3. nm. Gamma iron is very weakly magnetic (paramagneti 2 per cent at 1130°C. The third temperature effect occurs at 910°C. Here, gamma iron is transfo, into alpha iron with a body centred cubic lattice having a lattice constant a= 0.29 nm. Itis non-magnete The Jast and the fourth retardation is observed at 768°C. It corresponds to alpha iron. The aj form of iron is highly magnetic and is one tht exists at room temperature. I can dissolve only a yey small amount of carbon, the maximum being about 0.025 per cent at 723°C and 0.0025 per cent at ron rature. Thus it is evident from the illustration, that there are actually two allotropic forms of ‘iron-the low temperature modification, alpha iron; and the high temperature form, gamma iron. These changes are reversible; i.e., same allotropic forms are observed during heating. Manganese exists in four forms, o, B, y and 6. Tin has a metallic form at ordinary temperature (white or B) but a non-metallic form (gray or a) with the structure of diamond, below about 13%¢ Several metals that are hcp at lower temperatures transform to bec at high temperatures; these include zirconium, titanium, thallium, lithium and beryllium. Metals that are hep at low temperature, sometine, transform to foc at high temperatures, e.g.. calcium, lanthanum, and scandium. Similarly, cobalt which is stable in the hep form at low temperatures is fec at high temperatures. Generally, the ductility, malleability, and softness of pure metals depend to a large extent onthe ease with which planes of atoms can glide over one another. Gliding takes place along the most closely packed planes and the directions of the gliding in these planes follow the lines of most closely packed atoms. In foc and in hep structures gliding is nearly always parallel to the close packed atomic planes. The forces of interactions between positive ions and “electron gas” determine such properties of metals as thermal expansion and melting point. The “electron gas” theory of metals also accounts for their high electrical and thermal conductivity as compared with other solids. ‘The mathematically perfect crystal is an exceedingly useful concept. In actual crystals, however imperfections or defects are always present and their nature and effects are often very important io understanding the properties of crystals. This is because some properties of materials such as stiffness ‘density and electrical conductivity which are termed structure-insensitive, are not affected by the presence of defects in crystals while many of the properties of greatest technical importance such as mechanic strength, ductility, crystal growth, magnetic hysteresis, dielectric strength, conduction in semiconductors Which are termed structure-sensitive are greatly affected by the relatively minor changes in crs! Siructure caused by defects. Ordinary materials, however, contains imperfections of various kinds ta! Produce both useful properties and also such undesirable effects as causing the strength to decreas? below that of a perfect crystal. Some of the co mmon defects found in crystals are discussed below: : The structural imperfections can be classified on the basis of their ‘geometry as point, li A and volume imperfections. The common types of point defects in solid ‘materials can be divided in! three classes: (1) lattice-site defects, ve carbon up ty we(a) Vacancies Schottky defect (6) Interstitialcies Frenkel defect (c) Compositional defects (i) Substitutional impurity (d) Electronic defects 3. Line defects: (a) Edge dislocation (b) Screw dislocation (ii) Interstitial impurity 4. Surface defects: (a) Grain boundaries (b) Twin boundaries (c) Tilt boundaries (d) Stacking fault 5. Volume defects. Thermal Vibrations ‘Atoms on a mathematically perfect lattice should occupy exactly the sites to which they are attached. It has been observed that no crystal is perfectly rigid, since it can be deformed by finite forces. Hence, it is possible to displace atoms from their ideal sites with a finite expenditure of energy due to thermal vibrations. The frequency of vibration is almost independent of temperature, but the amplitude increases with increasing temperature, When the vibration becomes strong enough the atoms may break the bonds between them and this corresponds to the solid actually melting and becoming liquid, the corresponding temperature is melting temperature. Since the atoms interact with one another, they tend to Vibrate in synchronism; that is, groups of atoms tend to move in the same direction, somewhat as waves on the ocean, Because the energy of a particular type of wave can be measured in units known as phonons, the thermal energy of the entire solid specimen is represented quite simply by a certain collection of phonons, each one of which is pictured as a special kind of ‘particle’. The thermal vibration of atoms of a solid, as it is, does not seriously disturb the perfection of the crystal. Every atom on the average is, inits proper position, Each atom, therefore, has requisite number of nearest neighbours at proper spacing. Point Defects Point imperfections are lattice errors at isolated lattice points. As the name implies, they are imperfect Point-like regions in the crystal and, therefore, they may be referred to as zero-dimensional imperfections. A point defect extends its influence only a few atom diameters beyond its lattice position. A point ‘imperfection comes about, as a rule, because of the absence of a matrix atom (an atom that would be Present in a perfect crystal), > presence of an impurity atom or a matrix atom in the wrong place. The ‘most common point defects in a crystal of a pure element are described below. Vacancies A vacancy is the simplest point defect in a crystal. This refers to a missing atom or vacant atomic site, Such defects may arise either from imperfect packing during the original crystallisation or from thermal Vibrations of the atoms at high temperatures. In the latter case, when the thermal energy due to vibration 4 Ciis increased there is an increased probability that individual atoms will jump out of their Positions of lowest energy. For most crystals, this thermal energy is of the order of 1 eV per vacancy. Vacancies be single or two or more of them may condense into a di-vacancy or tri-vacancy [Fig. 4.32 (a)], @ © © Fig. 4.32 Point defects in crystals In a close-packed arrangement of atoms if the atomic packing factor is low, an extra atom may be lodged within the crystal structure. This is known as interstitials. An atom can enter the interstitial void or space between the regularly positioned atoms only when it is substantially smaller than the parent atoms [Fig. 4.32 (a)], otherwise it will produce atomic distortion. Interstitialcies may also be mono- interstitial, di-interstitials, and tri-interstitials. The vacancy and interstitialcy are, therefore, inverse phenomena. Schottky Defects and Frenkel Defects In non-metallic crystals, the formation of a vacancy involves a local readjustment of charge in the surrounding crystal such that charge neutrality is maintained in the crystal as a whole. Thus, if in an ionic crystal there is a vacancy in a positive-ion site, charge neutrality may be achieved by creating vacancy in a neighbouring negative-ion site. Such a pair of vacant sites is called Schottky defect [Fig. 4.32 (b)]. This is closely related to vacancies, On the other hand, if the charge neutrality is maintained by having a positive ion in an interstitit! Position, the pair constitutes a Frenkel defect [Fig. 4.32 (c)] closely related to interstitialcies. Close packed structures have fewer interstitialcies and Frenkel defects than vacancies and Schotth) defects, as additional energy is required to force the atoms in their new positions, In spite of the care taken in the preparation of c1 In fact, as a result of thermal fluctuations, crystal. Formally such a defect might be prod site and placing it on the surface. This act req an increase in the entropy. In thermal equili present which can be estimated as follows: If E, is the energy required to take an atom fro the surface (called the enthalpy of formation of the associated with the generation of n isolated vacant sit Interstitialcies | rystals, vacancies are always present in all crystals. vacancies are produced and destroyed constantly in the luced by plucking an interior atom out of its regular latioe luires energy. Moreover, the disorder increases resulting librium, a certain number of lattice vacancies, are alva)$ M a lattice site inside the crystal to a lattice site Point imperfection), nE,, is the increase in Gates tes. The total number of ways in which we cam PICup n-atoms from the crystal consisting of N atoms is given by: N! (N=n)!n! since disorder increases due to the creation of n vacancies the corresponding increase in entropy js given by: This inturn produces a change in free energy F, F=U-TS N! = nE, ~ kyT log —S* 9a OB N= ayia ‘The second term on the right hand side can be simplified by using Stirling approximation: log x! = xlog x—x Consequently, F=nE, = kgT'(N logN - (N-n) log(N = n) ~n log n] Free energy in thermal equilibrium at constant volume must be minimum with respect to changes oF] Loz (=n) [=] -0=8,-t,rI0e [= | (N=”) Thus, (IN = n) exp- Ekg) Ifn << N, we can neglect n in (Nn); so that, n= Nexp(-E/kgD) If E,= 1 eV and T= 1000 K; then, Ls 16 ae N n 4 291 x 10%= 10% N 91x ‘The equilibrium concentration of vacancies decreases as the temperature decreases. 41D “CHAPTER 4Table 4.8 Enthalpy of formation of vacancies in some crystals Crystal E, [kifenol} in 0? | E, in eVivacancy kr 17 0.08 ca 38.0 0.39 Pb 48.0 0.50 Zn 49.0 051 Mg 56.0 0.58 Al 68.0 0.70 Ag 106.0 1.10 cu 1200 * 1.24 Ni 168.0 1.74 In ionic crystals, the formation of paired vacancies is most favoured i.e., an equal number of Positive and negative ion vacancies are produced. The formation of pairs makes it possible to keep the surface of the crystal electrostatically neutral, The number of pairs can be related to the total numberof atoms present in the crystal on following the same procedure as adopted in pure atomic crystals. ‘The different ways in which n separated pairs can be formed are: p=|—__ [jw =! Increase in entropy is given by; S=kglog P N! with corresponding change in free energy: (N=n)In F=U-TS = nE, ~ kgT log where, E, is the energy of formation of a pair, AAs before we now apply Stirling's approximation to simplify the factorial term. 2 N ie, log (asl = 2[logN! — log — n)! — log nt) = 21N log N—N~ (NV ~n) log(N ~ n) + (Nn) =n log n +n) 2IN log N — (WV ~n) login —n) — n log n)Thus, free energy, ral Sears P= nE, ~ 2ksTIN log N ~ (N~n) log(N—n) ~n log 1} Differentiating the above equation with respect to n, we get: N- = E,-2k,T log [<2] At equilibrium, the free energy is constant, so that: (W-ny E, ~ 2kgT log [< =0 Ey (N-n) war ~he[ 2 = explE,/2kgT) n= Nexpe E,2k,1) oF _ |, Bp~ 2kaP [0 + log(v—n) + 1 — log n—1] Provided n << N. In NaCl crystal, E, = 2.02 eV and at random temperature: ie, Proceeding in the same way as in the case of Schottky defect, we can calculate the number of Frenkel defects in equilibrium at a temperature T. Let in a perfect crystal, E, be the energy required to displace an atom from a regular lattice site to an interstitial position. N, be the number of interstitial atoms. N be the number of atoms. (4.12) Now the total number of ways in which n Frenkel defects can be formed will be given by: N N, P=! (W—mint|*|(, vm CHAPTER 4‘The corresponding increase in entropy due 10 the creation of Frenkel defect MN NM! | S= ky log! Cy mpint (N= aint which in tum produces a change in free energy: F=U-TS NM Ni = nF, kgT 108) Cy n)tnt (N, —n) In! Using Stirling's approximation for logarithmic term, we get: N Ni Nl , log} (N= nyinl (N, —n)! Jos (y= nyint * 18 (IW, —n)inl = Nlog N +N, log N,— (N-1n) log(N-n) -(N,- 1) log(N,-n) —2n logn Substituting this value of a logarithmic term in the expression for free energy and then differentiating with respect to n, we get: i. At equilibrium, the free energy is constant, so that: [Fl] in|, =? aT log (N=n)(N, -n) aaa — kT log or E, (N=n)(N, =n) =) NN, aT log “3 taking N >> n and N, >> n. Thus, E, = kyT (log (NN,) - 2 log n] 1 or log n= <1 -st "= Dlog (NN) — 9 n= (NN)'? exp(— E/2kyT) showing that n should be proportional to [NN]!Compositional Defects Compastional defects arise from impurity atoms during original crystallisation, Impurity atoms corsiderad_ a defo in Perfect latice are responsible forthe functioning of most semiconductor devices. They occur on a lattice point asa substitutional impurity or as an interstitial impurity. A substitutional impurity is created when a foreign atom substitu a 8 s ites for or replaces a parent atom inthe lattice [Fig. 4.33 (a)]. In brass, zinc is a substitutional atom in the copper lattice. ne ® Fig. 4.33 Compositional defects; (a) Substitutional impurity, (b) Interstitial impurity ‘An interstitial impurity is a small-sized foreign atom occupying an interstice or space between the regularly positioned atoms [Fig. 4.33 (b)]. Electronic Defects Enrrs in charge distribution in solids are termed electronic defects. This does not imply that deviations from smooth uniformity of charge within the volume of a unit cell are defects. Far from it, the charge isribution is actually non-uniform. However, departures from the normal regularity of charge distribution orenergy are electronic defects. Deviations of spatial distribution or charge commonly accompany the geometrical or structural crystal defects just discussed. For example, an impurity atom may have a charge quite different from that of the host atoms and hence may produce a local electronic disturbance. Similarly, a vacancy or interstitial is sure to produce electrical-charge deviations. In addition to these, the electron in a geometrically perfect lattice may themselves move in such a way as to produce local fluctuations in charge. Furthermore, the electrons may absorb varying amounts of thermal energy so that their motion through the lattices is altered. These so-called electronic imperfections are primarily Recessary to explain electrical conductivity and related phenomenon in solids. Perhaps the most prominent ¢xample of this is the creation of positive and negative charge carriers. This effect is responsible for the Operation of p-n junction and transistors. Production of Point Defects {h addition to point defects formed by thermal fluctuations, point defects may be created by other Means also, Table 4.9 illustrates how the fraction of vacant lattice sites in a metal increases rapidly with - One method of producing an excess number of point defects at a given temperature is by. Suenching (quick cooling) from a higher temperature. Another method of creating excess ae isby SeVere deformation of the crystal lattice, for example, by hammering or rolling. While the lattice still ‘elans its general crystalline nature, numerous defects are ad — - i i int defects is by external bombardment by atoms or high- cy it ti of cai ars pn re ens ns ar The fst pace eles withthe late atoms and displaces them, thereby forming a print fest. The "umber prodiced in this manner is not dependent on temperature but depends only on the nature ofthe “Ystal and on the bombarding particles. CHAPTER 4ae Table 4.9 Fquilibriam Jes in a metal Approximate fraction of vacant Pemperatare. (70) lattice sites 500 1x10 1000 1x 105 1500 1x 104 2000 1x10 Line Imperfections If a plane of atoms lies only partway through a crystal, the edge of such a plane is a defect in the form of a line, and is, known as dislocations. There are in general, two types of dislocations: (a) Edge of dislocation and (b) Screw dislocation. Both these types are formed in the process of their solidification or crystallization of the metal mainly in the process of their deformation. These dislocations are the most striking defects and are responsible for the useful property of ductility in metals, ceramics and crystalline polymers. Discussing the edge dislocation first, Fig. 4.34 (a) shows a perfect crystal, the top sketch depicting a three-dimensional view and the bottom one showing the atoms on the front face. The perfect crystal is considered to be made up of vertical planes parallel to one another and to the side faces. If one of these vertical planes does not extend from the top to the bottom of the crystal but ends partway within the crystal, as the Fig. 4.34 (6), a dislocation is present. In the perfect crystal, the atoms are in equilibrium positions and all the bond lengths are of the equilibrium value. In the imperfect crystal on the right, jut above the edge of the incomplete plane, the atoms are squeezed and are in a state of compression. The bond lengths have been compressed to smaller than the equilibrium value. Just below the edge, the atoms are pulled apart and are in a state of tension. The bond lengths have been stretched to above the normal values. The distorted configuration extends all along the edge into the crystal. Thus as the region of maximum distortion is centred around the edge of the incomplete plane, this distortion represeais a line imperfection and is called an edge dislocation. (b) ig. 4.34 An incomplete plane Fig. 4.31 Plete plane in a crystal results in an edge dislocation It should be noted that the dislocation of Fig, 4.35 (a) etely ae . 4. Tepresents a defect that runs complet through the erystal from front to back. This extra plane indicated ya Fig 435 (a may be either abovebelow the slip plane shown by the dashed line AC as in the 4.35 (b). In the former case, the dislocation (PQ) is said to be positive and is denoted by the symbol .L; in the latter case, it (P’Q’) is said to be negative and is denoted by the symbol T, where the horizontal line in the symbol represents the slip plane and the vertical line the incomplete plane. The magnitude and direction of the displacement are determined by a vector called the Burgers vector which is perpendicular to the dislocation line. Screw Dislocation ‘The second basic type of dislocation is the screw or Burgers dislocation. In this, the atoms are displaced in two separate perpendicular to each other. Figure 4.36 is a simple example of screw dislocation. The plane ABCD is the slipped area. The upper portion of the crystal has been sheared by an atomic distance (as shown by the shaded area) to the right relative to the lower portion. No slip has taken place to the right of AD and AD is a dislocation line. Here, the dislocation is parallel to its Burgers vector or shear vector. The designation ‘screw’ for this lattice defect is derived form the fact that the lattice planes of the crystal spiral the dislocation line AD. Fig. 4.35 Positive and negative edge dislocations A Fig. 4.36 Formation of screw dislocation CHAPTER 4Burgers Vector ‘The Burgers vector of a dislocation is an important property of a dislocation because, if the Burgers Vector and the orientation of the dislocation line are known, the dislocation is completely desctibeg This indicates how much and in what direction the lattice above the slip plane appears to have been shifted with respect to the lattice below the slip plane. Figure 4.37 shows a method of determining the Burgers vector applied to an edge dislocation. Iti first necessary to choose arbitrarily a positive direction for the dislocation and then to find out the vector which closes a circuit (line of arrows). In the present case, a clock-wise circuit of atom-to-atom steps is considered round a dislocation. It is seen that 4 fails to close the circuit when repeated in a perfect lattice B unless completely by a closure vector equal to the Burgers vector b, which is found normal to the dislocation. In Fig. 4.38 for a screw dislocation, the Burgers circuit fails to close by the amount indicated by the Burgers vector b, which is parallel to the dislocation line. Surface Imperfections Surface imperfections of a structural natural arise from a change in the stacking of atomic planes 0” across a boundary. The change may be one of the orientations or of the stacking sequence of the plan®* In geometric concept, surface imperfections are two-dimensional. They are of two types: External internal. | Lite fe Ty yay y +f Fig. 4.37 Burgers vector for edge dislocation Fig. 4.38 Burgers vector for screw dislocation_ersral Prisics 135) The external type is just what its name implies, the imperfections represented by a boundary. The most obvious boundary is the external surface. Although we may visualise a surface as simply a terminus of the crystal structure, we should appreciate the fact that the atoms on the surface cannot be compared with the atoms within a crystal: The surface atoms have neighbours on one side only, while atoms inside the crystal have neighbours on either side of them. This is shown in Fig. 4.39. Since these surface atoms are not entirely surrounded by others, they possess higher energy than that of internal atoms. This energy of the surface atom, for most metals, is of the order 1 J/m?. External Surface Imperfections Internal Surface Imperfections Internal surface imperfections are manifested by such defects as grain boundaries, tilt boundaries, twin boundaries, and stacking faults. Fig. 4.39 External surface defects Grain Boundaries Grain boundaries are those surface imperfections which separate crystals or grains of different orientation in a polycrystalline aggregation during nucleation or crystallisation. The shape of a grain is usually influenced by the presence of surrounding grains. The boundary atoms in two randomly oriented grains, therefore, cannot have a perfect complement of surrounding atoms. As a result, a region of transition exists in which the atomic packing is imperfect. In the boundary where the crystals or grains change abruptly orientation difference between neighbouring grains is more than 10-15°, and the boundaries are known as high-angle grain boundaries. These imperfections in the grain boundary enable the microscopist to see them, for in a transparent crystalline material they may scatter light and in opaque material they can be etched chemically. Although a grain boundary is two-dimensional, it has a definite thickness of 2 to 10 or more atomic distances. The mismatch of the orientation of adjacent grain produces a less efficient packing of the atoms at the boundary. Thus, the atoms along the boundary have a higher energy than those within the grains. The boundary between two crystals which have different crystalline ‘arrangements or different compositions, is called an interphase boundary or commonly an interface. CHAPTER 4Tilt Boundaries Tilt boundary is another surface imperfection. This is called low-angle boundary as the orientation difference between two neighbouring crystals is less than 10°. This is why the disruption in the boundary is not so drastic as in the high-angle boundary. In general, low-angle boundaries can be described Suitable arrays of dislocation. A low-angle tilt boundary is composed of edge dislocation lying ong above the other in boundary. The angle or tilt will be @ = +> where, b is the magnitude of the Burger ‘vector and D is the average vertical distance between dislocations (see Fig. 4.40), Boundary Fig. 4.40 Tilt boundary Twin Boundaries Another planar surface imperfection is a twin boundary. The atomic arrangement on one side of a twin boundary is a mirror reflection of the arrangement on the other side. Twin boundaries occur in pair, such thatthe orientation change introduced by one boundary is restored by the other. The region between the pair of boundaries is called the twinned region, Twin boundaries are easily identified under 32 optical microscope. Twins which form during the process of recrystallization are called annealing twins and those which form during plastic deformation of the material are called deformation twins (see Fig. 4.41). Stacking Defect A stacking faults a surface imperfection that arise from the stacking of one atomic plane out of sequen? on another while the lattice on either side of the fault is perfect. For example, the stacking sequence in an ideal foc crystal may be described as ABC ABC ABC ... . But the stacking fault might change sequence to ABC AC ABC... Faults in the stacking sequences of fee erystals are shown in Fig. 442Twin boundaries Fig. 4.41 Twin boundary Fig. 4.42 Faults in stacking sequences (a) Intrinsic fault (b) Extrinsic fault (c) Twin fault Volume Defects Volume defects such as cracks may arise when there is only small electrostatic dissimilarity between the stacking sequences of close packed planes in metals. Further when clusters of atoms are missing, a large vacancy or void is got which is also a volume imperfection. Foreign particle inclusions, large voids or non- crystalline regions which have the dimensions of the order of 0.20 nm are also called volume imperfections. Physical properties of crystalline solids are different in different directions in them. ie., Crystalline solids are anisotropic with respect to many of the physical properties. Hence a method of representation of planes and directions has become inevitable in the studies of crystal structure. W.H, Miller introduced the usage of a set of three integers, Miller indices, to represent a set of parallel planes and these indices When put inside square brackets are also used to indicate the directions. Miller indices of different sets of parallel planes have already been discussed. Let us consider one such plane of Miller indices (h k J) Nearest to the origin within the unit cell of a cubic crystal. Here h k / are related to the orientation of the plane with reference to the crystal axes. The fractional coordinates of intercept of the plane (h kJ) on the 4, b, c axes are I/h, V/k, 1/1 respectively.