Thermodynamic work

G. F. C. Rogers and Y. R. Mayhew, Engineering Thermodynamics, Work and Heat Transfer, 2nd ed., Longman Group, London, 1967, p. 551. 

An inversion of these arguments indicates that release agents should exhibit several of the following features (/) act as a barrier to mechanical interlocking (2) prevent interdiffusion (J) exhibit poor adsorption and lack of reaction with at least one material at the interface (4) have low surface tension, resulting in poor wettabihty, ie, negative spreading coefficient, of the release substrate by the adhesive (5) low thermodynamic work of adhesion ... 

Many of these features are interrelated. Finely divided soHds such as talc [14807-96-6] are excellent barriers to mechanical interlocking and interdiffusion. They also reduce the area of contact over which short-range intermolecular forces can interact. Because compatibiUty of different polymers is the exception rather than the rule, preformed sheets of a different polymer usually prevent interdiffusion and are an effective way of controlling adhesion, provided no new strong interfacial interactions are thereby introduced. Surface tension and thermodynamic work of adhesion are interrelated, as shown in equations 1, 2, and 3, and are a direct consequence of the intermolecular forces that also control adsorption and chemical reactivity. 

Ener Requirements Practically aU the energy needed to run an ultranlter is depolarization energy. The thermodynamic work... 

Most of the various strategies which have been proposed to predict relative adhesive interfacial strength are based on thermodynamics. One may define, without ambiguity, as shown in Fig. 3, a thermodynamic work of adhesion , Wa,... 

Fig. 3. Definition of thermodynamic work of adhesion, Wa (a) disjoining surfaces in vacuum (b) disjoining surfaces in fluid medium m and (c) disjoining surfaces in presence of vapors from adhesive.

The most-often cited theoretical underpinning for a relationship between practical adhesion energy and the work of adhesion is the generalized fracture mechanics theory of Gent and coworkers [23-25] and contributed to by Andrews and Kinloch [26-29]. This defines a linear relationship between the mechanical work of separation, kj, , and the thermodynamic work of adhesion ... 

Combination of Eq. 7 or Eq. 8 with the Young-Dupre equation, Eq. 3, suggests that the mechanical work of separation (and perhaps also the mechanical adhesive interface strength) should be proportional to (I -fcos6l) in any series of tests where other factors are kept constant, and in which the contact angle is finite. This has indeed often been found to be the case, as documented in an extensive review by Mittal [31], from which a few results are shown in Fig. 5. Other important studies have also shown a direct relationship between practical and thermodynamic adhesion, but a discussion of these will be deferred until later. It would appear that a useful criterion for maximizing practical adhesion would be the maximization of the thermodynamic work of adhesion, but this turns out to be a serious over-simplification. There are numerous instances in which practical adhesion is found not to correlate with the work of adhesion at ail, and sometimes to correlate inversely with it. There are various explanations for such discrepancies, as discussed below. 

The JKR theory relates the interfacial-force-induced contact deformation to the thermodynamic work of adhesion between solids, and provides a theoretical... 

The van der Waals and other non-covalent interactions are universally present in any adhesive bond, and the contribution of these forces is quantified in terms of two material properties, namely, the surface and interfacial energies. The surface and interfacial energies are macroscopic intrinsic material properties. The surface energy of a material, y, is the energy required to create a unit area of the surface of a material in a thermodynamically reversible manner. As per the definition of Dupre [14], the surface and interfacial properties determine the intrinsic or thermodynamic work of adhesion, W, of an interface. For two identical surfaces in contact ... 

When the surfaces are in contact due to the action of the attractive interfacial forces, a finite tensile load is required to separate the bodies from adhesive contact. This tensile load is called the pull-off force (P ). According to the JKR theory, the pull-off force is related to the thermodynamic work of adhesion (W) and the radius of curvature (/ ). 

In an appropriately designed experiment, it is possible to measure the pull-off force (Ps), contact radius (a versus P, ao and aj, and the separation profile outside the contact zone (D versus j ). From these measurements, it is possible to determine the thermodynamic work of adhesion between two surfaces, if the contacting bodies are perfectly elastic. 

The premise of the above analysis is the fact that it has treated the interfacial and bulk viscoelasticity equally (linearly viscoelastic experiencing similar time scales of relaxation). Falsafi et al. make an assumption that the adhesion energy G is constant in the course of loading experiments and its value corresponds to the thermodynamic work of adhesion W. By incorporating the time-dependent part of K t) into the left-hand side (LHS) of Eq. 61 and convoluting it with the evolution of the cube of the contact radius in the entire course of the contact, one can generate a set of [LHS(t), P(0J data. By applying the same procedure described for the elastic case, now the set of [LHS(t), / (Ol points can be fitted to the Eq. 61 for the best values of A"(I) and W. 

The energy release rate (G) represents adherence and is attributed to a multiplicative combination of interfacial and bulk effects. The interface contributions to the overall adherence are captured by the adhesion energy (Go), which is assumed to be rate-independent and equal to the thermodynamic work of adhesion (IVa)-Additional dissipation occurring within the elastomer is contained in the bulk viscoelastic loss function 0, which is dependent on the crack growth velocity (v) and on temperature (T). The function 0 is therefore substrate surface independent, but test geometry dependent. 

The horizontal line at the bottom of the pressure-volume diagram of Figure 4 traces the other tv o strokes of the four-stroke cycle. On the exhaust stroke, from 5 to 6, the rising piston expels most of the remaining combustion products from the cylinder. On the intake stroke, from 6 to 7 (= 1), the descending piston inducts a fresh charge for repetition of the cycle. The net thermodynamic work developed in this cycle is proportional to the area enclosed by the pressure-volume diagram. In the ideal case, both the exhaust and intake strokes occur at atmospheric pressure, so they have no effect on the net output work. That justifies their exclusion from the thermodynamic representation of the ideal Otto... 

All physical human activities involve doing thermodynamic work, which the body supplies from the chemical energy stored in foods. 

Energy intake is only part of the equation. We can also adjust our energy balance by exercising. Various forms of exercise require different average energy outputs. Exercise involves doing thermodynamic work. The table in the next column Indicates that the amount of work depends on the type of exercise and the amount of mass being displaced. 

G is, as a thermodynamic work function, a measure of the driving force (the work-producing potential) of a redox process. For a naturally occurring process,... 

We could summarize by saying that thermodynamic work w is energetically equivalent to the lowering or raising of a weight (like the water of the waterfall, above), as discussed below. 

The first law of thermodynamics states that energy may be converted between forms, but cannot be created or destroyed. Joule was a superb experimentalist, and performed various types of work, each time generating energy in the form of heat. In one set of experiments, for example, he rotated small paddles immersed in a water trough and noted the rise in temperature. This experiment was apparently performed publicly in St Anne s Square, Manchester. Joule discerned a relationship between energy and work (symbol w). We have to perform thermodynamic work to increase the pressure within the tyre. Such work is performed every time a system alters its volume against an opposing pressure or force, or alters the pressure of a system housed within a constant volume. 

The more recent statistical thermodynamic work approaches the... 

There are two principal approaches to build OTEC power plants. The first approach called the open OTEC cycle involves a flash boiler to obtain steam directly from the warm surface ocean water. The open OTEC cycle requires a very large turbine. The second approach is called the closed OTEC cycle, which involves heat exchangers and a secondary thermodynamic working fluid such as ammonia or freon to reduce the size of the plant. 

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