Viscoelastic extensibility

During the creep of PET and PpPTA fibres it has been observed that the sonic compliance decreases linearly with the creep strain, implying that the orientation distribution contracts [ 56,57]. Thus, the rotation of the chain axes during creep is caused by viscoelastic shear deformation. Hence, for a creep stress larger than the yield stress, Oy,the orientation angle is a decreasing function of the time. Consequently, we can write for the viscoelastic extension of the fibre... 

Before concluding this discussion of cell walls, we note that the case of elasticity or reversible deformability is only one extreme of stress-strain behavior. At the opposite extreme is plastic (irreversible) extension. If the amount of strain is directly proportional to the time that a certain stress is applied, and if the strain persists when the stress is removed, we have viscous flow. The cell wall exhibits intermediate properties and is said to be viscoelastic. When a stress is applied to a viscoelastic material, the resulting strain is approximately proportional to the logarithm of time. Such extension is partly elastic (reversible) and partly plastic (irreversible). Underlying the viscoelastic behavior of the cell wall are the crosslinks between the various polymers. For example, if a bond from one cellulose microfibril to another is broken while the cell wall is under tension, a new bond may form in a less strained configuration, leading to an irreversible or plastic extension of the cell wall. The quantity responsible for the tension in the cell wall — which in turn leads to such viscoelastic extension — is the hydrostatic pressure within the cell. 

The model is now further developed to incorporate the viscoelastic extension of the fibre. To this end, we make the simple asssumption that the time-dependent part of the creep strain of the fibre arises solely from the rotation of the chains towards the fibre axis direction as result of the shear deformation of crystallites. This yields for the fibre extension as a function of the time t during creep caused by a stress a... 

Esterase Cladosporium cladosporioides Film, fibrs Determination of tensile strength, viscoelasticity, extension behavior, viscosity Hydrolysis, change of physical properties [93]... 

The limited viscoelastic extensibility of rubber strands determines according to the theory of Bueche and Halpin [69] the fracture of elastomers. The authors assume... 

The outlined scheme is shown to yield stable solutions for non-zero Weissenberg number flows in a number of benchmark problems (Swarbric and Nassehi, 1992b). However, the extension of this scheme to more complex problems may involve modifications such as increasing of elemental subdivisions for stress calculations from 3 x 3 to 9 x 9 and/or the discretization of the stress field by biquadratic rather than bi-linear sub-elements. It should also be noted that satisfaction of the BB condition in viscoelastic flow simulations that use mixed formulations is not as clear as the case of purely viscous regimes. 

Much more information can be obtained by examining the mechanical properties of a viscoelastic material over an extensive temperature range. A convenient nondestmctive method is the measurement of torsional modulus. A number of instmments are available (13—18). More details on use and interpretation of these measurements may be found in references 8 and 19—25. An increase in modulus value means an increase in polymer hardness or stiffness. The various regions of elastic behavior are shown in Figure 1. Curve A of Figure 1 is that of a soft polymer, curve B of a hard polymer. To a close approximation both are transpositions of each other on the temperature scale. A copolymer curve would fall between those of the homopolymers, with the displacement depending on the amount of hard monomer in the copolymer (26—28). 

The elongation of a stretched fiber is best described as a combination of instantaneous extension and a time-dependent extension or creep. This viscoelastic behavior is common to many textile fibers, including acetate. Conversely, recovery of viscoelastic fibers is typically described as a combination of immediate elastic recovery, delayed recovery, and permanent set or secondary creep. The permanent set is the residual extension that is not recoverable. These three components of recovery for acetate are given in Table 1 (4). The elastic recovery of acetate fibers alone and in blends has also been reported (5). In textile processing strains of more than 10% are avoided in order to produce a fabric of acceptable dimensional or shape stabiUty. 

Eracture mechanics concepts can also be appHed to fatigue crack growth under a constant static load, but in this case the material behavior is nonlinear and time-dependent (29,30). Slow, stable crack growth data can be presented in terms of the crack growth rate per unit of time against the appHed R or J, if the nonlinearity is not too great. Eor extensive nonlinearity a viscoelastic analysis can become very complex (11) and a number of schemes based on the time rate of change of/have been proposed (31,32). 

It has been also shown that when a thin polymer film is directly coated onto a substrate with a low modulus ( < 10 MPa), if the contact radius to layer thickness ratio is large (afh> 20), the surface layer will make a negligible contribution to the stiffness of the system and the layered solid system acts as a homogeneous half-space of substrate material while the surface and interfacial properties are governed by those of the layer [32,33]. The extension of the JKR theory to such layered bodies has two important implications. Firstly, hard and opaque materials can be coated on soft and clear substrates which deform more readily by small surface forces. Secondly, viscoelastic materials can be coated on soft elastic substrates, thereby reducing their time-dependent effects. 

Via an ad hoc extension of the viscoelastic Hertzian contact problem, Falsafi et al. [38] incorporated linear viscoelastic effects into the JKR formalism by replacing the elastic modulus with a viscoelastic memory function accounting for time and deformation, K t) ... 

Over the years there have been many attempts to simulate the behaviour of viscoelastic materials. This has been aimed at (i) facilitating analysis of the behaviour of plastic products, (ii) assisting with extrapolation and interpolation of experimental data and (iii) reducing the need for extensive, time-consuming creep tests. The most successful of the mathematical models have been based on spring and dashpot elements to represent, respectively, the elastic and viscous responses of plastic materials. Although there are no discrete molecular structures which behave like the individual elements of the models, nevertheless... 

For example, at MW = 4 X 10, c = 12 g/liter, and at MW = 5 X 10, c " = 62 g/liter. A polymer solution with concentration c > c is called a semidilute solution because mass concentration is low yet repulsive interactions between solutes are strong. Thermodynamics, viscoelasticity, and diffusion properties of semidilute polymer solutions have been studied extensively since the 1960s. 

Interpretation of data obtained under the conditions of uniaxial extension of filled polymers presents a severe methodical problem. Calculation of viscosity of viscoelastic media during extension in general is related to certain problems caused by the necessity to separate the total deformation into elastic and plastic components [1]. The difficulties increase upon a transition to filled polymers which have a yield stress. The problem on the role and value of a yield stress, measured at uniaxial extension, was discussed above. Here we briefly regard the data concerning longitudinal viscosity. 

Though experimental data on suspensions of fibers in Newtonian dispersion media give more or less regular picture, a transition to non-Newtonian viscoelastic liquids, as Metzner noted [21], makes the whole picture far or less clear. Probably, the possibility to make somewhat general conclusions on a longitudinal flow of suspensions in polymer melts requires first of all establishing clear rules of behavior of pure melts at uniaxial extension this problem by itself has no solution as yet. 

Dynamic mechanical measurements for elastomers that cover wide ranges of frequency and temperature are rather scarce. Payne and Scott [12] carried out extensive measurements of /a and /x" for unvulcanized natural mbber as a function of test frequency (Figure 1.8). He showed that the experimental relations at different temperatures could be superposed to yield master curves, as shown in Figure 1.9, using the WLF frequency-temperature equivalence, Equation 1.11. The same shift factors, log Ox. were used for both experimental quantities, /x and /x". Successful superposition in both cases confirms that the dependence of the viscoelastic properties of rubber on frequency and temperature arises from changes in the rate of Brownian motion of molecular segments with temperature. 

It has often been pointed out for a long time that the hysteresis energy given from the hysteresis loop under large extension is too big compared with the viscoelastic dissipation energy. For example, the hysteresis loop given from the stress relaxation is only 20%-30% of that from the stress-strain curve, when both measurements are performed at the same relaxation time and the... 

Contrary to the phase separation curve, the sol/gel transition is very sensitive to the temperature more cations are required to get a gel phase when the temperature increases and thus the extension of the gel phase decreases [8]. The sol/gel transition as determined above is well reproducible but overestimates the real amount of cation at the transition. Gelation is a transition from liquid to solid during which the polymeric systems suffers dramatic modifications on their macroscopic viscoelastic behavior. The whole phenomenon can be thus followed by the evolution of the mechanical properties through dynamic experiments. The behaviour of the complex shear modulus G (o)) reflects the distribution of the relaxation time of the growing clusters. At the gel point the broad distribution of... 

The ratio of extensional viscosity r e to shear viscosity r s is known as the Trouton ratio, which is three for Newtonian fluids in uniaxial extension and larger than three for non-Newtonian fluids. For a viscoelastic fluid such as a polymer in solution, the uniaxial extensional viscosity characterizes the resistance of the fluid... 

The strength and extensibility of a noncrystallizable elastomer depend on its viscoelastic properties (28,29), even when the stress remains in equilibrium with the strain until macroscopic fracture occurs. In theory, such elastomers have a time- or rate-independent strength and ultimate elongation, but such threshold quantities apparently have not been measured, though rough estimates have been made (28,30). 

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