Modulus, viscoelastic properties

The elastic and viscoelastic properties of materials are less familiar in chemistry than many other physical properties hence it is necessary to spend a fair amount of time describing the experiments and the observed response of the polymer. There are a large number of possible modes of deformation that might be considered We shall consider only elongation and shear. For each of these we consider the stress associated with a unit strain and the strain associated with a unit stress the former is called the modulus, the latter the compliance. Experiments can be time independent (equilibrium), time dependent (transient), or periodic (dynamic). Just to define and describe these basic combinations takes us into a fair amount of detail and affords some possibilities for confusion. Pay close attention to the definitions of terms and symbols. 

In principle, the relaxation spectrum H(r) describes the distribution of relaxation times which characterizes a sample. If such a distribution function can be determined from one type of deformation experiment, it can be used to evaluate the modulus or compliance in experiments involving other modes of deformation. In this sense it embodies the key features of the viscoelastic response of a spectrum. Methods for finding a function H(r) which is compatible with experimental results are discussed in Ferry s Viscoelastic Properties of Polymers. In Sec. 3.12 we shall see how a molecular model for viscoelasticity can be used as a source of information concerning the relaxation spectrum. 

Fig. 21. Dynamic viscoelastic properties of a low density polyethylene (LDPE) at 150°C complex dynamic viscosity Tj, storage modulus G and loss modulus G" vs angular velocity, CO. To convert Pa-s to P, multiply by 10 to convert Pa to dyn/cm, multiply by 10.

Acoustic Measurements. Measurement of the propagation of ultrasonic acoustic waves has been found useful for determining the viscoelastic properties of thin films of adhesives. In this method, the specimen is clamped between transmitting and receiving transducers. The change in pulse shape between successive reverberation of the pulse is dependent on the viscoelastic properties of the transmitting material. Modulus values can be calculated (267,268). 

With appropriate caUbration the complex characteristic impedance at each resonance frequency can be calculated and related to the complex shear modulus, G, of the solution. Extrapolations to 2ero concentration yield the intrinsic storage and loss moduH [G ] and [G"], respectively, which are molecular properties. In the viscosity range of 0.5-50 mPa-s, the instmment provides valuable experimental data on dilute solutions of random coil (291), branched (292), and rod-like (293) polymers. The upper limit for shearing frequency for the MLR is 800 H2. High frequency (20 to 500 K H2) viscoelastic properties can be measured with another instmment, the high frequency torsional rod apparatus (HFTRA) (294). 

For a fiber immersed in water, the ratio of the slopes of the stress—strain curve in these three regions is about 100 1 10. Whereas the apparent modulus of the fiber in the preyield region is both time- and water-dependent, the equiUbrium modulus (1.4 GPa) is independent of water content and corresponds to the modulus of the crystalline phase (32). The time-, temperature-, and water-dependence can be attributed to the viscoelastic properties of the matrix phase. 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

Investigation of the linear viscoelastic properties of SDIBS with branch MWs exceeding the critical entanglement MW of PIB (about -7000 g/mol ) revealed that both the viscosity and the length of the entanglement plateau scaled with B rather than with the length of the branches, a distinctively different behavior than that of star-branched PIBs. However, the magnitude of the plateau modulus and the temperature dependence of the terminal zone shift factors were found to... 

Equation (52) allows us to estimate the impact of viscoelastic braking on the capillary flow rate. As an example, we will consider that the liquid is tricresyl phosphate (TCP, 7 = 50 mN-m t = 0.07 Pa-s). The viscoelastic material is assumed to have elastic and viscoelastic properties similar to RTV 615 (General Electric, silicone rubber), i.e., a shear modulus of 0.7 MPa (E = 2.1 MPa), a cutoff length of 20 nm, and a characteristic speed, Uo, of 0.8 mm-s [30]. TCP has a contact angle at equilibrium of 47° on this rubber. 

We have called composite gels which vary in elastic modulus in electric or magnetic fields ER or MR gels. In this section, the viscoelastic properties of some ER or MR gels are presented... 

An example of the utility of these expressions is given in Figure 1 where the log (real modulus) is plotted against temperature for two test specimens of EPDM. The first test specimen is represented by o s, while the second specimen is represented by the dashed lines, which are 95% confidence limits calculated from the expressions in Table II and it viscoelastic properties. The measurements were made three weeks apart. 

Distributions of relaxation or retardation times are useful and important both theoretically and practicably, because // can be calculated from /.. (and vice versa) and because from such distributions other types of viscoelastic properties can be calculated. For example, dynamic modulus data can be calculated from experimentally measured stress relaxation data via the resulting // spectrum, or H can be inverted to L, from which creep can be calculated. Alternatively, rather than going from one measured property function to the spectrum to a desired property function [e.g., Eft) — // In Schwarzl has presented a series of easy-to-use approximate equations, including estimated error limits, for converting from one property function to another (11). 

The dynamic viscoelastic properties of acetylated wood have been determined and compared with other wood treatments in a number of studies. Both the specific dynamic Young s modulus (E /j) and tan S are lower in acetylated wood compared with unmodified wood (Akitsu etal., 1991, 1992, 1993a,b Korai and Suzuki, 1995 Chang etal., 2000). Acetylation also reduces mechanosorptive creep deformation of the modified wood (Norimoto etal., 1992 Yano etal, 1993). In a study of the dynamic mechanical properties of acetylated wood under conditions of varying humidity, it was concluded that the rate of diffusion of moisture into the wood samples was not affected by acetylation (Ebrahimzadeh, 1998). 

In this introduction, the viscoelastic properties of polymers are represented as the summation of mechanical analog responses to applied stress. This discussion is thus only intended to be very introductory. Any in-depth discussion of polymer viscoelasticity involves the use of tensors, and this high-level mathematics topic is beyond the scope of what will be presented in this book. Earlier in the chapter the concept of elastic and viscous properties of polymers was briefly introduced. A purely viscous response can be represented by a mechanical dash pot, as shown in Fig. 3.10(a). This purely viscous response is normally the response of interest in routine extruder calculations. For those familiar with the suspension of an automobile, this would represent the shock absorber in the front suspension. If a stress is applied to this element it will continue to elongate as long as the stress is applied. When the stress is removed there will be no recovery in the strain that has occurred. The next mechanical element is the spring (Fig. 3.10[b]), and it represents a purely elastic response of the polymer. If a stress is applied to this element, the element will elongate until the strain and the force are in equilibrium with the stress, and then the element will remain at that strain until the stress is removed. The strain is inversely proportional to the spring modulus. The initial strain and the total strain recovery upon removal of the stress are considered to be instantaneous. 

More recently, Lin and Masuda [47] measured the viscoelastic properties of polypropylene melts filled with small (0.15 pm) and larger (4.0 pm) calcium carbonate particles. The dynamic modulus and viscosity were found to rise with filler loading especially at low frequencies. With highly filled compositions (at... 

The dynamic mechanical thermal analyzer (DMTA) is an important tool for studying the structure-property relationships in polymer nanocomposites. DMTA essentially probes the relaxations in polymers, thereby providing a method to understand the mechanical behavior and the molecular structure of these materials under various conditions of stress and temperature. The dynamics of polymer chain relaxation or molecular mobility of polymer main chains and side chains is one of the factors that determine the viscoelastic properties of polymeric macromolecules. The temperature dependence of molecular mobility is characterized by different transitions in which a certain mode of chain motion occurs. A reduction of the tan 8 peak height, a shift of the peak position to higher temperatures, an extra hump or peak in the tan 8 curve above the glass transition temperature (Tg), and a relatively high value of the storage modulus often are reported in support of the dispersion process of the layered silicate. 

Fig. 6 Variation of viscoelastic properties as a function of strain amplitude of uncrosslinked and dynamically vulcanized blends at 180°C (a) storage modulus, (b) loss modulus. CD2 TPV prepared by preblending, PD2 TPV prepared by phase mixing, SD2 TPV prepared by split addition...

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