Point defect stresses

The microstmcture and imperfection content of coatings produced by atomistic deposition processes can be varied over a very wide range to produce stmctures and properties similar to or totally different from bulk processed materials. In the latter case, the deposited materials may have high intrinsic stress, high point-defect concentration, extremely fine grain size, oriented microstmcture, metastable phases, incorporated impurities, and macro-and microporosity. AH of these may affect the physical, chemical, and mechanical properties of the coating. 

Fig. 5.18. The resistivity of shock-compressed silver foils in excess of that caused by pressure is shown as a function of shock stress. This excess is thought to be due to shock-induced concentrations of point defects ([75D01], after Graham [81G02]).

For the deformation of NiAl in a soft orientation our calculations give by far the lowest Peierls barriers for the (100) 011 glide system. This glide system is also found in many experimental observations and generally accepted as the primary slip system in NiAl [18], Compared to previous atomistic modelling [6], we obtain Peierls stresses which are markedly lower. The calculated Peierls stresses (see table 1) are in the range of 40-150 MPa which is clearly at the lower end of the experimental low temperature deformation data [18]. This may either be attributed to an insufficiency of the interaction model used here or one may speculate that the low temperature deformation of NiAl is not limited by the Peierls stresses but by the interaction of the dislocations with other obstacles (possibly point defects and impurities). 

In impure metals, dislocation motion ocures in a stick-slip mode. Between impurities (or other point defects) slip occurs, that is, fast motion limited only by viscous drag. At impurities, which are usually bound internally and to the surrounding matrix by covalent bonds, dislocations get stuck. At low temperatures, they can only become freed by a quantum mechanical tunneling process driven by stress. Thus this part of the process is mechanically, not thermally, driven. The description of the tunneling rate has the form of Equation (4.3). Overall, the motion has two parts the viscous part and the tunneling part. 

This is the kinetic equation for a simple A/AX interface model and illustrates the general approach. The critical quantity which will be discussed later in more detail is the disorder relaxation time, rR. Generally, the A/AX interface behaves under steady state conditions similar to electrodes which are studied in electrochemistry. However, in contrast to fluid electrolytes, the reaction steps in solids comprise inhomogeneous distributions of point defects, which build up stresses at the boundary on a small scale. Plastic deformation or even cracking may result, which in turn will influence drastically the further course of any interface reaction. 

This chapter is concerned with the influence of mechanical stress upon the chemical processes in solids. The most important properties to consider are elasticity and plasticity. We wish, for example, to understand how reaction kinetics and transport in crystalline systems respond to homogeneous or inhomogeneous elastic and plastic deformations [A.P. Chupakhin, et al. (1987)]. An example of such a process influenced by stress is the photoisomerization of a [Co(NH3)5N02]C12 crystal set under a (uniaxial) chemical load [E.V. Boldyreva, A. A. Sidelnikov (1987)]. The kinetics of the isomerization of the N02 group is noticeably different when the crystal is not stressed. An example of the influence of an inhomogeneous stress field on transport is the redistribution of solute atoms or point defects around dislocations created by plastic deformation. 

The resulting strain is also periodic with the same angular frequency but generally lags behind the stress because time is required for the growth (or decay) of the anelastic strain contributed by the point-defect re-population during each cycle. The strain may therefore be written... 

Solution. Using a torsion pendulum, find the anelastic relaxation time, r, by measuring the frequency of the Debye peak, cup, and applying the relation cupr = 1. Having r, the relationship between r and the C atom jump frequency F is found by using the procedure to find this relationship for the split-dumbbell interstitial point defects in Exercise 8.5. Assume the stress cycle shown in Fig. 8.16 and consider the anelastic relaxation that occurs just after the stress is removed. A C atom in a type 1 site can jump into two possible nearest-neighbor type 2 sites or two possible type 3 sites. Therefore,... 

Use Eq. 11.12 to show that a dislocation in a crystal possessing a uniform nonequilibrium concentration of point defects and a uniform stress field will... 

Show that regardless of the orientation of a straight dislocation line and its Burgers vector, there will exist a stress system that will convert the dislocation line into a helix whose axis is along the position of the original dislocation when the point-defect concentration is at the equilibrium value characteristic of the stress-free crystal. Use the simple line-tension approximation leading to Eq. 11.12. 

This internal pressure effect may actually be quite general in Mbssbauer effect studies of small particles, as discussed by Schroeer et al. for the recoil-free fraction (156) and the isomer shift (157). In addition, Schroeer (152) has summarized a number of origins for Mossbauer parameters being particle size dependent. Thus, from the above discussion, it seems apparent that a priori particle size determination using the recoil-free fraction, quadrupole splitting, or isomer shift is not possible for an arbitrary catalytic system. However, the "experimental calibration of these parameters, which not only facilitates particle size measurement, may also provide valuable information about the chemical state (e.g., electronic, defect, stress) of the small particles. This point will be illustrated later. 

A correlation between the total momentum of impinging ions per deposited boron atom and the c-BN deposition has been observed. In this model, c-BN formation is correlated with the momentum-drive process, such as the formation of point defects in conjunction with the stress-induced phase transformation. 

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