Lectures 1 and 2: Structure

• Structure of materials roadmap

• State of matter and bonding

• Descriptors: concept and function

• Generic descriptors: Free volume and pair

distribution function

Suggested readings:
• Allen and Thomas, The Structure of Materials, Chapters 1 and 2.1
• Callister, Materials Science and Engineering, Chapter 1
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 Structure of materials – old view
Materials can be divided into groups:

•  Metals:

•  Polymers/plastics:

•  Ceramics: compounds of metallic & non-

metallic elements (oxides, carbides,
nitrides, sulfides)
 Structure of materials – new view

•  New view: defined by structure/descriptors

•  e.g. crystals: long range translational order
(examples include all classes of materials)

•  What do we then mean when we talk about

“structure of materials”?

What is the major difference between the old and the new views?
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 Bonding and atomic structure

•  The fundamental “building blocks” of materials are

atoms

•  Atomic interactions result in bonds that derive from the

atoms’ electronic structure, and the bonds play a critical
role in determining the structure and properties of
materials

•  Interatomic bonds are responsible for the condensed

phases of matter—liquids, glasses, crystals, quasicrystals,
and liquid crystals—that comprise materials

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 Bonding è structure?

•  Two materials with the same chemical composition, but

different structure often have different properties
•  SiO2 is a common material – can you name it?

Si
O

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 Bonding è structure è properties ?

From The Structure of Materials, Allen and Thomas,copyright 1999 John Wiley and Sons, Inc. 7
Reproduced with permission of John Wiley and Sons, Inc.
 Symmetry
• Understanding bonding is important, but it is not the only parameter that
determines the structure.
• Every material has a characteristic symmetry and often the properties of
materials exhibit special symmetry.
• The theory of crystallography enumerates the set of ways that
elementary symmetry operations (translation, rotation, reflection, and
inversion) can combine to make one-, two-, and three-dimensional crystals.

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 Defects

• Real materials—even single crystals—lack perfect order and

imperfections in ideal structures often have a profound effect on
properties.
• Imperfections may be organized into features which have
characteristic length scales that far exceed those of the
material’s structural units.
• What kind of imperfections do you know?

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 Structure of materials - roadmap

Noncrystalline state Crystalline state and symmetry Liquid-crystalline state

•  liquids •  lattices •  nematic
•  glasses •  space groups •  smectic
•  diffraction
•  quasicrystals

•  Processing and assembly

•  Properties
•  Applications

Microstructure imperfections
•  equilibrium defect
•  line defects
•  stacking faults
•  grain boundaries

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 State of matter

• Let's start thinking about materials (and matter in general)

• We all know that most materials exist in one of the three different
forms (let's define them):

• Gas

• Liquid

• Solid

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Why do liquids solidify and what
kind of solids can they form?

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 Bonding forces and energies

• negligible forces for large interatomic

separation

• as atoms come closer to each other,

competing forces: attractive and
repulsive forces, both of which depend
on distance and details of the structure

• attractive forces: ionic, covalent,

metallic, van der Waals

• repulsive forces: interaction among

electron clouds (important at small
distances)

• no net forces at distance r0 (approx.

0.3 nm for many atoms), corresponding
to bonding energy E0

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 Order and disorder … a bit of thermo

• For solidification process to happen, thermal energy has to be

comparable or smaller to the bonding energy

• Equilibrium structural state of a system minimizes the free energy

• The relative free energy is the Gibbs function G:

Thermodynamics is
important for
E: internal energy
P: pressure understanding equilibrium
V: volume states of materials
T: absolute temperature
S: entropy

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 Solid materials
We will mostly deal with solid materials
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers
crystalline SiO2

Si Oxygen
Amorphous (noncrystalline) materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling

noncrystalline SiO2

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 Solid materials

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Non dense, random packing

Energy

typical neighbor
bond length

typical neighbor r
bond energy

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 Example of a disordered solid: glass

• Crystalline materials:
-- crystallize at melting
temp, Tm
-- have abrupt change in

Crystallization
spec.vol. at Tm
Volume

• Glasses:
-- do not crystallize
-- change in slope in spec.
vol. curve at glass transition
temperature, Tg
-- at Tg, the thermal energy
kT is lower than the
interaction energies in the
liquid state
-- solidification and a large
change in viscosity
From P. G. Debenedetti and F. H. Stillinger, Nature 410, 259 (2001). Used with permission.
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 Noncrystalline solids

•  Metals usually form crystalline solids (but not always!)

•  Ceramic materials can be either crystalline or amorphous
•  Polymers can be completely noncrystalline or semicrystalline

•  Depending on the processing parameters (namely, the cooling rate),

most liquids can solidify as a noncrystalline solid
•  For example, for metals – extremely rapid cooling is required

•  In reality, some materials can solidify only in glass form

•  These are materials with unit components that contain too much
disorder to crystallize
•  Example: linear molecules (polymers) made of various components

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 Applications of noncrystalline materials

From The Structure of Materials, Allen and Thomas,copyright 1999 John Wiley and Sons, Inc
Reproduced with permission of John Wiley and Sons, Inc.
 Noncrystalline state

• Disorder is an essential feature of the noncrystalline state

• In a completely disordered material the positions of the constituents are

uncorrelated (only gasses at low pressures approach complete disorder)

• Liquids and glasses are nearly incompressible (in contrast to gasses that can be
compressed) è molecules are densely packed è some correlation in their mutual
positions

• Liquids and glasses have short-range order but lack translational symmetry that is
necessary for long-range order of ordered crystals

• The goal is to define a structural descriptor that quantifies this short range order

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 Short vs. long range order

What exactly do we mean by these terms?

Short range order:

Long range order:

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 Structure of materials

• The structure of materials concerns the quantitative

description of the materials structural arrangements on
all relevant length scales

• Most useful pieces of a material contain vast numbers of

atoms and it is impossible and not even useful to quantify
each atom’s position.

• It is useful to devise sets of descriptors that characterize

small structural units that comprise the material and how
such units typically link together.

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