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DIFFUSION IN SOLIDS

Thermal activation energy leads to motivation or vibration of atoms about their mean position in a solid. At higher temperatures, the vibrations are quite high and the atoms start moving from one lattice position to another position. This diffusion of species in solid state is promoted by defects such as vacancies, impurities (interstitial, grain boundaries, substitutional atoms, dislocations). However , the state of difference (i.e, velocity of molten atoms or rate of mixing) in solid state is quite smaller compared to liquids and gaseous states, where mixing is completed in a matter of seconds. When two or more liquids or gases are introduced in a container, they mix well within seconds. On the other hand, when two different solids come in contact, the state of mixing is verty slow and determined by a number of factors, such as : 1. Temperature 2. Composition gradient 3. Nature of solids :- crystal structures, atomic bonds, relative sizes of atom, presence of crystal defects like vacancies, grain boundaries, dislocation, etc. Chemical composition variation in the solid is the basic DRIVING FORCE for diffusion in solid state. Diffusion of atoms takes place in a direction such that compositional variation is minimized so that the solid gets a homogeneous composition. The rate of diffusion (and hence compositional homogenisation is determined by temperature to a large extent and to lesser extent on the nature of solids. DIFFUSION COUPLE Consider a between Cu and Ni. The compositional variation across the boundary before, during and after complete diffusion is shown in the figure.

While diffusion takes place on at any temperature at above 0 K, the state of diffusion is not substantial below 0.5 Tm (Tm = m.p of metal). At temperature near M.P, complete diffusion is possible in several hours. But below 0.3 Tm, the rate of diffusion is qute low and the diffusion couple stays without much compositional variation foe several years. For all practical purposes in engineering, the effect of diffusion can be neglected below 0.3 Tm. MECHANISMS OF DIFFUSION 1. Vacancy diffusion : this is the main mechanism of diffusion with substitutional solid solution. An atom leaves its lattice position to occupy a nearby vacancy, leaving behind a vacancy. Net transport of atoms is thus achieved.

As the fraction of vvs increases with increasing temperature, the rate of diffusion increases with temperature, reaching max near the M.P of the metal. 2. Interstitial diffusion : If the diffusing atom is an interstitial atom, (like C,N,H in iron or steel) , then such atom move from one interstitial position to an adjacent interstitial position by squeezing through normal lattice as shown. Vacancies are not needed for this mechanism. Lattice vibrations at high temperatures (0>0.5Tm) sufficiently proximate this mechanism.

The rate of interstitial diffusion is quite faster as the atoms (C,N,H,O) are much smaller in size compared to bigger atoms. 3. Zenar ring mechanism : This involves cooperative movement of a group of atoms in circular path. The four atoms shown in the fig. rotate, each moving a place ahead or behind. The diffusing atom show marked thus moves forward or inward. 4. Diffusion along defects : Defects like dislocations, grain boundaries are distorted regions in the crystal and represent higher energy regions.Diffusion defects is quite faster in temperature range 0.5 to 0.6Tm.If this is predominant mode of atom transport, the diffusion process is correspondingly called g-b diffusion and pipe diffusion (i.e, along dislocation lines). The activation energy for these mechanism is lower at 0.5 Tm compared to volume diffusion. Volume diffusion is the process through the regular lattice. However at higher temperature (>0.8 Tm), the activation energy for volume diffusion also becomes much lower, and hence volume diffusion becomes the predominant mode of owing to its straight path of diffusion.

FLICKS LAW OF DIFFUSION

Consider unidirection diffusion at a given temperature at a given temperature across a width of dx, where the concentration gradient of the diffusing species is (dc/dx) . Then Flicks first law states that the flux of atoms is directly proportional to the concentration gradient or J = -D (dc/dx) Where J = flux of atoms = no of atoms per un it time. J= dc/dx = concentration gradient = D = diffusivity or diffusion coefficient = Thus the driving force for the diffusion coefficient is concentration gradient along the diffusion direction. The - sign indicates that diffusion takes place in a decreasing concentration of decreasing species. DIFFUSIVITY : (D) : The value of D depends strongly on temperature and generally varies with

Thus D increases exponentially with temperature and the rate of diffusion correspondingly increases reaching maximum or minimum the M.P. The kinetics of diffusion ( how fast diffusion process is completed) is determined by temperature. At lower temperatures (<0.3Tm), the rate is quite low and can be neglected, though there is a driving force in terms of comparison gradient. It is only at temperature more than >0.5Tm, diffusion becomes appreciable owing higher diffusivity coefficient. DDD values depend on a number of other factors apart from temperature. They are : 1. Type of bonding : Ionic and covalent crystals having lower D values, owing to the presence of ions and directionality of bonding. Compared to them, metals exhibit much high values owing to lack of positive and negative ions and bond directionality. 2. Relative size of diffusing atom compared to the parent atoms.

Activation Energy (Q) : For diffusion at a given temperature depends on the predominant mechanism of diffusion. Thus, if D values for Cr diffusion in steels is much higher compared to D values for C in steels, since Cr diffuses through vacancy mechanism while C diffuses by interstitial mechanism. Similarly, if the mechanism is gb- diffusion pipe diffusion, then the Q value correspondingly rises. Extensive data on diffusion coefficients for different systems have been emptly determined and compiled in diffusion hand book.

FICKS SECOND LAW :