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  • 1
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystal structure and polymorphism induced by uniaxial drawing of a poly(aryl ether ketone) [PEDEKmK] prepared from 1,3-bis(4-fluorobenzoyl)benzene and biphenyl-4,4′-diol have been investigated by means of transmission electron microscopy (TEM), electron diffraction (ED), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) techniques. The melting and recrystallization process in the temperature range of 250-260°C, far below the next melting temperature (306°C), was identified and found to be responsible for the remarkable changes in lamellar morphology. Based on WAXD and ED patterns, it was found that crystal structure of isotropic-crystalline PEDEKmK obtained under different crystallization conditions (melt-crystallization, cold-crystallization, solvent-induced crystallization, melting-recrystallization, and crystallization from solution) keeps the same mode of packing, i.e., a two-chain orthorhombic unit cell with the dimensions a = 0.784 nm, b = 0.600 nm, and c = 4.745 nm (form I). A second crystal modification (form II) can be induced by uniaxial drawing above the glass transition temperature, and always coexists with form I. This form also possesses an orthorhombic unit cell but with different dimensions, i.e., a = 0.470 nm, b = 1.054 nm, c = 5.064 nm. The 0.32 nm longer c -axis of form II as compared with form I is attributed to an overextended chain conformation due to the expansion of ether and ketone bridge bond angles during uniaxial drawing. The temperature dependence of WAXD patterns for the drawn PEDEKmK suggests that form II can be transformed into the more stable form I by relaxation of overextended chains and relief of internal stress at elevated temperature in absence of external tension.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure, morphology and polymorphism induced by uniaxial drawing of poly(ether ether ketone ketone) [PEEKK] have been studied by transmission electron microscopy (TEM), electron diffraction (ED) and wide angle X-ray diffraction (WAXD). On the basis of WAXD and ED patterns, the crystal structure of unoriented PEEKK is determined to have two-chain orthorhombic packing with unit cell parameters of a = 0.772 nm, b = 0.600 nm, c = 1.004 nm (form I). A stress-induced crystal modification (form II) is identified and found to possess a two-chain orthorhombic lattice with unit cell dimensions of a = 0.461 nm, b = 1.074 nm, c = 1.080 nm. The 7.5% increase in c-axis dimension for form II is attributed to an overextended chain conformation, arising from extensional deformation during uniaxial drawing and fixed “in-situ” through strain-induced crystallization. The average ether-ketone bridge bond angles in form II crystal are determined to be 148.9° by using standard bond lengths. The crystal morphology of PEEKK bears a great similarity to that of PEEK. The crystals grow in the form of spherulites and have the b-axis of unit cell radial. The effects of draw rate on strain-induced crystallization and induction of form II structure are also discussed.
    Additional Material: 11 Ill.
    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: Poly(etheretherketon) (PEEK)/4,4′-Dihydroxydiphenylsulfon (DHDPS)-Multiblock-Copolymere mit Diphenyloxysulfon(DPOS)-Gehalten zwischen 4,9 und 36,6 Gew.-% wurden aus DHDPS und fluorterminierten PEEK-Oligomeren hergestellt. Das zahlenmittlere Molekulargewicht (Mn) der PEEK-Oligomeren variierte zwischen 470 und 4900. Der Einfluß der Zusammensetzung auf die Eigenschaften der Copolymeren wurde untersucht. Es wurde keine Mikrophasenseparation beobachtet. Die Copolymeren bildeten ein homogenes System mit guter Phasenverträglichkeit. Bei den Copolymeren mit höchstens 23,1 Gew.-% DPOS wurde eine kristalline Struktur beobachtet. Röntgenweit- und Kleinwinkelstreumessungen ergaben eine rhombische Kristallstruktur, wie sie auch bei PEEK gefunden wird. Die Verteilung der Schichtdicken der kristallinen und amorphen Regionen ist relativbreit. Mit Zunahme des DPOS-Gehalts (oder der Abnahme des zahlenmittleren Molekulargewichts der PEEK-Segmente) nahmen der Kristallinitatsgrad und der Schmelzpunkt der Copolymeren ab, und die Glastemperatur (Tg) nahm schrittweisezu.
    Notes: Poly(ether ether ketone) (PEEK)/4,4′-dihydroxydiphenyl sulfone (DHDPS) multiblock copolymers with a content of the diphenoxysulfone (DPOS) moiety between 4.9 and 36.6wt.-% were synthesized by the reaction of DHDPS and fluorine-terminated PEEK oligomers. The number-average molecular weight of PEEK oligomers (Mn) was varied from 470 to 4900. The effect of the compositional variation on the properties was investigated. Microphase separation was not observed. The copolymers formed a homogeneous system having good compatibility. The copolymers whose DPOS contents are not exceeding 23.1 wt.-% (Mn of PEEK segment ≥ 865) have crystalline structure.From the measurements of wide- and small-angle X-ray scatterings it was revealed that the crystal structure of the copolymers is rhombic, equal to PEEK, and the distribution of the thickness of the crystalline and amorphous regions is very broad. The degree of crystallinity and the melting point of the copolymers decreased and the glass transition temperature (Tg) gradually rose with the increase of the DPOS content (or the decrease of Mn of the PEEK segment).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 59 (1996), S. 905-914 
    ISSN: 0021-8995
    Keywords: 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: Poly(ether ether ketone ketone)-poly(ether sulfone) (PEEKK/PES) block copolymers were prepared from the corresponding oligomers via a nucleophilic aromatic substitution reaction, and the Mn of the PEEKK segment was fixed at 12,000, while the Mn's of the PES segment ranged from 250 to 12,680. The different properties of the copolymers were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The results showed that the relationship between Tg and compositions of copolymers approximately followed the formula 1/Tg = W2/Tg2. The PES content and the segment length of the copolymers had a significant influence on their melting points and crystallization behavior. The thermal properties and dynamic mechanical behavior of the copolymers were also studied. In the study of isothermal crystallization, the copolymers have the same nucleation mechanism and crystal growth as that of pure PEEKK. Owing to the introduction of the PES segment into the PEEKK main chain, it increases the free energy which forms the critical crystal nucleus and produces a resistant action to the whole crystallization process of the PEEKK segment. © 1996 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 61 (1996), S. 1999-2007 
    ISSN: 0021-8995
    Keywords: 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: The melting behavior of semicrystalline poly(ether ether ketone ketone) (PEEKK) has been studied by differential scanning calorimetry (DSC). When PEEKK is annealed from the amorphous state, it usually shows two melting peaks. The upper melting peaks arise first, and the lower melting peaks are developed later. The upper melting peaks shown in the DSC thermogram are the combination (addition) of three parts: initial crystal formed before scanning; reorganization; and melting-recrystallization of lower melting peaks in the DSC scanning period. In the study of isothermal crystallization kinetics, the Avrami equation was used to analyze the primary process of the isothermal crystallization; the Avrami constant, n, is about 2 for PEEKK from the melt and 1.5 for PEEKK from the glass state. According to the Lauritzen-Hoffman equation, the kinetic parameter of PEEKK from the melt is 851.5 K; the crystallization kinetic parameter of PEEKK is higher than that of PEEK, and suggests the crystallizability of PEEKK is less than that of PEEK. The study of crystallization on PEEKK under nonisothermal conditions is also reported for cooling rates from 2.5°C/min to 40°C/min, and the nonisothermal condition was studied by Mandelkern analysis. The results show the nonisothermal crystallization is different from the isothermal crystallization. © 1996 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 18 (1997), S. 99-105 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Five kinds of poly(aryl ether ketone)s (PAEKs) having para-substituted linear molecular chains were synthesized via nucleophilic substitution reaction of the corresponding difluoro- and dihydroxy-compounds. The glass transition temperature and melting temperature of the PAEKs measured through differential scanning calorimetry in addition to those of other PAEKs reported are approximately proportional to the logarithm of the ratio of the mole fractions of ketone and ether groups in the repeating unit of the PEAKs. On the other hand, this ratio does not affect the crystal structure of the PAEKs.
    Additional Material: 5 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: The evolution of crystallinity and polymorphism during hot-drawing of amorphous poly(ether ether ketone ketone) (PEEKK) as a function of strain rate, draw ratio, and temperature was investigated. In modification I, the competition of chain extension and molecular alignment is responsible for the strain rate and temperature dependence. Modification II crystallization is basically controlled by chain extension during stretching. The former can be transformed into the latter via relaxation during stretching or annealing at elevated temperature.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 197 (1996), S. 1643-1650 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of a novel poly(aryl ether ketone) [PEDEKmK] was investigated via polarizing optical microscopy (POM), TEM, DSC, SAXS and electron diffraction (ED). A distinct change in lamellar thickness, orientation, and spherulitic morphology was observed due to crystal melting and recrystallization. However, the crystal packing mode is found to be identical before and after the recrystallization process.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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