Time-Dependent Effects

Dan N 1996 Time-dependent effects in surface forces Current Opinion Colloid Interface Sol. 1 48-52... 

The other models can be appHed to non-Newtonian materials where time-dependent effects are absent. This situation encompasses many technically important materials from polymer solutions to latices, pigment slurries, and polymer melts. At high shear rates most of these materials tend to a Newtonian viscosity limit. At low shear rates they tend either to a yield point or to a low shear Newtonian limiting viscosity. At intermediate shear rates, the power law or the Casson model is a useful approximation. 

Thixotropy and Other Time Effects. In addition to the nonideal behavior described, many fluids exhibit time-dependent effects. Some fluids increase in viscosity (rheopexy) or decrease in viscosity (thixotropy) with time when sheared at a constant shear rate. These effects can occur in fluids with or without yield values. Rheopexy is a rare phenomenon, but thixotropic fluids are common. Examples of thixotropic materials are starch pastes, gelatin, mayoimaise, drilling muds, and latex paints. The thixotropic effect is shown in Figure 5, where the curves are for a specimen exposed first to increasing and then to decreasing shear rates. Because of the decrease in viscosity with time as weU as shear rate, the up-and-down flow curves do not superimpose. Instead, they form a hysteresis loop, often called a thixotropic loop. Because flow curves for thixotropic or rheopectic Hquids depend on the shear history of the sample, different curves for the same material can be obtained, depending on the experimental procedure. 

Time-dependent effects ate measured by determining the decay of shear stress as a function of time at one or more constant shear rates (Fig. 7)... 

Results from measurements of time-dependent effects depend on the sample history and experimental conditions and should be considered approximate. For example, the state of an unsheared or undisturbed sample is a function of its previous shear history and the length of time since it underwent shear. The area of a thixotropic loop depends on the shear range covered, the rate of shear acceleration, and the length of time at the highest shear rate. However, measurements of time-dependent behavior can be usehil in evaluating and comparing a number of industrial products and in solving flow problems. 

In summary, then, design with polymers requires special attention to time-dependent effects, large elastic deformation and the effects of temperature, even close to room temperature. Room temperature data for the generic polymers are presented in Table 21.5. As emphasised already, they are approximate, suitable only for the first step of the design project. For the next step you should consult books (see Further reading), and when the choice has narrowed to one or a few candidates, data for them should be sought from manufacturers data sheets, or from your own tests. Many polymers contain additives - plasticisers, fillers, colourants - which change the mechanical properties. Manufacturers will identify the polymers they sell, but will rarely disclose their... 

Recently, Dinwiddie et al. [14] reported the effects of short-time, high-temperatme exposures on the temperature dependence of the thermal conductivity of CBCF. Samples were exposed to temperatures ranging from 2673 to 3273 K, for periods of 10, 15, and 20 seconds, to examine the time dependent effects of graphitization on thermal conductivity measured over the temperature range from 673 to 2373 K. Typical experimental data are shown in Figs. 7 and 8 for exposure times of 10 and 20 seconds, respectively. The thermal conductivity was observed to increase with both heat treatment temperature and exposure time. 

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. 

Dynamic loading in the present context is taken to include deformation rates above those achieved on the standard laboratorytesting machine (commonly designated as static or quasi-static). These slower tests may encounter minimal time-dependent effects, such as creep and stress-relaxation, and therefore are in a sense dynamic. Thus the terms static and dynamic can be overlapping. 

The present review shows how the microhardness technique can be used to elucidate the dependence of a variety of local deformational processes upon polymer texture and morphology. Microhardness is a rather elusive quantity, that is really a combination of other mechanical properties. It is most suitably defined in terms of the pyramid indentation test. Hardness is primarily taken as a measure of the irreversible deformation mechanisms which characterize a polymeric material, though it also involves elastic and time dependent effects which depend on microstructural details. In isotropic lamellar polymers a hardness depression from ideal values, due to the finite crystal thickness, occurs. The interlamellar non-crystalline layer introduces an additional weak component which contributes further to a lowering of the hardness value. Annealing effects and chemical etching are shown to produce, on the contrary, a significant hardening of the material. The prevalent mechanisms for plastic deformation are proposed. Anisotropy behaviour for several oriented materials is critically discussed. 

Some deactivation processes lower the number of active sites So- Others add mass transfer resistances. In either case, they cause a reduction in the reaction rate that is reflected in a time-dependent effectiveness factor ... 

The number of active sites is a multiplicative factor in the rate of the main reaction. See for example Equations (10.11) and (10.16). Thus, the decline in reaction rate can be modeled using a time-dependent effectiveness. A reasonable functional form for the time-dependent effectiveness factor is... 

Do not infer from the above discussion that all the catalyst in a fixed bed ages at the same rate. This is not usually true. Instead, the time-dependent effectiveness factor will vary from point to point in the reactor. The deactivation rate constant kj) will be a function of temperature. It is usually fit to an Arrhenius temperature dependence. For chemical deactivation by chemisorption or coking, deactivation will normally be much higher at the inlet to the bed. In extreme cases, a sharp deactivation front will travel down the bed. Behind the front, the catalyst is deactivated so that there is little or no conversion. At the front, the conversion rises sharply and becomes nearly complete over a short distance. The catalyst ahead of the front does nothing, but remains active, until the front advances to it. When the front reaches the end of the bed, the entire catalyst charge is regenerated or replaced. 

Hydrodynamic effects on suspended particles in an STR may be broadly categorized as time-averaged, time-dependent and collision-related. Time-averaged shear rates are most commonly considered. Maximum shear rates, and accordingly maximum stresses, are assumed to occur in the impeller region. Time-dependent effects, on the other hand, are attributable to turbulent velocity fluctuations. The relevant turbulent Reynolds stresses are frequently evaluated in terms of the characteristic size and velocity of the turbulent eddies and are generally found to predominate over viscous effects. 

Section V, other quantum effects are indeed present in the theory and we will discuss how these contribute both to the deviation of the conductivity from the law and to the way the heat capacity differs from the strict linear dependence, both contributions being in the direction observed in experiment. Finally, when there is significant time dependence of cy, the kinematics of the thermal conductivity experiments are more complex and in need of attention. When the time-dependent effects are included, both phonons and two-level systems should ideally be treated by coupled kinetic equations. Such kinetic analysis, in the context of the time-dependent heat capacity, has been conducted before by other workers [102]. 

Motohashi Y, Miyazaki Y. 1990. Time-dependent effects on trichloroethylene on motor activity in rats. Chronobiology International 7 193-201. 

Kempinas WG, Favaretto ALV, Melo VR. 1994. Time-dependent effects of lead on rat reproductive functions. J Appl Toxicol 14 427-433. 

Ke, L., Eisenhour, C., Bencherif, M., Lukas, R. Effects of chronic nicotine treatment on expression of diverse nicotinic acetylcholine receptor subtypes. I. Dose- and time-dependent effects of nicotine treatment. J. Pharmacol. Exp. Ther. 286 825, 1998. 

Thixotropy is one of the reversible time-dependent effects that constitute nonideal behavior (Fig. 54). 

Rheopexy, a reversible time-dependent effect like thixotropy, is a rare phenomenon in pigmented systems. Rheopectic fluids increase in viscosity t with time when sheared at a constant shear rate D or a constant shear stress t until they approach a viscosity maximum (Fig. 53). 

Low temperature can lead to embrittlement of plastics. This is not seen as a time-dependent effect, but it can be the cause of rapid failure should environmental degradation be followed by a fall in temperature. 

A similar effect is observed when increased concentrations of the Ab-ALP conjugate were utilized to study the time-dependent effect on response, while keeping other reagents and their incubations constant. At any fixed time interval, the response observed (Figure 19.3) was found to be directly dependent on the protein concentration of the Ab-ALP conjugate. 

When a polymer is extruded through an orifice such as a capillary die, a phenomenon called die swell is often observed. In this case, as the polymer exits the cylindrical die, the diameter of the extrudate increases to a diameter larger than the diameter of the capillary die, as shown in Fig. 3.9. That is, it increases in diameter as a function of the time after the polymer exits the die. Newtonian materials or pure power law materials would not exhibit this strong of a time-dependent response. Instead they may exhibit an instantaneous small increase in diameter, but no substantial time-dependent effect will be observed. The time-dependent die swell is an example of the polymer s viscoelastic response. From a simplified viewpoint the undisturbed polymer molecules are forced to change shape as they move from the large area of the upstream piston cylinder into the capillary. For short times in the capillary, the molecules remember their previous molecular shape and structure and try to return to that structure after they exit the die. If the time is substantially longer than the relaxation time of the polymer, then the molecules assume a new configuration in the capillary and there will be less die swell. 

Randomization If one is concerned about time-dependent effects (for example, analyzer response drift, or chemical aging effects in the calibration standards), then the order of preparation and analysis of calibration samples in the design should be randomized. 

If fobs t, the magnetic moment is blocked in one of the potential wells, a state that corresponds to stable magnetization in a bulk magnet. If the measurement time is of the same order as the relaxation time (fobs i ), dynamical time-dependent effects are observed. 

Toxicogenomic approaches may be used to characterize molecular impacts on a global scale across a variety of conditions, including dose and time-dependent effects. In a dose-dependent manner, mouse embryos exposed in utero to heavy metals (arsenic, cadmium (Cd), and methylmercury) show alterations on the gene level in association with increased developmental effects, including... 

Characterization Robust assessment of dose- and time-dependent effects Able to identify more sensitive measmes of toxicity Expensive, usually low amoimt of replicates... 

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