Glass Science & Technology

1. Introduction
Where Yeungnam University is
 Overview of Daegu
Seoul

 Location: SE part of the Korea Peninsula Daegu

 Population: About 2.5 million
 Climate: Mild weather (high15°C, low 5°C) Busan

 Tourism: 5 UNESCO World Heritage sites

Yeungnam University Campus
 Facts of YNU
Establishment 1945 two independent colleges
1967 two colleges merge to YNU
Location Gyeongsan (main campus)
Daegu (medical school)
Size of Campus 900 acres
Type Private
Total Enrollment 24,000 (undergraduate)
3,000 (graduate)
Number of school 15 colleges (46 departments)
(10 engineering depts)
2 independent schools
11 graduate schools

Number of faculty 1100

 Facts of MSE
School of Materials Science & Engineering

Establishment 1973 (Dept of Metallurgy)

& history 1986 (Dept of Ceramic Engineering)
1995 (merge to one school, 2 majors)

Total Enrollment 500 (undergraduate)

50 (graduate)

# of faculty 20

2001 selected as one of top 10 in Materials Science Field

by the Korean Ministry of Education
 Name G. Year Title

Augi
Effects of HA and CMP Blasting & Acid Etching
Wulan 2006. 2
of Ti Implant Surface on Bone Cell Attachment
Haryadi

Ikhwan Comparative Study on Ti Surface Modified

2010. 2
Hidayat by Grit Blasting & Acid Etching for Dental Implants

Ekavianty Effect of C3S and Hardener on Compressive Strength

2012. 2
Prajatelistia and Setting Properties in Calcium Phosphate Cement

Asywendi Ti Surface Modification by Hydrothermal Treatment

2015. 2
Rukini with Various Solutions for Cell Behaviors
 Course Information

Text/Reference Books :
High Performance Glasses, Blackie (1992)
Chemistry of Glasses, 2nd Edition, A. Paul (1990)
Fundamentals of Inorganic Glasses, 2nd ed, A. K. Varshneya,
Society of Glass Technology (2014)
Glass Science 2nd edition, R. H. Doremus, Pergamon (1994)
High Performance Glasses, M. Cable & J. M. Parker, Blackie (1992)
Glass-Ceramic Technology, W. Holand & G. Beall, Am Cer Soc (2002)
Advanced Ceramic Technologies & Products, Springer (2012)

Instructor: Sukyoung Kim

E-mail: [email protected]
 SWOT Analysis of Glass

Strengths Weaknesses
- Transparent / Color - Brittle
- Forming/size/shape - Melting @ HT
- Resistant to chemical, water - Sharp broken pieces
- Heavier than plastics
- No UV degradation/ long life
- Rigid than others
- Easy cleaning
- Low price

Opportunities Threats
- Safe for food, drug - Plastics (light, cheap)
- Functional glass - Transparent ceramics
- New applications - Metallic alloys
Low E glass
Hall of Mirrors at the Palace of Versailles
 Brief History of Glass 5000 – 1000 BC

Date Place & Activity

5000 BC Mesopotamia & Egypt, batching sea sands, marine
shells, and sea weed ash to create crude glassy
materials
1,500 BC Containers, Touthmosis III, sand molds with sand
core and removed by scraping
900 BC In Syria, Rhodes, Greece,
glass production begins,
glass recipes begin to be
formulated
 Natural Glasses

① obsidian ; mainly black or dark grey < 3% H2O

② pitch stone ; dark blue, reddish, green or black > 3% H2O
 Brief History of Glass : 1000 BC – 0 AD

Date Place & Activity

650 BC 1st Glassmaking handbook,
Assyrian Assurbanipal’s Library,
http://search.eb.com/bol/topic?eu=9976&sctn=1#s_top

500 BC Venetian glass artists begin to

create vases and glass pieces
using glass rolls.
50 BC Phoenician glassblowing
flourishes to create art glass
 Brief History of Glass : 0 AD – 1000 AD

25 BC - 400 AD Roman empire enables rapid

development and expansion of glass melting,
working, and forming technology in the
Mediterranean region Roman Empire
100 AD Glass cost rapidly declines and for the first
time becomes available to less than the
aristocracy
http://search.eb.com/bol/topic?eu=15951&sctn=1#238645
470 to 1000 AD Dark Ages cast an oppressing shadow
over all sorts and types of human endeavor
and development
Roman Empire
 Historical Overview (from J. Zarzycki)

• Glass is one of the most ancient materials known to mankind.

In prehistoric times - natural glass (obsidian) for knives, arrow tips in Greece
12,000B.C. - enamel on pottery (in Egyptian fireplace - sand+soda ash)
4,500B.C. - discovered the glass manufacturing method in Mesopotamia.
3,000B.C. - ancient glass objects made in Egypt. (Na2O-CaO-SiO2)
1,200B.C. - modern glassmaking: fiber, dishes, bottles (Egypt, then Syria)
900B.C. - glass center (Cyprus, Rhodes, Greece, Italy)
500 B.C. - multicolored vases (Venice )
100 B.C. - new technique from Italy by Alexander (Alexandria in Egypt)
200 A.D. - invention of glass blowing (Syria)
 Development of Modern Glasses 1
Newton - optical dispersion in glass (1642-1727)
Fraunhofer - manufacture of optical glass (1780-1825)
Zeiss/Abbe/ Schott - instrument, physics, manufacture, respectively,
- looking into glass scientifically first (1880-1900)
Adams/Williamson - law of stress release in glass (1920 ~)
Lebedev - crystallite hypothesis (1921)
Griffith - fracture of glass (1924)
Turner/Winks - amorphous phase separation (1926)
Zachariasen - random network theory (1932)
Warren - x-ray diffraction analysis of glass (1934)
Randall/Cooper/Rooksby - x-ray diffraction analysis (1934)
Dalton - glasses contain dissolved gases (1935)
- photosensitive glass (Ag, Au) (1937)
 Development of Modern Glasses 2

Dietzel - field strength concept/crystal chemistry (bond strength)(1942)

Tool - fictive temperature concept (1949)
Baynton - semiconducting glasses (1953)
Ritland - transformation range behavior (1954~1956)
Stooky - catalyzed crystallization of glass (1957)
Mckinnis - melting history of glass (1959)
- observation of glass structure change
Greene - bubbles in glass (1959)
Pilkington Brothers - patent the float glass process in England (1959)
Moriya - microstructure/strength of glass (1960)
Roy - liquid immisibility in glass - crystallization (1960)
Vogel - microstructures (TEM) (1960)
 Development of Modern Glasses 3

Ernsberger/Charles/Hills - mechanical chemistry related to glass strength (1962)

Snitzer - glass laser (1962)
Bates - application of ligand field theory (1962)
Kistler - stress in the surface by ion exchange (1962)
Stookey - photochromic glasses (1964)
Johnson - redox behavior (Equilibrium) (1964)
Pearson - electrical switching (1964)
Hammel/Cahn/Goldstein - spinodal decomposition theory (1965)
Hammel/Cahn - thermodynamics of glass (1965)
Ohlberg/Hammel - liquid immisibility in Na2O-CaO-SiO2 (1965)
Cahn/Charles - thermodynamics of glass melt (1965)
predicting microstructure using electron microscope
 Development of Modern Glasses 4

Gubanov - application of band theory to non-crystalline solid (1967)

LaCourse - anion impurities in semiconducting glasses (1968)
Douglas/Zaman - deduced the amber glass color center (1968)
Corning Glass Works - 1st silica optical fiber produced at using CVD (1971)
Roy - discard the random network theory (1971)
Maurer/Schultz - low loss fiber optics (SiO2)(1970-1972)
Uhlmann - kinetic treatment of glass formation (1972)
Weber - fluoride glasses (BeF2) (1972)
Jack - nitride glasses - N2 dissolves in silicate melts (1978)
Yoldas - Sol-Gel glass in bulk (1978)
Poulain/Lucas - discover first fluoride glass in Rennes, France (1984)
Present Day - Glass R/D is moving to non-oxide glass chemistries
(halide glasses, chalcogenide glasses, chalco-halide glasses)
and non-traditional melting processing (sol-gel, CVD).
Classification of Non-crytalline by Starting Materials
Classification According to Starting Materials

A. Glasses from Vapors

1. Glasses from the Melts (quenching)

oxide glasses - SiO2, B2O3, GeO2, P2O5
chalcogenide glasses
metallic glasses

2. Amorphous Solids from Solutions

glasses formed by drying of gels
amorphous precipitates
electrolytic deposition of amorphous layers
Classification According to Starting Materials

B. Glasses from Vapors

3. Amorphous Layers from the Gaseous Phase

thermal evaporation under vacuum
cathode sputtering
decomposition of amorphous layers in a glow discharge
decomposition of amorphous layers in CVD

C. Glasses from Solids

4. Transformation of Crystalline Solids to Amorphous State

oxidation of crystalline surface
shock wave
intense irradiation
decomposition reaction
mechanical treatment of crystalline solids
 Material State & Volume with Temperature

Temp low high

Matter molecules
solid liquid vapor plasmas
state atoms

Reaction solidification melting vaporization dissociation ionization

Volume small large

 Material State Change (vitrification)

Temp low high

Matter molecules
glass liquid vapor plasmas
state atoms

Reaction vitrification melting vaporization dissociation ionization

Volume small large

 Classification of Inorganic Materials

Crystalline Non-crystalline

Melt Amorphous Solid

Single Poly
crystal crystalline
Amorphous Glassy

Si Metals Film, Powder Oxide glass

Diamond Ceramics Carbon, Si Metallic glass
Atomic Arrangement of Various Materials

single crystal polycrystalline amorphous

Crystalline solid Non-crystalline solid

Crystalline materials Non-crystalline

-solids - solids, liquids
Amorphous
- solids
Glasses
- oxides
- non-oxides
 Glass

2. Definitions
 Examples of Matter State

Materials

Matter state solid g liquid vapor atom plasma

Atomic
ordered non-ordered
arrangement
crystalli
v melted vaporized dissociated ionized
Material zation
chemistry/ metals
Sate of
bonding ceramics ionization
chemical bonds
polymers
 Classification of Non-Crystalline Solids

Non-Crystalline Solids

Amorphous Materials Glasses

- Most vapor deposited films - Most super-cooled Liquids

- Spontaneously decomposes - Vapor deposited phases
without softening stable enough to exhibit Tg
- Lack internal stability - Gels and sols that exhibit Tg
Various Forms prepared from Melts or Solutions

To glasses
- quenching,
- drying of gels
- electrolytic deposition
To amorphous films
- electrolytic deposition
To amorphous solids
- drying of gels
- amorphous precipitates
Structural & Thermodynamic Standpoints of Materials

Materials Structure Thermodynamics

Thermodynamically
Gas no short- & long-range order
Equilibrium

short-range order, thermodynamically

Liquid
but no long-range order Equilibrium

short-range order, thermodynamically

Amorphous
but no long-range order non-equilibrium
thermodynamically
Crystalline short- & long-range order
equilibrium
 Features of Glassy State

Glassy materials have many unique features

– Lack of long range repeatable order,

– Non-crystalline structure

– Typically produced from liquid state by quenching

– Exhibits what is known as the glass transition Tg

 Definitions of Glass

- University of Sheffield (1920’s)

“Glass is an amorphous, structureless solid”

- G.W. Morey (1938)

“A glass is an inorganic substance in a condition
which is continuous & analogous to the liquid state of that substance,
but which as a result of a reversible change in viscosity
has attained so high a degree of viscosity
as to be for all practical purposes a rigid solid”

- ASTM (1949)
“Glass is an inorganic product of fusion which has cooled
to a rigid condition without crystallization”
 Definitions of Glass

- J.D. Mackenzie, D.R. Secrist (1960, 1958)

an inorganic substance analogous to a rigid liquid.

- 1991 J. Zarzycki
“Glass is a non-crystalline material that exhibits
a glass transition which is the temperature or range of temp
that define the region where the properties of the material
change continuously from those of a solid to those of a liquid”
 Two Definitions of Glass
We can classify the glass definitions in terms of two points of view.

1) Concentration on the conventional preparation method :

- cooling from the liquid state, w/o crystallization occurring,
until the material becomes a rigid solid through in its viscosity.

2) Focus on the structure of a glass :

- amorphous solid, w/o long range order or periodicity
in atomic arrangement

* However, neither definition appears to be ideal

because glass can be prepared by the other methods (see next sec).
Non-Crystalline, Amorphous, & Glassy States

- non-crystalline materials : includes solids and liquids

- amorphous materials : only solids
- glassy materials : supercooled solids under Tg

Non-crystalline

Amorphous

Glass
Non-Crystalline, Amorphous, & Glassy States

- Amorphous solid state has a more comprehensive meaning,

broader than that of the vitreous (glassy) state.

- Vitreous state (term) is restricted to

1) solids obtained from melts, or
2) solids produced by other methods
& obtained in a compact form, thin films, wires or fibers.

ex) Amorphous (not glasses) :

1) highly dispersed powders,
such as precipitation products from aqueous solutions,
including certain hydroxides, sulfides, & selenides
2) intermediate products resulting from certain reactions w/ solids,
as well as thermally unstable gels.
 Amorphous Inorganic Materials

Materials Examples
SiO2
quartz glass, sheet glass 16Na2O-12CaO-72SiO2
Inorganic glasses
optical glass, 53La2O-37B2O3
(oxides & fluorides)
fluoride glass 5ZrO2-5Ta2O5
NaF-BeF2
silica gel, silica-alumina SiO2,
Gel
(absorbent, catalyst) SiO2-Al2O3
Amorphous
Se film for Xerox, Se
semiconductors
photoelectric film for TV cathode As40Se30Te30
- chalcogenides
amorphous S.C. for solar cell Si, Ge
- amorphous elements
glassy carbon
Amorphous carbon C
carbon black & film
soft ferrite alloy Fe80P13C7
Amorphous metals
high strength alloys Co70Fe5Si15B10
 Glass

3. Glass Structure
Vol & Enthalpy Change with Temperature
XRD Patterns of 3 Type Materials
 Two Models of Glass Structure

(1) Crystallite Model

- exhibit broad peaks, if particle size is < 0.1㎛
- composed of assemblages of very small crystals (crystallites)

(2) Random-Network Model

- lacking symmetry and periodicity in 3D networks or arrays,
- no unit of the structure is repeated at regular intervals.
- In 1932, Zachariasen proposed (Zachariasen hypothesis)

Zachariasen's rules relating to the amorphous state

(1) each oxygen atom must be linked to no more than two cations,
(2) C.N. of oxygen atoms surrounding a cation must be small (3 or 4),
(3) oxygen polyhedra share corners with each other, not edges or faces,
(4) in 3D network, at least 3 corners of each polyhedron must be shared.
Atomic Radial Distribution Function, RDF
 Glass

4. Glass Formation
 Material State & Phenomena during Melting Process

Raw Form Quench Anneal Pro

Process Mixing Melting Refining
matls ing ing ing duct
Super
Solid
State Solid (powder) Melt (liquid) -cooled
(glass)
liquid
Homoge
Disso- nization
Pheno Mix Vitrifi Remove
Powders & (pores, Shaping
-mena ture cation stress
melting foreign
matters)
 V-H Change with Temperature

glass

crystal Liquid vapor plasma

Enthalpy / Volume increase of system

V-T Relation among Crystalline, Liquid, & Glass
 Factors that Influence Glass Formation
1. Electronegativity and Bond Type - oxide glasses (SiO2, B2O3, GeO2, P2O5)
1) a certain area of the periodic table (B, Si, P, Ge) - glass former
2) Conditional glass former - Al2O3, Ga2O3, Bi2O3, SeO2, TeO2
- do not form glasses alone, but w/ certain other non-glass forming oxides
- ex) CaO- Al2O3
2. Viscosity
- Viscosity is related to the structure and bonding that is present.
- high viscous liquids above their melting points
ex) SiO2 : m.p. 1715 ℃ = 107 poise
non-glass former (water) = 10-2 poise
3. Structural Effect - Zachariasen's rules (1932)
- glass formers should be capable of forming an extended 3D structure
w/o any long range order.
4. Bond Strength - Criteria of Sun & Rawson
- correlations btn structural features & glass forming tendency of simple oxides
- Sun suggested : M-O bond strength important. (≥330 kJ/mol)
- Rawson modified Sun's criterion &
related glass-forming tendency to the ratio of bond strength : melting temp
 Amorphous Materials (Glass Formers)

elements Si, S, Se, Te, As, etc.

- common glasses
oxides
- H-bond glasses : HPO3, etc.
- fluorides : BeF2, etc.
halide compounds
- chlorides : ZnCl2, etc.
chalcogenides As2S3, GeS2, As2Se3, etc
Inorganics
carbonates MgCO3 + K2CO3, etc.
NaNO3 + Ca(NO3)2,
salts of nitric acid (nitrates)
KNO3 + Ca(NO3)2, etc.
K SO + H2SO4,
salts of sulphuric acid (sulfates) 2 4
K2SO4 + Tl2SO4, etc.
metal alloys Pd-Si, Te-Ge, etc
Intermediates various silicones
Organics polystyrene, polyethylene, glucose, etc.
Viscosity of Materials (Glass Formers)
Bonding
Strength
Glass Formers & Others
 Components of Glasses
1. Network Forming Oxides
(1) Glass-Forming Oxides (glass-formers)
- SiO2, B2O3, GeO2, and P2O5 readily form glasses on their own
(2) Conditional Glass-Formers
- TeO2, SeO2, MoO3, WO3, Bi2O3, Al2O3, Ga2O3, & V2O3
2. Network Modifiers
- provide extra oxygen ions but do not participate in the network.
- generate two nonbridging Os to terminate each tetrahedron (↓η & Tg)
- alter glassy properties such as n, σ, α.
(1) Stabilizers - e.g., CaO, MgO, Al2O3
- improve chemical durability and/or prevent crystallization
(2) Fluxes - e.g., Na2O, K2O and B2O3
- added to lower Tm & working temp of silicate glasses
3. Intermediates
- not network formers or modifiers, but contribute in part to network str.
- TiO2, ZnO, Al2O3, ThO2, ZrO2, etc
4. Colorants
- produced colored glasses under oxidation or reduction atmosphere.
5. Decolorizers -
6. Opacifiers - produce opal glass
7. Mineralizer - promote the crystallization in glasses.
 Inorganic Glasses & Its Manufacturing

Type of glass Manufacturing method

- SiO2, B2O3, Ge2O3, &
Oxide - Quenching of melts
P2O5 system
Glasses - Firing of gel
- Complex compound
- Quenching of melts
Halogen compound
TeCl, TeBr, TeI, TeXAs
- Quenching of melts
Chalcogenide compound - Vac deposition, Sputtering,
Non- TeCl, TeBr, TeI, TeXAs
oxide - Supe quenching of melts
Glasses Alloys Fe; Fe(Zr,Hf,Nb)B, Fe(Cr,Mo)(C, B)Ln
Non-Fe-; Zr.Ti.Ni.Be, Pt.Cu.P, Ca.Mg.Zn
C Pyrolysis of organics
Si Glow discharge of SiH4
 Three Criteria for Glass Formation

1) structural criteria (atomistic hypotheses)

2) bonding criteria
3) kinetic criteria

- kinetic problem involving the rate of nucleation & crystal growth

; the rate at which thermal energy can be extracted from the cooling liq

- Two-stage processes of crystallization

- formation of crystal nuclei
- their subsequent crystal growth

- Kinetic condition for glass formation

- above two-stage processes should be slow.
(the low rate of nucleation & crystal growth)
Xtallized Fraction in T-T-T vs Cooling T Curves with Time

▶ Turnbull (1969)
Factors which affect the tendency of liquids to form glasses.
- cooling rate
- density of nuclei
- various material properties ;
like crystal-liquid surface tension & entropy of fusion
 Glass

5. Crystallization
 Glass Ceramics (crystallized glasses)

- Polycrystalline solids prepared by the controlled crystallization of glasses,

which occurs by carefully regulated heat-treatment schedule.

- In many cases, the crystallization can be taken almost to completion

but a small proportion of residual glass-phase is often present.
 Difference between glass-ceramics &
traditional ceramics (both crystalline phases)
In glass-ceramics,
- produced by crystal growth from homogeneous glass phase,
- crystallized crystals (nucleation & crystal growth)

But in traditional ceramics,

- introduced when the ceramic composition is prepared.
- original or recrytallized crystals during sintering
Many superior properties
high strength/impact resistance low electrical conductivity
low dielectric loss low chemical reactivity
low thermal expansion a range of optical properties
from clear to opaque/white
- discovered by Stookey in 1960, Corning Glass
nucleating agent - NaF, TiO2, Cr2O3, P2O5, ZrO2, fluorides
- application : cook-ware in oven, stove-top ware,
table-ware for hot food, low expansion circuit boards
Comparison among glass, G-Ceramic, Porcelain

Glass Glass-Ceramic Porcelain

Raw
Sand, Na2CO3, Calcite Clay, Silica, Feldspar
Materials
Powder pressing,
Float, Casting, Molding,
Forming Casting, Extrusion,
Pressing, Blowing
Injection, CIP

Heat T Quenching/annealing crystallization In Air, Vac, HP

Optical P Transparent, Colors Opaque Opaque

Mech. P Brittle Very strong Strong

Isotropic Anisotropic Anisotropic
Others
Complicate shape Complicate shape Simple shape
Heating Schedule for Glass Ceramics
Maxima of Nucleation & Crystal Growth
 Two Types of Nucleation of Glass

- homogeneous nucleation - at bulk materials

- heterogeneous nucleation - at surface or interface
by foreign particles, container surface
 Homogeneous Nucleation of Glass
@ below Tf (freezing point) or Tm
- crystal grows @ a finite rate of a finite number of nuclei,.

The stability of a new crystal in homogeneous nucleation

depends on two contributions :
(1) difference in free energy between two phases (glass/liquid-crystal)
(2) interfacial energy between two phases.

Temperature Energies

@ melting point or above - no difference in free energy

(liquid) - no interfacial energy

@ below melting point - lower free energy of crystals

(cooling) - interfacial energy existed
 Homogeneous Nucleation of Glass

If a crystal is r < r* → embryo (unstable)

because the decrease in ∆G
with reduction in size.
Nucleation stage If a crystal is r > r* → nucleus (stable)
because the growth is accompanied
by a decrease in ∆G.
embryo nucleus crystal
 Homogeneous Nucleation of Glass
N = the number of atoms per unit volume
Nr = the number of clusters of radius r per unit volume

Nr = the number of clusters (embryos) of radius r per unit volume

or the number of the embryo per unit volume
Ia = the rate at which atoms attached to the embryo embryo

The rate of nucleation I = Nr ｘ Ia

cluster
@ liquidus T, = 0, ∆T ↑ ～ ↑

@ large ∆T (>∆T), term dominates

the I decreases with further cooling after Imax.
Heterogeneous Nucleation of Glass

for 0 ≤θ≤π
Heterogeneous Nucleation of Glass

embryo nucleus crystal

Nucleating Agent for Heterogeneous Nucleation
The presence of heterogeneous nucleation which reduces ΔG*,
and will reduce the incubation time τhet .

With increasing efficiency of the nucleating particle,

the incubation time is reduced.

The potency of a nucleation catalyst can be expressed as

where τhom is the incubation time for the pure glass.

ex) For Na2O-P2O5 glass,

the order of potency of nucleation catalyst is
Au < Ag < Re < Pd < Pt < Ir
 Two Criteria for Nucleating Agent

There are two important criteria

of the effectiveness of a nucleation catalyst ;

1) interfacial energy between nucleation catalyst &

the primary crystal phase must be low (or low θ).

2) crystal structure must be closely similar

so that the lattice mismatch on low index plane
is not more than about 15 %.
 Types of Glass Crystallization

devitrification glass-ceramics Fluoride opal

 Epitaxial Crystal Growth

- oriented overgrowth
- a seed crystal which has a low-index planes
in which the atomic spacing & arrangement are similar
to those of one of the low-index planes in the crystal
that wishes to form,
- If there is no near match, then the liquid will not crystallize.

How much disregistry can be tolerated ?

- based on practice rather than theory.
- at least 15 % max. for metal systems
- 8 % max. for glass-ceramic systems
In general, most glass-ceramics have crystals of about 1 ㎛.
this means 1012 nuclei cm-3 of glass
 Crystal Growth

Nucleation stage Crystal growth stage

embryo nucleus crystal

 Crystal Growth
The rate of crystal growth depends on
the rate at which atoms arrive & remain at the surface of the nucleus,

1) when the nucleus is microscopic (but r > r*),

the growth rate will also be affected by the curvature of
the nucleus-liquid interface,
due to an increase in the interface energy with nucleus growing.

2) when the nucleus (crystal) becomes macroscopic in size,

the surface energy increase is negligible
in comparison w/ free energy decrease which occurs.
Thus, the large crystal can be treated as having a planar interface.
 Crystal Growth

where ΔGa = activation energy

s = the number of atoms across the interface
νo = the frequency of the thermal vibration of an atom
 Crystal Growth
net transfer of atoms from the liquid to crystal

crystal growth rate u

where λ ≈ ao = one interatomic spacing.

modification of Hilling & Turnbull equation

 Three Types of Crystal Growth
1) normal growth model
- atomically rough (many favorable sites)

2) surface nucleation growth model

- atomically smooth

3) screw dislocation model

- the number of imperfections is limited
(i.e., limited favorable sites)