and with the planes of the benzimidazole rings approximately parallel to the surface. The molecule is bound to the surface as a cation protonated at a piperazine nitrogen atom and is desorbed on complete deprotonation.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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