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  • 1
    Electronic Resource
    Electronic Resource
    Abfangreaktionen kurzlebiger Radikale, XI. Über die radikalische Substitution am Stickstoff: Der induzierte Zerfall von 2-Tetrazenen (1973)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 2395-2407 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Short-Life Radicals, XI. Free Radical Substitution at the Nitrogen Atom: The Induced Degradation of 2-TetrazenesThe radical degradation of tetraphenyl-2-tetrazene (1a) and 1,4-dicyclohexyl-1,4-diphenyl-2-tetrazene (1b) is found to be accelerated by trialkyltin hydride. Stannyl radicals attack at N-1 or N-4. In a SH2α reaction, N2, the corresponding stannylamine and a radical ·N(R)R′ are formed. The latter is scavenged by R3SnH giving the amine; or it recombines with a stannyl radical at low hydride concentrations. Dicarbizolyldiazene 1c reacts by the same way, but not so the dipiperidinodiazene (1d). Importance of stabilization of ground and transition states on the spontaneous and the induced degradation are discussed. Values of t1/2, k, ΔH±, and ΔS± are given. Stannyl radicals also accelerate the splitting of tetraphenylhydrazine.
    Notes: Der radikalische Zerfall von Tetraphenyl-2-tetrazen (1a) und 1,4-Dicyclohexyl-1,4-diphenyl-2-tetrazen (1b) wird durch Trialkylzinnhydrid beschleunigt. Beim Angriff von Stannyl-Radikalen an N-1 oder N-4 entstehen in einer SH2α-Reaktion N2, Stannylamin und ein Radikal ·N(R)R′, das durch R3SnH zum Amin abgefangen wird oder mit einem Stannyl-Radikal bei niedriger Hydrid-Konzentration rekombiniert. Auch Dicarbazolyldiazen 1c reagiert analog, nicht jedoch Dipiperidinodiazen (1d). Einflüsse der Stabilisierung von Grund- und Übergangszustand auf den Spontan- wie den induzierten Zerfall werden diskutiert, Werte für t1/2, k, ΔH* und ΔS* angegeben. Auch Tetraphenylhydrazin wird durch Stannyl-Radikale beschleunigt gespalten.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19731060737
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  • 2
    Electronic Resource
    Electronic Resource
    Abfangreaktionen kurzlebiger Radikale, VIII. Über die radikalische Substitution am Stickstoff: Reaktionen von 1-Aryl-triazenen mit Organozinn-hydriden (1972)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 105 (1972), S. 1540-1552 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Short-Life Radicals, VIII. Radical Substitution at the Nitrogen Atom: Reactions of 1-Aryltriazenes with Organotin HydridesStannyl radicals react with 1-aryltriazenes 1-12, attacking N3 and forming stannyl amines. The reaction proceeds by an SH2α mechanism; the arylazo group is displaced (“induced degradation”) and splits off N2. This is the only reaction in cases 1-5. With 6-12, however, an SH2γ displacement predominates. Here, substituents bound to N3 are able to form fairly well stabilized radicals. Stannyl radicals attack N1, displace the substituent from N3 and form trialkylstannyl triazenes 10-12, 15, 20, which are surprisingly stable because of pentacoordination at the tin atom. The free-radical fragments abstract hydrogen from the tin hydride, releasing new stannyl radicals, which propagate the chain reaction. Hydrostannation of the azo group has not been observed. It is shown that stannyl radicals are capable of reversible addition across the azo double bond.
    Notes: Stannylradikale R3Sn⋅ können 1-Aryl-triazene 1-12 and N3 unter Bildung von Stannylaminen angreifen. Dabei wird in einer SH2α-Reaktion die Arylazogruppe verdrängt (“induzierter Zerfall”) und spaltet N2 ab. Dies tritt bei 1-5 ausschließlich ein. Bei 6-12, die an N3 einen als Radikal stabilisierten Substituenten tragen, überwiegt jedoch eine SH2γ-Reaktion. Der Angriff eines Stannylradikals an N1 verdrängt dabei den Substituenten von N3. Es entstehen Trialkylstannyl-triazene 10-12, 15 und 20, durch Pentakoordination am Zinnatom überraschend stabil. H-Abstraktion aus dem Organozinnhydrid stabilisiert die abgespaltenen Molekülfragmente. Die hinterbleibenden Stannylradikale setzen die Reaktionskette fort. Hydrostannierung der Azodoppelbindung wird nicht beobachtet. Es wird gezeigt, daß sich Stannylradikale reversibel an die Azodoppelbindung addieren können.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19721050510
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  • 3
    Electronic Resource
    Electronic Resource
    Chemical derivatization as a mean to improve contact angle goniometry of chemically heterogenous surfaces (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 699-709 
    Details
    ISSN: 0887-624X
    Keywords: contact angle goniometry ; chemical derivatization ; plasma treatment ; polyethylene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plasma-oxidized polyethylene (O-PE) was derivatized with various chemicals and the advancing and receding contact angles with water, formamide, and tricresylphosphate were measured. The contact angles were used to evaluate the surface free energy (SFE) components in terms of the Lifshitz-van der Waals-acid base (LW-AB) model. The derivatization was directed to couple alkyl chains to carbonyl, hydroxyl, and carboxyl groups generated on the surface of O-PE. Carbonyl groups were treated with hydrazine and then reacted with dodecanoyl chloride. Hydroxyl groups were first reacted with reactive dicarboxylic acid dichlorides or cyanuric chloride, respectively, and then with alkylamines because the direct bonding of long-chain alkyl carboxylic acid chlorides proceeds slowly and is, therefore, completed by surface restructuring. Carboxyl groups were chlorinated and in a second step reacted with alkylamines. The bonding of C12-alkyl chains can be sensitively detected by the LW part of the SFE. Concerning the receding contact angles, it is pointed out that the carbonyl groups are present on the surface in a higher concentration than hydroxyl and carboxyl groups. The combination of contact angle goniometry (CAG) and chemical derivatization reactions supplies semiquantitative information about functional groups in the uppermost surface layer. In this way, a major shortcoming of CAG can be overcome. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080320408
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  • 4
    Electronic Resource
    Electronic Resource
    Vacuum-ultraviolet induced oxidation of the polymers polyethylene and polypropylene (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2013-2025 
    Details
    ISSN: 0887-624X
    Keywords: vacuum ultraviolet oxidation ; polyethylene ; polypropylene ; plasma-polymer interaction ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emission from low-pressure microwave plasmas in the vacuum-ultraviolet (VUV) region (λ 〈 200 nm) was investigated in order to use these plasmas as light sources for the study of the VUV photochemistry of polyethylene (PE) and polypropylene (PP) as part of the study of plasma-polymer interaction. These polymers, immersed in low-presure oxygen, were exposed to radiation with wavelengths down to 112 nm, the cut off of magnesium fluoride used as a window to separate the polymer specimen from the plasma light source. Total oxygen incorporation in the surface [O], and the formation of hydroxyl, carbonyl, and carboxyl groups were measured using XPS in combination with chemical derivatizations, particularly their dependence upon the radiation spectrum and the oxygen pressure around the sample. In most experiments the surface oxygen concentration [O] attained a constant value that appears to be related to the initial oxidation rate; this suggests a competition between oxygen incorporation and chain scission reactions, followed by the removal of volatile oxidation products. PE is usually oxidized to a higher level than PP, the latter appearing to be more susceptible to reaction with atomic oxygen than PE. A general initiation mechanism for the VUV experiments is proposed that allows us to explain the observed differences in behavior between PE and PP, and the results obtained under different irradiation conditions. The nature of oxidation products is in both cases very similar to what is observed after direct plasma treatment of the polymers. We conclude that short wavelength radiation contributes very appreciably to the observed surface modification effects during plasma treatment of PE and PP. © 1995 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1995.080331208
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  • 5
    Electronic Resource
    Electronic Resource
    The influence of vacuum-ultraviolet radiation on poly(ethylene terephthalate) (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1511-1516 
    Details
    ISSN: 0887-624X
    Keywords: poly(ethylene terephthalate) ; surface treatment ; VUV photochemistry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) was exposed to radiation from different kinds of low-pressure plasmas in an oxygen atmosphere. The lower wavelength limit of the spectrum investigated, λ = 112 nm, is the cut-off of magnesium fluoride used for separating the specimen chamber from the plasma light source. The total surface oxygen concentration, and the formation of hydroxyl, carbonyl, and carboxyl groups were evaluated from XPS measurements in combination with chemical derivatizations, and their dependences on the radiation spectrum and the oxygen pressure in the sample chamber have been investigated. © 1996 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    A Sampler for Total Suspended Particulates with Size Resolution and high sampling efficiency for large particles (1989)
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 6 (1989), S. 74-80 
    Details
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For a field intercomparison of various widely used dust samplers, a reference instrument was needed. Based on a Wide Range Aerosol Classifier (WRAC), several improvements were introduced compared with the original design including mass flow control of the samplers and the plenum air, brushless threephase blowers, hyperbolic inlets and generally a more compact design, allowing for more comfortable operation. In addition, for measurement of small particle size distributions, a Hauke high-volume, low-pressure impactor (LPI 150/0.15) was included, so that size distribution information with cuts at 0.12, 0.30, 1.19, 3.14, 10.2, 20.4, 37.4 and 60 μm could be obtained. In addition, the aspiration efficiency was measured under in situconditions and parallel measurements were performed with the two reference samplers built so that the performance was well characterized.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ppsc.19890060112
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  • 7
    Electronic Resource
    Electronic Resource
    Measurement of the Influence of Directed Particle motion on the turbulent particle deposition velocity by means of laser-doppler anemometryDedicated to Professor Kurt Leschonski on the occasion of his 60th birthday (1991)
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 12-15 
    Details
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dry deposition of particles from the atmosphere is not well understood for reasons of surface variabilities and mutual interactions between surface and particles. However, even relatively simple influences of physical parameters have so far resisted successful parameterization, although some progress has been achieved. There is no general way to determine the relative contributions of stochastic turbulent and Brownian diffusion and directed motions (i. e. sedimentation) to the total deposition velocity since they contribute in a nonlinear manner to the total deposition velocity. The directed motion is an unknown function of atmospheric turbulence, the particle diffusion coefficient Dp and the sum of all directed particle motions by thermophoresis, diffusiophoresis, photophoresis, electrophoresis, sedimentation etc. Practically nothing is known about the action of the first three forces and even the easily accessible electrophoresis has not been considered relevant for deposition of atmospheric particles. Because it is relatively easy to change an electric field with all other parameters kept constant and measure the absolute difference in total deposition velocity the following experimental Laser-Doppler study was intended to show the feasibility of the field-changing-technique and the magnitude of the effects without quantitatively determining the electrical mobility distribution as a function of particle size.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ppsc.19910080104
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  • 8
    Electronic Resource
    Electronic Resource
    Untersuchung zur phasengrenzseitigen Hemmung der Wasserstoffeffusion bei wasserstoffbeladenen Vergütungsstählen (1993)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 44 (1993), S. 342-344 
    Details
    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: Investigation into the effusion behaviour of hydrogen in quenched and tempered steelsThe effusion behaviour of hydrogen in quenched and tempered steel was investigated by means of the ultrasonic damping technique (USDT). The material 34CrMo4 was used in three tempering conditions (I: 850 N/mm2, II: 1000 N/mm2 and III: 1200 N/mm2). The influence of effusion behaviour of different media (imidazole, imidazolidine and EDTA) in dependence of the exposure time was determined. Additionally volumetric permeation experiments and the determination of the hydrogen embrittlement-index (VH) were performed.The results revealed, that the USDT basically is suitable for the quantitative, non destructive measurement of hydrogen in quenched and tempered steel.The investigations showed a significant influence of different parameters on the reproducibility of the results. Especially the influence of media, the microstructure and the coupling of the testing button on the material surface are important for the reliability of the results by using the USDT under practical conditions.
    Notes: Mit Hilfe der Ultraschalldämpfungsmessung (USD) als zerstörungsfreies Prüfverfahren wurde der Einfluß des Auslagerungsmediums auf das Effusionsverhalten des Wasserstoffs in Stahlproben untersucht. Die Auslagerungsmedien waren Imidazol, Imidazolidin, EDTA und Wasser. Die Proben aus dem Vergütungsstahl 34CrMo4 lagen in den drei Vergütungsstufen I (RmI: 850 N/mm2), II (RmII: 1000 N/mm2) und III (RmIII: 1200 N/mm2) vor. Zur Überprüfung der Ergebnisse aus der USD wurden der Wasserstoffversprödungsindex VH ermittelt und volumetrische Permeationsversuche durchgeführt.Die Untersuchungsergebnisse lassen darauf schließen, daß die USD prinzipiell zur quantitativen Erfassung von Wasserstoff geeignet ist.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19930440804
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  • 9
    Electronic Resource
    Electronic Resource
    Radikalische 1,3-Wanderung von Arylazogruppen  -  CIDNP-Effekt bei p-Tolylprotonen (1970)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 82 (1970), S. 813-814 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19700821913
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  • 10
    Electronic Resource
    Electronic Resource
    N-Silyl-1,4-dihydropyridyle, eine neue Klasse stabiler Radikale (1972)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 84 (1972), S. 894-895 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19720841812
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