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Crystal Defects

Perfect crystals do not exist; even the best crystals have 1ppb defects. defects are imperfections in the regular repeating pattern and may be classified in terms of their dimensionality (Point vs. Extended).

1.

Point Defects A. Vacancies given a perfect crystal (e.g. of Cu), an atom can be placed on the outside of the cell to produce a vacancy ( ); remember atom migration. e.g. TiO has 1:1 stoichiometry and NaCl structure, but has 15% vacancies on the Ti sites and 15% vacancies on the O sites. Both sets of vacancies are disordered.

Crystal Defects
driving force? movement of the atom requires breaking (endothermic) and making (exothermic) of bonds. Because the atom is moving from an internal site (w/say 6 bonds) to an external site (w/say 3 bonds), there are more bonds broken than being made, so this is an overall endothermic process. counteracting this is an obvious large increase in disorder (from perfect crystal to defect); in addition, atoms around the vacated site can vibrate more, further increasing the disorder.
G(n) = nH nTS G(n)
max min n= #defects

Implications: a) n 0; G = 0, so no driving force. b) there is some min value of n which is most stable. c) there is some minimum n after which G becomes positive. d) as T nmin and nmax will also increase.

Crystal Defects
B. Ionic Crystal Defects in pure metal compounds, dont need to worry about electroneutrality. in an ionic crystal, the interior and surface must remain neutral. Shottky Defect take anions and cations and place them on surface in equal numbers. stoichiometric effect: equal numbers of anion and cation vacancies. may be randomly distributed, but tend to cluster because of oppositely charged vacancies. most important with alkali halides. at room temp, ~1 in 1015 pairs vacant in NaCl, so 1mg sample has ~10,000 Shottky Defects.

1)

Crystal Defects
2) Frenkel Defect take cation out of position and cram it into an interstitial site (void between normal atomic position). Ag+ surrounded by 4Cl- stabilizes this defect. tendency for vacancy and interstitial to form nearby pair. also a stoichiometric deffect (vacancies = interstitials).

Crystal Defects
3) Color Centers (aka F-center; Ger: farbenzentre) electron trapped in an anion vacancy. possible mechanism: high energy radiation (x-ray, -ray) interacts with alkali halide, causing halide to lose an electron. The electron moves through the crystal until it encounters a halide vacancy. It is trapped there by strong electrostatic forces (i.e. 6 cations!). a series of energy levels are available for the electron within the vacancy; often in the visible region (deep purple in KCl; smoky quartz; amethyst). found for a series of alkali halides: absorption energy, Emax a-1.8 a= cubic lattice parameter (length of the edge of the
cubic unit cell).

Note: E is inversely proportional to a.

Crystal Defects
Large E; little a.

Emax a-1.8

Large a; little E.

Crystal Defects
2. Extended Defects. have seen that many vacancies are initially random, but can cluster when vacancy density gets high, the material will try to do something to get rid of them. A. Sheer Planes e.g. ReO3: bright red, Re Oh h.s. d7, conducting. normal crystal (cut through face); note metalcontaining Ohs with shared corners. when heated, the compound starts losing O atoms; these vacancies tend to line up in a plane through the center of a unit cell. the structure sheers itself ( unit cell length) so that the octahedrons now have shared edges. There are more and more sheer planes as Os are lost.

Crystal Defects
B. Dislocations. important class of defect; responsible for the malleability of metals; explains the process of work hardening of metals. dislocations are line-defects; instead of the loss of atoms (as with point defects), they can be looked at as an extra partial line or plane of atoms. looks like a perfect crystal, but if you look at the figure from a low angle, you see an extra partial line.

Crystal Defects
edge dislocations are easily moved by slipping; like a carpet: too heavy to drag, but can move small wrinkle.

the presence of a distortion relaxes the requirement that entire planes of interatomic bonds must distort and break simultaneously for plastic* deformation to occur. Instead, plastic deformation can accompany the motion of a dislocation through a crystal.
*plastic = irreversible elongation (e.g. pulling wire) by movement of planes.

Crystal Defects
can get rid of dislocations; this gets rid of maleability and material becomes brittle (e.g. bend Cu wire). movement of dislocations is key to plastic deformation, therefore, increasing resistance to deformation (strengthening the metal) requires either eliminating the distortions or preventing them from moving (pinning them). dislocations are often pinned by other defects in the crystal; new dislocations are created during deformation and become pinned by the initial dislocation. the build-up of pinned dislocations leads to the hardening of the metal in a process known as work hardening.

Crystal Defects
e.g. moving an entire rug requires lots of energy. A single wrinkle serves as a dislocation in facilitating the movement of the rug; at any time only a small part of the rug moves, so little energy required. work hardening is like having multiple tangled wrinkles in the rug---one wrinkle pins the other.

a work-hardened metal can be softened again by annealing (heating) at high temperatures; increased thermal motion allows atoms to rearrange and go to lower energy states. so, work hardening adds edge dislocations so that planes no longer slip.

Crystal Defects
can strengthen materials with sheer planes by adding impurities.

edge dislocation strains bond lengths, etc.

if impurity prefers shorted bond lengths, then this is a stable situation. Cu + Zn bronze Cu + Sn brass

Stress & Strain


Experiment: measure width and length of wire; pull and re-measure; repeat.
initial = pull = breaks at = some materials, e.g. glass break after a certain point; brittle fracture. linear portion reversible.
~0.1%

= stress = force/unit area =

cross-sectional area (larger diameter would require more force to break). strain = l/lo change in length/ initial length

again, linear portion reversible, so below yield point no permanent elongation occurs = elastic deformation

yield strength increases as dislocations increase. distortions get tangled up like spaghetti; too many cause material to become brittle. e.g. Fe sword: add impurities and pound; becomes hard; dislocations climb to surface; anealing makes material soft by getting rid of distortions.

o
~20%

above yield point plastic elongation occurs.

Burgers Vectors (Bergers Circuit)


Way to describe dislocation.
4 3 3 4 3 4 3 4

Above: Burgers circuit for dislocation-free material. To Right: Do same with dislocation and end up past starting point. Vector b = distance to get back to curcuit.

note compressed bonds and elongated bonds.

Burgers Vectors
Screw dislocation with Bergers vector. Note direction is direction of screw axis. Crystals often will grow along screw dislocation.

Impurities and Doping


Impurities are elements present in the material that are different from those in the compound formula. Dopants are intentionally added impurities (to make alloys or affect changes in properties). Alloy formation most likely when dopant anions and cations are close in size to original material. Isovalent dopants: substitution species have the same charge. NaCl:AgCl Na1-xAgxCl (alloy on cation site) AgBr:AgCl AgBr1-xClx (alloy on anion site) Aleovalent dopant: substitution species has different charge. vacancy NaCl:CaCl2 could be either Na1-2xCax xCl interstitial or Na1-xCaxClClxi either could happen; experimentally, first is found.

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