# Defects Introduction. Bonding + Structure + Defects. Properties

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1 Defects Introduction Bonding + Structure + Defects Properties

2 The processing determines the defects Composition Bonding type Structure of Crystalline Processing factors Defects Microstructure

3 Types of Defects Point defects: atoms missing or in irregular places in the lattice (vacancies, interstitials, impurities) Linear defects: groups of atoms in irregular positions (e.g. screw and edge dislocations) Planar defects: the interfaces between homogeneous regions of the material (grain boundaries, external surfaces) Volume defects: extended defects (pores, cracks)

4 Point defects: vacancies & self-interstitials Vacancy : a lattice position that is vacant because the atom is missing. Interstitial : an atom that occupies a place outside the normal lattice position. It may be the same type of atom as the others (self interstitial) or an impurity interstitial atom. Self interstitial Vacancy

5 The equilibrium number of vacancy sites due to thermal vibration, N v, may be obtained by applying the following relation: N s N v N s Q exp k T b Where is the number of regular lattice sites, is the Boltzmann constant, Q v is the energy needed to form a vacant lattice site in a perfect crystal, and T the temperature in Kelvin v k b Note, that the above equation gives the lower end estimation of the number of vacancies, a large numbers of additional (nonequilibrium) vacancies can be introduced in a growth process or as a result of further treatment (plastic deformation, quenching from high temperature to the ambient one, etc.)

6 Example : estimate the number of vacancies in Cu at room temperature. The Boltzmann s constant k B = 1.38 * J/atom-K = 8.62 * 10-5 ev/atom-k The temperature in Kelvin T = 27 o C = 300 K. k b T = 300 K * 8.62 * 10-5 ev/k = ev The energy for vacancy formation Q v = 0.9 ev/atom The number of regular lattice sites N s = N A ρ/acu N A = * atoms/mol ρ = 8.4 g/cm 3 Acu = 63.5 g/mol N v N s exp k Q T N v = 7.4 *10 7 vacancies/ cm 3 b v

7 Other point defects: self-interstitials, impurities Schematic representation of different point defects: (1) vacancy; (2) self-interstitial; (3) interstitial impurity; (4,5) substitutional impurities The arrows show the local stresses introduced by the point defects.

8 Self-interstitial Self-interstitials in metals introduce large distortions in the surrounding lattice. The energy of self-interstitial formation is ~ 3 times larger as compared to vacancies (Qi ~ 3xQv). Equilibrium concentration of self-interstitials is very low (less than one self-interstitial per cm 3 at room temperature).

9 Impurities Impurities - atoms which are different from the host All real solids are impure. Very pure metals 99.99% - one impurity per 106 atoms May be intentional or unintentional Examples: carbon added in small amounts to iron makes steel, which is stronger than pure iron. Boron added to silicon change its electrical properties. Alloys - deliberate mixtures of metals Example: sterling silver is 92.5% silver 7.5% copper alloy. Stronger than pure silver.

10 Solid Solutions Solid solutions are made of a host (the solvent or matrix) which dissolves the minor component (solute). The ability to dissolve is called solubility. Solvent: in an alloy, the element or compound present in greater amount Solute: in an alloy, the element or compound present in lesser amount Solid Solution: "homogeneous maintain crystal structure "contain randomly dispersed impurities (substitutional or interstitial) Second Phase: as solute atoms are added, new compounds / structures are formed, or solute forms local.whether the addition of impurities results in formation of solid solution or second phase depends on the nature of the impurities, their concentration and temperature, pressure

11 Factors for high solubility: Atomic size factor - atoms need to fit solute and solvent atomic radii should be within ~ 15%. Crystal structures of solute and solvent should be the same. Electronegativities of solute and solvent should be comparable (otherwise new inter-metallic phases are encouraged). Generally more solute goes into solution when it has higher valency than solvent

12 Interstitial Solid Solutions Carbon interstitial atom in BCC iron Carbon interstitial atom in BCC iron. Interstitial solid solution of C in α-fe. The C atom is small enough to fit, after introducing some strain into the BCC lattice.

13 Factors for high solubility: For fcc, bcc, hcp structures the voids (or interspaces) between the host atoms are relatively small, so the atomic radius of solute should be significantly less than solvent. Normally, max. solute concentration 10%, (2% for C-Fe)

14 Composition / Concentration Composition can be expressed in Atom percent (at %): number of moles (atoms) of a particular element relative to the total number of moles (atoms) in alloy. For two-component system, concentration of element 1 in at % is C 1= n m 1 X100% n m 1+ n m 2 Weight percent (wt %): weight of a particular element relative to the total alloy weight. For two-component system, concentration of element 1 in wt. % is C= m 1 X100% m 1 + m 2 weight percent, useful when making the solution atom percent, useful when trying to understand the material at the atomic level

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18 Edge and screw dislocations There is a second basic type of dislocation, called screw dislocation. The screw dislocation is parallel to the direction in which the crystal is being displaced (Burgers vector is parallel to the dislocation line). Find the Burgers vector of a screw dislocation. How a screw dislocation got its name?

19 Interfacial Defects External Surfaces Surface atoms have unsatisfied atomic bonds, and higher energies than the bulk atoms Surface energy, γ (J/m2) Surface areas tend to minimize (e.g. liquid drop) Solid surfaces can reconstruct to satisfy atomic bonds at surfaces. Grain Boundaries Polycrystalline material comprised of many small crystals or grains. The grains have different crystallographic orientation. There exist atomic mismatch within the regions where grains meet. These regions are called grain boundaries. Surfaces and interfaces are reactive and impurities tend to segregate there. Since energy is associated with interfaces, grains tend to grow in size at the expense of smaller grains to minimize energy. This occurs by diffusion (Chapter 5), which is accelerated at high temperatures.

20 High and Low Angle Grain Boundaries Depending on misalignments of atomic planes between adjacent grains we can distinguish between the low and high angle grain boundaries

21 Tilt and Twist Grain Boundaries Low angle grain boundary is an array of aligned edge dislocations. This type of grain boundary is called tilt boundary (consider joint of two wedges) Transmission electron microscope image of a small angle tilt boundary in Si. The red lines mark the edge dislocations, the blue lines indicate the tilt angle

22 Low-energy twin boundaries with mirrored atomic positions across boundary may be produced by deformation of materials. This gives rise to shape memory metals, which can recover their original shape if heated to a high temperature. Shape-memory alloys are twinned and when deformed they untwin. At high temperature the alloy returns back to the original twin configuration and restore the original shape.

23 Dislocations in Nickel (the dark lines and loops), transmission electron microscopy image, Manchester Materials Science Center. High-resolution Transmission Electron Microscope image of a tilt grain boundary in aluminum, Sandia National Lab.

24 Twist boundary - the boundary region consisting of arrays of screw dislocations (consider joint of two halves of a cube and twist an angle around the cross section normal) Twin Boundaries :Low-energy twin boundaries with mirrored atomic positions across boundary may be produced by deformation of materials. This gives rise to shape memory metals, which can recover their original shape if heated to a high temperature. Shape-memory alloys are twinned and when deformed they untwinned. At high temperature the alloy returns back to the original twin configuration and restore the original shape.

25 Bulk or Volume Defects Pores - can greatly affect optical, thermal, and mechanical properties Cracks - can greatly affect mechanical properties Foreign inclusions - can greatly affect electrical, mechanical, and optical properties A cluster of microcracks in a melanin granule irradiated by a short laser pulse. Computer simulation by L. V. Zhigilei and B. J. Garrison.

26 Atomic Vibrations Heat causes atoms to vibrate Vibration amplitude increases with temperature Melting occurs when vibrations are sufficient to rupture bonds Vibrational frequency ~ 1013 Hz Average atomic energy due to thermal excitation is of order k b T

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