3.

Solidification & Crystalline Imperfections

solidification (casting process) of metals divided into two steps (1) nucleation formation of stable nuclei in the melt (2) growth of nuclei into crystals (3) formation of a grain structure

formation of stable nuclei two main mechanisms a. homogeneous nucleation liquid metal is cooled below freezing point, slow-moving atoms bond together to create homogeneous nuclei nucleus larger than critical size, can grow into a crystal embryo smaller than critical size, continuously being formed and 1 redissolved in the molten metal

two kinds of energies involved in homogeneous nucleation: (1) the volume free energy GV free energy difference between the liquid and solid GV = 4/3r3Gv (2) the surface energy Gs the energy needed to create a surface for the spherical particles Gs = 4r2 : specific surface free energy of the particle total free energy GT = GV + Gs GT = 4/3r3Gv + 4r2

r* : critical radius GT reaches the maximum 2

when r = r* 2 r* = - Gv critical radius versus undercooling

d(GT)/dr = 0

critical nucleus size mainly determined by GV amount of undercooling increases, the critical nucleus size decreases the relationship is 2Tm r* = Hf T : surface free energy Tm: freezing temperature Hf : latent heat of fusion 3 T: amount of undercooling

ex. calculate the critical radius of homogeneous nucleus forms from pure liquid Cu. Assume T = 0.2Tm ( = 1.77 10-7 J/cm2, Tm = 1083oC, Hf = 1826 J/cm3) calculate the number of atoms in criticalsized nucleus at this undercooling
T = 0.2Tm = 1356 K 0.2 = 271 K 2Tm 2(1.77 10-7 J/cm2)(1356 K ) r* = = (1826 J/cm3)(271 K) Hf T = 9.70 10-8 cm volume of nucleus = 4/3 (9.70 10-8 cm)3 = 3.82 10-21 cm3 Cu: FCC structure, unit length a = 3.61 10-8 cm 4 atoms per unit cell volume of unit cell = (3.61 10-8 cm)3 = 4.70 10-23 cm3 3.82 10-21 cm3 number of atoms = 4 = 325 atoms 4.70 10-23 cm3

b. heterogeneous nucleation occurs in a liquid on the surface of its container, insoluble impurities and other structural materials that lower the critical free energy required to form a stable nucleus 4

the surface energy to form a stable nucleus on the nucleating agent is lower much smaller amount of undercooling is required to form a stable nucleus crystal growth and grain formation nuclei crystals grains polycrystalline solidified metal containing many crystals grains crystals in solidified metal grain boundaries the surfaces between the grains two major types of grain structures: (1) equiaxed grains crystals grow about equally in all directions, commonly found adjacent to a cold mold wall (2) columnar grains long, thin, coarse grains, created when metal solidifies 5

rather slow in the presence of a steep temperature gradient columnar grains grow perpendicular to the mold surface
Al ingot

solidification of single crystals solidification takes place around a single nucleus, no other crystals are nucleated and grow the interface temperature between solid and liquid must be slightly lower than m.p. of solid and the liquid temperature must increase beyond the interface
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single-crystal gas turbine airfoil

Si single crystal Czochralski method

metallic solid solution metal alloy mixture of two or more metals or a metal (metals) and a nonmetal (nonmetals) ex. cartridge brass: 70% Cu + 30% Zn Ni-base superalloy Inconel 718: about 10 elements in its nominal composition solid solution solid that consists o two or more elements atomically dispersed in a singlephase structure (1) substitutional solid solution solute atoms can substitute for parent solvent atoms in a crystal lattice ex. (111) plane in an FCC crystal lattice

Hume-Rothery rules: the following conditions are favorable for extensive solid solubility of 8 one element in another:

(a) the diameters of the atoms of the elements must not differ by more than about 15% (b) the crystal structures of the two elements must be the same (c) no appreciable difference in the electronegativites of the two elements (d) two elements should have the same valence ex. Using the following data, predict the relative degree of atomic solid solubility of the elements in copper
Cu Zn Pb Si Ni Al Be atomic radius 0.128 nm 0.133 nm 0.175 nm 0.117 nm 0.125 nm 0.143 nm 0.114 nm
Cu-Zn +3.9% 0.1 B

crystal structure FCC HCP FCC diamond cubic FCC FCC HCP

electronegativity 1.8 1.7 1.6 1.8 1.8 1.5 1.5

valence +2 +2 +2, +4 +4 +2 +3 +2

r predict solubility exp. 38.3%

Cu-Pb Cu-Si +36.7% -8.6% 0.2 0 E C 0.1%

Cu-Ni Cu-Al Cu-Be -2.3% +11.7% -10.9% 0 0.3 0.3 A C C 19.6%

9 16.4%

11.2% 100%

(2) interstitial solid solution the solute atoms fit into the spaces between the solvent atoms, the spaces are called interstices interstitial solid solution can form when one atom is much larger than another C in -Fe max. 2.08% C can dissolve

ex. calculate the radius of the largest interstitial void in FCC -Fe lattice
2R + 2r = a 2R = 2 (R + r) 2R=R+r r = ( 2 - 1) R = 0.414 R = 0.414 0.129 nm = 0.053 nm
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crystalline imperfection zero-dimensional or point defects one-dimensional or line defects (dislocation) two-dimensional or planar defects three-dimensional or volume defects (1) point defects vacancy atom is missing, may be created by local disturbances during the crystal growth atomic arrangements in an existing crystal plastic defromation, rapid cooling bombardment with energetic particles interstitialcy or self-interstitial an atom in a crystal can occupy an interstitial site between surrounding atoms can be introduced by irradiation

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Schottky imperfection two oppositely charged ions are missing form an ionic crystal a cation-anion divacancy Frenkel imperfection a cation moves into an interstitial site, and a cation vacancy is created vacancy-interstitialcy pair the presence of these defects in ionic crystals increases their electrical conductivity

impurity is also a type of point defect (2) line defects (dislocations) crystalline solids are defects that cause lattice distortion centered around a line formed by plastic deformation, vacancy condensation, and atomic mismatch 12

two types of dislocations a. edge dislocation created by the insertion of an extra half plane of atoms above

slip or Burgers vector displacement distance of atoms around the dislocation and is perpendicular to the edgedislocation line region of compressive strain where the extra half plane is, region of tensile strain below the extra half plane

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b. screw dislocation formed by applying upward and downward shear stress to a perfect crystal that have been separated by a cutting plane

the slip vector is parallel to the dislocation line most dislocations are of the mixed type

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(3) planar defects external surface the most common type of planar defect, the atoms on the surface are bonded to other atoms only on one side, the higher energy associated with these atoms makes the surface susceptible to reaction grain boundaries a narrow region between two grains of about 2~5 atomic diameters in width and a region of atomic mismatch between adjacent grains

the higher energy of grain boundaries and more open structure make them more favorable for nucleation and growth of 15 precipitates

twin or twin boundary a region in which a mirror image of the structure exists across a plane or a boundary ex. twin boundaries in the grain structure of brass

small-angle tilt boundary small-angle twist boundary

misorientation angle is generally < 10o small-angle boundaries are regions of high energy and tend to strengthen a metal

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stacking faults or piling-up faults one or more of the stacking planes may be missing, give rise to another twodimensional defect ex. ABCABAACBABC in FCC crystal ABAABBAB in HCP crystal (4) volume defects a cluster of point defects join to form a three-dimensional void or a pore a cluster of impurity atoms join to form a three-dimensional precipitate the size from a few nm to cm

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identification of microstructure and defects (1) optical metallography technology at the m level (magnification 2000) information about grain size, grain boundary, existence of various phases, internal damage, defects may be extracted sample preparation: i grinding stage ii polishing stage smooth, mirror-like surface must be produced after polishing stage iii etching process the atoms at the grain boundary will be attacked at a much more rapid rate than the atoms inside the grain tiny groves along the boundaries are produced grain size and average grain diameter American Society for Testing and Materials (ASTM) method N = 2n-1 n : grain-size number n < 3 : coarse-grain, 4 < n < 6 : medium-grain 7 < n < 9 : fine-grain 18 n > 9 : ultra-large grain

average grain diameter d = C/(nL M) C = 1.5 constant M : magnification nL : the ratio of the number of grains intersected by a line of known length schematic diagram of optical microscope

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microstructure observed in optical microscope

low-carbon steel (magnification 100)

magnesium oxide (magnification 225)

ex. 64 grains/in2 in a photomicrogarph of a metal are observed at a magnification of 100. What is the ASTM grain size number? N = 2n-1 64 = 2n-1 20 n=7

(2) scanning electron microscopy (SEM)

used for microscopic feature measurement, fracture characterization, microstructrue studies, thin coating evaluation, surface contamination examination, failure analysis wide range of magnification 15 ~ 100,000 resolution to about 5 nm easy to prepare sample, often coated with Au SEM of intergranular corrosion fracture

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schematic diagram of SEM

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(3) transmission electron microscopy (TEM) important technique for studying defects and precipitates (secondary phase) in materials resolved features in the nm range samples have a thickness of several hundred nm and sample preparation is complex bright-field image the direct electrons dark-field image the scattered electrons

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schematic diagram of TEM

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(4) high-resolution transmission electron microscopy (HRTEM) has a resolution of about 0.1 nm allowing viewing of crystal structure and defects at the atomic level sample must be significantly thin 10 ~ 15 nm HRTEM image of several dislocations forming a small-angle boundary

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(5) scanning probe microscopes (SPM) tools allow scientist to analyze and image materials at the atomic level (a) scanning tunneling microscope (STM) invented by Binnig and Rohrer in early 1980s extremely sharp tip (made of W, Ni, Pt-Ir, Au, or carbon nanotube) to probe the surface constant current mode constant height mode

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(b) atomic force microscope (AFM)

contact mode short-range repulsive force noncontact mode long-range attractive force AFM can be applied to all materials even nonconductor

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