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ENGI 5911: Chemistry & Physics of Materials II

Week 2 Dr. Amy Hsiao Winter 2014

Crystal Defects and Types of Imperfections

Processing

Vacancy atoms Interstitial atoms Substitutional atoms Dislocations Grain Boundaries

Point defects

Thermal vibrations Crystal growth Alloy strengthening

Cold working, forging

Line defects Area defects

Solidification, welding

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CRYSTALS AS BUILDING BLOCKS

Some engineering applications require single crystals:
--diamond single crystals for abrasives
(Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission.)

--turbine blades

Crystal properties reveal features of atomic structure.

--Ex: Certain crystal planes in quartz fracture more easily than others.

POLYCRYSTALS
Most engineering materials are polycrystals.

1 mm
Nb-Hf-W plate with an electron beam weld

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Solidification
Grains can be - equiaxed (roughly same size in all directions) - columnar (elongated grains)
~ 8 cm

heat flow Columnar in area with less undercooling

Shell of equiaxed grains due to rapid cooling (greater T) near wall

Solidification
Solidification- result of casting of molten material
2 steps
Nuclei form Nuclei grow to form crystals grain structure

Start with a molten material all liquid

nuclei

liquid

crystals growing

grain structure

Crystals grow until they meet each other

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Solidification of Alloys

This micrograph (left) is an image of the 3D structure of dendrites in a cobalt-samariumcopper alloy, taken with a scanning electron microscope.

This micrograph (right), taken with a reflected light microscope, shows the appearance of dendrites of a copper-tin alloy when observed as a 2D section through the 3D structure.

Photos from University of Cambridge, http://www.doitpoms.ac.uk/tlplib/solidification_alloys/dendritic.php http://www.youtube.com/watch?v=S07fPo45BvM

Two common point defects in metal structures are the vacancy and the interstitial.

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Point Defects

Vacancy = unoccupied atom site in the crystal structure Interstitial = a site occupied by an atom not normally occupied by an atom in the perfect crystal structure

Two common point defect structures in compound structures are the Schottky defect and the Frenkel defect. Note their similarity to the structures shown.

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Point Defects
Vacancies:

-vacant atomic sites in a structure.

Vacancy
distortion of planes
Self-Interstitials:

-"extra" atoms positioned between atomic sites.

selfinterstitial
distortion of planes
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Solid Solution Complete Chemical Miscibility

Solid solution of Cu in Ni along a (100) plane. This is a substitutional solid solution with copper atoms (solute) substituting for nickel atoms (solvent) on fcc atom sites. Hume-Rothery Rules for complete miscibility in metallic solid solutions:
Solid solution of nickel in copper shown along a (100) plane. This is a substitutional solid solution with nickel atoms substituting for copper atoms on fcc atom sites.

Less than 15% difference in atomic radii The same crystal structure Similar electronegativities (ability of the atom to attract an electron) The same valence

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Random, substitutional solid solution of NiO in MgO. The O2 arrangement is unaffected. The substitution occurs among Ni2+ and Mg2+ ions.

A substitutional solid solution of Al2O3 in MgO is not as simple as the case of NiO in MgO. The requirement of charge neutrality in the overall compound permits only two Al3+ ions to fill every threeMg2+ vacant sites, leaving oneMg2+ vacancy.

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Iron oxide, Fe1xO with x 0.05, is an example of a nonstoichiometric compound. Similar to the case of Figure 4.6, both Fe 2+ and Fe3+ ions occupy the cation sites, with one Fe2+ vacancy occurring for every two Fe3+ ions present.

Ordering of the solid solution in the AuCu3 alloy system. (a) Above ~390C, there is a random distribution of the Au and Cu atoms among the fcc sites. (b) Below ~390C, the Au atoms preferentially occupy the corner positions in the unit cell, giving a simple cubic Bravais lattice. (From B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd ed., Prentice Hall, Upper Saddle River, NJ, 2001.)

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Interstitial solid solution of carbon in -iron. The carbon atom is small enough to fit with some strain in the interstice (or opening) among adjacent Fe atoms in this structure of importance to the steel industry. [This unit-cell structure can be compared with that shown in Figure 3.4b.]

Point Defects in Alloys

Two outcomes if impurity (B) added to host (A):

Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. (e.g., Cu in Ni)

Interstitial solid soln. (e.g., C in Fe)

Solid solution of B in A plus particles of a new phase (usually for a larger amount of B)
Second phase particle --different composition --often different structure

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Imperfections and Metal Processing

Solution hardening of alloys is the introduction of foreign atoms to serve as obstacles to dislocation motion. This is the restriction of plastic deformation by forming solid solutions.

Application of HumeRothery rules Solid Solutions

1. Which of these elements would be completely soluble in each other?
Element Atomic Radius (nm) 0.1278 0.071 0.046 0.060 0.1445 0.1431 0.1253 0.1249 0.1241 0.1246 0.1376 0.1332 Crystal Structure FCC Electronegativity 1.9 Valence

Cu-Ni, Cu-Pd, Ni-Pd: all H-R rules ok, completely soluble All others do not satisfy at least one of the Hume-Rothery rules.

Cu C H O Ag Al Co Cr Fe Ni Pd Zn

+2

FCC FCC HCP BCC BCC FCC FCC HCP

1.9 1.5 1.8 1.6 1.8 1.8 2.2 1.6

+1 +3 +2 +3 +2 +2 +2 +2

Table on p. 118, Callister 8e. 20

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Imperfections in Solids
Linear Defects (Dislocations)
Are one-dimensional defects around which atoms are misaligned

Edge dislocation:
extra half-plane of atoms inserted in a crystal structure b to dislocation line

Screw dislocation:
spiral planar ramp resulting from shear deformation b to dislocation line Burgers vector, b: measure of lattice distortion

Line Defects - Dislocations

Dislocation motion requires the successive bumping of a half plane of atoms
(from left to right here). Bonds across the slipping planes are broken and remade in succession. Dislocations slip planes incrementally... The dislocation line separates slipped material on the left from unslipped material on the right.

Atomic view of edge dislocation motion from left to right as a crystal is sheared.

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Imperfections in Solids
Edge Dislocation

Edge dislocation. The linear defect is represented by the edge of an extra half-plane of atoms. (From A. G. Guy, Elements of Physical Metallurgy, Addison-Wesley Publishing Co., Inc., Reading, MA, 1959.)

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Definition of the Burgers vector, b, relative to an edge dislocation. (a) In the perfect crystal, an m n atomic step loop closes at the starting point. (b) In the region of a dislocation, the same loop does not close, and the closure vector (b) represents the magnitude of the structural defect. For the edge dislocation, the Burgers vector is perpendicular to the dislocation line.

Line defects are associated primarily with mechanical deformation where point defects result mainly from thermal agitation.

For an edge dislocation, the dislocation line runs along the edge of the extra row of atoms. The Burgers vector is perpendicular to the dislocation line.

Screw dislocation. The spiral stacking of crystal planes leads to the Burgers vector being parallel to the dislocation line.

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Line Defects 1D Imperfection

For a screw dislocation, the crystal planes are stacked spirally around the dislocation line and the Burgers vector is parallel to the dislocation line.

Imperfections in Solids
Screw Dislocation
Screw Dislocation

Dislocation line Burgers vector b (a)

b (b)

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Mixed dislocation. This dislocation has both edge and screw character with a single Burgers vector consistent with the pure edge and pure screw regions.

Line Defects 1D Imperfection

Most linear defects in real materials are a combination of edge and screw dislocations, and the Burgers vector is neither perpendicular or parallel to the dislocation line but keeps a fixed orientation in space that describes and is consistent with both pure line defect regions.

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Edge, Screw, and Mixed Dislocations

Mixed

Edge Screw
Adapted from Fig. 4.5, Callister 7e. 31

Dislocation Motion

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Dislocations as Strengthening Mechanisms

Mechanism of dislocation climb. Obviously, many adjacent atom movements are required to produce climb of an entire dislocation line.

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Imperfections and Metal Processing

Cold working of metals is the deliberate deformation of the metal at relatively low temperatures. While the deformation makes a stronger material, the metal becomes more difficult to deform as the extent of deformation increases. This is because cold working produces dislocations that hinder the motion of other dislocations. Slip planes must be free of obstructions to move easily.

Annealing is the heat treatment of metals so as to allow structural relaxations, or in the above cases, the highly stressed crystals grains to restructure into more nearly perfect crystalline structures. Allows for atomic diffusion and deformation.

Planar Defects 2D Imperfections

Grain Boundary = region of mismatch between two adjacent single crystals (grains) meeting at different orientations.

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Planar Defects
Grain Boundary = region of mismatch between two adjacent single crystals (grains) meeting at different orientations.

Grain boundaries: are produced by the solidification process, for example. have a change in crystal orientation across them. impede dislocation motion.

Polycrystalline Materials
Grain Boundaries
regions between crystals transition from lattice of one region to that of the other slightly disordered low density in grain boundaries
high mobility high diffusivity high chemical reactivity

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Planar Defects in Solids

One case is a twin boundary (plane) Essentially a reflection of atom positions across the twin plane. Stacking faults For FCC metals an error in ABCABC packing sequence Ex: ABCABABC

A twin boundary separates two crystalline regions that are, structurally, mirror images of each other.

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Planar Defects

A twin boundary separates two crystalline regions that are mirror images of each other, usually resulting from a deformation.

Simple grain-boundary structure. This is termed a tilt boundary because it is formed when two adjacent crystalline grains are tilted relative to each other by a few degrees (). The resulting structure is equivalent to isolated edge dislocations separated by the distanc e b/, where b is the length of the Burgers vector, b. (From W. T. Read, Dislocations in Crystals, McGraw-Hill Book Company, New York, 1953. Reprinted with permission of the McGraw-Hill Book Company.)

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Typical optical micrograph of a grain structure, 100. The material is a low-carbon steel. The grain boundaries have been lightly etched with a chemical solution so that they reflect light differently from the polished grains, thereby giving a distinctive contrast. (From Metals Handbook, 8th ed., Vol. 7: Atlas of Microstructures of Industrial Alloys, American Society for Metals, Metals Park, OH, 1972.)

Specimen for the calculation of the grain-size number, G, 100. The material is a low-carbon steel similar to that shown previously. (From Metals Handbook, 8th ed., Vol. 7: Atlas of Microstructures of Industrial Alloys, American Society for Metals, Metals Park, OH, 1972.)

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Anisotropy in sy
Can be induced by rolling a polycrystalline metal

- before rolling

- after rolling

rolling direction

235 mm

- isotropic
since grains are approx. spherical & randomly oriented.

- anisotropic
since rolling affects grain orientation and shape.

Recap: Solid Solution Substitutions as a Strategy for Strengthening

Impurity atoms distort the lattice & generate stress. Stress can produce a barrier to dislocation motion.

Smaller substitutional impurity

A B
Impurity generates local stress at A and B that opposes dislocation motion to the right.

Larger substitutional impurity

C D

Impurity generates local stress at C and D that opposes dislocation motion to the right.

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How an impurity atom generates a strain field in a crystal lattice, thereby causing an obstacle to dislocation motion.

Recap: Reducing Grain Size as a Strategy for Strengthening

Grain boundaries are barriers to slip. Barrier "strength" increases with Increasing angle of misorientation. Smaller grain size: more barriers to slip.

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Optical Microscopy
Useful up to 2000X magnification. Polishing removes surface features (e.g., scratches) Etching changes reflectance, depending on crystal orientation.

crystallographic planes

Micrograph of brass (a Cu-Zn alloy)

0.75mm

Optical Microscopy
Grain boundaries...

are imperfections, are more susceptible to etching, may be revealed as dark lines, change in crystal orientation across boundary.

polished surface surface groove grain boundary

Photo: L.C. Smith and C. Brady, the National Bureau of Standards, Washington, DC [now the National Institute of Standards and Technology, Gaithersburg, MD].)

(a)

Fe-Cr alloy
(b)

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Close-Packed Directions in Slip

At small strains, the arrangement of the bubbles does not change. This is elastic deformation of the raft. The bubbles change shape and move slightly apart in an effort to maintain the lowest energy close-packed configuration. At larger stains, plastic deformation occurs. The bubble raft rearranges by dislocation motion. Notice how dislocation motion occurs along three directions in the raft. These are the close-packed directions, along which the distance between bubble centers is smallest.
University of Cambridge http://www.doitpoms.ac.uk/tlplib/dislocations/index.php

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