Viscoelasticity temperature dependence

The radiation and temperature dependent mechanical properties of viscoelastic materials (modulus and loss) are of great interest throughout the plastics, polymer, and rubber from initial design to routine production. There are a number of laboratory research instruments are available to determine these properties. All these hardness tests conducted on polymeric materials involve the penetration of the sample under consideration by loaded spheres or other geometric shapes [1]. Most of these tests are to some extent arbitrary because the penetration of an indenter into viscoelastic material increases with time. For example, standard durometer test (the "Shore A") is widely used to measure the static "hardness" or resistance to indentation. However, it does not measure basic material properties, and its results depend on the specimen geometry (it is difficult to make available the identity of the initial position of the devices on cylinder or spherical surfaces while measuring) and test conditions, and some arbitrary time must be selected to compare different materials. 

The theory relating stress, strain, time and temperature of viscoelastic materials is complex. For many practical purposes it is often better to use an ad hoc system known as the pseudo-elastic design approach. This approach uses classical elastic analysis but employs time- and temperature-dependent data obtained from creep curves and their derivatives. In outline the procedure consists of the following steps ... 

Micro-mechanical processes that control the adhesion and fracture of elastomeric polymers occur at two different size scales. On the size scale of the chain the failure is by breakage of Van der Waals attraction, chain pull-out or by chain scission. The viscoelastic deformation in which most of the energy is dissipated occurs at a larger size scale but is controlled by the processes that occur on the scale of a chain. The situation is, in principle, very similar to that of glassy polymers except that crack growth rate and temperature dependence of the micromechanical processes are very important. 

The viscoelastic nature of the matrix in many fibre reinforced plastics causes their properties to be time and temperature dependent. Under a constant stress they exhibit creep which will be more pronounced as the temperature increases. However, since fibres exhibit negligible creep, the time dependence of the properties of fibre reinforced plastics is very much less than that for the unreinforced matrix. 

The time/temperature-dependent change in mechanical properties results from stress relaxation and other viscoelastic phenomena that are typical of these plastics. When the change is an unwanted limitation it is called creep. When the change is skillfully adapted to use in the overall design, it is referred to as plastic memory. 

Viscoelasticity A combination of viscous and elastic properties in a plastic with the relative contribution of each being dependent on time, temperature, stress, and strain rate. It relates to the mechanical behavior of plastics in which there is a time and temperature dependent relationship between stress and strain. A material having this property is considered to combine the features of a perfectly elastic solid and a perfect fluid. 

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... 

For the investigation of the time and the temperature dependence of the fibre strength it is necessary to have a theoretical description of the viscoelastic tensile behaviour of polymer fibres. Baltussen has shown that the yielding phenomenon, the viscoelastic and the plastic creep of a polymer fibre, can be described by the Eyring reduced time (ERT) model [10]. The shear deformation of a domain brings about a mutual displacement of adjacent chains, the... 

Sugiyama, M. and Norimoto, M. (1996). Temperature dependence of dynamic viscoelasticities of chemically treated woods. Mokuzai Gakkaishi, 42(11), 1049-1056. 

A unified approach to the glass transition, viscoelastic response and yield behavior of crosslinking systems is presented by extending our statistical mechanical theory of physical aging. We have (1) explained the transition of a WLF dependence to an Arrhenius temperature dependence of the relaxation time in the vicinity of Tg, (2) derived the empirical Nielson equation for Tg, and (3) determined the Chasset and Thirion exponent (m) as a function of cross-link density instead of as a constant reported by others. In addition, the effect of crosslinks on yield stress is analyzed and compared with other kinetic effects — physical aging and strain rate. 

The time and temperature dependent properties of crosslinked polymers including epoxy resins (1-3) and rubber networks (4-7) have been studied in the past. Crosslinking has a strong effect on the glass transition temperature (Tg), on viscoelastic response, and on plastic deformation. Although experimental observations and empirical expressions have been made and proposed, respectively, progress has been slow in understanding the nonequilibrium mechanisms responsible for the time dependent behavior. 

The total deformation in the four-element model consists of an instantaneous elastic deformation, delayed or retarded elastic deformation, and viscous flow. The first two deformations are recoverable upon removal of the load, and the third results in a permanent deformation in the material. Instantaneous elastic deformation is little affected by temperature as compared to retarded elastic deformation and viscous deformation, which are highly temperature-dependent. In Figure 5.62b, the total viscoelastic deformation is given by the curve OABDC. Upon unloading (dashed curve DFFG),... 

When a polymer is used as a structural material, it is important that it be capable of withstanding applied stresses and resultant strains over its useful service life. Polymers are viscoelastic materials, having the properties of solids and viscous liquids. These properties are time- and temperature-dependent. 

Figure 5. Temperature dependence of viscoelastic property of ozonized lignin/epoxy resins cured with hexamethylenediamine. Ozonized lignin content in DGEBA (1) 0 PHR (2) 20 PHR (3) 40 PHR (4) 80 PHR.

Although most physical properties (e.g., viscosity, density, heat conductivity and capacity, and surface tension) must be regarded as variable, it is of particular value that viscosity can be varied by many orders of magnitude under certain process conditions (5,11). In the following, dimensional analysis will be applied exemplarily to describe the temperature dependency of the viscosity and the viscosity of non-Newtonian fluids (pseudoplastic and viscoelastic, respectively) as influenced by the shear stress. 

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. 

Spin-spin relaxation times (T2) in polymer systems range from about 10-5 s for the rigid lattice (glassy polymers) to a value greater than 10-3 s for the rubbery or viscoelastic state. In the temperature region below the glass transition, T2 is temperature independent and not sensitive to the motional processes, because of the static dipolar interactions. The temperature dependence of T2 above Tg and its sensitivity to low-frequency motions, which are strongly affected by the network formation, make spin-spin relaxation studies suitable for polymer network studies. 

The viscoelastic properties are highly temperature-dependent so that the maximum temperature should be always specified and taken into account. Polymers at room temperature behave by different ways i.e. hard solids, elastic liquids, rubbers, etc [1,7]. 

The viscoelastic response of polymer melts, that is, Eq. 3.1-19 or 3.1-20, become nonlinear beyond a level of strain y0, specific to their macromolecular structure and the temperature used. Beyond this strain limit of linear viscoelastic response, if, if, and rj become functions of the applied strain. In other words, although the applied deformations are cyclic, large amplitudes take the macromolecular, coiled, and entangled structure far away from equilibrium. In the linear viscoelastic range, on the other hand, the frequency (and temperature) dependence of if, rf, and rj is indicative of the specific macromolecular structure, responding to only small perturbations away from equilibrium. Thus, these dynamic rheological properties, as well as the commonly used dynamic moduli... 

In view of these complexities, it is remarkable that Eq. 4.1-4 represents numerous metal-metal, dry frictional data rather well, for both the static and sliding cases. Polymers, on the other hand, exhibit an even more complex frictional behavior on metal. This is, perhaps, not surprising, since the physical situation involves a relatively soft, viscoelastic, and temperature-dependent material in contact with a hard, elastic, and much less temperature- and rate-dependent material. Empirical evidence of these complexities is the nonlinear relationship between the frictional force and the normal load... 

With viscoelastic models used by an increasing number of researchers, time and temperature dependence, as well as strain hardening and nonisotropic properties of the deformed parison can, in principle, be accounted for. Kouba and Vlachopoulos (97) used the K-BKZ viscoelastic constitutive equation to model both thermoforming and parison membrane stretching using two-dimensional plate elements in three-dimensional space. Debbaut et al. (98,99) performed nonisothermal simulations using the Giesekus constitutive equation. 

PTFE is known to undergo two crystalline first-order transitions at 19° and 30° and three viscoelastic relaxations have been observed. The temperature dependence of the relaxations (a,8,Y) as determined by dielectric and anelastic measurements is shown in the relaxation map of Figure 10 along with the temperatures of the crystalline phase transitions (vertical dotted lines) Also indicated in Figure 10 are the results of rotational diffusion rates obtained in this study. 

The temperature dependence of the T2 relaxation time of well-defined end-linked poly(propylene oxide) (PPO) networks [43] is shown in Figure 10.1 [44]1. The distinguishing feature of T2 relaxation in the case of viscoelastic networks is the high temperature plateau that is observed at temperatures well above the Tg [45-49]. 

On the basis of our experimental results presented so far, the overall viscoelastic behavior of these triblock copolymers shows an elasticity-dominance over the viscosity. After reaching the critical mass density, where the static elasticity es reaches the maximum, these triblock copolymers collapse into the subphase and form hydrated brushes and these anchored brushes may be responsible for the result that the surface viscosities drop to around the 0 value at r. A distinctive difference between two types of polymers, sample I (PEO-PPO-PEO) and sample II (PPO-PEO-PPO), is the temperature dependence of r where both static elasticity and dilational viscosity show kinds of transitions. V of sample I increases with increasing temperature while that of sample II does not change with temperature. 

There are several analytical tools that provide methods of extrapolating test data. One of these tools is the Williams, Landel, Ferry (WLF) transformation.14 This method uses the principle that the work expended in deforming a flexible adhesive is a major component of the overall practical work of adhesion. The materials used as flexible adhesives are usually viscoelastic polymers. As such, the force of separation is highly dependent on their viscoelastic nature and is, therefore, rate- and temperature-dependent. Test data, taken as a function of rate and temperature, can be expressed in the form of master curves obtained by WLF transformation. This offers the possibility of studying adhesive behavior over a sufficient range of temperatures and rates for most practical applications. Fligh rates of strain may be simulated by testing at lower rates of strain and lower temperatures. 

Finally it may be remarked that the dynamic viscoelastic properties of plasticized cellulose derivatives seem to give no evidence of any unusual temperature dependence of the chain conformations. Thus, Landel and Ferry (162, 163, 164) successfully applied the method of reduced variables [see, for example, Ferry (6)] to various concentrated solutions of cellulosic polymers, and found that the temperature reduction factors were quite similar to those for other flexible polymers such as poly(isobutylene). 

Schwakzl, F., and A. J. Staverman Time-temperature dependence of linear viscoelastic behavior. J. Appl. Phys. 23, 838—843 (1952). 

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