Solid surfaces elastic flow

In the molten state polymers are viscoelastic that is they exhibit properties that are a combination of viscous and elastic components. The viscoelastic properties of molten polymers are non-Newtonian, i.e., their measured properties change as a function of the rate at which they are probed. (We discussed the non-Newtonian behavior of molten polymers in Chapter 6.) Thus, if we wait long enough, a lump of molten polyethylene will spread out under its own weight, i.e., it behaves as a viscous liquid under conditions of slow flow. However, if we take the same lump of molten polymer and throw it against a solid surface it will bounce, i.e., it behaves as an elastic solid under conditions of high speed deformation. As a molten polymer cools, the thermal agitation of its molecules decreases, which reduces its free volume. The net result is an increase in its viscosity, while the elastic component of its behavior becomes more prominent. At some temperature it ceases to behave primarily as a viscous liquid and takes on the properties of a rubbery amorphous solid. There is no well defined demarcation between a polymer in its molten and rubbery amorphous states. 

Plastic deformation (strain). When two surfaces of ductile materials are placed in contact and the load exceeds the elastic limit of one of the two materials, plastic deformation or strain occurs. The plastic deformation of one surface when two surfaces are in solid-state contact can occur in the presence or absence of lubricants. In fact, in some instances, the presence of lubricants can increase the deformability of the solid surfaces by a mechanism such as the Rehbinder effect. Plastic deformation of the solid surface is, therefore, observed in the presence of lubricants. Plastic deformation is accommodated by the generation of slip lines for dislocation flow in the solid surface. Dislocations are line defects in the solid and they are site of higher energy state on the surface. Thus, they interact or react more rapidly with certain chemical agents than do the bulk surfaces (Buckley, 1981 Lunarska and Samatowicz, 2000). 

In Chapter 3 we will show that the modulus of surface elasticity is really quite a complex quantity. Whereas the flow properties of liquid/air and liquid/liquid interfaces are determined strongly by elastic forces, the solid/liquid interface is mainly related to wetting processes. 

For the transport of heavy ions to a solid surface coated with an adherent water film, like aluminium oxide, the visco-elastic properties of electric field forces and the concentration of heavy ions may be important for the rate of adsorption. For this reason we need information not only on relaxations restricted to a surface of an extended liquid, but also on the adherent water layer at the adsorbents. The last issue may be a bridge to the thermodynamics and flow properties of thin liquid films have been studied by some excellent research groups. 

The resistance to motion that a solid experiences while moving across a surface is called friction. Frictional forces between solids affect the sliding between two solid materials and are strongly related to the type and nature of the interfaces and thin films existing at the surface of these solids. Deformation phenomena like elasticity, flow and creep, adhesion, friction, and lubrication arise during sliding of two solids over each other. 

Substances in this category include Krypton, sodium chloride, and diamond, as examples, and it is not surprising that differences in detail as to frictional behavior do occur. The softer solids tend to obey Amontons law with /i values in the normal range of 0.5-1.0, provided they are not too near their melting points. Ionic crystals, such as sodium chloride, tend to show irreversible surface damage, in the form of cracks, owing to their brittleness, but still tend to obey Amontons law. This suggests that the area of contact is mainly determined by plastic flow rather than by elastic deformation. 

A third definition of surface mobility is essentially a rheological one it represents the extension to films of the criteria we use for bulk phases and, of course, it is the basis for distinguishing states of films on liquid substrates. Thus as discussed in Chapter IV, solid films should be ordered and should show elastic and yield point behavior liquid films should be coherent and show viscous flow gaseous films should be in rapid equilibrium with all parts of the surface. 

At the instant of contact between a sphere and a flat specimen there is no strain in the specimen, but the sphere then becomes flattened by the surface tractions which creates forces of reaction which produce strain in the specimen as well as the sphere. The strain consists of both hydrostatic compression and shear. The maximum shear strain is at a point along the axis of contact, lying a distance equal to about half of the radius of the area of contact (both solids having the same elastic properties with Poisson s ratio = 1/3). When this maximum shear strain reaches a critical value, plastic flow begins, or twinning occurs, or a phase transformation begins. Note that the critical value may be very small (e.g., in pure simple metals it is zero) or it may be quite large (e.g., in diamond). 

The surface molecules are under a different force field from the molecules in the bulk phase or the gas phase. These forces are called surface forces. A liquid surface behaves like a stretched elastic membrane in that it tends to contract. This action arises from the observation that, when one empties a beaker with a liquid, the liquid breaks up into spherical drops. This phenomenon indicates that drops are being created under some forces that must be present at the surface of the newly formed interface. These surface forces become even more important when a liquid is in contact with a solid (such as ground-water oil reservoir). The flow of liquid (e.g., water or oil) through small pores underground is mainly governed by capillary forces. Capillary forces are found to play a very dominant role in many systems, which will be described later. Thus, the interaction between liquid and any solid will form curved surface that, being different from a planar fluid surface, initiates the capillary forces. 

If a sample shows elastic, solid-like deformation below a certain shear stress ay and starts flowing above this value, ay is called a yield stress value. This phenomenon can occur even in solutions with quite low viscosity. A practical indication for the existence of a yield stress value is the trapping of bubbles in the liquid Small air bubbles that are shaken into the sample do not rise for a long time whereas they climb up to the surface sooner or later in a liquid without yield stress even if their viscosity is much higher. A simple model for the description of a liquid with a yield stress is called Bingham s solid ... 

Chemical vapor deposition (CVD) is an atomistic surface modification process where a thin solid coating is deposited on an underlying heated substrate via a chemical reaction from the vapor or gas phase. The occurrence of this chemical reaction is an essential characteristic of the CVD method. The chemical reaction is generally activated thermally by resistance heat, RF, plasma and laser. Furthermore, the effects of the process variables such as temperature, pressure, flow rates, and input concentrations on these reactions must be understood. With proper selection of process parameters, the coating structure/properties such as hardness, toughness, elastic modulus, adhesion, thermal shock resistance and corrosion, wear and oxidation resistance can be controlled or tailored for a variety of applications. The optimum experimental parameters and the level to which... 

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