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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 269 (1991), S. 421-432 
    ISSN: 1435-1536
    Keywords: Melt spinning ; polyethylene ; mechanical properties ; chain entanglements ; network
    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 Melt-spinning experiments were carried out at high quenching rates. Mechanical properties (elongation at break, natural draw ratio, and elastic recovery) have been measured. Significant variations of these quantities were observed when extrusion conditions were changed. This has been attributed to different states of the entanglements within the melt, which are directly transferred into the solid state. This intercorrelation between melt and solid-state properties has been substantiated in the case of rapidly cooled samples, where a poor crystallization on one side and a simultaneous good conservation of melt history on the other side are provoked.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 270 (1992), S. 331-348 
    ISSN: 1435-1536
    Keywords: Melt spinning ; polyethylene ; mechanicalproperties ; entanglements ; knots ; 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 Melt spinning experiments of polyethylene, using a high quenching rate have been carried out. Molecular weight has been varied. From measurements of the mechanical properties of the monofilaments produced it is concluded that melt history influences the solid state behavior. This is reflected in the hypothesis of a transference of knots, preexisting in the melt into the solid state. Measurements of the elastic recovery allow to offer an interpretation, in which this network of knots does not percolate, until a critical value of the molecular weightM c knot≈105 is surpassed. The possible influence of these knots on the mobile entanglements is discussed.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 275 (1997), S. 432-439 
    ISSN: 1435-1536
    Keywords: Key words Microhardness ; polyethylene ; entanglements ; amorphous layer
    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  Microhardness of a series of linear PE samples with a wide range of molecular weights has been determined. The influence of the mode of crystallization from the melt on the mechanical properties has been examined. It is shown that crystal hardness is correlated to the thickness of the amorphous layer for each series of samples. A new expression which describes the microhardness (H) of polyethylene as a function of the average distance between stable entanglements (knots) s is proposed. A value of s=360 Å, for the mean length between knots in the network is obtained. Analysis of data reveals that the H value can be expressed in terms of the following morphological parameters: 1) average number of chain folds in a lamellar crystal, 2) the nature of the interface between the crystalline and the amorphous layer and 3) the linear crystallinity.
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  • 4
    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: Summary We were interested in the problem: exist intermediate states between the discrete dielectric relaxation mechanism of a pure polymer, if the polymer is dissolved? For our investigations we took polyacrylmethacrylate (PMMA) (iso- and syndiotactic) as solute and toluene (nearly nonpolymer) as solvent. The investigations of 15 % and 48 % PMMA jellies have shown that in the jellies there existes large demixed ranges of PMMA, operating as crosslinks. Our dielectric investigations allow the following conclusions. There are none of new relaxation mechanism in solutions for PMMA which exist already in the pure polymer with one exception: There exist a discrete relaxation process, caused by a complex between toluene and PMMA. The dissolved PMMA-molecules show the same mechanism as the pure polymer, the PMMA in the concentrated regions of crosslinks show the β-mechanism of pure PMMA. The fact, that only a discrete number of PMMA-relaxation-mechanism exist, is a consequence of the chainstructure of the PMMA-molecules: The intramolecular interaction is dominant.
    Notes: Zusammenfassung Ausgangspunkt war die Fragestellung nach eventuell auftretenden Zwischenzuständen zwischen den Relaxationsmechanismen (α, β usw.) für ein reines Polymeres bei Lösung des Polymers. Für unsere Untersuchungen wählten wir als Polymer das Polyacrylmethacrylat (PMMA) (iso- und syndiotaktisches) und als Lösungsmittel das wenig polare Toluol. Die Strukturuntersuchungen an Gelen von 15%iger und 48%iger PMMA-Konzentration ergaben, daß die Gele teils große entmischte PMMA-Regionen als Vernetzungsstellen aufwiesen. Mit Hilfe von Messungen der dielektrischen Relaxation wurden folgende Ergebnisse erzielt: Abgesehen von einem lösungsmittelbeeinflußten Bewegungsmechanismus gibt es keine neuen PMMA-Bewegungsmechanismen über die hinaus, die am reinen Polymeren auftreten. Die gelösten PMMA-Moleküle im Gel weisen demnach denselben Mechanismus wie die reine Polymere auf, das PMMA in den konzentrierten Vernetzungsregionen zeigt den β-Mechanismus des reinen PMMA auf. Die Tatsache, daß es nur eine diskrete Anzahl von PMMA-Bewegungsmechanismen gibt, wird durch die Molekülstruktur der Kette erklärt. Hierbei zeigte sich, daß die intramolekulare Wechselwirkung von dominierendem Einfluß ist.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 17 (1978), S. 28-32 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Experimente zum isothermen Schmelzspinnen wurden mit dem „Rheotens“ an einer extrudierten Polyäthylenschmelze durchgeführt. Messungen von Abzugskraft, Abzugsgeschwindigkeit und Querschnittsprofil des extrudierten Stranges bei variierenden Ausstößen führten zur Bestimmung der Dehnviskosität als Funktion von Dehngeschwindigkeit und Deformationszeit. Es konnte nachgewiesen werden, daß die Deformationszeit besser als die Dehngeschwindigkeit zur Charakterisierung der Dehnviskosität von extrudierten Schmelzen geeignet ist.
    Notes: Summary Isothermal continuous stretching experiments with a Rheotens apparatus were carried out on an extruded polyethylene melt. Measurements of the tensile force, the thread velocity and the thread profiles for various mass flow rates resulted in the determination of the elongational viscosity as a function of the strain rate and the deformation time. It was found that the deformation time is a more suitable general parameter than the strain rate for the characterization of the elongational viscosity of extruded polymer melts.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 19 (1980), S. 507-516 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary The mechanical properties of partially crystalline thermoplastic materials are characterized mainly by crystallinity, orientation of the chain molecules and number of tie molecules between the lamallae. These quantities can be controlled by the meltspinning process of PE. The crystallinity is given by the temperature of the cooling medium. The orientation is controlled by the take-up velocity of the spinning apparatus. The number of tie molecules is governed by the melt temperature, the molecular weight and the kinetics of deformation of the melt. The number of tie molecules is the higher the lower the extensibility of the melt. A hard-elastic fiber i.e. a monofilament of high elastic recovery could be produced by decreasing the number of tie molecules. The mechanism of the hard-elastic fiber is discussed under this point of view.
    Notes: Zusammenfassung Die mechanischen Eigenschaften teilkristalliner Thermoplaste werden im wesentlichen charakterisiert durch die Kristallinität, durch die Orientierung der Kettenmoleküle und die Anzahl der Verbindungsmoleküle zwischen den Kristallamellen. Diese Größen können beim Schmelzspinnprozeß von Polyäthylen gezielt gesteuert werden. Die Kristallinität kann durch die Temperatur eines Abkühlbades beeinflußt werden. Die Orientierung ist durch die Abzugsgeschwindigkeit regelbar. Die Anzahl der Verbindungsmoleküle kann durch Schmelzentemperatur, Molekulargewicht und Deformationskinetik der Schmelze geändert werden. Die Anzahl der Verbindungsmoleküle ist um so höher, je geringer die Dehnbarkeit der Schmelze ist. Eine elastische Hartfaser, d. h. ein Faden mit hoher elastischer Erholung, kann durch Minimalisierung der Anzahl der Verbindungsmoleküle hergestellt werden. Der Mechanismus der elastischen Hartfaser wird unter diesem Gesichtspunkt diskutiert.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 268 (1990), S. 440-446 
    ISSN: 1435-1536
    Keywords: Microhardness ; polyethylene ; molecularweight ; folded-chainlamellae ; melting ; surfacefreeenergy ; entanglements
    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 microhardness of a series of melt crystallized samples of linear polyehtylene was investigated in a wide range of molecular weights. The x-ray long period was analyzed to study the variation of the hardness-derived constantb as a function of molecular weight (M η). It is pointed out thatb offers a measure of the hardness depression due to the finite thickness of the lamellar crystals. The data obtained show that the increase and final leveling-off (forM η 200 000) ofb withM η parallels the concurrent increase of the surface free energy, as derived from DSC experiments. Results are discussed using the concept og chain folded lamellae as thermodynamically stable non-homogeneous microphases. Comparison of experimental and calculated data supports the view that the number of molecular entanglements, segregated onto the defective surface boundary of the heterogeneous crystals influence the shearing mechanism within the “mesocrystals” and thereby control the yield behavior of the material.
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  • 8
    ISSN: 1435-1536
    Keywords: Polyethylene-carbon black composities ; injection-molding ; electron microscopy ; small angle x-rax diffraction ; 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 morphology and structure of high molecular weight linear polyethylene (M w 450000) filled with carbon black and processed using molds that introduce an elongational flow component during injection molding has been examined using electron microscopy and x-ray diffraction techniques. The study of fracture surfaces reveals the display of shish-kebabs oriented along the injection direction with segregated longitudinal channels of carbon black particles. Molecular and lamellar changes in orientation are, furthermore, studied across the thickness of the moldings. It is shown that addition of carbon black particles to injection-molded polyethylene induces significant changes in lamellar orientation. Thus, while lamellar overgrowth proceeds perpendicular to the fiber axes within carbon free channels, lamellae grow randomly within carbon-enriched regions where flow is less pronounced.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 269 (1991), S. 859-866 
    ISSN: 1435-1536
    Keywords: Van der Waalsnetwork ; polyethylene ; compression ; injectionmolding ; biaxialdeformation
    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 compressive stress-strain behavior of biaxially oriented polyethylene (PE), obtained by pressing uniaxially oriented samples, is described with the aid of the van der Waals equation of state. Results are discussed in terms of two parameters: the biaxiality (B) and the biaxial draw ratio (〈λ〉), which offer a measure of the strain along the two principal directions and of the average draw ratio on the film plane, respectively. Comparison of experimental and calculated data indicates that after compression up to very large deformations the maximum average strain (λ m ), which is proportional to the square root of the chain length of the network, remains constant. This result supports the view that the network of entanglements is not destroyed after compression. Experiments carried out on isotropic melt crystallized PE show the presence of a network having a not very different chain length. Finally, it is shown that the segment length of this network is close to the X-ray long period of the initial structure. This result implies the existence of a high density of entanglements (∼two entanglements every three adjacent lamellae), which are rejected into the defective layer of the crystals.
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  • 10
    ISSN: 1435-1536
    Keywords: Polyethylene ; melt spinning ; mechanical properties ; crystallization ; entanglements ; knots
    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 Investigations of the influence of crystallization conditions and molecular weight on mechanical properties of melt spum monofilaments have been carried out in previous studies [1, 2]. The present results emphasize the influence of crystallization upon two classes of molecular entanglements present in the melt: 1) mobile entanglements with short life times; 2) long living knots as a superstructure of the entanglement network. On the other hand, it is shown that the former number of entanglements controls the thickness of the crystalline lamellae. It is pointed out that knots also have a specific influence on morphology. Knots form the amorphous phase of a semicrystalline polymer and are mechanically active. The present model is comparatively discussed in light of Peterlin's plastic deformation model and Kilian's van der Waals Network Theory.
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