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  • 1
    Electronic Resource
    Electronic Resource
    Palo Alto, Calif. : Annual Reviews
    Annual Review of Materials Research 28 (1998), S. 533-562 
    ISSN: 0084-6600
    Source: Annual Reviews Electronic Back Volume Collection 1932-2001ff
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Polymer phases can be described in the same way as phases in other condensed matter using a number density operator and its correlation functions. This description requires the understanding of symmetry operations and order at different atomic and molecular levels. Statistical mechanics provides a link between the microscopic description of the structure and motion and the macroscopic thermodynamic properties. Within the limits of the laws of thermodynamics, polymers exhibit a rich variety of phase transition behaviors. By definition, a first-order phase transition describes a transformation that involves a sudden change of thermodynamic properties at its transition temperature, whereas higher-order phase transitions are classified as critical phenomena. Of special interest is the role of metastability in phase and phase transition behaviors. Although a metastable state possesses a local free energy minimum, it is not at the global equilibrium. Furthermore, metastable states can also be associated with phase sizes. Metastable behavior is also observed in phase transformations that are impeded by kinetic limitations along the pathway to thermodynamic equilibrium. This is illustrated in structural and morphological investigations of crystallization and mesophase transitions, liquid-liquid phase separation, vitrification, and gel formation, as well as combinations of transformation processes. In these cases, the metastable state often becomes the dominant state for the entire system and is observed over a range of time and size scales. This review describes the general principles of metastability in polymer phases and phase transitions and provides illustrations from current experimental works in selected areas.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1572-8935
    Keywords: Amorphous ; Crystal ; Lamellae ; Miscibility ; Nylon 6 ; Phase separation ; Polyimide ; Triblock copolymer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract A series of new nylon 6-b-polyimide-b-nylon 6 (triblock) copolymers have been synthesized via condensation polymerization of the polyimide component and anionic polymerization of the nylon 6 component. The polyimide component is prepared from bisphenol-A dianhydride (BisA-DA) and bisaniline-P diamine (BisP) with end-capped functional groups. After the polyimides are dissolved in caprolactam, the nylon 6 anionic polymerization is initiated by the functional groups of the polyimides. The triblock copolymers can be dissolved in both m-cresol and 1,6-hexanediol. Of the two components present in the copolymers, nylon 6 crystallizes partially and BisA-DA/BisP is amorphous. Based on differential scanning calorimetry, dynamic mechanical analysis, wide angle X-ray diffraction, small angle X-ray scattering and transmission electron microscopy experiments, the copolymer films prepared from the 1,6-hexanediol solution are phase separated. The BisA-DA/Bis P and the nylon 6 components show little miscibility in the inter-lamellar amorphous region. However, in the films prepared from the m-cresol solution both components are largely miscible in the inter-lamellar amorphous region. This is due to the different solvation power of the two solvents with respect to the polyimide and nylon 6.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 907-910 
    ISSN: 1572-8943
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0959-8103
    Keywords: polyimide ; m-cresol ; phase structure ; morphology ; phase boundary diagram ; gel/sol transition ; DSC ; polarized light microscopy ; 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: An organo-soluble aromatic polyimide has been synthesized from 3,3′, 4,4′-bis(phenyltetracarboxylic) dianhydride (BPDA) and 2,2′-bis (trifluoromethyl)-4,4′-diaminobiphenyl (PFMB) via a one-step polymerization in m-cresol. The phase boundary diagram for this system has been established by differential scanning calorimetry, polarized light microscopy (PLM) and wide angle X-ray diffraction (WAXD) experiments. A crystallosolvate form I has been found over the entire concentration region at low temperatures. When the temperature is increased, an isotropic phase has been observed below concentrations of about 40%. In the relatively high concentration region between 45 and 95%, a transition from the crystallosolvate from I to a crystallosolvate form II has been observed. Form II exhibits a different WAXD pattern. In a narrow concentration region between the isotropic and the crystallosolvate form II (40-45%), a biphase behavior has been found. The birefringence of this region may be an indication of a liquid crystalline phase. The BPDA-PFMB polymer crystal has been found in the very high concentration region (〉95%) for temperatures 〉250°C. The morphologies of these phases have been investigated via PLM and transmission electron microscopy. Above the gel/sol transition temperature, the form I shows negative birefringent spherulites consisting of thin lamellae. The form II exhibits a tendency of positive birefringent spherulites. Possible mechanisms of the formation of the metastable phase morphology and their associations with the mechanical gel/sol transition are also discussed.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two polyimides having the same backbone chemical structure and different pendant side groups at the 2- and 2′-positions of the diamine, the six methylene units capped with 4-cyanobiphenyl end groups and trifluoromethyl, were synthesized (6FDA-6CBO and 6FDA-PFMB). Surface-enhanced Raman scattering and surface optical second harmonic generation measurements show that after rubbing the major change in 6FDA-PFMB surface appears in the orientation of the dianhydride, which was originally planar, but becomes tilted with respect to the surface plane. In the case of 6FDA-6CBO, rubbing also causes the originally planar 4-cyanobiphenyls to tilt away from the surface and assume an azimuthally anisotropic distribution.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several series of new b-nylon 6-b-polyimide-b-nylon 6 triblock copolymers were synthesized via a condensation polymerization of polyimide segments and anionic polymerization of the nylon 6 components. Crystallization and phase behavior of these triblock copolymers have been studied with varying polyimide block molecular weights and copolymer compositions as well as chemical structures (and therefore, different solubility parameters) of the polyimide components. Furthermore, in-situ and solution blends have also been prepared in order to compare the phase behaviors of the triblock copolymers. Wide angle X-ray diffraction experiments indicate that in these triblock copolymers, only nylon 6 components crystallize and polyimides do not take part in the crystals. From isothermal crystallization kinetics studies carried out in differential scanning calorimetry experiments, the miscibility of the polyimide components with nylon 6 critically affects the crystallization rate of these triblock copolymers. When the polyimide composition is low and its solubility parameter is similar to that of the nylon 6 components, the polyimides mix with the amorphous part of the nylon 6 components and are located in the inter-lamellar region. This can be identified by monitoring the change of α-relaxation temperature and activation energy measured using a dynamic mechanical method and by examining the crystalline lamellar morphology under small angle X-ray scattering experiments. Microphase separation can also be recognized by transmission electron microscopy using an OsO4 vapor staining technique. As the difference of solubility parameters between these two components as well as the block molecular weight of the polyimides increase, microphase separation between the two components in the triblock copolymers can be found.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 16 (1995), S. 533-542 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Based on our differential scanning calorimetry observations, a polyether 1 synthesized from 4′-[2-(4-hydroxyphenyl)propyl]-4-biphenylol and 1,9-dibromononane shows multiple transition behavior during cooling and heating. Furthermore, these transition temperatures do not exhibit significant supercooling dependence. Detailed analyses of the wide-angle X-ray diffraction powder and fiber patterns at different temperatures have indicated that highly ordered smectic F and G phases exist in this polyether and are differentiated from traditional crystalline phases.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 1439-1451 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new polymide was synthesized from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 2,2-dimethyl-1,3-(4-aminophenoxy)propane (DMDA), and abbreviated to be BTDA-DMDA. This polymer possesses three relaxation processes which have been observed through dynamic mechanical and dielectric analyses above-150°C. The α relaxation process has been assigned to be the glass transition and occurs at about 250°C with an apparent activation energy of 420kJ/mol. Two subglass relaxation processes are a β relaxation process at around 100-170°C in a frequency range from 0,1 Hz to 100 kHz with an activation energy of 182 kJ/mol and a γ relaxation process occurs at around -80°C with an activation energy of 44 kJ/mol. Carbon-13 solid state nuclear magnetic resonance experiments were carried out for the study of molecular dynamics at different temperatures. The results indicate that the γ relaxation is responsible for an oscillation and π flipping motion of the two phenoxy rings in the DMDA portion. The β relaxation was shown to pertain to the kHz-motion of the aromatic imide rings in the BTDA portion. The molecular motion of the DMDA and BTDA protions are largely decoupled from each other in the frequency region studied.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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