Strained melt

The crystallisation from strained melt as for instance in a blown film or in the jet during fibre spinning produces a row nucleated structure. " Linear nuclei are formed parallel to the strain direction. They contain more or less extended polymer chains. Secondary epitaxial nucleation on the surface of such linear row nuclei produces folded chain lamellae which are oriented perpendicular to the strain (Fig. 6). In such a case the sample exhibits a high uniaxial orientation of chain axes in the strain direction with random orientation of the a- and b-axes perpendicular to it. If the growing lamellae exhibit a helical twist the chain orientation in the strain direction is very soon replaced by the orientation of the axis of maximum growth rate (b-axis in the case of polyethylene) perpendicular to the strain direction and a more random orientation of the remaining two axes (a- and c-axes in the case of polyethylene) with a maximum in the strain direction. Such a row nucleated structure has parallel cylindrical spherulites (cylindrites) as its basic supercrystalline element. 

Since the row nuclei in the crystallising strained melt act as reinforcing frame structure carrying most of the load in the strained liquid, the not yet crystallised melt inside the frame is able to relax almost completely. It hence either crystallises in conventional manner on the surface of the row nuclei yielding the cylindrites or forms new conventional primary nuclei yielding spherulites as shown by electron microscopy of thick nylon 6 fibres as spun. The coexistence of both structural elements in the fibre as spun with a very small fraction of material in row nuclei explains the poor mechanical properties of such a material and the similarity of fibrous structure obtained after drawing with that obtained from purely spherulitic films. 

Ziabicki and Jarecki have studied the effect of thermodynamic and hydro-dynamic parameters on the orientation distribution of the nuclei, to explain oriented fibrillar growth. Wu has also taken a thermodynamic approach to stress induced crystallization of cross-linked rubbers and its effect on morphology. He considers that extended chain crystals are only formed above the zero-strained melting point, Tva, and folded crystals are formed below Tm if the molecules are stretched less than some critical amount. 

Gaylord RJ, Twardowski TE, Douglas JF (1988) The localization model of rubber elastieity and the deformation of a network formed by cross-linking a strained melt Polym Bull 20 (3) 305-310... 

Young s modulus (CPa) Tensile strength (MPa) Fracture strain [%) Melting point (°C)... 

Fig. 5.62. iPP, development of shish kebabs in a strained melt followed by measurements of the Hght intensity after the passage of a beam through a sample (crossed polarizers). The direction of strain is 45° against the crossed polarizers. From Korn-held et al. [62]... 

Non-Newtonian Fluids Die Swell and Melt Fracture. Eor many fluids the Newtonian constitutive relation involving only a single, constant viscosity is inappHcable. Either stress depends in a more complex way on strain, or variables other than the instantaneous rate of strain must be taken into account. Such fluids are known coUectively as non-Newtonian and are usually subdivided further on the basis of behavior in simple shear flow. 

Modified ETEE is less dense, tougher, and stiffer and exhibits a higher tensile strength and creep resistance than PTEE, PEA, or EEP resins. It is ductile, and displays in various compositions the characteristic of a nonlinear stress—strain relationship. Typical physical properties of Tef2el products are shown in Table 1 (24,25). Properties such as elongation and flex life depend on crystallinity, which is affected by the rate of crysta11i2ation values depend on fabrication conditions and melt cooling rates. 

A method for measuring the uniaxial extensional viscosity of polymer soHds and melts uses a tensile tester in a Hquid oil bath to remove effects of gravity and provide temperature control cylindrical rods are used as specimens (218,219). The rod extmder may be part of the apparatus and may be combined with a device for clamping the extmded material (220). However, most of the mote recent versions use prepared rods, which are placed in the apparatus and heated to soften or melt the polymer (103,111,221—223). A constant stress or a constant strain rate is appHed, and the resultant extensional strain rate or stress, respectively, is measured. Similar techniques are used to study biaxial extension (101). 

Rheometric Scientific markets several devices designed for characterizing viscoelastic fluids. These instmments measure the response of a Hquid to sinusoidal oscillatory motion to determine dynamic viscosity as well as storage and loss moduH. The Rheometric Scientific line includes a fluids spectrometer (RFS-II), a dynamic spectrometer (RDS-7700 series II), and a mechanical spectrometer (RMS-800). The fluids spectrometer is designed for fairly low viscosity materials. The dynamic spectrometer can be used to test soHds, melts, and Hquids at frequencies from 10 to 500 rad/s and as a function of strain ampHtude and temperature. It is a stripped down version of the extremely versatile mechanical spectrometer, which is both a dynamic viscometer and a dynamic mechanical testing device. The RMS-800 can carry out measurements under rotational shear, oscillatory shear, torsional motion, and tension compression, as well as normal stress measurements. Step strain, creep, and creep recovery modes are also available. It is used on a wide range of materials, including adhesives, pastes, mbber, and plastics. 

A crystalline or semicrystalline state in polymers can be induced by thermal changes from a melt or from a glass, by strain, by organic vapors, or by Hquid solvents (40). Polymer crystallization can also be induced by compressed (or supercritical) gases, such as CO2 (41). The plasticization of a polymer by CO2 can increase the polymer segmental motions so that crystallization is kinetically possible. Because the amount of gas (or fluid) sorbed into the polymer is a dkect function of the pressure, the rate and extent of crystallization may be controUed by controlling the supercritical fluid pressure. As a result of this abiHty to induce crystallization, a history effect may be introduced into polymers. This can be an important consideration for polymer processing and gas permeation membranes. 

Decompositions may be exothermic or endothermic. Solids that decompose without melting upon heating are mostly such that can give rise to gaseous products. When a gas is made, the rate can be affected by the diffusional resistance of the product zone. Particle size is a factor. Aging of a solid can result in crystallization of the surface that has been found to affect the rate of reaction. Annealing reduces strains and slows any decomposition rates. The decompositions of some fine powders follow a first-order law. In other cases, the decomposed fraction x is in accordance with the Avrami-Erofeyev equation (cited by Galwey, Chemistry of Solids, Chapman Hall, 1967)... 

Well, that is the case at the low temperature, when the rubber has a proper modulus of a few GPa. As the rubber warms up to room temperature, the Van der Waals bonds melt. (In fact, the stiffness of the bond is proportional to its melting point that is why diamond, which has the highest melting point of any material, also has the highest modulus.) The rubber remains solid because of the cross-links which form a sort of skeleton but when you load it, the chains now slide over each other in places where there are no cross-linking bonds. This, of course, gives extra strain, and the modulus goes down (remember, E = [Pg.61]

Fig. 22.4. The random walk of o chain in a polymer melt, or in a solid, glassy polymer means that, on average, one end of the molecule is -yJn)A away from the other end. Very large strains (=4) are needed to straighten the molecule out.

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