7.1 INTRODUCTION The matter in this wonderful world is found to exist in three states viz, solids, Tiquids and ga 8, We know that some solids are brittle, some are ductile, some are malleable some are strong, some are weak, some are good conductors of heat and electricity some are bad conductors of heat and electricity, some are magnetic, some are non-magnetic and so on, but all these materials are composed of atoms and molecules, ‘The constituent particles, ic., atoms (or) molecules of matter are held together by the forces of attraction. The attractive forces which hold the constituent particles of a substance together are called bonds. The reason for these different properties of the solids are due to their structure. the behaviour of the solid materials is closely related to the structure of the material. In this chapter, we are going to discuss the different crystal structures and their properties. 7.2 CLASSIFICATION OF SOLIDS — If we examine the solid materials with which we come across daily, we shall find that most of them do not have any characteristic difference in their outward appearance. But, if we examine them under a microscope, we shall find that these materials have different internal atomic structures. Based on the internal atomic structure, the solids can be classified into two categories namely (i) Crystalline and (ii) Non-crystalline (or) Amorphous solids. 7.3 CRYSTALLINE SOLIDS (OR) CRYSTALS | Crystalline solids (or) crystals are those in which the constituent atoms (0") molecules are arranged in an orderly fashion throughout, in a three dimensional pattern. |. Each atom (or) molecule is fixed at a definite point in space, at a definite distance from each other and in a definite angular orientation to all other atoms (01) ]} molecules surrounding it. Therefore, crystalline solids have well defined geometrical pattern). ic., they have well defined faces and angles between them. a practical example, we can say that in a crystal, the atoms are arrangedea (Gea Further, when a erystal breaks, all the broken pieces will have a regular shape The ertlline solids have directional properties and therefore they are ralled anisotropic substances. A crystalline material will be in two forms viz., in which the solid contains only one crystal. These single (i Single erystal, ficially from their vapour (or) liquid state. crystals are produced artil which has an aggregate of many small crystals (or) grains (i) Poly crystal, m rain boundaries. These crystals will have a sharp melting separated by well defined point. Examples for crystalline solids: Diamond, Copper, Platinum, Silver, Polonium, Gold, Aluminium, Molybdenum, Nickel, Cadmium, Iron etc. Crystallography: The study of the geometric form and other physical properties af erystalline solids, using X-rays (or) electron beam (or) neutron beam etc., is termed as the science of crystallography. Note: Grains: The ‘aré-also known as grains. "Grain. boundary: The boundary separating the two adjacent grains is called grain boundary. Whiskers: Whiskers are nothing but artificially produced crystals. They are produced under some special conditions| so that, they do not have any structural defects. 7.4 AMORPHOUS SOLIDS (OR) NON-CRYSTALLINE SOLIDS “Amorphous” means “without form”. In amorphous solids, the constituent particles i.e., atoms (or) molecules are ot arranged in an orderly fashion. In other way, we can say that in amorphous ds the same atomic groups are arranged randomly in all directions. These solids have no directional properties and therefore they are called Substances, These amorphous solids do not have a sharp melting point. amples for amorphous solids; Plastics, Rubber and Glass.7.5 DIFFERENCES BETWEEN CRYSTALLINE AND NON-CRYSTALLINE MATERIAL Se ‘Crystalline material _—'|_Non-erystallin 1. |They have a definite and regular geometrical shapes which extend] geometrical shape. throughout the crystal. 2. | They are anisotropic. They are isotropic. 3. |They are most stable. They are less stable. 4, |They have sharp melting point. | They do not have sharp melting point. 5. |Examples: Diamond, NaCl, KCl,|Examples: Glasses, _ Plastics, Copper, Iron, etc. Rubber etc. They do not have definite 7.6 FUNDAMENTALS OF CRYSTALS AND ITS STRUCTURE Crystal: Crystal is a regular polyhedral form bounded by smooth surfaces, which is formed by chemical compound under the action of its interatomic forces, when passing from the state of liquid (or) gas to that of a solid, under suitable conditions. The phase change from liquid (or) gas to solid is called crystallization. The crystal structure gives the arrangement of atoms within a crystal. Determination of crystal structure with the help of X-ray is known as X-ray crystallography. X-rays are most widely used to study the crystal structure because, the wavelength of X-rays (10°? to 10°" m) are almost equal to that of the inter atomic distances and hence diffraction can easily occur, when they are are passed through the crystals. ‘Fundamental. crystallographic terms (definitions) collection of points in space are called space lattice (or) mment about any particular point is in everyway the same. (or)ee ES fi A geometrical representation of the crystal structure interms of lattice points are called space lattice, provided the environment about every point is identical to that of every other point. ie, space lattice is an idealised geometrical (imaginary) concept by which crystal structures can be described. Explanation We know each crystal consists of a large number of atoms. 9000 Now let us consider the cross-section of 2000 acrystal as shown in fig (7.1). Here, it is found that the atoms are arranged in a regular pattern. 0000 From the figure, it may be noted that each ©0000 atom, present in the crystal has its surroundings identical to that of every other atom. Fig. 74 Now, if we replace all the atoms by points e e's corresponding to the centres of all atoms, then the resulting collection of points shown in fig (7.2). is called 9 9 © a lattice. This is the case of a two dimensional lattice (or) plane lattice, o.8 6° Similarly, the group of lattice points in the three limensional pattern is known as crystal lattice (or) space Jattice and is as shown in fig 7.3. Fig. 7.2 ‘ It may be noted that in a crystal lattice each point has its surroundings identical to that of every other point. 3. Lattice points ° _ Lattice points denote the position of atoms (or) * , molecules in the crystal. (fig. 7.4 (a)] (or) The points in the space lattice are called lattice points. Fig. 73 Basis (or) Motif is an unit assembly of atoms (or) molecules which are Wied with respect to the position of lattice points, identical in composition,Engineering Physics: aT meat te: o 0 0 0 “#0 80 60 ag 0000 0000 oe 8 ee 0 0 0 0 #0 90 80 a 0000 0000 wee pee oe = eet 0000 e000 et o ci oto opin ta 0000 °° Fig. 7.4 (a) Fig. 7.4 (b) Fig. 7.5 Lattice Basis Crystal Structure The number of atoms in the basis may be 1 (or) 2 (or) 3 or it may go even above 1000. Example, Aluminium and Barium has the basis of one atom. In NaCl and KCI, the basis is two atoms and in CaF, the basis is three atoms. But there are structures for which the basis can have more than 1000 atoms. 5. Crystal structure The crystal structure is formed by the addition of basis [fig. 7.4(b)] to every lattice point of the lattice [fig. 7.4 (a)]. The logical relation for crystal structure is as shown in fig. 7.4(a), 7.4 (b) and 7.5. ie., Fig. 7.4(a) + Fig. 7.4(b) = Fig. 7.5. ie, [Space lattice Basis S Crystal structure: _ ordering (or) alignment of its molecules in the space. ‘ Lattice planes A set of parallel and equally spaced planes in a space lattice, which are ormed with respect to the lattice points are called lattice planes. The different ways of drawing the lattice planes for the array of lattice points ‘shown in fig. 7.6 (a) to 7.6 (e). |7. Unit cell Definition The unit cell is defined as the smallest geometric figure, the translational repetition of which in all over the three dimensions gives the actual crystal ‘ure. (or) ider a parallelogram ABCD of side B? When the parallelogram ABCD dly by any integral multiple of (or) array may be obtained. i., fal may thus be reproduced. 1 ABCD is called a unit cell and Fig. 7.7 fa unit cell is not unique. It can be constructed in many oneal PC} Dy (or) A, B,C, D, etc., without affecting the symmetry eoEngineering Physlen ap) 78 We can extend the same proce a three dimensional case also. The fig. 7.8 shows the unit cell (shaded portion) in the three dimension, which on repeatation over all the three directions viz x, y and z, we can get the total crystal structure, As a practical example, the unit cell may be considered as the brick of a wall. Here the wall represents the crystal, We know that the shape of the wall will depend upon the shape of the brick. Similarly, the shape of the crystal will depend upon the shape of the unit cell. Note: Other terms used to represent a unit cell: The unit cell is also known as basic cell (or) basic unit or} fundamental unit (or) fundamental elementary pattern (or) building block (or) lattice uni z 8. Lattice parameters (or) Unit cell parameters The fig. 7.9 shows a unit cell of a three dimensional crystal lattice. z The lines drawn parallel to the lines of intersection of any three faces of the unit cell Ee which do not lie in the same plane are called Z| crystallographic axes. . : y The intercepts a, b and c are nothing but At [7 | the edges of the unit cell, (i.c., the distance een two lattice points) which defines the nsions of an unit cell. These intercepts mown as its primitives (or) characteristic . ; ercepts on the axes. Fig. 7.9 Lattice parameters These three quantities a, b and c are also called the fundamental translational rs (or) axial lengths, The angles between (a, b), (b,c) and (c, a) are denoted and B respectively. These three angles (a, Bandy) are called interfacial Both, the intercepts (a,b,c) and interfacial angles (ct,B,) constitutes the [parameters (or) cell parameters of the unit cell,1e actual size of the unit cell can be determined by knowing the va values Th . .d interfacial angles. of intercepts an | Primitive cell A primitive cell is the simplest type of unit cell which contains only one point per unit cell (contains lattice points at its corner only). Example: Simple Cubic (SC) 10. Non-primitive Cell If there are more than non-primitive cell. BCC and FCC contains more than one lattice point per unit per unit cell is two (BCC), three and four rimitive, triply primitive and ‘one lattice point in an unit cell, it is called a Example: t cell. If the number of lattice points (FCC), then the unit cell is called doubly p' i quadruply primitive respectively. 7.7 THE CRYSTAL SYSTEMS Crystals are classified into 7 crystal systems on the b viz, @) axial lengths a,b,c and (ii) interfacial (axial) angles 0 BY asis of lattice parameters ‘The 7 basic crystal systems are riclinic 2. Monoclinic 3. Orthorhombic 4. Tetragonal 5. Hexagonal nal (or) Rhombohedral and 7. Cubic. czystal systems are discussed briefly one by one 2 follows: é crystal system / | crystal system, all the three crystal axes > pel ficular to each other. The axial lengths are ifferent) along the three axes, as shown Fig. 740 we | HD FC at Pe Y# 90° as only one form i.e, Simple.2. Monoclinic crystal system In monoclinic crystal system, two of the axes are perpendicular to cach other, but the third i obliquely inclined. ‘The three axial lengths different along the axes as shown in fig. 7.1L: ec ‘ atb#te Lattice parameters are &® [ ] a= B=90° #7 Fig. 7.11 Monoclinic lattices may be in any one of these two forms viz, simple (or) base centred. 3. Orthorhombic crystal system In orthorhombic crystal system, the three crystal axes are perpendicular to each:other. In this ~ system, all the three axial lengths are of unequal lengths (different), as shown in fig, 7.12. Lattice parameters are (‘ nhac | a=B=y7=90° Fig. 7.12 Orthorhombic lattice may be in any one of these four forms i.e., simple, (or) base centred (or) body-centred (or) face centred. “4, Tetragonal crystal system Ht In tetragonal system, the three crystal axes are AL, | Perpendicular to each other. Two of the three axial Ba ||-Jengths are the same, but the third axial length is eV ferent, as shown in fig, 7.13 Fig. 7.13 “Lattice parameters are ww = | @=b# a= B=7=90° agonal lattices may be in any one of these two forms viz, Simple (of)H exagonal crystal system . . hexagonal crystal system, two of the crystal axes 120° apart. While the third is perpendicular to both ae of them. ‘The axial lengths are the same along the axes that 120° apart, but the axial Jength along the third axis n in fig. 7-14. | a=b#c H atice parameters are Lo [ccpear srr" Fig, 714 Hexagonal latice has only one form i Simple | 1 } { ) fig. 714, ifwe neglect the shaded portion, we "unit cell of HCP similar to other crystal systems. 6. Trigonal (or) Rhombohedral crystal system > In trigonal crystal system, the three axes are inclined to each other at an angle other than 90°. The three axial | Jengths are equal along the axes, as shown in fig. 75. Lattice paramet ce | fae PB fers are a=p=7490" Trigonal lattice has only one form i.e., simple. Fig. 7.15 pic crystal system a crystal system, the three crystal axes are pet fe aie is the same along all the three axis pendicular t0 each other ices may be in es any one of these three | Cable $C) (or) Body.Centred Cubic At ‘ntred Cubic (FCC)7.8 BRAVAIS LATTICES Bravais, in 1880, showed that there are 14 possible types of space lattices in the 7 crystal systems as shown in Table 7.1. Table 7.1 Simple (or) Primitive Monoclinic Simple (or) Primitive, Base Centred Orthorhombic Simple (or) Primitive, Body Centred, | Face Centred and Base Centred Tetragonal Simple (or) Primitive and Body Centred. Hexagonal Simple (or) Primitive Trigonal Simple (or) Primitive Cubic SC (or) Primitive (P), BCC and FCC According to Bravais, in space lattice from the 7 crystal systems such that, all the lattice points have exactly the same surroundings. These 14 space lattices are called the Bravais lattices. there are only 14 possible ways of arranging points The 14 possible Bravais lattices drawn from the in fig. (7.17) below. A.Triclinic atbFCae hey #90 2.Monoclinic : atb¥ea=fp=90+y 7 crystal systems are shown Aa Day Simple Base centred Fig. 7.17LOrthorhomble atbye, amfimy= 90° Tidy centred Base centred Face centred ‘Simmple 4.Tetragonal system acbdc, ampayn 9. Body centered 6. Rhombohedral(Tigona) asb=ca=paysor° ‘Simple 7.Cubie system a=b= ca=p=y= Lk Ae / a ley Face centred (FCC) Rody centred (BCC) als Lattices of seven crystal systems7.9 SEVEN CRYSTAL SYSTEMS AND FOURTEEN BRAVATS LATTICES Table 7.2 shows the seven crystal systems, which are divided into 14 Bray, lattices along with the unit cell parameters and examples. Table 7.2 ‘The Seven Crystals Systems, divided into 14 Bravais lattices Bravals lattice | siprcdy 0s | DOU ei 1, | Triclinic ‘Simple atbtc CuSQs, K2Cr207 az Bey290° Simple Gre NagSO4, FeSO, a=B=90° +7 Base-centred NO2SO3 3. | Onhorhombic Simple KNOs, BaSOs, MgSOs Base-centred Sulphur, Topaz Body-centred Face-centred NiSO4,SnO2, Indium, white tin Simple a=btc Body-centred ae Simple Tourmaline, Quartz Trigonal (Rhombohedral) Simple CaSQx, Bi, Sb, Calcite Simple NaCl, CaF, NaClOs Body-centred Face-centredSS a grRUCTURE OF CUBIC AND HEXAGONAL sysTey ic system ic structure is the simplest t 7 i the cubic struct plest type of ‘array in whi se postions at the comers, faces and also at the centre Sie Ge be be ul types of lattices possible in this system depending on the peau ae the iS of the se points (ators) i the unit cell, viz. 1. Simple Cubic (SC) (or) Primitive (P) 2, Body Centred Cubic (BCC) and 3, Face Centred Cubic (FCC) In simple cubic lattice, there is one at each of the eight corners of the unit fl, as shown in fig. (7.18). Example: Polonium 2. Ina body centred cubic (BCC) lattice, tte atoms are located at all the eight comers ‘ad in addition, one more atom is located at tte centre of the unit cell, so called the body centred atom, as shown in fig. 7.19. Examples: Tungsten, Chromium, Molybdenum, etc., 3. Ina face-centred cubic (FCC) lattice, aon are located at all the eight corners |in addition the atoms are located in all the ee a fashion of one in each face of it cell as shown in fig. 7.20 at each of the twelve atoms are located e onal face and se packed structure, the centre of top hexag' nd 2 atoms, one at tlcontre of bottom hexagonal fice, nis, there are J more atoms in the middle layer, situated Inberyeen the top and bottom hexogonal face of the cell, in alternative vertical fas as shown in Vig. 7.21. another at the Alam with these ator Hexamples: Magnesium, Osmium, Cobalt, titanium, ce Fig. 7.21 PARAMETERS DETERMINING THE CRYSTAL STRUCTURE OF MATERIALS ss some of the important parameters which are used to describe 7AL Let us dis the crystal structure, 1, Number of atoms per unit cell (or) Effective number The total number of atoms present in (or) shared by an unit cell is known as mumber of atoms per unit cell. 2. Atomic radius Atomic radius is defined as half of the distance between any two nearest neighbour atoms which have direct contact with each other, in a crystal of a pure element, It is usually expressed in terms of cube edge a. 3. Co-ordination number Co-ordination number is the number of nearest neighbouring atoms to a particular atom (or) Co-ordination number is the number of nearest neighbours directly surrounding a given atom. 4. Atomic packing factor (or) packing density (or) density of packing ‘Atomic packing factor is defined as the ratio between the volume occupied by the total number of atoms per unit cell (v) to the total volume of the unit cell (V). Volume occupied by the total number of atoms per unit cell Total volume of the unit cell Total Number of atoms per_unit cell x Volume of one atom pr = Lotal Number of atoms per_unit cel Comore fer), A Total volume of the unit cell Let us discuss all the above parameters one by one for a SC, BCC, FCC, HCP & Diamond structures, ie., APF= = )7.12 SIMPLE CUBIC STRUCTURE [SC] 1. Number of atoms per unit cell In simple cubic the number of atoms per unit cell depends on the number of comer atoms only. Definition The total number of atoms present in (or) shared by an unit cell is known as number of atoms per unit cell. Explanation Figure 7.22 (a) shows the unit cell of a simple cubic structure. In this case, there are only 8 atoms, one at each corner of the cube (or) the unit cell. But in actual crystals, each and every corner atom is shared by 8 adjacent unit cells. Therefore, each corner atom is common for 8 adjacent unit cells (Refer fig. : : Fig. 7.22 (a) Simple cub 7.25). In other way we can say that each comer atom /"& 722 (@) Simple cubic contributes only 1/8" of its part to a single unit cell. <. Total number of atoms per unit cell =}% total number of comer atoms = 3x8 => 1 In otherwords, the effective number of lattice points in a simple cubic structure is one. Thus, simple cubic is a primitive cell. Aliter Proof 2. Atomic Radius \' | neighbour atoms which have direct contact with each other. We can also find the total number of atoms per unit cell by simply adding all 1/8 as shown in fig. 7.22 (b). ie., Total number of atoms per unit cell. +5=1 Fig. 7.22 (b) D ion Atomic radius is defined as half of the distance between any two nearest Atomic radius (r) can be expressed in terms of cube edge a and vice versa. all the atoms are assumed to be spherical in shape.Explanation i ie 5 is In Simple Cubic (SC) structure the corner atoms touch each other along the edges as shown in fig. 7.23, Let us consider one face (front face) of the simple cubic structure as shown in fig. 7.24. Here, the nearest neighbour distance is the lattice constant a= 2r, 1 Fig, 7.23 Fig. 7.24 3. Co-ordination number Definition Co-ordination number is the number of nearest neighbouring atoms to a particular atom. (or) Co-ordination number is the number of nearest neighbours directly surrounding a given atom. Explanation Simple cubic unit cell consists of 8 comer ‘atoms. Let us consider any one corner atom say X, shared by 5 8 unit cells as shown in Fig. 7.25. For this particular atom ‘X’ there are 4 nearest neighbour atoms, shown as 1, 2, 3, and 4 in its own B 2 plane (horizontal plane) and there are 2 more nearest atoms, one directly above (atom 5) and the other one directly below (atom 6). All the atoms, other than these six atoms lie at Fig. 7.25 greater distances from the X atom. «. The total number of nearest neighbours for X-atom =4+2>6 Hence, the coordination number for simple cubic is 6.| Note: ‘Similarly, even’ ifiwe consider. any other corner atom, 4 _ then too the total number of nearest neighbours \.e., the _ Co-ordination number will be the same. | 4. Atomic | Definition Atomic packing factor is defined as the total number of atoms per unit cell to the Packing Factor [APF] ratio of the volume occupied by the total volume occupied by the unit cell. Volume occupied by the total number . f atoms per unit cell (vy) r F=——_Ol Moms perunitcell ____(v) te AEF Total volume of the unit cell ) APF= No. of atoms per unit cell x Volume of one atom | (or) APF= Total volume of the unit cell Explanation In simple cubic, The number of atoms per unit cell Volume of 1 atom (spherical) sgn L We know that the radius of atom in simple cubic r=a/2 Volume occupied by the total number of atoms per unit cell =ixd ‘| g ] Volume of the unit cell (V) = length x breadth x height. We know that for a cubic system, length = breadth = height = a (or) Therefore, we can say that 52% occupied by atoms and remaining of the unit cell of SC is 48% of the volume is. vacant, ‘Thus, the pack density Is 52%, Since the packing density ts very low, SC has loosely packed structure,7.13 BODY CENTRED CUBIC STRUCTURE [BCC] 1. Number of atoms per unit cell In BCC the number of atoms per unit cell depends on the number of comer atoms and body centred atoms. Det ition The total number of atoms present in (or) shared by an unit cell is known as number of atoms LA per unit cell. Explanation In BCC structure we have two types of atoms viz, (i) Comer atoms and (ii) Body centred atoms .e., there are 8 corner atoms, one at each corner Fig. 7.26 (a) of the unit cell and one body centred atom at the centre of the unit cell as shown in fig. 7.26 (a). (i) Number of corner atoms per unit cell Each and every comer atom is shared by 8 adjacent unit cells. “i The total number of comer atoms per unit cell =yx8= . (ii) Number of body centred atoms per unit cell ‘The body centred atom is shared by that particular unit cell alone and is not shared by any other unit cell. The Number of body centred atoms per unit cell =1x1=1 . Total number of atoms | _ { Totalnumber of corneratoms+ per unit cell in BCC Total number of body centred atoms =14+1=2 Aliter Proof We can also find the total number of atoms per unit cell by simply adding all 1/8's and a complete 1 as shown in fig. 7.26 (b) i.e, Total number of atoms per unit cell = Ltd ttt ayh (febdedede =1+1 Fig, 7.26 (6)—= 2. Atomic Radius Definition ‘Atomic radius is defined as half of the distance between any two nearest neighbour atoms which have direct contact with each other. ‘Atomic radius (r) can be expressed in terms of cube edge a and vice versa. Here all the atoms are assumed to be spherical in shape. Explanation In BCC structure, the corner atoms do not touch each other. But each comer atom touches the body centred atom along the body diagonal as shown in fig. 7.27. Therefore, the two corner atoms (A and D) situated at the opposite ends can be joined by drawing a diagonal as shown in fig 7.28. Fig. 7.27 Fig. 7.28 From the geometry of the fig 7.28, we can write (AD) =(A@*+ (CD)? = (AB) + (BO? + (CD (or) (ADP =a? +a? +a? =30" (or) AD=av3- (1) From Fig 7.28, the diagonal of the cube AD=4r, (2) rad 2. From equations (1) and (2) 2 3. Co-ordination Number Definition Co-ordination number is the number of nearest neighbouring atoms 10 a Particular atom, A(or) Co-ordination number is the number of nearest neighbours directly surrounding a given atom. Explanation In BCC structure, there will be one body centred atom at the centre of the unit cell and eight atoms at the 8 comers of the unit cell as shown in Fig. 7.29. The comer atoms do not touch each other. But each comer atom touches the body centred atom along the body diagonal. Thus, for an atom X at the body centre obviously, there are 8 nearest neighbours (corner atoms). Hence, the co-ordination number body centred cubic structure is 8. Fig, 7.29 Note: The coordination number can also'be determined in another| way by taking the reference atom as comer, atom as follows. We know that in a BCC structure, each comer atom is surrounded by eight other body centred unit cells. Therefore, the nearest adjacent neighbours of any corner atom are the eight body centred atoms of the surrounding eight, unit cells. Thus, the coordination number is 8. 4. Atomic Packing Factor [APF] Definition Atomic packing factor is defined as the ratio of the volume occupied by the total number of atoms per unit cell to the total volume occupied by the unit cell. Volume occupied by the total number ie, APR of atoms per unit cell moy Total volume of the unit cell (v) (or) APF = No. of atoms per _unit cell x Volume of one atom. Total volume of the unit cell Explanation In body-centred cubic structure, The number of atoms per unit cell =2 z. Volume of 2 atoms (spherical) =ixi ne We know that the radius of atom in BCC is . +(e++ Atomic packing factor (APF) = —z (or) APF=1 [APF = 0.68 Therefore, we can say that 68% of the volume of the unit cell of BCC is occupied by atoms and remaining 32% of the volume is vacant, Thus the packing density is 68%. Since the packing density is greater than simple cubic, it has tightly packed structure, when compared to SC. 7.14 FACE CENTRED CUBIC. STRUCTURE [Fcc] 1. Number of atoms per unit cell In FCC the number of atoms per unit cell depends on the number of corner atoms, body centred atom and face centred atom. _ || Definition The total number of atoms present in (or) shared LEST | by an unit cell is known as number of atoms per unit cell, 3 | Explanation wa |___In FCC, we have two types of atoms viz (i) comer X/ | atoms and (ii) face centred atoms. There are 8 comer atoms, one at each.comer of the unit cell and six atoms at the centres of six faces of unit cell as shown in fig 0 (a). Fig. 7.30 (a)(i) Number of corner atoms per unit cell. Each and every corner atom is shared by 8 adjacent unit cells. ami 1 “The total number of comer atoms per unit cell =x 8 (ii) Number of face centred atoms per unit cell. centred atom is shared by only two unit cells, which lie on either Each face x face centred atoms in an unit cell. side of the atom. Similarly we have si «= The total number of face centred atoms per unit cell =3x6=3 J The total number of atoms | _ Total number of comer atoms + “) per unit cell in FCC Total number of face centredatoms =1+3=4 Aliter Proof We can also find the total number of atoms per unit cell by simply adding all L's and all 12's as shown in fig. 7.30 (b). Fig, 7.30 (b) i.e. Total number of atoms per unit cell = TA yl (srareebrararien }(peaeaee22) =1+3=42, Atomic Radius Definition Atomic radius is defined as half of the distance between any two nearest neighbour atoms which have direct contact with each other. Atomic radius (7) can be expressed in terms of cube edge a and vice versa. Here all the atoms are assumed to be spherical in shape. Explanation In FCC structure, the corner atoms do not touch each other, But each corner atom touches the face centred atoms along the diagonal of the face of the cube as shown in fig. 7.31. Therefore, the two corner atoms (A andC) situated at the opposite ends of the same face can be joined by drawing a diagonal as shown in fig. 7.32. From the geometry of the fig. 7.32, we can write (acy = (ABP + (BO? aa+a r) (AO)? = 20? 2 ACzaY2 But from fig 7.32, the diagonal of the cube AC=4r SS ~~ Yj Aid J — Fig. 7.3276 _ Engineering Physic >| +. From equations (1) and (2) we can write 4r=av2 a 2 4 Atomle radius r=—— Note: From the atomic radius of BCC and FCC we can write the) If laltica constants as u= and a= we respectively. Therefore the lattice constants ‘a’ for BCC and FCC are in the ratio of Y2: V3 3. Co-ordination Number Definition Co-ordination number is the number of nearest neighbouring atoms to a particular atom, (or) Co-ordination number is the number of nearest neighbours directly surrounding a given atom, Explanation In FCC structure, there are 8 corner atoms, and six face centred atoms, one at the centre of each face. To calculate the coordination number, for FCC, let us consider a comer atom (X) as shown in Fig, 7.33. In its own plane it has 4 face centred atoms (1 2, 3, 4) as nearest neighbours, In a plane which Ii just above this corner atom, it has 4 more face centred atoms (5, 6, 7, 8 st neighbours. And, similarly in a plane which lies just below this corer atom it has 4 more face centred atoms, (9, 10, 11, 12) as nearest neighbours. Pig. 7.33 The (otal number of nearest atoms to any comer atom is Hence, the coordination number is 12. Note:fal Physics. 4, Atomic Packing Factor [APF] Definition ‘Atomic packing factor is defined us the ratio of the volume occupied by the toal number of atoms per unit cell to the total volume occupied by the unit cell. Volume occupied by the total number te ApPe of atoms per unit cell _w ie, APP= Foal volume of the unit cell () pr= No. of atoms per_unit cell x Volume of one atom (on) AEF Total volume of the unit cell Explanation In face-centred cubic structure, The number of atoms per unit cell =4 . Volume of 4 atoms =4 wha? We know that the radius of the atom in FCC r <. Volume occupied by the atoms per unit cell oie ] ( ya ton] a 2N2 9, 3) 4x4x4 3 <. Volume occupied by the atoms per unit cell v==% 2 Volume of the unit cell for a cubic system (V) = “+ Atomic Packing factor (APF) = (or) APF=n Therefore, we can say that 74% of the volume of the unit cell of FCC is occupied by atoms and remaining 26% of the volume is vacant, Thus, the packing density is 74%. | ___ Since the packing density is very high, the FCC structure has closely (or) | Aghtly packed structure,7.15 HEXAGONAL CLOSELY PACKED STRUCTURE (HCP) Tn the HCP stricture, an unit cell contains three types of atoms viz, (i) 12 comer atoms, one at cach Top Layer and every comer of the hexagon, as Th. shown in fig. 7.34 (ii) 2 base centred atom, one at the top face of the hexagon and another Le insta Lape at the bottom face of the hexagon as > | ec he a shown in fig. 7.34. (iii) In addition to comer and | base atoms, 3 atoms are situated 7 inbetween the top and bottom face of hexagon, in alternate vertical faces. Also = Bawom Layer note that these atoms are situated inside ny 1 the faces, so that they can’t be shared Fig. 734 by other unit cells, as shown in fig. 7.34. Thus it is obvious that each unit cell shares 14 atoms (12 comer atoms + 2 base atoms) with other unit cells and contains 3 atoms within that unit cell. The common examples of this type of structure are Magnesium, Zinc, Zirconium, Cadmium etc. My, 7. The calculation of 1. Coordination number, 2. Number of atoms per unit cell, 3. Atomic radius and 4. Packing factor are explained below. 1. Co-ordination number ‘The HCP sturcture is considered to have three layers viz., (i) Bottom layer (B,,) (ii) Top layer (T;,) and (iii) Middle layer (M,) as shown in Fig. 7.34. In the top and bottom layers, the base centred atom is surrounded by six corner atoms. In the middle layer, we have 3 atoms stacked inside the unit cell as shown in Fig. 7.34. Let us consider two unit cells as shown in Fig. 7.35. Let ‘x’ be the reference atom taken in the bottom layer (BL,) of unit cell-1 (or top layer {7L,) of unit cell 2). This atom has 6 neighbouring atoms in its own plane. Further, at a distance of c/2, it has 3 atoms in the middle | ayer (ML,) of unit cell-] and 3 more atoms inthe middle layer (ML) of unit cell-2, Therefore, the total number of neighbouring atoms are 64343512, Thus, the coordination number is 12, 2, Number of atoms per unit cell We know in HCP, there are 3 types of atoms Hvis, G comer atoms (ii) Base atoms and (iii) middle layer atoms, (i) Number of corner atoms per unit cell Each comer atom is shared by six surrounding hexagon unit cells as shown in fig. 7.36. Similarly, we have 12 comer atoms in an unit cell z The number of corner atoms per unit cell | x12=2 Fig. 7.36 Gi) Number of base centred atoms per unit cell. Each base atom is shared by two unit cells as shown in fig. 7.36, Similarly ‘we have two base centred atoms in an unit cell, +. The number of base centred atoms per unit cell =4x2=1 (ii) Number of middle layer atoms per unit cell The 3 atoms situated at the middle layer, within the body of the unit ccll are fully contributing to that particular unit cell alone i.c., they are not shared by any other unit cells. 2. The total number of middle layer atoms per unit cell =3 + The total number of atoms. per unit cell in HCP structure hs Moneta tame {worse fea | ‘ middle lay per unit cell per unit cell peruniteal f=2+143=6 Number of atoms per unit cell in HCP structure 3. Atomic radius To find the atomic radius of the HCP structure, consider any two corner atoms, It has to be noted that, +h and every corner atom touches cach other, therefore hey are the nearest neighbours. igure (7.37), we can write“, a= 2r (or) r=a/2 the atomic radius is r=a/2ole ee 4. Relation between ‘c’ and ‘a [é ratio | In hexagonal system, let the height of the unit cell be ‘cand the distance between two neighbouring atoms is ‘a’. Let [.J.K,L, MN are the comer atoms and O be the base atom in the bottom layer of HCP structure and P,Q,T are the middle layer atoms, as shown in fig 7.38. Consider the arrangement of atoms /, N, 0 and P as shown in fig. 7.38 Here, J, N and O represents the bottom layer atoms and P represent the middle layer atom. Now, let us draw the normal line OR from O to the line IN, which bisects the line IN at a.point R. Consider a triangle IRO, . _ Fig. 7.38 cos 30° =F (on OR = Ol cos 30° 5 Since OI =a and cos 30°=V3/2 we can write or=a ww) If ‘S’ is the ortho centre for friangle INO, then it is found that the length of ‘OS? is equal to 2 of OR. ie.) os=20R [Refer Fig. 7.38] Substituting the value of ‘OR’ from equation (1) we get =2,8 os=5a75 (oy os=— 2) In triangle SOP, OP* = 0S? + SP” : 3)| - = wl) r Equation (4) gives the axial ratio (=) for an hep structure. 5. Atomic Packing Factor (APF) We know Atomic Packing Factor =Yolume ofthe stoms peruniteell) (5) As Since the base atom ‘O' in the bottom layer and the atom ‘P” in the middle layer touch each other, here OP We know the distance between the middle layer and the bottom layer is ¢/2, .. i.e. SP: < Substituting the values of OP, OS and SP in equation (3), we get, (or) (or) Volume of the unit cell (V) ‘App = Number of atoms per unit cell x volume of one stom ‘Volume of the unit cell. Number of atoms per unit cell in HCP structure = 6. Volume of one atom (spherical) = $ x +. Volume of all the atoms in a unit cell (=6x3nF We know the radius of atom in HCP is r=a/2, therefore we can write 13 * o=Fe{§] +. Volume occupied by all the atoms per unit (=n? For HCP, the volume of the unit cell(V)= Area of the base x height (7) ‘Area of the base = Area of six triangles [refer fig 7.38] 16) “Area of the base = 6X area of the one triangle (ONT) From fig, 7.38 the area of the triangle ont=3 (IN) (RO) Substituting the value of RO from the equation (1) we get aa ‘Area of triangle ONI =haxth a -. Area of the base (or) Area of the base 382 a 8) We know that the height ot the hep structure = ¢ (9) +. Substituting equations (8) and (9) in equation (7) we get 313 2 (10) Volume of the unit cell m=3 ha xe Substituting equations (6) and (10) in equation (5), we getTherefore we can say that 74% of the volume of the unit cell of HCP is occupied by atoms and remaining 26% of the volume is vacant, Thus, the packing density is 74%, which is the same as that of FCC structure. Hence, HCP structure is also termed as tightly (or) closely packed structure. 7.16 DIAMOND CUBIC STRUCTURE Diamond has Face Centred Cubic (FCC) structure with the basis of two carbon atoms, viz, ‘X” and‘Y’. The ‘X’ atom is located with an origin of (0, 0, 0) and the ¥ atom is located with an origin of (é a (ie) one quarter of the way along the body diagonal as shown in fig 7.39. Fig. 7.39 from fig 7.39, we can see that the diamond structure is formed due bination of two interpenetrating FCC sub lattices, having the origin nd (1/4, 1/4, 1/4), along the body diagonal. now discuss some of the important parameters of the diamond.(a 1. Number of atoms per unit cell In diamond, we have 3 types of atoms viz., Comer atoms, represented by *C’ in fig. 7.39 Face centred atoms, represented by ‘F” in fig. 7.39 Four atoms present inside the unit cell represented as 1, 2, 3 and 4, in fig 7.39. The three types of atoms positions projected on a cube face is as shown in fig. 7.40. Fig. 7.40 (i) Number of comer atoms per unit cell Each comer atom is shared by 8 unit cells. Similarly, we have 8 comer atoms in an unit cell. : 1 ++ The number of comer atoms per unit cell = 5x8 =1atom (ii) Number of face centred atoms per unit cell Each face centred atom is shared by 2 unit cells. Similarly, we have 6 face centred atoms. ~. The number of face centred atom per unit cell =4x6=3.atoms (iti) Number of atoms inside the unit cell Inside the unit cell, we have 4 atoms, represented by 1, 2, 3, 4 in fig 7.39, which is shared by that particular unit cell alone. Total number of atoms per unit cell =1+3+4=82, Atomic radius We know that atomic radius is defined as half the distance between any two nearest neighbour atoms, which have direct contact with each other. Here, the comer atoms do not have contact with each other and the face centred atoms also do not have contact with the comer atoms. But both the face centred atoms and the comer atoms have contact with the 4 atoms (1, 2, 3, 4) situated inside the unit cell as shown in Fig. 7.39. From fig. 7.39, we can see that the nearest two neighbours which have direct contact (shown by double line) are atoms ‘X’ and ‘Y’. Let us draw perpendicular to the Y atom, which meets the unit cell at a point ‘Z’ as shown in fig. 7.39, which is at a distance of a/4. ©. From fig. 7.41 (a) (XY)? = (XZ + (ZV)? = (AD? + (121+ 2 a y a y a y (C8) ; ead x 167 16°16 » My, 2 “ oxy? 3 Ty 2 3a Fig. 741 Since XY=2r, we can write nae aot 4P= ie The lattice constant a= * Coordination number "We know the coordination number is the number of the nearest neighbouring to a particular atom. n fig. 7.39, the number of nearest atoms (shown by double Tine) for Y (4) Therefore, the coordination ‘number of diamond is 4. | | j |Note: jinThe coordination number Is found’ to be the!same ‘evan It is calculated) with fecal to ato srsayi(2) (8), 4 (or) “comer, (or) face cen sad 4, Atomic packing factor We know that Volume occupied by the atoms per unit cell (v) Oo Volume of the ut cell (V) Atomic packing factor (APF) = Volume occupied by 1 atom (spherical) afar In diamond we have 8 atoms per unit cell -. Volume occupied by all the ‘8’ atoms per unit cell (W=8x$ nr We know that atomic radius for diamond strucutre r= 479. 3 . Volume occupied by the atoms per unit cell (v)=8x4 4.038 w 2) :. Volume occupied by the atoms per unit cell ee Since diamond has cubic structure, the volume of the unit cell (V)=a? __... (3) Substituting equations (2) and (3) in (1) we get 3 (apn = 5 ws mN3 APF 16 «. Packing density = 34% Thus we can say that 34% of the volume of the unit cell in diamond cubic strucutre is occupied by atoms and the remaining 66% of the volume is vacant. Since the packing density is very very low, it.is termed as very loosely packed structure.= 7.17 COMPARISON CHART FOR SC, BCC, FCC, HCP AND DIAMOND STRUCTURES The parameters determining the crystal structure of SC, BCC, FCC, HCP and diamond are given for comparison, in Table 7.3. TABLE - 7.3 7 anes 1. | Atoms per unit cell 2. | Atomic radius 3. Coordination number 4. [Atomic packing factor 5. |Packing density 52% 68% 74% 74% 34% Examples 7.18 RELATION BETWEEN LATTICE CONSTANT AND DENSITY Let us consider a cubic crystal of following parameters, viz., (i) “The lattice constant of the cell (i) The number of atoms per unit cell (iii) The atomic weight of the crystalline substance (or) compound =M (iv) The density of the unit cell =p (v) The Avagadro’s number = [Avagadro’s number gives the number of molecules per kilogram mole of s of each molecule =M Thus the mass of 1 molecules (or) mass of un unit cell ny 7 oii Mass of an unit cell + Density of an unit cell 18 P= Yotume of an unit cell We know that the volume of the unit cell = a? i 3_Mn Lattice constant a” =~ (or) Latti Np tomic weight x Number of atoms per unit cell 1.” Avagadro Number x density Therefore, using the above equation, we can calculate the lattice constant ++ Lattice constant a 7.19 MILLER INDICES Introduction planes, passing through the lattice points called lattice planes. The different ways | 1,2, 3, 4, 5, 6) in which the lattice planes can be chosen are as shown in fig. 7.42. We know, that crystals are made up of large number of parallel equidistant Fig, 7.42The perpendicular distance between any two adjacent planes is called Interplanar distance (d) Thus, in-a crystal, there exists different direction and different planes, each having its characteristic interplanar spacing. Therefore, it is necessary to locate these directions and planes for a crystal. To identify the direction and to designate (to choose) a plane in a crystal, Miller, a scientist suggested a method as discussed below. Miller indices Miller introduced a’ set of three numbers to designate a plane in a crystal. This set of three numbers are known as Miller indices of the concerned plane. Definition Miller indices are defined as the reciprocal of the intercepts made by the plane on the crystallographic axes which are reduced to smallest numbers. (or) Miller indices are the three smallest possible integers, which have the same ratio as the reciprocals of the intercepts of the plane concerned along the 3 axes. Let us consider a plane ABC which cuts 3 along the X-axis, 1 unit along the ¥ — axis Find the intercepts made by the plane along the three axes and express the ts in terms of multiples of axial lengths hitiples' of the fundamental vectors).i.c.. ercepts are 3a: Ib: 2cSS Step 2: / Find the coefficients of the intercepts i.c., 31,2 Step 3: 1 Find the reciprocal of these numbers ? Step 4: Convert these reciprocals into whole numbers by multiplying each and every reciprocal with their least common multiplier (LCM). 1 1 1 Since 6 is the LCM in this case, we get 6x3 6xT 6x5 ©. Wehave= 2 6 3 Step 5: Enclose these numbers in a bracket like this > () ie, (2-6 3). This represents the indices of the given plane and is called the Miller indices of the plane. Miller indices are generally denoted by (hkl). Thus, we can write a.bic for any system and h:k:1= i for cubic system. Par Miller indices should be enclosed only in this bracket ie, > ( ) re should not be any commas inbetween the numbers. the Miller indices are say (2 6 3) means it should be read as two six three, d not as two hundred and sixty three. ie direction of plane can be represented by enclosing the Miller indices in quare bracket (e.g) [2 6 3] i :tive Miler Indices can, be rep Ifa plane is parallel to any one of the coordinate axis, then its intercept "will be at infinity. Hence, the Miller index for that particular axis is zero. mple: In fig 7.44 (a) the plane has unit intercept along y axis and xand.z axis, <. Miller indices are (+ + ele (0 1 0) plane passing through the origin has non zero intercepts. equally spaced parallel planes have the same Miller indices (hk 1) Miller indices of the planes have the same ratio like (8 4 4), 1 1), then these planes are said to be parallel to each other. ato find all such planes. its the axis on the negative side of the origin, then the ding Miller index will be negative, as shown in fig. 7.44 ©).(011) Coe ac norma te XYZ Examples y (1.00) Planes normal te X atie (19) Cube face normal to the V auls x Pe radia Tae xe normal vo XY sus, (sepee long sandy sis p Fig. 7.44(0) Fig. 7.44 (70 0) Planes on -ve x axis Fig. 744(0) Fig. 7.44(0) From the figure 7.45 (a), (b) and (c), we can see that the planes have intercepts on the positive axes. Therefore, the Miller indices of the plane ABCD [fig. 7.45 (a)], BFGC [fig. 7.45(b)] and AEFB (fig. 7.45 (0)] are (100), (010) and (001) respectively. 2 a , 5 Hi 4 2 , | Gireay ) era t o i ae oonrine Fig. 7.45(a) Fig. 7.45(b) Fig. 7.45(0) Fig, 745From the fig, 7.46 (a), (b), and (c), we can see that the planes have intercepts over the negative axes, ‘Therefore, the Miller indices for the planes EFGH fig, [7.46 (a)], EHDA fig. (7.46 (b)] and HGCD fig. [7.46(c)] are (10.0), (0 1 0) and (0 01) respectively. Goo Pine (070) Plane (004) Plane Fig. 7.46(a) Fig. 7.46(6) Fig. 7.46(c) Fig. 7.46 7.21 PROCEDURE FOR SKETCHING THE PLANE FROM THE GIVEN MILLER INDICES So far, we have discussed how to get the Miller indices for a given plane (or) sketched diagram. Now we are going to discuss how to sketch (or) draw the diagram for any given Miller indices, by the following procedure. Suppose the Miller indices are say (4 2 4), ie, h=4; k=2; [=4Step (ii) Represent the reciprocals in terms of 2 intercepts along the axial units ie. along the X,Y and Z axes respectively, by multiplying the reciprocals by the LCM. Ligydi gy PAR GAR AKG . Wegetl:2:1 (ie.) a:2b:¢ a,c (or) g2b:5 Now sketch the plane with intercepts of Fig. 7.47 a2,bandc/2 along the X,YandZ axes respectively as shown in fig. (7.47) 7.22 COMMON PLANES IN A SIMPLE CUBIC STRUCTURE Though many number of planes can be z drawn in a cubic structure, the most common planes in a simple cubic structure are (1 0 0), (110) and (1 1 1). These planes can be sketched by the following method. (a) Plane (100) In this case h= 1, k=O and/=0. (100) Plane The reciprocals of fh, k, and / are i: Fig. 7.48 Multiplying by LCM we get (ie. 1 xt: ixtey xt We get 1: ++ The intercepts are 1a’: 0: 20 : Now, sketch the plane with intercepts 1 unit along X axis and parallel to | yanaz axis respectively as shown in fig. (7.48)In this case h=1,k= Land /=0 1 The reciprocals of h, kand! are + 7 Multiplying by LCM we get Miixtiixt Ixpilxpi leg (110) Plane Fig. 7.49 T ==From the law of direction cosines, we can write cos” «.’ + cos” B’ + cosy’ = 1 (hy (bby (aly AF He ]+ ZS ]=1 ae 4a” 4a? | Sieeshe (or) & (or) ww (2) erplanar distance (d) We know thdt interplanar distance is the distance between two successive mes. Since ‘d’ is the distance between the two planes ABC and A’ BY C’, we write the interplanar distance (d) as Substituting equations (1) and (2) in equation (3) we get 2a Interplanar distance d= aoa ees eee Py a dea ay +k +0) A) quation (4) represents the interplanar distance, which is the same as that distance between the origin and the first plane, represented by equationFor other’ ‘eystal systems, such as Triclinic, corthorhombie etc., the relation between the Interplanar distance (d) and, the axial lengths (a, b, ©) Is given by 1 qh K +g 7.24 INTERPLANAR DISTANCES IN SC, BCC AND FCC The interplanar distances for various planes in Simple Cubic (SC), Body Centred Cubic (BCC) and Face Centred Cubic (FCC) can be determined as follows: Simple Cubic (SC) a (i) The interplanar distance between (100) planes is dw" eae" Peo +o a : : a Gi) The interplanar distance between (110) planes isd, =———— VPP +e (ii) ‘The interplanar distance between (111) planes is d,,,=———* + VWerer 3 14 2 digg: dyigid)yy=1:5=:—— to? duno? din = Ve (or) Body Centred Cubic (BCC) Gi) In BCC, for (100) planes, we have additional (100) planes in the midway of such planes. ‘. Interplanar distance between (100) planes is dy0= 5 Myosc =a/2 Gi) For (110), there is no additional plane (fig. 7.55) Fig. 7.55a ce The interplanar distance between (110) planes is dg = (4)10)sc= a ii) For dy, we have additional (111) planes, in the midway of such planes, a 1 c+ The interplanar distance between (111) planes is dj, = 5 dudse=5 5 Face Centred Cubic (FCC) (i In FCC, for (100) planes, we have additional (100) planes in the mid way of (100) planes as shown in fig. 7.56 -. The interplanar distance between (100) planes is aye0 =F Cra =$ (i) Similarly for (110) planes, we have additional (110) planes in the midway of such planes. ‘The interplanar distance between (110) 4 1 a planes is dyig="9 (diidlsc= 5 Ve (iii) For (111) planes, there are no additional planes .. The interplanar distance between (111) planes x #8 d= dsc Ye 409 410? i= 9 yp Ve (09, dp do? dins= (or)