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  • 1
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 9 (1969), S. 172-181 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Neither the fringed-micelle, fringed-fibril or extreme folded-chain models explain the morphological and mechanical properties of highly drawn polyethylene. The modified folded-chain model, assuming that a substantial fraction (between 5 and 30 percent) of the molecules do not fold back at the crystal surface but go through the “amorphous” surface layer and enter the next crystal, avoids the insufficiencies of the above mentioned models.The elastic modulus and tensile strength of drawn polyethylene, both increasing with draw ratio, are to a large extent the consequence of the molecules bridging the quasi-amorphous layers and interconnecting the folded-chain lamellae oriented more-or-less perpendicular to the machine direction. The folds create enough space for the accommodation of more-or-less extended tie molecules in the quasi-amorphous layers between the lamellae. Electron microscopy and calorimetry of samples as drawn, annealed and/or etched with fuming nitric acid support the model.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 17 (1977), S. 183-193 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Under uniaxial tensile load, the plastic deformation of unoriented crystalline polymers first transforms the lamellae into a fibrous structure. Usually the drawing is inhomogeneous with a neck propagating through the sample. The higher the draw ratio, the higher the axial elastic modulus as a consequence of the larger fraction of taut tie molecules in amorphous layers connecting the crystalline blocks of each microfibril. As a consequence of the almost 1/(1 - α) times higher strain of amorphous layers under tensile load, the taut tie molecules are much more strained than the chains in crystal blocks. Hence, their contribution to elastic modulus is substantially higher than one would guess from their fraction β. This is more so in polyethylene with higher crystallinity (α = 0.8) than in nylon 6 with low crystallinity (α = 0.5). Even for the highest modulus polyethylene E = 70 GPa ∼ 0.3 × Ec, one needs less than 7.5 percent of taut tie molecules. The plastic deformation of the fibrous structure markedly enhances the number of interfibrillar tie molecules in nylon 6 and to a lesser extent in polyethylene and polypropylene. Homogeneous drawing without a neck transforms the whole sample into a fibrous structure rather uniformly so that for a long while one has the lamellar and fibrillar morphology side by side. The end effect on the structure obtained does not differ appreciably from inhomogeneous drawing with neck propagation. The drawing of polymers with a liquid crystal structure yields a highly aligned fibrous structure with very few chain folds and an exceptionally high elastic modulus and strength. But the axial connection of individual highly oriented and ordered domains is affected by a relatively small fiaction of tie molecules, and this is responsible for reduction of the elastic modulus below the value of the ideal crystal lattice.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 19 (1979), S. 118-124 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: As a rule, the large increase of elastic modulus with increasing draw ratio obtainable in highly-drawn or extruded semicrystalline polymers is not reflected in a similarly large increase of strength. This is closely connected with the wellknown fact that with increasing plastic deformation one obtains fibrous material with decreasing strain to break. The axial elastic modulus is mainly caused by the taut tie molecules which bridge the amorphous layers between consecutive crystal blocks and thus provide an efficient axial force transmission through the sample. The defects at the ends of microfibrils interrupt this transmission because they contain few if any taut tie molecules connecting the end of microfibril with adjacent fibrillar elements. As a consequence of the small number of such ends, they only marginally reduce the elastic modulus. But as the mechanically weakest areas of the fibrous material, they drastically depress the strength. They fail as soon as the strain concentration upon them reaches their strain to break. The growth and coalescence of resulting microcracks finally lead to bulk fracture as the growing crack reaches critical dimensions.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 14 (1974), S. 627-632 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: During extrusion the main deformation and orientation of macromolecules is achieved by the flow component with longitudinal gradient. The orientation increases drastically if some solidification occurs during flow, yielding row-nucleated cylindrites and even fully oriented hard elastomers. In all cases the basic elements are stacks of very thin (∼100Å) folded-chain lamellae connected by very few tie molecules. The plastic deformation of the solid transforms the original lamellar material into the extremely well oriented fibrous structure with high anisotropy of physical properties. The basic element are the highly aligned, very long and thin microfibrils bundled into fibrils. The axial strength of microfibrils is caused by the great many taut tie molecules connecting as almost crystalline bridges the crystalline blocks across the interposed amorphous layers. In plastic deformation of fibrous material the fibrils are sheared and longitudinally displaced. The latter mode is responsible for almost all the observed elongation. It smooths the structural defects on the surface of fibrils caused by the ends of microfibrils and thus produces a better lateral fit of fibrils resulting in rapidly increasing resistance to plastic deformation. The former mode extends the interfibrillar tie molecules and hence drastically increases their fraction per amorphous layer.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 126-137 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: The elongation and orientation of randomly coiled macromolecules in a strained melt or solution reduces their entropy and thus increases the crystallization or melting temperature of the ideal lattice. At any given temperature of experiment this enhances nucleation and crystal growth rate. As a rule, linear primary nuclei are formed. They contain more or less extended chains. The existence of row nuclei reduces the local gradient in the liquid to such an extent that further crystallization proceeds by epitaxial overgrowth of folded chain lamellae. Densely packed cylindrites are formed with the ribbon-like lamellae radiating from the central row nucleus. The irregular shish-kebab structure observed in stirred or sonicated solutions seems to be formed by subsequent exial deformation of cylindrites in the flow field. It displaces the lamellae irregularly and thus produces a great many microfibrillar elements parallel to the original row nuclei. The almost completely extended chains in the shish yield a high elastic modulus and tensile strength for exial loading. The shish-kebab morphology in fibers as spun does not affect to a great extent the mechanical properties obtainable by subsequent drawing. The lamellae are transformed into microfibrils in very much the same manner as in spherulitic samples. But the highly regular orientation of lamellae seems to result in a more uniform drawing and hence a stronger fiber. In an extremely high temperature and pressure gradient, the melt extrusion produces hard elastomers where the lamellae of the cylindrites seem to be locally stapled. Upon application of tensile load in the extrusion direction, the intervening sections bend like beams, thus forming thin holes extending in the direction perpendicular to the load. The holes enormously enhance the permeability for gases and liquids. The elastic bending of lamellae yields the high recoverable strain and low tensile modulus.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 18 (1978), S. 488-495 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: The annealing of drawn samples mobilizes the almost fully extended amorphous tie molecules which try to assume the thermodynamically required random conformations. The sample shrinks if annealed with free ends which permits the crystal blocks on different microfibrils and connected by almost fully extended taut tie molecules to move towards the position they had before plastic deformation. Hence the annealed sample has irretrievably lost most of its high axial elastic modulus which in the sample as drawn was caused by the high fraction of taut tie molecules. With fixed ends no shrinkage is possible so that the partial relaxation of interfibrillar taut tie molecules still lets them connect far away blocks. If their fraction is large enough so that in spite of the high surface to volume ratio which drastically depresses the crystallization temperature they can crystallize they do so after cooling to room temperature. The new axial crystalline bridges restore the high elastic modulus of the material before annealing, partially stabilize the sample against shrinkage during a new annealing, but also cause the dead bend effect which is the consequence of the replacement of flexible taut tie molecules in still amorphous conformation by rigid crystalline bridges. The drawing or extrusion at high temperature produces some annealing effects comparable with those of cold drawn material annealed with fixed ends.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 23 (1983), S. 734-742 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: At a fixed vapor pressure p of the penetrant and constant temperature of the experiment, the sorption S = c/p or concentration c of the ethylacetate vapor in the uniaxially strained low density polyethylene (LDPE) increases most rapidly at low strains. If, however, on the basis of strain relaxation one separates the total strain ∊ into an elastic ∊e, and a plastic ∊pl, deformation, one obtains an almost linear increase of the concentration c or sorption S of the sorbate with elastic strain ∊e. The separation of ∊ = ∊e + ∊pl depends very much on the time th the sample is kept elongated and the vapor pressure p of the sorbate. The elastic component decreases and the complementary plastic fraction increases with th and p. An almost stationary state is reached after th of about 1/2 h. The calculation of the diffusion coefficient Ds1 from the first sorption immediately after the stretching is affected by this slow adjustment in the interval 0 ≤ th ≤ ½h and shows a pseudo maximum at a strain of ∊∼ = 10 percent. The first desorption experiment and all the later sorptions and desorptions yield the same DD = DS 〈 DS1 that is the correctly calculated diffusion coefficient D. The coefficient D decreases with the strain ∊ or ∊e in contrast with the expected increase of Da of the amorphous component. Such an increase of Da is expected as a consequence of the fractional free volume (FFV) increase caused by the elongation. According to the FFV concept, a decrease of the measured apparent diffusion coefficient D = ψDa requires that with increasing ∊, the tortuosity factor ψ decreases faster than the increase in Da.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 18 (1978), S. 1062-1067 
    ISSN: 0032-3888
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: The fibrous material obtained by drawing or extrusion exhibits a more than linear increase in the axial elastic modulus with draw ratio, a much slower increase in tensile strength and a decrease in strain to break. The reason for such a behavior is found in the existence of structural defects of fibrous material, which is composed of very long and narrow microfibrillar elements. At their ends the axial connection by taut-tie molecules is almost completely interrupted. Hence the transfer of tensile stress through such a defect is only possible by lateral shift of the load to adjacent microfibrils. The incompleteness of this transfer, the excess straining of the material in the defect area, and the relatively easy axial displacement of the ends of microfibrils favor the local formation of microcracks which grow and coalesce with close-by microcracks until a critical size crack is formed and the strained sample fails. The process is favored by a high elastic modulus of microfibrils which is practically identical with that of the drawn or extruded sample. Hence the fibrous polymer fails at lower strain the higher its axial elastic modulus, i.e., the higher the draw ratio.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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