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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 26 (1993), S. 5219-5226 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 255 (1977), S. 1138-1138 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1435-1536
    Keywords: Thermoplastic elastomers ; SAXS ; deformation ; morphology
    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 The scattering behavior of undrawn and drawn annealed bristles of thermoplastic elastomers with conventional and higher molecular weight based on poly (butylene terephthalate) as hard segments and poly (ethylene glycol) as soft segments in a ratio of 49/51 wt.% is studied. Small-angle x-ray scattering (SAXS) measurements with an area detector are carried out on single bristies under or without applied stress and with deformations up to 300%. At low macrodeformations (ε≤30–40%) the morphology of the predrawn samples represents assemblies of parallel crystalline lamellae positioned perpendicular to the stretching direction. These morphological characteristics remain unchanged within the entire deformation range (up to ε=300%) for the predrawn samples of lower molecular weight. For the initially undrawn sample of larger molecular weight reversible orientation and disorientation of the crystallites (microdomains) is established in the same deformation range. Common morphological features are found for the predrawn and undrawn samples with increased molecular weight at medium (ε=50–150%) and high (ε=150–300%) deformation ranges. For both samples in an unloaded relaxed state the x-ray patterns can be explained by a zig-zag arrangement of crystalline lamellae, i.e., the microdomains are inclined to the stretching direction. After loading, the microdomains transform to a position perpendicular to the stretching direction. This observed morphological transition is found to be reversible and becomes more pronounced with progressing deformation. It is suspected to contribute to reversible macrodeformations of thermoplastic elastomers in many cases and may be related to the large amount of tie-molecules created during solid-state reactions in those materials.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 256 (1978), S. 115-124 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Es wird der molekulare Mechanismus des nichtlinearen Zusammenhangs zwischen den Übergangstemperaturen (Tg bzw. Tm) und der äußeren Spannung diskutiert. Auf Grund der thermomechanischen Kurven (Deformation - Temperatur), aufgenommen bei verschiedenen äußeren Spannungen an verstreckten und getemperten PET Fasern, wird festgestellt, daß die Übergangstemperaturen (Tg und Tm) von der äußeren Spannung abhängig sind. Die beobachteten Maxima für die beiden Temperaturen Tg und Tm bestätigen die theoretischen Ergebnisse vonCiferri undSmith undFrenkel, die eine Kristallisation der orientierten Polymeren mit Kettenfaltung oder Spiral-Bildung annehmen. Von dem Bonart-Hosemann-Modell ausgehend wird eine Erklärung für die festgestellte Zunahme von Tm, nach welcher eine Abnahme und wieder neue Zunahme folgt, mit progressiv wachsender äußerer Spannung vorgeschlagen: bei niedrigen Spannungswerten findet eine Orientierung von Makromolekülen in nichtkristallinen Bereichen statt, nach welcher eine Entfaltung von Ketten in den Kristalliten eintritt und zuletzt (bei höchsten Spannungen) eine extreme Verstreckung mit zusätzlicher Orientierung stattfindet. Dieser Mechanismus wird von Infrarotmessungen gestützt. Die dargestellten thermomechanischen Daten in den Koordinaten äußere Spannung/Schmelztemperatur gegen Deformation bestätigen die vonFlory theoretisch berechnete Kurve. Die experimentellen Kurven demonstrieren, daß (1) die Kristallisation mit negativer Deformation sowie (2) die Regenerierung der amorphen Phase und ihre zusätzliche Verstreckung physikalisch realisierbare Situationen sind, wenn die Kristallisation mit Kettenfaltung oder Spiral-Bildung auftritt. Es ist damit gezeigt, daß thermomechanische Messungen ein erfolgreiches Mittel zur Untersuchung des Kettenfaltungsproblems darstellen. Die experimentellen Daten sind ein neuer Beweis für die Existenz von regulärer Kettenfaltung auch im kristallinen PET.
    Notes: Summary The molecular mechanism of the nonlinear relationship between the transition temperatures (T g resp.Tinm) and the outer tensile stress is discussed. On the basis of thermomechanical curves (deformation-temperature) taken at different external tensile force on drawn annealed PET fibers and films it has been shown that the transition temperatures depend nonlinearly on the applied tension stress. The maxima observed for bothT g andT m confirm the theoretical results ofCiferri andSmith andFrenkel assuming a crystallization of oriented polymer with chains in folded or helical conformation. A reasonable explanation is proposed for the increase ofT m followed by decrease and again increase with progressively rising of the applied tension stress using the model ofBonart-Hosemann for structure of semicrystalline polymers: at low tension values an orientation of macromolecules in noncrystalline zones takes place followed by defolding of chains from crystallites and finally (at highest tension values) an extreme stretching with additional orientation proceeds. This mechanism is supported by infra-red measurements. The thermomechanical data plotted as external tension divided by the corresp. melting temperature versus deformation confirm the theoretical curve derived byFlory. The experimental curves demonstrate that (1) the crystallization under strain with negative elongation as well as (2) the regeneration of the amorphous phase and its additional stretching are physically realisable situations when the crystallization is accompanied by chain folding or building of helices. It is shown that the thermomechanical method could be used as a simple tool for investigating the chain folding problem. The data reported are an additional proof of the existence of regular folded chains in the crystalline PET too.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1435-1536
    Keywords: Thermoplastic elastomers ; deformation behavior ; x-ray scattering ; long spacing
    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 The scattering behavior of pre-drawn and annealed bristles of a highly deformable poly(ether ester) themoplastic elastomer based on poly(butylene terephthalate) as hard segments and poly(ethylene glycol) as soft segments in a ratio of 57/43 wt.-% is studied. Small-angle x-ray seattering measurements with an area detector are carried out on bristles with and without application of stress up to 195% relative deformation. Two-dimensional scattering patterns are used for morphological characterization of the sample. At small deformations one morphology peak is found, corresponding to a periodicity that changes affinely with deformation. The morphology of the smaple represents assemblies of mutually parallel crystalline lamellae, positioned perpendicular to the stretching direction both under and without stress. When macrodeformation increases a second peak appears, and a four-point pattern is observed in the relaxed state. In this intermediate deformation range coexisting morphologies contribute to the scattering. Additional contributions arise from lamellae, which are inclined to the stretching direction, as well as from lamellae, which are again perpendicular to the stretching direction, as a result of microfibril relaxation and loss of interfibrillar contacts. At large deformations the latter morphology dominates and the 2D-scattering pattern again shows a two-point character. A morphological model for this behaviour is discussed, where the break of interfibrillar contacts during deformation and the inhomogeneous stress field in the sample play an important role.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1435-1536
    Keywords: Gelatin ; crosslinking ; drawing ; oriented films ; dymeanie mechanical properties
    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 This study is an extension of previous work on cellulosics [(1994)Colloid Polym Sci 272: 284, 393] that showed that unusually good mechanical properties can be obtained by drying a swollen network of semirigid chains in a state of strain. This novel approach is applied in this investigation to gelatin, because of its attractive environmental characteristics but poor mechanical properties in the unmodified form. Since drawing of non-crosslinked gelatin is not practical, crosslinking by formaldehyde was used, followed by swelling, drawing and drying at fixed length. Mechanical tests were performed in static and dynamic modes. In this way improvements of Young's modulusE, and stress at breakσ b were determined as a function of gelatin concentration during drying. An increase inE andσ b up to 2–3 times, and in the dynamic modulusE′ up to 6 times, was obtained when the draw ratio λ reached 4–5, after whichE, E′, andσ b were found to decrease. Such behavior is explained by the highest orientation being achieved at λ=4–5, as proved by x-ray analysis. At λ=10–20 the orientation is lost due to relaxation of chain segments, which is preceded by partial destroying of the network structure (chemical and physical), possibly via chain scission, but probably mostly by the pulling out of chains from crystallites. In any case, the mechanical properties become poor again. The improvements reported above were referred to the undrawn but crosslinked gelatin. Compared to the starting isotropic non-crosslinked material, the improvement is slightly higher. The observation that the improvements are less than those obtained for the cellulosics is explained by the coexistence of interpenetrating chemical and physical networks, which is typical of gelatin. This structural feature drastically reduces the orientability of the chains and the improvements that can be expected in the mechanical properties.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Biotechnology techniques 12 (1998), S. 889-892 
    ISSN: 1573-6784
    Keywords: Gelatin ; degradation ; proteinases ; subtilisin ; formaldehyde-crosslinking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A general method is proposed for characterizing the enzymatic degradability of formaldehyde-crosslinked gelatin which is simple and uses subtilisin as a readily available, commercial alkaline proteinase. Solubilization of gelatin involved dissolution of species not chemically bonded to the crosslinked network, as well as the soluble fractions resulting to the enzymatic degradation. There was a linear relationship between the complete solubilization time of the gelatin and its exposure time to the formaldehyde crosslinking procedure. © Rapid Science Ltd. 1998
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1435-1536
    Keywords: Key words Gelatin ; crosslinking ; drawing ; oriented films ; dynamic mechanical properties ; glass transition
    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  This second part of a systematic study of the properties of crosslinked-oriented gelatin involves the effects of orientation and water content on the glass transition temperature T g and on the melting behavior. The samples were the same as those in the preceding study, and their transition temperatures were determined by both differential scanning calorimetry and dynamic mechanical thermal analysis. The crosslinked gelatin which had been room-conditioned showed two transition temperatures: the lower one was attributed to T g of the water-plasticized gelatin, and the higher one was interpreted as T g of dried gelatin superimposed by melting. A rather unusual situation arose because of the fact that the T g and melting temperatures T m (217 and 230 °C, respectively) are so similar. Using water as plasticizer not only decreases T g but produces imperfect crystallites which melt below the T g of the system. The presence of the amorphous phase in the glassy state would presumably make it essentially impossible to define a melting point or crystallization temperature in the normal manner, as an equilibrium between crystalline and amorphous phases.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1435-1536
    Keywords: Key words Poly(ethylene terephthalate) ; microhardness ; crystallinity ; high molecular weight
    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  Poly(ethylene terephthalate) (PET) was annealed in vacuum at different temperatures (190–260 °C) for different times (10 min–24 h) in order to examine the mechanical properties (microhardness) of PET samples with a wide range of molecular weights (10 000–120 000). Short annealing times result in a twofold decrease in mol. wt. due to hydrolytic decomposition. However, long annealing times give rise to a substantial molecular weight increase. It is found that microhardness (H) rises linearly with the degree of crystallinity obtained during up-grading of mol. wt. and its extrapolation leads to H-values of completely crystalline PET, H PET c=405 MPa for samples with conventional mol. wt. and of 426 MPa for samples with mol. wt. higher than 30 000. It is shown that the increase of mol. wt. for each set of samples with a given range of degree of crystallinity also causes a slight increase of H. The influence of mol. wt. upon hardness is discussed in the light of the changes in the physical structure (crystallinity, crystal thickness) which is formed at given heat treatment conditions.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 262 (1984), S. 445-449 
    ISSN: 1435-1536
    Keywords: melt annealing ; crystallization ; nylon-6 ; “memory” effect ; calorimetry
    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 The effect of melt annealing duration at 260 °C-high above melting temperature on the crystallization of nylon-6 with various molecular weights (between 5 800 and 255 500) using dilatometric and calorimetric (DSC) techniques has been studied. The samples were laboratory synthesized, purified and characterized by GPC. It was found that the crystallization behavior of nylon-6 depends strongly on the melt annealing duration as well as on the molecular weight. This effect is explained by the gradual destruction of the crystallization centers during annealing of the melt. The experimental data support the well known “memory” effect and the recently observed accumulative “memory” effect on the same polymer
    Type of Medium: Electronic Resource
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