UNIT 1

Introduction: Engineering material is that part of inanimate matter which is useful to an Engineer in the practice of his profession. Materials dealt with in life sciences and other materials like food, chemicals, medicines, and explosives are excluded from the purview of engineering materials. Engineering materials can be broadly categorized in three groups according to their nature and characteristics; i) ii) Metals and alloys E.g. Al, Cu, Ag, Au, Steel, Cast Iron, Brass, Bronze, Invar Organic Polymers E.g. Plastics Fibers Rubber iii) : Poly Vinyl Chloride, Polyethylene : Nylon, Terylene : Natural rubber (Polyisoprene)

Ceramics and glasses E.g. Silica, Soda lime glass, concrete, cement

In addition to the three broad groups, a number of composite materials (mixture of the above basic groups) are also in vogue E.g. - Concrete, Metal reinforced plastics, Glass Fibre reinforced plastics, Cermets, carbon fibre reinforced plastics Materials exhibit various types of internal structure, which can be studied only at various levels of observations, aided by the magnification and resolution of the device employed. The higher the magnification, the finer is the level. Magnification up to one million times using Transmission Electron Microscope or Field Ion Microscope is now possible. Depending on the level, one can classify the internal structure as ; i) ii) iii) iv) v) vi) Atomic structure (electronic and nuclear structure) Crystal structure Grain structure Imperfection structure Phase structure Macro structure

The key to the development and use of engineering materials is to understand the relationship between the levels of internal structure and the physical, chemical & mechanical properties of materials. There are numerous factors which can influence the level of internal structure which requires thorough understanding of concepts like equilibrium & kinetics geometry of crystals arrangement of atoms sub-structural imperfections in crystals

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CRYSTAL STRUCTURE

diffusion of elements in solids phase transformation micro-structure of single & multi-phase crystals

Materials can be broadly classified as crystalline and non- crystalline or amorphous solids. In crystalline solids, the arrangement of atoms is in a periodically repeating pattern. In amorphous solids (such as glass), no regularity in arrangement of atoms is found. In fact, glass is said to be a super-cooled liquid. Before understanding crystal structures, it is necessary to know the concept of space lattice. A space lattice is defined as an array of points in three dimensions in which every point has surroundings identical to those of every other point in the array. E.g. in 2D space, a square or hexagonal lattice is possible. Unit cell is the smallest unit which, when repeated in space infinitely, will yield a space lattice. A 3D space lattice is generated by repeated translation of 3 non-coplanar vectors a, b & c. There are only 14 distinguishable ways of arranging points in 3D space conforming to the definition of space lattice and they are referred to as Bravais lattices. Bravais lattices are described in terms of 7 crystal systems.

a, b & c are 3 non-coplanar vectors; , & are angles between the vectors

Crystal system I. Cubic a =b=c = = = 90

1. Simple Cubic (SC)

Unit cell or Bravais Lattice 2. Body Centred Cubic 3. Face Centred Cubic (BCC) (FCC)

II. Tetragonal a =b c = = = 90

4. Simple Tetragonal (ST)

(Face centered atoms at all the 6 sides) 5. Body Centered Tetragonal (BCT)

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III. Orthorhombic a b c = = = 90

6. Simple Orthorhombic (SO)

7. Side centred Orthorhombic (SCO)

8. Body Centred Orthorhombic (BCO)

9. Face Centred Orthorhombic (FCO)

(Face centered Points at all the six sides) IV. Rhombohedral a =b=c = = 90 10. Simple Rhombohedral Points are at all the 8 corners

V. HEXAGONAL a =b c = = 90 = 120

11. Simple Hexagonal

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VI. MONOCLINIC a b c = = 90

12. Simple Monoclinic

13. Side Centred Monoclinic

Points at all 8 corners VI. TRICLINIC a b c 14. Simple Triclinic

Points at all 8 corners One Point each at center of side face

Points at all 8 corners The Bravais lattice or the Unit cell as described above have inherent symmetry. The symmetry elements comprise rotation / translation and reflection operations. The unit cells are arranged in decreasing order of symmetry, Simple cubic having highest symmetry and Triclinic having least symmetry. Crystal structure is a combination of space lattice with a basis. BCC lattice + 1 Cr atom at each point in the space lattice gives rise to BCC crystal of Cr Hexagonal lattice + 1 Zn atom at each lattice point and at the centre of tetragon results in Hexagonally Closed Packed (HCP) structure of Zn There are infinite ways of arranging atoms around each point in a bravais lattice. For example, in one form of Mn there are 29 atoms grouped around each BCC space lattice. In protein structures, the no. of atoms for the basis could be as high as 10,000.

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CHARACTERESTICS OF CRYSTAL STRUCTURES The important characteristics of each crystal structure are : i) Effective or average no. of atoms, Neff It is the no. of atoms exclusive to the unit cell and will vary with the unit cell. ii) Co-ordination number It is the no. of equi-distant neighbours that an atom has in unit cell and will vary with the unit cell. iii) atomic diameter The lattice parameter and atomic diameter (closest distance of approach) are directly related and will vary with the unit cell. iv) atomic packing This is described by the atomic packing factor which is the ratio of volume occupied by the atoms and volume of the unit cell. Atomic packing factor is also called atomic packing efficiency. The above characteristics of each crystal structure viz Simple cubic, BCC, FCC and HCP will be discussed below. Characteristics of Body Centred Cubic (BCC) Structure Effective or average no. of atoms, Neff = Nc / 8 + Ni / 1 = 8 / 8 + 1 = 2. Where Nc is the no. of corner atoms. In BCC, there are 8 corner atoms and each corner atom is shared by 8 unit cells (4 above and 4 below) and N i is the inside atom in the unit cell. Co-ordination number is 8. This can be visualised by focussing on the centre atom which has corner atoms as nearest neighbours. In this lattice, the atoms are touching in the Body diagonal. Hence, 3 a = 4r, Where a is the lattice parameter and r is the atomic radius. v 2 x 4/3 r3 8 r3 Atomic Packing Factor = ----- = ----------------- = ----------------- = 0.68 V a3 3 (4r /3 )3 v: vol. of atoms occupied in the unit cell ; V : vol. of Unit cell

Metals such as Iron, Sodium, Chromium and Tunsten have this structure. Characteristics of Face Centred Cubic (FCC) Structure Effective or average no. of atoms, Neff = Nc / 8 + Nf / 2 = 8 / 8 + 6 / 2 = 4. Where Nc is the no. of corner atoms. In FCC, there are 8 corner atoms and

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each corner atom is shared by 8 unit cells (4 above and 4 below)and N f is the face centred atom in the unit cell ( each face centred atom is shared by two adjacent cells). Co-ordination number is 12. For any atom in given plane, there are 4 nearest neighbour atoms in the same plane and 4 atoms in the plane just above and 4 atoms in the plane just below. In this lattice, the atoms are touching in the Face diagonal. Hence, 2 a = 4r, Where a is the lattice parameter and r is the atomic radius. v Atomic Packing Factor = ----V v: = 4 x 4/3 r3 16 r3 ----------------- = --------------- = 0.74 a3 3 (4r /2 )3 V : vol. of Unit cell

vol. of atoms occupied in the unit cell ;

Metals such as Iron, Copper, Nickel, Aluminum, Silver and Gold have FCC structure. Compared to Simple cubic and BCC, FCC is closely packed structure. Characteristics of Hexagonally Closed Packed structure (HCP) Effective or average no. of atoms, Neff = Nc /6 +Nf /2 + Ni /1 = 12 / 6 + 2 / 2 + 3 = 6. Where Nc is the no. of corner atoms. In HCP, there are 12 corner atoms and each corner atom is shared by 6 atoms in the same plane ; Nf is the face centered atom, there are 2 atoms in the unit cell ( each face centered atom is shared by two adjacent cells) ; Ni is the inner atoms and there are 3 atoms in the unit cell. Co-ordination number is 12. For any atom in given plane, there are 6 nearest neighbour atoms in the same plane, 3 atoms in the plane just above and 3 atoms in the plane just below. In this lattice, the atoms are touching in the Basal plane. Hence, a = 2r, Where a is the lattice parameter and r is the atomic radius. In HCP, the lattice height c is related to lattice parameter. Hence c / a ratio needs to be calculated.

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c/a RU RT PT c/a

= 2 PT / RS = RS2 SU2 = a2 a2 / 4 = 3 a/2 = 2 / 3 RU = a / 3 2 RT2 = PR = a2 a2 / 3 = a 2 / 3 = [2 a 2 / 3] / a = (8/3) = 1.633

Volume of the unit cell, V V = area of hexagon x height = 6 x area of triangle x height = 6 x [ x AB x OC ] x c { AB = OA = OB = a ; OC = a2 a2/4 = 6 x [ x a x 3 / 2 a ] x c = [ 3 3 a2 c ] / 2 6 x 4/3 r3 6 x 4/3 r3 Atomic Packing Factor = ----------------- = ----------------= 0.74 V [ 3 3 a2 c ] / 2 Where, a =2r; c = [ (8/3) x a]

Metals such as Zn and Mg have HCP structure. Compared to Simple cubic and BCC, HCP is closely packed structure. CRYSTAL IMPERFECTIONS Ideal crystals are those which are obtained by combining a basis of atomic arrangement and a space lattice and the no. of such combinations is infinite. On the other hand real crystals are finite and have occasional disruptions in periodicity within a crystal. The disrupted regions are called imperfections and are very small in volume, usually less than 0.01% of total volume. While the presence of imperfections may not alter certain properties like Melting point, density, chemical activity etc their presence even in ppm (parts per million) may significantly influence certain mechanical and electrical properties. For e.g. presence of vacancies will influence phase transformations in alloy systems ; presence of small aluminum impurities (introduced as dopants) in Silicon will change transistor action. Crystalline imperfections can be classified as : Point imperfections Line imperfections Surface imperfections

Volume imperfections like pores, foreign inclusions etc are those that are inherited during manufacturing processes. All imperfections cause local strains. For e.g.

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consider Fe-C system. At high temperature, C atoms occupy octahedral voids of FCC Iron. While the size of the void is 0.53 , the size of C atom is 0.71 . Hence, when C atoms occupy the void space, it will cause local strain and this also imposes maximum solubility for C atoms which is around 2% in FCC Fe. At room temperature, Iron exists in BCC form and the solubility limit is much lower. Role of imperfections in Engineering materials : Role of Imperfections in Engineering materials is vital in several of their characteristics. Some of them are: metal flow & fracture characteristics; crystal growth; electrical properties such as semi-conducting behaviour , dielectric strength ; diffusion mechanism ; creep characteristics of metals & alloys ; annealing & precipitation ; oxidation & corrosion ; yield strength, fracture strength, ductility, thermal conductivity Point imperfections These are also known as zero dimensional imperfections, each of them having a size of one or two atom diameters. Types of Point imperfections are :

Vacancy -

substitutional Impurity

interstitial Impurity

n N where

= n N Hf R

vacancies. These are missing atomic sites. Equilibrium concentration of vacancies is given by the following equation: Hf exp ( - ) RT : no. of vacancies at given temperature : Avagadro No. = 6.023 x 1023 atoms per mole : enthalpy of formation of vacancy : Gas constant = 8.134 J / mol / K Substitutional & interstitial impurities Substitutional impurity is that which substitutes the atomic site of the parent atom and interstitial impurity is that which occupies the void space in the parent crystal in between the atoms without dislodging the parent atoms. Frenkel and Schottky defects These are imperfections in ionic crystals. In these, the formation of Point defect is subject to the basic requirement that the electrical neutrality is maintained. An ion displaced from a regular site to an interstitial site is called Frenkel defect. A

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pair of one cation (+ ion) and one anion (- ion) missing from the crystal is called Schottky defect. Line imperfections : Line imperfections are known as dislocations. In a geometric sense these are one -dimensional and play a major role in strength and ductility of materials. Types of dislocations are as under: Edge dislocation Screw dislocation Curved dislocation ( a mixture of edge and screw dislocation and the dislocation line extends upto the free surface) Dislocation loop ( a mixture of edge and screw dislocation and the dislocation line ends in itself within the crystal)

Edge dislocation : Edge dislocation is one wherein there is an incomplete vertical plane of atoms. Atoms above the edge of the incomplete plane are squeezed and hence in a state of compression. Atoms below the edge are pulled apart and hence in a state of tension. Edge dislocation is characterized by Burgers Vector.

Consider a perfect crystal and make a circuit of equal no. of atomic steps in + & axis of x and equal no. of atomic steps in + & - axis of y direction staring from Point P as shown. This is called Burgers circuit. In this case we return to the same point.

Burgers circuit in a Burgers circuit in a perfect crystal crystal with a edge dislocation If a similar Burgers circuit is made in a crystal with an edge dislocation, the end point Q is different from starting Point, P. The vector QP is perpendicular to the

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dislocation line vector t. Edge dislocation is characterized by a symbol which is positive i.e. the extra half plane is above the edge of the dislocation and the atoms above the edge are in a state of compression.. Negative dislocation (T) has extra half plane below the edge and the atoms above the edge are in a state of tension. Screw dislocation : Screw dislocation is one where the atoms are arranged in a helical form unlike assemblage of vertical planes in a perfect crystal.

Burgers vector in a Perfect crystal

Burgers vector in a crystal with a screw dislocation

If a Burgers circuit is made in a crystal with a screw dislocation, the starting point P and the end point Q is not the same. The Burgers vector QP is parallel to the dislocation line vector t. Positive screw dislocation is represented by a symbol wherein the dislocation and Burgers vector are parallel and in the same direction. Negative screw dislocation is represented by a symbol and Burgers vector are anti-parallel Comparison between Edge and Screw dislocation Sl. No. 1. Edge dislocation Screw dislocation wherein the dislocation

In a lattice with edge dislocation, an In a lattice with screw dislocation, extra half plane of atoms is present there is a distortion and the atoms arrange themselves in a spiral path inside the crystal If the extra half plane is present above the dislocation line, then the dislocation is termed as positive edge dislocation and It is denoted by a symbol () and if the extra half plane is present below the dislocation line, then the dislocation is termed as negative edge dislocation and it is denoted by a symbol (T) If the helical path takes a Left Hand screw direction, the screw dislocation is termed as Negative screw dislocation and is denoted by a symbol Positive screw (RH screw) is denoted by a symbol

2.

3. 4.

An edge dislocation lies perpendicular An screw dislocation lies parallel to to the Burgers vector b the Burgers vector b The shear stress required to move an The shear stress required to move an

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edge dislocation is less 5. 6. The speed at which dislocation moves is high the

screw dislocation is more edge The speed at which dislocation moves is low the screw

The movement of edge dislocation is The movement of screw dislocation is in the direction of Burgers vector perpendicular to the direction of Burgers vector Edge dislocation aids the process of Screw dislocation also aids the slip to cause plastic deformation process of slip to cause plastic deformation Schematic dislocation diagram of edge Schematic dislocation diagram of screw

7.

8.

Properties of dislocations : -

dislocations have distortional strain energy associated with them. The strain energy per unit length is given by (G b2/2), where G is Rigidity modulus and b is the Burgers vector dislocations are classified as either Full dislocations (where the Burgers vector is an integral multiple of lattice translation) or partial dislocation (where the Burgers vector is a fraction of lattice translation). Full dislocation with Burgers vector b1 tends to break down to partial dislocations b2 & b3 if b12 > b22 + b32 dislocations move under the influence of shear stress dislocations interact with each other and also with other point imperfections and cause either increase or decrease of strength of materials.

Surface imperfections : These are 2-Dimensional in geometric sense and refer to regions of distortions having a thickness of few atomic diameters. All the surface imperfections are associated with surface energies. Following are the various types of surface

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imperfections : external surface grain boundary tilt boundary stacking faults twin boundary

External surface is a surface imperfection because atomic bonds are broken at the surface. For e.g. consider FCC crystal. While the interior planes of atoms have a co-ordination number (or nearest neighbours) of 12, the surface atoms have only a co-ordination number of 9. Grain boundaries are caused during solidification in polycrystalline materials. When several crystals nucleate and grow, they eventually impinge on one another and at the meeting regions, the atoms are distorted. The distorted regions are only few atom diameters in thickness. The crystal orientation sharply changes at the grain boundary and the orientation difference is normally more than 10 - 15. The number of nearest neighbours at such regions in FCC crystal is 11 as compared to 12 in the interior. These are also referred to as high angle boundaries Tilt boundaries are those which are formed when there is a compilation or accumulation of dislocations in a single region. In such regions the orientation difference between the crystals is less than 10. These are referred to as low angle boundaries

Stacking faults are planar imperfections created by stacking arrangement of atomic planes. For e.g. consider stacking arrangement of planes in FCC crystal. It is ABCABCABCABC.. where A is the first layer of atoms ; B is the next layer of atoms with centres of atoms occupied by say triangle with apex up ; C is layer over B with centres of atoms occupied by say triangle with apex down.. It may so happen that there is a stacking fault in the sequence; ABCABCBCABC.. In such a case, the nearest neighbour still remains 12. But the fault causes small surface energy associated with it. Twin boundary is planar imperfection caused as a result - 12 -

of slight disturbance in the atomic arrangement. Atomic arrangement on one side of a twin boundary is a mirror reflection of the arrangement on the other side. Twin boundaries occur in pairs. The region between the twin boundaries is called twinned region. Twins can form either during annealing (annealing twins) or during deformation (deformation twins). Tin cry is one example of deformation twin. Numerical problem 1. Aluminum of lattice parameter of 0.405 nm has FCC crystal structure. Calculate its atomic radius = 4r a Hence, r = ----2 2 = 0.405 --------- = 0.1432 nm 2 2

2 a 2.

Aluminum has FCC crystal structure. Its density is 2700 kg/m3. Calculate its unit dimensions and atomic diameter. Given at. Wt. = 26.98 ; Avagadro No. = 6.023 x 1023 mxn Axn 4 x 26.98 = ----------- = ----------- = ---------------------- = 2.7 (gm / cc) 3 3 a N xa 6.023 x 1023 x a3 m = mass of one atom ; n = no. of atoms in the unit cell a = lattice dimension ; N = Avogadro Number ; A = Avogadro No. ; Dia. 2r = 2.86 x 10-10 m [2 a = 4 r ]

Density () where,

a = 4.05 x 10-10 m

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aw law states that the flux is directly proportional to the concentration gradient (dc/dx) ;

to the difference in flux across adjacent planes. It is also stated as "the rate of compositional change

Atomic Diffusion
Diffusion refers to movement of atoms in solids. Structural control in a solid to achieve optimum properties is dependent on the rate of diffusion. Examples where the diffusion process is of relevance are carburisation in steels ; oxidation of metals ; introduction of dopants in semiconductor solid state materials etc. Diffusion is a mass flow process by which atoms change their positions under the influence of thermal energy and a gradient like concentration gradient, electrical & magnetic field gradient. Diffusion process can be characterized by Ficks first law under steady state and Ficks second law under non-steady state conditions. Ficks first law of diffusion Consider a solid system of A and B atoms and consider only B atoms are moving unidirectionally. Let the flow of atom7s be characterized by a parameter called flux, J, no. of moles of atoms flowing per unit area per unit time.

-D

dc C2 C1 = - D [ ----------- ] dx X2 X1

where D is diffusion coefficient ; negative sign indicates that the flow is from higher to lower concentration. Ficks first law is only applicable under steady state conditions, i.e. the flux is constant at different cross sections and at different times. Example of applicability of this law is diffusion of hydrogen through walls of a steel tank under pressure.

Ficks second law of diffusion

Consider a solid system of A and B atoms where only B atoms are moving unidirectionally under nonsteady state conditions i.e. flux is not constant at different cross sections and at different times.

Consider two planes of unit area separated by a distance x and Jx & Jx+x are the fluxes across the adjascent planes, then ;

c ( ) x = Jx - Jx + x t Solution of the above equation gives ; C( x, t) =

J Jx - (Jx + ) x x

2c D x2

x A B erf [ ] 2Dt

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R = 8.314 J / mol / Kelvin ; Q : Activation energy in kJ / mol D can also be directly given as data. erf (0) erf (- ) erf ( ) erf (-z)

; Do ; in m2/sec

= 0 = -1 = 1 = -z

erf (z) as a function of z will be given as data C ( x,0 ) = C0 for x > 0 and C( 0,t )= Cs Substituting these in eqn. (1) C0 = A - B erf ( ) = A B & Cs = A - B erf (0) = AHence equation (1) becomes Cs - Cx ----------Cs C0 Where , Cs : concentration at surface x : distance from interface C0 : original concentration in steel D : Diffusivity at given temp. Cx : concentration at point x Ficks second law is of direct practical relevance like carbon diffusion in steels ; oxygen diffusion in Aluminium cladded Al-Cu sheets etc. Diffusivity & activation energy Diffusivity or coefficient of diffusion (D) is defined as the amount of substance diffusing in unit time across an unit area through an unit concentration gradient. Its unit is m2/sec. The coefficient of diffusion of various materials vary with crystal structure & temperature. In a diffusion process, work must be done if the atoms have to migrate. To do this work, an energy barrier has to be overcome and this minimum energy to overcome the barrier is called activation energy. It depends on a number of factors : a small atom has a lower activation energy than a bigger atom movement of interstitial atoms require more energy than vacancy movement higher activation energy is required for atomic movements for those materials which are strongly bonded x = erf { --------- } 2 D t

Relation between D & activation energy :

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D = D0 exp [ -Q/RT] D is diffusion coefficient m2/sec ;D0 constant Q activation energy (J/mol R as constant (8.314 J/mol K T absolute temperature (K) Mechanism of diffusion Diffusion occurs as a result of repeated jumps of atoms from neighbouring sites. When atoms jump rapidly, a net mass flow occurs down a concentration gradient. Depending upon the nature of atomic species and matrix, there are various mechanisms of diffusion. Lattice diffusion, surface diffusion and pipe diffusion Lattice diffusion Here again there are three types, viz. i) ii) vacancy diffusion interstitial diffusion ii) interchange of atomic positions

Surface diffusion Grain boundaries and external surface aid in the process of diffusion. Pipe diffusion line imperfections also provide the path for diffusion). Although surface & Pipe diffusion have lower activation energy as compared to lattice diffusion, surface area being less, their possibilities are low. Factors affecting diffusion ; Diffusion is a mass flow process by which atoms change their positions and hence there are number of factors that influence its occurrence : Temperature : High temperature provides higher activation energy to the atoms and hence atomic diffusion is faster Crystal imperfections : If the crystal has higher number of imperfections, the rate of diffusion increases

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D0 : 0.7 x 10 4 m2/sec erf (z) Q : 157 kJ/mol 0.75 T : 1173 K 0.7112 0.3268 0.80 0.7421 0.35 0.3794 Atomic packing factor : Diffusion is easier and faster in Metals with less atomic packing factor. E.g. Diffusion is much slower in FCC iron (APF :0.74) as compared to BCC iron (APF : 0.68). z erf (z) z Grain Boundaries & Grain size: Diffusion is rapid along grain boundaries, since these have surface energy associated with them. However, since surface area is less, diffusion possibility is low. Finer the grain size, higher will be the grain boundary area and faster will be the diffusion. Atomic size : Diffusion occurs more readily when the size of atom is smaller. E.g. C in iron. 1. At 900 C, what is the time required to carburise a steel with an initial concentration of 0.2% C to 1.0% C at a depth of 0.2 mm . Assume a constant surface concentration of 1.4% C due to carburising atmosphere. x = erf { --------- } 2 D t

Cs - Cx ----------Cs C0

Cs = 1.4% ; C0 = 0.2% : Cx = 1.0% ;x = 0.2 x 10-3 m 1.4 1.0 ------------= erf (z) ; erf (z) = 0.3333 Hence , z = 0.306 1.4 0.2 Q 157 x 1000 -4 exp ( - ----------------- ) = 7.137 x10-12 m2/sec D = D0 exp [ - ---- ] ; D = 0.7 x 10 RT 8.314 x 1173 x Z = ---------= 0.306 2 D t 0.2 x 10-3 t = ----------------------------------= 0.1223 x 103 0.306 x 2 x 7.137 x 10-12 t 2. = 14980 seconds

A Carbon steel component is to be carburised at 920 C. What is the time required to carburise a steel with an initial concentration of 0.2% C to 0.4% C at a depth of 0.5 mm . Assume a constant surface concentration of 0.9% C due to carburising atmosphere. D (at 920C ) = 1.28 x10-11 m2/sec x = erf { --------- } 2 D t ; C0 = 0.2% : Cx = 0.4% ;x = 0.5 x 10-3 m

Cs - Cx ----------Cs C0 Cs

= 0.9%

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0.9 0.4 ------------0.9 0.2 Z t

erf (z) ;

erf (z) =

0.7142

Hence ,

z = 0.754

x = ---------= 0.754 2 D t 0.5 x 10-3 = ----------------------------------0.754 x 2 x 1.28 x 10-11 t =

= 0.00926 x 103 8578 seconds

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