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  • Chemistry  (13)
  • Poly(ethylene terephthalate)  (1)
  • 1
    ISSN: 1435-1536
    Keywords: Poly(ethylene terephthalate) ; lamellar morphology ; melting-recrystallization ; annealing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Structural changes occurring during crystallization of quenched amorphous poly(ethylene terephthalate) (PET) and subsequent cooling/heating cycles have been studied by real-time small-angle x-ray scattering (SAXS), using synchrotron radiation. Initial crystallization is found to occur by insertion of new lamellae between the existing ones, while rapid continuous melting/recrystallization happens when the cold-crystallized PET samples are heated above the previous highest annealing temperature. Such melting/recrystalization results in irreversible increases in the lamellar long period, the crystal thickness and the density difference between the crystalline and amorphous regions; in contrast, at temperatures below the prior highest crystallization temperature, the structural changes are dominated by reversible effects such as thermal expansion. However, throughout the entire temperature range up to the melting point around 250 °C, the crystal core thickness remains quite small, less than ca. 50 Å, and the linear crystallinity of lamellar stacks remains nearly constant around 0.3. Such a low crystallinity indicates the presence of thick order-disorder interfacial layers on the lamellar surface, whose thickness increases with temperature.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2879-2888 
    ISSN: 0887-624X
    Keywords: thermosetting cyanate networks ; foams ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general means of generating nanofoams from thermosetting materials was investigated. Foams were prepared from a thermosetting monomer copolymerized with a thermally labile material, such that the thermally labile coblock is the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis, leaving pores where the size and shape are dictated by the initial morphology. For this investigation the thermosetting resin was prepared from a cyanate monomer (4,4′-(hexafluoroisopropylidene) diphenyl-cyanate), with either poly(propylene oxide) or a propylene oxide-urethane copolymer as the thermally labile block. The propylene oxide-based oligomers were molecularly miscible with the cyanate resin over the entire range of compositions, and molecular weights investigated, but developed a two-phase structure upon reaction to form the polycyanurate thermoset. The molecular weight and composition of propylene oxide chemically incorporated into the polycyanurate was varied along with the curing condition, solvents, and catalyst. Dynamic mechanical and small-angle x-ray scattering measurements demonstrated a two-phase morphology in the cured networks wherein the propylene oxide domains are dispersed in the polycyanurate matrix. Upon decomposition of the propylene oxide component, however, the foam was found to collapse. Samples with the larger void size retained, to a large extent, their void composition upon the thermolysis of the propylene oxide component. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2919-2940 
    ISSN: 0887-6266
    Keywords: interdiffusion ; polymer interfaces ; dynamics ; reptation ; neutron reflection ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Neutron Reflection (NR) and Dynamic Secondary Ion Mass Spectroscopy (DSIMS) experiments were conducted on symmetrically deuterated polystyrene triblock bilayers (HDH/DHD) which directly probed the interdiffusion dynamics of the chains during welding. The HDH chains had their centers deuterated 50%, the DHD chains had their ends deuterated (25% at each end) such that each chain contained approximately 50% D. During welding, anisotropic motion of the chains produces a time-dependent oscillation (ripple) in the H and D concentration at the interface, which bears the characteristic signature of the polymer dynamics. These oscillations were compared with those predicted by Rouse, polymer mode coupling (PMC), and reptation dynamics. The following conclusions can be made from this study. (a) During the interdiffusion of high molecular weight HDH/DHD pairs, higher mobility of the chain ends caused a concentration oscillation which increased to a maximum amplitude, and eventually vanished at times, t 〉 τD. The amplitude, or excess enrichment found, was appreciably more than that predicted by Rouse and PMC simulations, and was only slightly less than that predicted from reptation simulations. (b) The oscillations were completely missing in the 30 and 50K HDH/DHD polymers, which are only weakly entangled. The lack of oscillations for the 30 and 50K pairs may be due to a combination of surface roughness and fluctuations of order 30 Å. (c) It was found that the position of the maximum in this ripple stayed at the interface during its growth. This is also consistent with reptation and has not been explained by other theories. (d) All dynamics models for linear polymers produce ripples, many of which are qualitatively similar to that predicted for reptation. However, each ripple bears the fingerprint of the dynamics in terms of its time-dependent shape, position, and magnitude, and the models are clearly distinguishable. Our results, in summary, support reptation as a candidate mechanism of interdiffusion at polymer(SINGLEBOND) polymer interfaces and its uniqueness is being further pursued. © 1996 John Wiley & Sons, Inc.
    Additional Material: 22 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 263-277 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rutherford backscattering spectrometry with a 2.1-meV He2+ion beam is used to measure the diffusion of iodine into polyamic acid and polyimide films. The iodine diffusion coefficient D decreases from its initial value of about 2X10-13cm2/s in polyamic acid to approximately 1.4 × 10-15cm2/s in partially cured polyimide, but then increases to a value of nearly 1.5 × 10-14 cm2/s in fully cured polyimide. This dramatic increase in D cannot be attributed to the “in-plane” biaxial orientation of the polyimide molecules since indential D's were found with isotropic specimens. Microvoids less than 2 nm in size caused by water and carbon dioxide formation during imidization may, however, give rise to the observed behavior. The results demonstrate that Rutherford backscattering spectrometry with its excellent depth resolution (better than 30 nm) and good sensitivity (50 ppm iodine can be detected) is very useful for measuring the diffusion of slowly diffusing species in glassy polymers.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 2131-2144 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The swelling behavior of poly(N, N'-bisphenoxyphenylpyromellitimide) (PMDA-ODA) using dimethylsulfoxide DMSO and N-methylpyrollidinone NMP was investigated by gravimetric means. For PMDA-ODA samples imidized on a substrate, the weight uptake was found to depend linearly on time over a temperature range from 25 to 150°C. For a given temperature of imidization, the equilibrium swelling concentration was found to be independent of the temperature at which the swelling studies were performed. However, the rate of solvent uptake depended strongly on the swelling temperature, yielding an activation energy of about 50 kJ/mol. In general, increasing the initial imidization temperature caused a decrease in the rate of swelling but did not alter the equilibrium swelling concentration. This swelling behavior resembles Case II diffusion typically seen in glassy polymers with some noteworthy exceptions. In cases, where PMDA-ODA was imidized in a free-standing state, no swelling was observed. However, deformation of these isotropic specimens was found to induce substantial swelling.
    Additional Material: 10 Ill.
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  • 6
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deformation of the aromatic polyimide poly{N,N′-bis(phenoxyphenyl)-pyromellitimide} (PMDA-ODA) has been investigated by x-ray scattering. PMDA-ODA, which exhibits a smecticlike ordering in the bulk can be elongated up to 70% at room temperature without a distinct yield point. Under strain, the diffraction pattern of the intramolecular spacing occurring at a Bragg spacing of 15.4 Å is elliptical. The ellipticity shows that the molecule changes its repeat distance along the chain axis. This may result from bond angle and bond length distortions. Consistent with this is a rapid recovery well below the glass transition temperature where all but 20% strain is recovered. This localized extension, however, cannot account fully for the macroscopic deformation applied, and, as such, a global orientation of the chains occurs, as evidenced by the arcing of the diffraction profiles. The retention of the intrachain reflection indicates that bundles of chain segments ordered in a smectic fashion orient as a unit maintaining a lateral chain-segment alignment. Finally, the scattering vector at which a small-angle scattering reflection occurs was found to be correlated to the coherence length determined by a Scherrer analysis of the ca. 15.4 Å intramolecular reflection. As the strain increased, the intensity and spacing of the small-angle scattering reflection increased parallel to the stretching direction and decreased perpendicular to this. This suggests that the origin of the small-angle scattering reflection arises from electron density fluctuations along the chain axis, as is typically seen in semicrystalline polymers.
    Additional Material: 14 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 253-257 
    ISSN: 0887-6266
    Keywords: porosity ; nanofoams ; polyimide ; voids ; infrared spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectroscopy has been used to determine the porosity of polymer nanofoams produced from block copolymers of an aromatic polyimide with either poly(propylene oxide) or poly(α-methyl styrene). It is shown that, with an independent measurement of the film thickness, both the absorption bands and the interference fringes can yield an accurate measure of the void content. The results obtained are in quantitative agreement with density gradient methods. © 1995 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 345-349 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Small angle X-ray scattering (SAXS) has been used to evaluate the size and concentration of voids in poly(N,N′-bis-(phenoxyphenyl)pyromellitimide), PMDA-ODA. Analysis of the angular dependence of the scattering indicates the presence of voids ranging from 50 to 150 Å in radius. Integrated SAXS demonstrated that the volume fraction of voids was 7 × 10-4. These results were supported by measurements of the attenuation factor as a function of the sample thickness.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Acta Polymerica 46 (1995), S. 60-63 
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction measurements on thin films of poly(hexyl-pentylsilane) cast on silicon substrates are presented. The polymer chains pack in a hexagonal lattice which is oriented such that the chains lie parallel to the surface. In addition, a remarkable degree of orientational order was found with the planes containing the neighbor molecules lying in the surface plane. Parallel to the film surface, the average crystallite size is 600 Å, while perpendicular to the surface, there is nearly perfect interchain stacking of the polymers throughout the thickness of the film.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Propellants, Explosives, Pyrotechnics 16 (1991), S. 27-30 
    ISSN: 0721-3115
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rapid thermal decomposition (dT/dt ≥ 70°C/s) of eubylammonium nitrate (CUBAN) and cubane-1, 4-diammonium dinitrate (CUBDAN) is described in terms of the temperature profile and gas products as a function of pressure (1-200 psi Ar). In this environment the full strain energy of cubane is not released simultaneously with the redox reactions that involve the ammonium nitrate site because C2H4 and/or C2H2 are evolved. No large hydrocarbons form during rapid thermolysis, although both salts sublime to some extent below 7 psi Ar. CUBDAN is the only alkyldiammonium dinitrate salt that we have found to sublimduring fast thermolysis. An estimated gas phase basicity of about 215 kcal/mol for the cubylamines is obtained from the tendency to release HNO3(g). This value is surprising in light of the basicity values for other primary amines.
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