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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 5246-5253 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 12296-12301 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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: Additionspolymere aus Bisphenol-A und Epichlorhydrin lassen sich mit Arylacryloylchloriden verestern. Die gebildeten Photoresists können mit UV-Licht (λ ≥ 280 nm) gehärtet werden. Aus FT-IR Messungen ergibt sich, daß die Netzwerkbildungsreaktion einem Zeitgesetz zweiter Ordnung gehorcht. DSC- und TGA-Messungen wurden durchgeführt. Die photovernetzten Polymeren weisen Glastemperaturen bis zu 171 °C auf und sind bis mindestens 350 °C thermisch stabil. Spektroskopische Daten werden aufgeführt.
    Notes: Addition polymers of bisphenol-A and epichlorohydrin can easily be esterified with aryl acryloyl chlorides to yield photosensitive polymers. The photoresists are curable with UV-irradiation (λ ≥ 280 nm). FT-IR measurements indicate that the network formation fonforms to second order kinetics. DSC and TGA measurements were carried out. The glass transition temperature of irradiated material is up to 171oC; the material is thermally stable up to 350oC. Spectral data are given.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Hyperfine interactions 80 (1993), S. 1121-1126 
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We determined the199mHg nuclear quadrupole interaction (NQI) by time differential perturbed angular correlation in the following ferrocenethiol complexes with mercury: ferrocenethiol (v Q =1253(4) MHz, η=0); 1,1′-ferrocenedithiol (47%v Q =1555(8) MHz, η=0.13(2); 25%v Q =726(19) MHz, η=0.81(2); rest unspecific); 2-ferrocenyl-ethanethiol (v Q =1306(6) MHz, η=0.17(1)); and a 1, 1′-bis (2-mercapto-propylthio)ferrocene oligomer (v Q =1411(5), η=0). All NQIs are rather large with small asymmetry parameters, indicating essentially linear S-Hg-S bonds. The only exception is the minority fraction in 1,2′-ferrocenedithiol which suggests the formation of a 1,3-dithia-2-mercura[3]ferrocenophane.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1572-9540
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Mössbauer absorption spectra of glassy block and copolymers with lowT G containing ferrocene have been recorded in a wide temperature range (4–330 K) to investigate the dynamical processes of the system, in the glassy state and around the glass transition. An inhomogeneous broadening due to conformational substates with different hyperfine parameters found at lower temperatures becomes motionally narrowed above 40 K. Whereas in the glassy state both the block and the copolymers reveal the same vibrational behaviour, we found differences in the vicinity of their respective glass transitions. For the block polymer an anomalous decrease of the recoilfree fractionf A was found above the static glass transition. In agreement with neutron data on other polymers we attribute this behaviour to an onset of motions of the ferrocene units of higher than 1010 Hz. For the copolymers, however, a departure of lnf A from linearity was detected already far below the staticT G. We propose that this is caused by residual solvents which allow an easier cooperative rearrangement of the segments even belowT G. First attempts to interpret the Mössbauer data by means of the predictions of the mode coupling theory are reported.
    Type of Medium: Electronic Resource
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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.
    Type of Medium: Electronic Resource
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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.
    Type of Medium: Electronic Resource
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  • 8
    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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