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  • 1
    Digitale Medien
    Digitale Medien
    Amsterdam : Elsevier
    International Journal of Radiation Applications & Instrumentation. Part C, 29 (1987), S. 65-69 
    ISSN: 1359-0197
    Quelle: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Thema: Chemie und Pharmazie , Energietechnik , Physik
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Amsterdam : Elsevier
    Radiation Physics and Chemistry 44 (1994), S. 557-565 
    ISSN: 0969-806X
    Quelle: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Thema: Chemie und Pharmazie , Energietechnik , Physik
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    ISSN: 1013-9826
    Quelle: Scientific.Net: Materials Science & Technology / Trans Tech Publications Archiv 1984-2008
    Thema: Maschinenbau
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials science 34 (1999), S. 379-384 
    ISSN: 1573-4803
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Thermally stabilised, unpigmented, rigid PVC samples, were exposed to accelerated photoageing at 40°C, 55°C and 70°C. The concentration profiles of photoproducts were determined on microtome slices (∼ 20 μm) parallel to the irradiated surface using IR (carbonyls) and UV (polyenic double bonds) spectrophotometry and by steric exclusion chromatography (Mn and Mw). They indicate that carbonyls and chain scissions predominate only in a thin superficial layer whereas polyconjugated double bonds and crosslinks predominate in a subcutaneous layer (∼300–400 μm). Tensile measurements show that the ultimate elongation decreases after an induction period whose duration is a decreasing function of temperature. The change of mechanical behaviour can be described in terms of a ductile-brittle transition shift mechanism in which crosslinking plays an important role. A tentative explanation of a such crosslinking induced transition is proposed in the discussion.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Journal of materials science 29 (1994), S. 569-583 
    ISSN: 1573-4803
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract For an ageing process involving the consumption of a small molecule (typically O2 or H2O) by reaction with the polymer, there are critical conditions of reaction rate and/or thickness above which the process becomes kinetically controlled by the diffusion of the small molecule in the polymer. Suitable lifetime prediction models must then involve the thickness distribution of reaction products. This latter can be predicted from Fick's law, modified by a term relative to the rate of consumption of the diffusing species by the chemical reaction. Some problems related to the use of this approach are examined here. It appears that, in the most frequent case, the thickness of the degraded layer is of the order of magnitude of D/k, where D is the diffusion coefficient and k the pseudo-first-order rate constant for reactant consumption. Some examples of application related to photochemical, radiochemical and thermochemical ageing are examined. It can, for instance, be shown that in photochemical or radiochemical ageing, the thickness of the oxidized layer (TOL) is proportional to the reciprocal of l β, where l is the radiation intensity and Β an exponent depending essentially on the radical chain mechanism. It is generally expected that in the case of thermal ageing, the TOL is a decreasing function of the temperature. Some consequences of diffusion control on accelerated and natural ageing methods are briefly examined. The consequences of the ageing-induced “skin-core” structure due to the diffusion control are examined. The main features of the observed polymer embrittlement can be explained in terms of fracture mechanics.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 47-64 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Die thermische Alterung von extrudierten Proben von mit Elektronenstrahlen vernetztem linearem Polyethylen wurde im Temperaturbereich von 110-170°C untersucht. Kurz- und langfristige Veränderungen der mechanischen (Dehnungs-)Eigenschaften wurden beobachtet; die entsprechenden Alterungsmechanismen werden auf der Basis ergänzender Sol-Gel-, Dichte-, FTIR- sowie gravimetrischer Messungen und Zugversuche an Mikrotomschnitten diskutiert.Zwei Mechanismen führen zu kurzfristigen Eigenschaftsänderungen: eine Nachvernetzung und eine Änderung der Kristallstruktur (bei Proben oberhalb ihrer Schmelztemperatur). Im vorliegenden Fall wurden die Polymeren im festen Zustand vernetzt, so daß die Änderung der Kristallstruktur zu einer erkennbaren Abnahme der Streckspannung (ca. 5 MPa) führte.Die langfristigen Veränderungen treten nach dem Ende der Oxidationsinduktionsperiode auf. Sie können als Übergang vom zähen in den spröden Zustand interpretiert werden, der durch Strukturänderungen sowohl auf molekularer (durch Kettenspaltung) als auch makroskopischer Ebene (durch diffusionskontrollierte Kinetik der Oxidation verursachte Kern-Schale-Struktur) hervorgerufen wird. Durch IR- und DSC-Analysen wurde festgestellt, daß wahrnehmbare Änderungen in der Dehnung erst kurz vor dem Ende der Induktionsperiode auftreten.
    Notizen: The thermal aging of extruded samples of electron beam-crosslinked linear polyethylene has been studied in the 110-170°C temperature range. Short and long term changes of mechanical (tensile) properties were observed, and the corresponding mechanisms are discussed on the basis of complementary sol-gel and gravimetric measurements on whole samples, and density, FTIR and tensile testing on microtome sections.Two mechanisms are involved in short term changes: a post-crosslinking and a change of the crystalline morphology (for samples exposed above the melting point). The latter effect is especially important in the case under study where the polymer was crosslinked in the solid state and leads to a noticeable decrease (∼5 MPa) of the yield stress.The long term changes take place after the end of the induction period of oxidation. They can be interpreted in terms of ductile-brittle transition induced by structural changes occurring on the macromolecular level (chain scission) as well as macroscopically (core-shell structure resulting of the diffusion control of oxidation kinetics). It appears that noticeable changes of ultimate elongation occur just before the end of the induction period as detected by IR or DSC method.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The thermal oxidation of β ray-crosslinked polyethylene (XLPE) was studied in temperatures ranging from 90 to 180°C. Various analytical methods were used for determination of an end of the induction period on bulk samples: gravimetry, ultimate tensile properties, density and color change. On microtome slices of ∼30 μm thickness the depth distribution of oxidation products, phenolic antioxidant, density and tensile ultimate properties were followed as a function of exposure time by respectively IR and UV spectrophotometry, densitometry and Microfoil Tensile Testing.Depending on the testing method different durations of induction period (DIP) were obtained. They increase in following order:Phenol depletion 〈 Ultimate elongation 〈 Density 〈 Carbonyl build-up ≤ Color change 〈 Weight loss.The difference between phenol depletion DIP and carbonyl build-up DIP can be considered as negligible at temperatures higher than the melting point (about 30%) but it reachs more than 100% at T〈 Tm.Different kinetic regimes of phenol consumption were observed depending on the exposure temperature. A mechanistic interpretation is proposed explaining the role of the stabilizer system in initially homogeneous and later heterogeneous oxidation of the bulk material.The Arrhenius law was applied to different durations of induction period. A discontinuity appeared in the melting point region (120-130°C) which is tentatively interpreted in terms of different stabilizer concentration in amorphous phase of semicrystalline material (T 〈 Tm) and in melt material (T 〉 Tm). On the basis of the presented complex study of polyethylene thermo-oxidation, different aspects of lifetime predictions are discussed.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 247 (1997), S. 73-89 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The thermal oxidation (in air between 70 and 150°C) of unstabilised camples of poly(4-methylpentene) (PMP) were studied by infrared spectrometry and by gravimetry. The behaviour was compared to PP exposed in the same conditions.The thermal oxidation was found to exhibit two well differentiated kinetic regimes both for PP as for PMP. The first regime predominates at temperature higher than 90°C. It is characterized by an activation energy of the pseudo induction period of about 100 kJ mol-1. The induction period of mass gain is about 1,8 time shorter than the induction period of carbonyl gain. These characteristics, and the fact that induction periods are of the same order for both polymers, are consistent with a «close loop mechanistic» scheme with unimolecular POOH decomposition. The advantages of this hypothesis compared to other proposed hypothesis (bimolecular POOH decomposition, heterogeneous oxidation...) are discussed. The main theoretical difficulty is that of explaining why the unimolecular process predominates, whereas POOH are obviously hydrogen bonded, even at very low conversions of the oxidation process. This point remains to be explained.The second kinetic regime predominates at temperature lower than 90°C. It is characterized by a considerably lower activation energy. We have examined many hypothesis to explain the existence of a transition at that temperature (where neither PMP nor PP display a physical transition). A first hypothesis is that unimolecular POOH decomposition is replaced by a bimolecular one, which can explain a decrease of the apparent activation energy of about 50%. The bimolecular initiation creates pairs of radicals (POO·+ PO·). It can be imagined that a part of them desactivate mutually by termination after rearrangement of PO· by β scission. In this case, the transition at 90°C could be also a result of the temperature induced change in molecular mobility. Above 90°C, the radicals would diffuse almost freely out of the cage. In contrast, below 90°C, termination would become competitive with diffusion. A supplementary research is needed to fully elucidate the cause of this transition at 90°C.The eventuality of the existence of spatial heterogeneity of the oxidation process has been discussed. It is well known that oxidation is heterogeneous at the morphological scale, but there is no evidence of heterogeneity at smaller scale, where the chemical kinetic would not be applicable.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 921-927 
    ISSN: 0887-624X
    Schlagwort(e): thermo-oxidation kinetics ; hydrocarbon polymers ; monomolecular and bimolecular hydroperoxide initiation ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Mechanistic schemes of radical oxidation of hydrocarbon polymers in which initiation is only due to unimolecular or bimolecular hydroperoxide decomposition have been studied. The results of their kinetic analysis have been compared with literature data relative to the thermal oxidation of polypropylene in solid state (60-160°C). These data are in remarkably good agreement with the “unimolecular” scheme whose main characteristics are: (1) the quasi-independence of the kinetic behavior with initial conditions (for low initial content of thermolabile structures), and (2) the fact that an arbitrarily defined induction period depends only on the rate constant of unimolecular hydroperoxide decomposition. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 683-690 
    ISSN: 0887-624X
    Schlagwort(e): anhydride-cured epoxy ; thermal oxidation ; chemiluminescence ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The chemiluminescence of three epoxy networks based on diglycidyl ether of biphenol A (DGEBA) crosslinked by respectively the phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), and methyl tetrahydrophthalic anhydride (MTHPA), was studied in the 180-240°C temperature range. Isothermal stationary and nonstationary (perturbed) experiments revealed that the behavior depends sharply on the anhydride structure. The higher emissivity of cycloaliphatic systems (MTHPA and HHPA) is explained in terms of hydrogen abstractibility on the hardener's moiety. The main difference between MTHPA and HHPA (intensity initially decreases for the former, increases for the latter) is explained by the consumption of the MTHPA double bonds in oxidative crosslinking processes. The results of perturbed experiments were essentially attributed to changes of alkyl radical concentration during the exposure under nitrogen. These changes can be modelled by a simple kinetic model taking into account the observed differences between the systems under study. © 1993 John Wiley & Sons, Inc.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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