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EP-crystal Structures and X-Ray Diffraction

The document explains the distinction between crystalline and amorphous materials, detailing their structural differences, properties, and examples. It covers concepts such as space lattice, basis, unit cell, primitive cell, lattice parameters, and the seven crystal systems along with Bravais lattices. Additionally, it discusses coordination number, atomic radius, packing factors, and provides derivations related to lattice constants and Miller indices in crystal structures.

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16 views19 pages

EP-crystal Structures and X-Ray Diffraction

The document explains the distinction between crystalline and amorphous materials, detailing their structural differences, properties, and examples. It covers concepts such as space lattice, basis, unit cell, primitive cell, lattice parameters, and the seven crystal systems along with Bravais lattices. Additionally, it discusses coordination number, atomic radius, packing factors, and provides derivations related to lattice constants and Miller indices in crystal structures.

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kotasrinivasaraokorivi
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UNIT-IT CRYSTAL STRUCTURES & X-RAY DIFFRACTION. J. Distinguish between crystalline and amorphous materials. Basing on their structure solids are classified into two groups. They are 1) CRYSTALLINE 2) NON - CRYSTALLINE or AMORPHOUS CRYSTALLINE SOLIDS ‘NON-CRYSTALLINE SOLIDS A solid is said to be crystalline ifts atoms or | A solid is said to be non crystalline or ‘molecules are arranged in the periodic manner, | amorphous ifthe atoms are arranged in. the irregular manner Crystalline solids are anisotropic. te Their The amorphous solids are isotropic ie. They Physical properties are different in ‘have same physical properties in different directions. all directions. Crystalline solids have sharp melting and They don’t have sharp melting and boiling boiling points points Crystalline solids have long range order of | Non crystalline have short range order of atomic forces atamic forces Examples: Rock salt, calcite, sugar Examptes: Glass, rubber, plastic 2. Explain the terms Space lattice, Basis and Unit cell, LATTICE POINTS: lattice points are imaginary points in space about which the atoms are located ‘SPACE LATTICE: Def :- An infinite array of points in three dimensional space such that the environment around each oint is same is known as space lattice. BASIS: A group of atoms, ions or molecules (that are identical in composition. arrangement and orientation associated with each lattice point) is called the BASIS. Space lattice + Basis = Crystal structure, ‘Basis ansocated with each lteepolnt a2 000 0, O° @) Pe oleae 5 Tor - oO oO. soo 239999 20 0 00,0 Ssceesee oF eh “Or Je! ict ot io iO: Oe (0, 10) ot 3. What is a unit cell? UNIT CEL Def: It is defined as the smallest fundamental building block of minimum atoms, the repetition of which in three dimensions gives the actual crystal structure, *Unit cell represents fully the characteristics of the crystal. “The choice of unit cell is not unique. ie. unit cell can be chosen inno, of ways % This region ABCD is called a unit cell Similarly PORS is also another unit cell .The unit cell can be chosen in number of ways, ‘In three dimensions it is called parallelepiped. NOTE: The size and shape of unit cell can be described by the lattice parameters. 4. What is a primitive cell? how does it different from unit cell. Is Unit cell of Simple Cubic lattice a Prin ive or not? Why? Primitive cell: It is defined as a unit cell which contains lattice points at corners only. It has only one lattice point. Note: (1) It is not necessary that UNIT CELL should be PRIMITIVE. 2) Non Primitive Cell: If a Unit cell contains more than one lattice point then it is called Non Primitive cell A unit cell may contain any number of lattice points, But a primitive cell has only one lattice point. The simple cubic lattice is primitive, It has 8 corner atoms. Each corner atom contributes 1/8 of its volume. 8X 1/8 =1. Since it has atoms only at its corners, it is primitive, 5. What are lattice parametres? LATTICE PARAMETERS OF AN UNIT CEL! The unit cell is shown in fig with 3 crystalographic axes X, ¥, Zand the intercepts a, b, ¢ are dimensions of unitcell called PRIMITIVES. The angles between three crystallographic axes are known as interfacial angles. The angle betweeny & z= a i The angle betweenz & x =B The angle between x & y = Here the basic lattice parameters are Primitives a, b & ¢ Interfacial angles a, B & y Lattice parameter and angles of a unit cel 6. Describe seven crystal systems with diagrams. (Or) What is Bravais Lattice and Ilustrate Bravais lattices, SEVEN CRYSTAL SYSTEMS AND BRAVAIS LATTICES % There are 32 classes of systems based on geometry, symmetry and internal structure of the crystal .All these are categorized in to 7 crystal systems. % Depending on the values of lattice parameters BRAVIAS showed that they are 14 ways of arranging points in space such that all points have exactly the same environment. The seven crystal systems are: 1) Cubic 2) Tetragonal 3) Orthorhombic 4) Monoclinic 5) Triclinic 6) Trigonal 7) Hexagonal Type of Bravais Latti fe anot-|k ct lates ound ravats attice parameters Examples lattice 7 Cubic PLE NaCl, diamond Tetragonal BI Ag, KH:PO« 3 Orthorhombic POLF KNOs ; P 4 Monoclinic Z CaSO. . clini P Ki 5 Trielinic ee pe ys 00! C1207 se 6 Trigonal P i a Calcite Fe 7 He P 2 lexagonal Pre Quar P -primitive or simple F face centered 1 -body centerd C -base centered CUBIC SYSTEM. + In the cubic system the crystal is made up of three equal axes at right angles to each other. a=b=c; a=f=y = 90" It exists in three forms, (A) SIMPLE CUBIC: In this the particles are only at the corners of the unit cell (B) BODY CENTERD CUBIC: In this the particles are only at the corners as well as at the center of the unit cell (C) FACE CENTERD CUBIC: In this the particles are only at the corners as well as at the center and each face of the of the unit cell TETRAGONAL SYSTEM. ‘+ In this the three axes are at right angles to each other and two axes are equal. It exists in two forms a) primitive (p) _b) body centered (I) a =b#cand a=f=y=90" ial Tetragonal ORTHORHOMBIC SYSTE! + This system includes the crystals in which crystallographic axes are unequal but they are right angles to each other. a#b#c and a = f= ee = 90°. It exists in four forms Orthorhombic MONOCLINIC SYSTE! + In this type of crystals the three axes are unequal and one axis perpendicular to other 2 axes. ie,a¢b#¢cand a=f-9P ty Itexists in 2 forms, They are primitive(P) and body center(C) Monoclinic TRICLINIC SYSTEM: + In this system the three axes and angles are unequal. atbécandat pty £9” Itexists in only one form. It is primitive : TRIGONAL SYSTEM: * In this system the crystals are made up of three equal angles with 2 equal angles. a=b=canda=f=7490. Itexists in only ‘one form. It is primitive. HEXAGONAL SYATEMS : % The system has 8 faces .In this system 2 axes are equal in length in one plane lying at 120° and third one is perpendicular to this plane. a = b#c¢ &a=f= 9M y 120 It exists in only one form. Hexagonal 7.Define coordination number, atomic radius, nearest neighboring distance and packing factor of unit cell.” NEAREST NEIGHBOUR DISTANCE : The distance between the centers of two nearest neighboring atoms are called NEAREST NEIGHBOUR DISTANCE. ATOMIC RADIUS: tis defined as half of the distance between neighboring atoms in a crystal. COORDINATION NUMBER: Tis defined as the no, of equidistant nearest neighbors that an atom has ina given structure. Note : More closely packed structure has greater coordination number ) Coordination number of simple cubic form is 6. ii) Coordination number of BCC form is 8. it) Coordination number of FCC form is 12. Atomic Packing factor (Packing Fraction) : Iris the ratio of volume occupied by the atoms in an unit cell (y) to the total volume of the unit cell (V).It is also known as packing fraction. i.e. P.F = v/V J nr? AP. (OF ATOMS IN UNITCELL me Lal PP oLUME OF UNITCELL— a Now we will discuss the 3 main structures and their packing fraction values. 8.Show that FCC is the most closely packed of the three cubic structures by working out the packing factors. ‘STRUCTURE AND PACKING FRACTION OF SIMPLE CUBIC ‘+ The simplest and easiest structure is simple cubic structure. There are 8 corner atoms situated at the eight corners of the unit cell. The corner atoms touch each other. Each corner atom touches 6 atoms. Hence each atom is surrounded by 6 equidistant nearest neighbours hence the coordination number is 6. Each corner atom contributes 1/8 to the unit cell, the effective number of atoms t0 the unit cell is one. Hence the unit cell is primitive cell. This structure is a loosely packed one. ATOMIC PACKING FACTOR IN SC STRUCTURE: ATOMIC PACKING FACTOR IN SC STRUCTURE: Let 'r’ be the radius of atom. ‘a’ be the lattice parameter.(a=2r) The effective no of atoms per unit cell = 1 i.e. Ne=1 Volume of unit cell=aé Volume of atom = Sn Figunit cell of simple cubie structure Atomic packing factor = volume of atom / volume of unit cell = Sn /@ On substituting r =a/2 (or) a= 2r we get Atomic Packing Fraction = II/6 = 0.523 = 52 % Alomic Packing Fraction of simple cubic structure is 0.523 = 52% Ex: Polonium STRUCTURE AND PACKING FRACTION OF BODY CENTERED CUBIC % There are 8 atoms at the corners of the unit cell and one atom at the center. The corner atoms do not touch each other but each corner atom touches the central atom, Since the corner atom at the center touches eight corners of the unit cell, hence the coordination number is 8. * The effective number of atoms in the unit cell =sxh ate 8 atoms/cell ATOMIC PACKING FACTOR IN BCC STRUCTURE: Let ’be the radius of atom. ‘a’ be the lattice parameter. From the right triangle ABC, AC? = AB? + BC? va AC=\3a - And also from the figure body diagonal A From equations (1) and (2), we have V3 a = 4r = a=4r\3 The effective no of atoms per unit cell = 2 ie. Ne=2 Volume of unit cell=a? Volume of atom= ine Atomic packing factor = volume of atoms/volume of unitcell 2x (4/anr3) _ 8/3? * (8p Atomic Packing Fraction OF BCC structure is 0.68 or 68% Ex: Tungsten, Sodium, Iron and chromium ‘STRUCTURE AND PACKING FRACTION OF FACE CENTERED CUBIC. CO: It has eight atoms at the corners of the unit cell and six atoms at the centres of six faces of the cube. Each atom at the corner is shared by eight unit cells and each atom at the centre of the face is shared by two unit cells. The no. of atoms per unit cell = 8% (1/8) + 6% (V2) = 4 atoms/cell The unit cell of FCC structure is non-primitive. For the atom at the centre of the ‘faces there are 12 atoms at the same distance. Hence the Co-ordination number is 12. B T= 0.68 ~ 68% ATOMIC PACKING FACTOR IN FCC STRUCTURI From the figure it is clear that AC = V2a and also AC = 4r. Hence its face diagonal = 4r = xa = a=2N2r a =2N2xr Packing factor = volume of atoms / volume of unit cell = v/V = 4 (4/3tir*) _ (16/3)? @ evr) 0.74 = 74% In FCC structure, 74% of its volume is occupied by the atoms and the remaining 26% is empty. FCC has the highest packing density. It is tightly packed BCC Structures. Ex: Cu, Al and Ag have this type of structure, FCC is most closel 9.Derive the relation between lattice constant (a) and density () of the crystal. Relation between lattice constant (a) and density (p) of the mate Consider a unit cell of mass ‘m’, density ‘p’ (row) and lattice constant ‘a’ We know that density p=m/V=m/a3 Mass of the unit cell m= pa3 Let n-—--> number of molecules per unit cell and M----> Molecular weight Ne Mass of each molecule = molecular weight = M/Na Avogadro's number Mass of ‘n’ molecules= nM/Na From above equations pa’= nM/Ny=>a?= nM/pNa b= [apn] > Avogadro's number Lattice parameter and angles ofa unit cell X-RAY DIFFRACTION INTRODUCTION: * There are large no of lattice points in a crystal + Lattices planes are imaginary lines passing through lattice points. A crystal consists of a set of parallel and equidistant lattice planes The perpendicular distance between adjacent planes is called INTER PLANER SPACING. % Miller introduced a method to locate the planes and directions for crystals 1. What are Miller indices? How they are obtained? (oR) y Describe the Procedure to Derive Miller Indices PLANES IN CRYSTALS, MILLER INDICES * Fig shows a plane ABC with intercepts of 3 axial units along x- axis and 2 axial units along y-axis and 1 axial unit on z-axis. ures ta pane AC 580 the numerical parameters of the _ plane ABC are 3, 2,1 . © The reciprocals of numericals in the given plane are 1/3, 1/2, 1/1 + Reduce the reciprocals with smallest numbers by multiply with L.C.M — (23 6) MILLER INDICES DEFINITION: ‘MILLER INDICES are defined as the reciprocals of the intercepts of the plane along the 3 axes when reduced to smallest number. These are denoted by chk) IMPORTANT FEATURES OF MILLER INDICES: It represents not only a single plane, but a set of parallel planes. Incase of MILLER INDICES a plane. ‘parallel to one of the coordinate axis has an _ intercept of infinity and index is zero for that axis. + The plane passing through the origin is defined in terms of a parallel plane having non zero intercepts. If (hk) are the miller indices ofa plane the plane cuts the x —axis into hequal parts, y _ axis cuts into k equal parts and z- axis into 1 equal parts. In (h kl) h having negative intercept. Ifa normal is drawn to a plane (h kl) the direction of normal is [hk 1] METHOD TO DERIVE MILLER INDICES: ‘ MILLER INDICES (h k |) for any plane can be obtained by the following procedure. Construct a plane ABC and find the miller indices of the plane ABC. + Let the periodicity along the three axes be a,b,c. Find the intercepts of the plane along. the three axes 2a, 3be&c.we can write in general pa, qb, re. ++ Divide them with translational vectors. In general page aah) 1 11 1 & Take the rec Is of intercepts —,—,~. In general —, + Take the reciprocals of inereepis 5. - In general > Convert the reciprocals into whole numbers by multiplying each with their L.C.M to get the smallest whole number. ie, ssc =3,2,6 In general Par par par Ts =P, prs PG po gir % Enclose them in small brackets as (3 2 6). In general (qr, pr, pq) This gives Miller Indices (h kl) of the plane. . Derive an expression for the inter-planar spacing in the cases of a cubic structure. DISTANCE OF SEPARATION BETWEEN SUCCESSIVE (h k l) PLANES: Let us consider a rectangular co-ordinate system with origin ‘0’ at any of the lattice points. Construct a plane ABC. Let (h kl) be the miller indices of the plane ABC. The direction of the plane is given by a normal drawn to the plane passing through the origin. ‘Let ON be the normal drawn to the plane ABC such that ‘ON’ =d. Let the normal makes angles 4, B, y withX, Y and Z axes. 04, OB and OC be the intercepts of the plane ABC. _X-intercept OA=a/h, Y-intercept OB=b/k. — Z- Intercept OC=cll, + From the figure Cosa = ON/OA= d/(a/h) = diva. Cos f = ON/OB=d/(b/k) = kdb. Cosy = ON/OC=d(cll) = dl /e, From the cosine rule cos? a +cos?f+cos?y =1 => Pa + PR + Pfc =1, is Inter planar separation * For acubie system, a=b ‘X-RAY DIFFRACTION AND CRYSTAL STRUCTURE (OR) EXPLAIN HOW X-RAY DIFFRACTION IS USED TO STUDY THE CRYSTAL STRUCTURE + The phenomenon of bending of light radiation when it comes across an obstacle in its path whose dimensions are comparable with the wavelength of incident radiation is known as diffraction % A ruled diffraction grating consists of grating spacing which is about 3 times of the central Portion of the visible light. So visible light exhibits diffraction when incident on a ruled diffraction grating. X-Rays are electromagnetic in nature. So they also should exhibit diffraction. The wavelength of X-rays is 14° which is nearly equal to the size of the atom. So X rays can be diffracted by atoms. % when an atom is exposed to monochromatic beam of X rays, the electrons are accelerated. These electrons re-emit the radiation at incident frequency. The emitted waves have spherical wave front centered about the atom, so the energy radiates in all directions, There are only few directions in which these wavelets reinforce to produce plane waves. These waves are said to produce diffraction. % The inter atomic spacing is 3 to 5 A°. The inter planar spacing is 2 A°and the wavelength of X-rays is 1 A°So X-rays can be used for crystal diffraction. % Depending upon the intensity of the scattered beam, we can get an idea of the inter planar spacing , position of atoms in unit cell, basis, directions and Miller Indices of a plane etc.. State and explain Bragg’s law of X-ray diffraction, W.L.Bragg and W.HBragg gave a simple relation relating the 0, 2, d [wavelength of the incident radiation .the angular positions of the scattered beams and inter planar spacing d]. % Statement: When a monochromatic beam of X-rays is incident on a crystal planes,each atom acts as a source of scattering radiation of the same wavelength. The rays interfere constructively or destructively will depend up on the path difference between the reflected rays .These two rays reinforce each other and produce an intense spot. 13 PRO! Let us consider a crystal of equidistant parallel planes with inter planar spacing d. * Consider a monochromatic beam of X-ray of wavelength & is incident ofan angle 8 to the atomic planes. The ‘dot’ represents the Position of atoms. Consider a ray AB incident on plane I at an atom Band reflected toC in the direction BC. a a ar % Another ray DE incident on Fi. 38, teen planes and tation ays ina sl crt plane Hat an 7 atom E, and reflected to F in the direction EF. % Draw two normals BG & BH from B on to the lines DE and EF respectively. % The path difference between the two rays ABC and DEF is (GE+EH). + From ABGE, sin=GE/BE = GE/d => GE =d sind. ¢ From ABHE, sin0=EH/BE = EH/d => EH =d sinO. Path difference = GE+EH = 2d sind. Bragg’s law states that the X-rays reflected from different parallel planes of a crystal interfere constructively when the path difference is integral multiple of the wavelength of X-rays, 2d sind =n. % This is Bragg’s law equation, Where n is order of diffraction + For first order maxima, n =1 => 2dsinO: + For second order maxima, n =2 => 2dsin0=22, et... Note: So Bragg’s reflection occur only for wavelength 2<2d => Wad

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