1 Crystal Defects Perfect crystal - every atom of the same type in the correct equilibrium position (does not exist at T > 0 K) Real crystal - all crystals have some imperfections - defects, most atoms are in ideal locations, a small number are out of place ˇ Intrinsic defects ­ present for thermodynamic reasons ˇ Extrinsic defects ­ not required by thermodynamics, can be controlled by purification or synthetic conditions ˇ Chemical defects (foreign atom, mixed crystals, nonstoichiometry) ˇ Geometrical defects (vacancy, interstitials, dislocations, boundaries, surface) Defects dominate the material properties, contribute to: Mechanical, Chemical, Electrical, Diffusion properties can be added intentionally 2 Crystal Defects Perfect crystal Real crystal 3 Classes of Crystal Defects Point defects (0D) places where an atom is missing or irregularly placed in the lattice structure ­ lattice vacancies, self-interstitial atoms, substitution impurity atoms, interstitial impurity atoms Linear defects (1D) groups of atoms in irregular positions ­ dislocations Planar defects (2D) interfaces between homogeneous regions of the material - grain boundaries, stacking faults, external surfaces Volume defects (3D) spaces of foreign matter ­ pores, inclusions 4 Classes of Crystal Defects 5 Point Defects ­ Metals Point defects - an atom is missing or is in an irregular position in the lattice ˇ self interstitial atoms ˇ interstitial impurity atoms ˇ substitutional atoms ˇ vacancies 6 Point Defects ­ Ionic Compounds perfect crystal lattice AB interstitial imputity cation vacancy anion vacancy substitution of a cation substitution of an anion BA antisite defect AB antisite defect 7 Types of Point Defects in Ionic Compounds ˇ Vacancy ˇ Interstitial ˇ Substitutional ˇ Frenkel ˇ Schottky Schottky: a pair of vacancies, missing cation/anion moved to the surface Frenkel: ions moved to interstitial positions, vacancies 8 Point Defects Schottky - equal numbers of vacancies at both A and B sites preserving charge balance. Encountered more commonly when metal ions are able to easily assume multiple oxidation states. Frenkel - encountered in open structures (wurtzite, sphalerite, etc) where coordination numbers are low and open structure provides room for interstital sites to be occupied Schottky Frenkel 9 Vacancies ˇ There are naturally occurring vacancies in all crystals ˇ Equilibrium defects ­ thermal oscillations of atoms at T > 0 K ˇ The number of vacancies increases as the temperature goes up ˇ The number of vacancies Nv = N exp(-Ha/RT) ­ N is the total number of sites in a crystal ­ Nv is the number of vacancies ­ Ha is the activation energy for the formation of a vacancy ­ R is the gas constant ­ Nv goes up exponentially with temperature T 10 Crystal Energies Point defects = equilibrium concentration, Enthalpy is positive, configurational entropy positive Minimum on free energy Extended defects = no equilibrium concentration, Enthalpy is HIGHLY positive, configurational entropy cannot outweight, no minimum on free energy Metastable ­ dislocations, grain boundaries, surface Heating - minimize free energy: polycrystalline single crystal grain growth Grains with high dislocation density consumed Atoms move across grain boundary 11 Interstitial Atoms ˇ An atom must be fairly small to fit into the interstitial voids ˇ Hydrogen and Helium can diffuse rapidly through metals by moving through the interstitial voids ˇ Interstitial Carbon is used to strengthen iron - it distorts the matrix ˇ The ratio of r/R is 0.57 ­ therefore it needs an octahedral hole ˇ There are octahedral and tetrahedral holes in both FCC and BCC ­ however the holes in BCC are not regular polyhedra ˇ The solubility of Carbon in FCC iron is much higher than in BCC iron 12 Typical point defects in crystals Alkali halides Schottky (cations and anions) Alkaline earth oxides Schottky (cations and anions) Silver halides Frenkel (cations) Alkaline earth fluorides Frenkel (anions) Typical activation energies for ion diffusion Na+ in NaCl 0,7 eV Cl- in NaCl 1 eV Schottky pair 2,3 eV (1 eV/molecule = 96.49 kJ/mol) 13 The addition of the dopant (an impurity) into a perfect crystal = point defects in the crystal NaCl heated in Na vapors Na is taken into the crystal and changes the compostion NaCl Na1+ x Cl Na atoms occupy cation sites an equivalent number of unoccupied anion sites Na atoms ionize, Na+ ions occupy the cation sites, the electrons occupy the anion vacancies ­ F centers ­ color This solid is now a non-stoichiometric compound as the ratio of atoms is no longer the simple integer Extrinsic Defects 14 Non-stoichiometric Compounds Vanadium oxide varies from VO0.79 to VO1.29 other examples: TiOx, NixO, UOx and LixWO3 Covalent compounds - held to together by very strong covalent bonds which are difficult to break, do not show a wide range of composition Ionic compounds - do not show a wide range because a large amount of energy is required to remove / add ions non-stoichiometry can be caused by doping or by a multi-valent element 15 Non-stoichiometric Compounds non-stoichiometric ionic crystals a multi-valent element - changes in the number of ions can be compensated for by changes in the charge on the ions, therefore maintaining charge balance but changing the stoichiometry non-stoichiometric compounds have formulae with non-integer ratios and can exhibit a range of compositions. They are formed by introducing an impurity (doping) or by the ability of an element to show multi-valent character. The electronic, optical, magnetic and mechanical properties of non-stoichiometric compounds can be controlled by varying their composition. 16 Dislocations Line imperfections in a 3D lattice ˇ Edge ˇ Screw ˇ Mixed 17 Edge Dislocation ˇ Extra plane of atoms ˇ Burgers vector ­ Deformation direction ­ For edge dislocations it is perpendicular to the dislocation line 18 Edge Dislocation 19 Screw Dislocation ˇ A ramped step ˇ Burgers vector ­ Direction of the displacement of the atoms ­ For a screw dislocation it is parallel to the line of the dislocation 20 Screw Dislocation 21 Deformation When a shear force is applied to a material, the dislocations move Plastic deformation in a material occurs due to the movement of dislocations (linear defects) The strength of the material depends on the force required to make the dislocation move, not the bonding energy Millions of dislocations result from plastic forming operations such as rolling and extruding Any defect in the regular lattice structure (point, planar defects, other dislocations) disrupts the motion of dislocation - makes slip or plastic deformation more difficult 22 Deformation Dislocation movement produces additional dislocations Dislocations collide ­ entangle ­ impede movement of other dislocations - drives up the force needed to move the dislocation - strengthens the material Applying a force to the material increases the number of dislocations Called "strain hardening" or "cold work" 23 Slip ˇ When dislocations move slip occurs ­ Direction of movement ­ same as the Burgers vector ˇ Slip is easiest on close packed planes ˇ Slip is easiest in the close packed direction ˇ Affects ­ Ductility ­ Material Strength 24 Schmidt's Law ˇ In order for a dislocation to move in its slip system, a shear force acting in the slip direction must be produced by the applied force. Slip direction Normal to slip plane Ao = F/A r = Fr / A - Resolved Shear Stress 25 Schmidt's Law ˇ Fr = F cos() = 0/cos() = cos() cos() Where: = Fr / A = resolved shear stress in the slip direction = F/Ao = unidirectional stress applied to the cylinder 26 Surface and Grain Boundaries ˇ The atoms at the boundary of a grain or on the surface are not surrounded by other atoms ­ lower CN, weaker bonding ˇ Grains line up imperfectly where the grain boundaries meet ˇ Dislocations can usually not cross grain boundaries ˇ Tilt and Twist boundaries ˇ Low and High angle boundaries 27 Low Angle Tilt Boundary Low Angle Tilt Boundary = Array of Edge dislocations sin b D = D = dislocation spacing b = Burgers vector = misorientation angle 28 Low Angle Twist Boundary Low Angle Twist Boundary = a Screw dislocation 29 Crystal Energies Point defects = equilibrium concentration, Enthalpy is positive, configurational entropy positive Minimum on free energy Extended defects = no equilibrium concentration, Enthalpy is HIGHLY positive, configurational entropy cannot outweight, no minimum on free energy Metastable ­ dislocations, grain boundaries, surface Heating - minimize free energy: polycrystalline single crystal grain growth Grains with high dislocation density consumed Atoms move across grain boundary 30 Effect of Grain Size on Strength ˇ In a small grain, a dislocation gets to the boundary and stops ­ slip stops ˇ In a large grain, the dislocation can travel farther ˇ Small grain size equates to more strength 31 Hall-Petch Equation y = 0 + K d ­1/2 y = yield strength (stress at which the material permanently deforms) d = average diameter of the grains 0 = constant K = constant 32 Control of the Slip Process ˇ Strain hardening ˇ Solid Solution strengthening ˇ Grain Size strengthening 33 Amorphous Structures ˇ Cooling a material off too fast - it does not have a chance to crystallize ˇ Forms a glass ˇ Easy to make a ceramic glass ˇ Hard to make a metallic glass ˇ There are no slip planes, grain boundaries in a glass 34 Amorphous Structures 35 Velocity of diffusion of particles (ions, atoms ...) in a solid - mass transport and concentration gradient for a given point in a solid! Ji = -Di ˇ ci/ x [ mol cm-2 s-1] (const. T) Ji: flow of diffusion (mol s-1 cm-2); Di: diffusion coefficient (cm2 s-1) ci/ x: concentration gradient (mol cm-3 cm-1) (i.e. change of concentration along a line in the solid!) dx dc D Adt dn J -== Diffusion 36 Diffusion - Fick's First Law J = diffusion flux [mol s-1 m-2] D = diffusion coefficient diffusivity [m2 s-1] dc/dx = concentration gradient A = area [m2] x diffusion flux Fick's first law describes steady state diffusion 37 Knowledge of D allows an estimation of the average diffusion length for the migrating particles: = 2Dt (: average square of diffusion area; t: time) Typical diffusion coefficients for ions (atoms) in a solid at room temperature are about 10-13 cm2 s-1. In solid state ionic conductors (e.g. Ag-ions in -AgI) the values are greater by orders of magnitude ( 10-6 cm2 s-1) 38 Diffusion coefficients show an exponential temperature dependence (Arrhenius type): D = D exp(-Q/kT) (D: D for T , Q: activation energy of diffusion, k: Boltzmann-faktor) The logarithmic representation of D verus 1/T is linear, the slope corresponds to the activation energy and the intercept to D . surface grain boundaries volume Ag in Ag C in Fe 39 Mechanics of Diffusion ˇ Primarily At Defects ­ Point Defects ­ Line Defects ­ Edge Defects ˇ Through Interstitial Spaces 40 Vacancy Diffusion ˇ Vacancies are holes in the matrix ˇ Vacancies are always moving ˇ An impurity can move into the vacancy ˇ Diffuse through the material 41 Interstitial Diffusion ˇ There are holes between the atoms in the matrix ˇ If the atoms are small enough, they can diffuse through the interstitial holes ˇ Fast!! 42 Other Mechanisms ˇ Grain Boundaries ˇ Surface 43 Activation Energy ˇ All the kinds of diffusion require a certain minimum energy to occur ˇ The activation energy ˇ The higher the activation energy, the harder it is for diffusion to occur ˇ The highest energy is for volume diffusion ­ Vacancy ­ Interstitial ˇ Grain Boundary diffusion requires less energy ˇ Surface Diffusion requires the least 44 Diffusion Rate ˇ High activation energy corresponds to low diffusion rates ˇ D = D0*exp(-Q/RT) ­ Where D is the diffusivity, which is proportional to the diffusion rate ­ Q is the activation energy ­ R is the gas constant ­ T is the absolute temperature 45 Diffusivity ˇ D is a function of temperature ˇ Thus the flux (J) is also a function of temperature 46