Part Ⅰ

STRUCTURE of MATERIALS and its

EFFECTS on PROPERTIES of
MATERIALS

1
 Chapter 2

Atomic Scale Structure:

Interatomic Bonding

2
I. Materials, Properties, Applications
and Synthesis

Materials Applications

3
I. Materials, Properties, Applications
and Synthesis

Materials Applications

Properties

4
I. Materials, Properties, Applications
and Synthesis

Synthesis, Processing
reactants Materials Applications
(operation Conditions)

Properties

5
II. Structure and Properties: Synthesis
and Applications
36

Synthesis ，Processing
reactants Materials Applications
operation conditions

Chemical
Composition

Structure
structure
Properties

6
III. Structure of Materials
shape
raw synthesis forming sintering fabrication material
materials products

Processing techniques
Structure Properties
and
( 結構 ) ( 性質 )
operation conditions

scale structure (~0.1nm)

Structure ：atomic
crystalline structure (>~10nm) F 4.11
Nano scale structure(>~10nm)
microscopic (scale) structure (>~0.1µm): SEM
macroscopic structure (>~0.1cm) F 4.12

7
IV. Atomic Scale Structure
F 12.15
(1) the types of atoms present,
·Different types of atoms (different chemical
formula)  different materials
·same type of atoms (same chemical formula)
Different coordination or different crystal structure
different materials
(2) the types of bonding between the atoms,
·Different types of bonding  different materials

(3) the way the atoms are packed together ： Chap 3

( atomic packing; coordination number )
• same type of atoms and same type of bonding
Different coordination or different crystal structure
different materials
※ Many materials properties are determined by the atomic scale
structure alone 8
V. Atomic Bonding in Solids
A. Types of Bonding
 primary (or chemical) bonds
 secondary (or van der Waals, or physical) bonds
 Mixed bonds

B. PRIMARY BONDS

◎ Three types of primary bonds F 2.7

 ionic
 covalent
 metallic
9
◎ Factors determining the type of bonding:
(1) electronegativity of each atom
◎ Electronegativity, EN(or x) , of an element:
relative tendency of that element to gain, or attract,
an electron (obtained by arbitrarily fixing the value
of H at 2.1)
Electropositive elements /Electronegative elements
(2) electronegativity difference between the atoms
(Δ EN, or Δx )

(3) valence electrons: the electrons that occupy the

outmost filled shell.
→ stable electron configurations:
S+P=8 (or 2 for small atoms, e.g., chemical bonding
10
H)
C-1. Covalent Bonding

◎ Covalent bonds form in compounds composed of

electronegative elements, especially those with four or
more valence electrons.
Since there are no electropositive atoms present, the
“ex-tra” electrons required to fill the valence shell of the
electronegative atoms must be obtained by sharing
electrons.
F 2.10
◎ r0 can be found using a similar equation:
F 12.15
FA(r ) + FR (r ) = 0 = A' / χ p– B' / χ q
◎ Covalent bonds are directional and not flexible.

11
◎ Bonding Forces and Energies

FN = FA + FR (2-2) F 2.8

FN: net force; FA: attractive force; FR: repulsive force

at equilibrium: FA+ FR = 0 (2-3)
r = r0 (≒3Å) (equilibrium spacing ： bond
length)
E =∫Fdr r (W = F · Lr , W = E ) r (2.4)
∞ ∞ ∞
EN = ∫ FN dr = ∫ FA dr +∫ FR dr = EA+ ER (2.5-7)
F = - dE / dr
E0: bonding energy 12
 C-2. Ionic Bonding

◎ This bond involves electron transfer from the

electropositive atom to electronegative atom.
◎ A high Δ EN between the atoms favors the
formation of ionic bonds.
F 2.4-1

◎ The attractive bonding forces are coulombic:

positive and negative ions.
F 2.9

13
14
◎ The bond-force curve and the bond energy curve F 2.4-2
◎ Equilibrium separation distance, r ° , occurs at the
value of r for which

FN(r) = FA ( r ) + FR ( r ) = 0
FA ( r) = |z1 z2| e2 /4Π ε0 r2 FR(r ) = –k/rm
r ° : bond length
(FA(r ) ≡ Fa ( x ), FR(r ) ≡ Fr ( x ), FN(r )≡ Ft ( x ) )

16
◎ Ionization potential, e.g., 5.14 eV for
Na  Na+ +e-
Electron affinity, e.g., 4.02 eV for F 2.4-2

C1 + e-  C1- C1-
Ui = 5.14 – 4.02 = 1.12 eV
E ( r ) = Ui — [|Z1Z2|e2/ (4 0 r)] + (B/ rn )
n = m–1, B = k/n (E(r) = U(r) )
◎ The relationship between E and r and will be referred
to as either the bond-energy curve or the bond-
energy well.
◎ The depth of the energy well (at r0 ) is the strength of
the bond, i.e., bond energy. The equilibrium separation
distance, r0, corresponds to the bond length.
17
C-3. Metallic Bonding (metals)

◎ Solids composed primarily of electropositive elements

containing three or fewer valence electrons are generally
held together by metallic bonds.
◎ The valence electrons form a “cloud” or “sea” of electrons
that surrounds the ion cores. The electrons are shared,
but they are not spatially localized. F 2.11
◎ Metallic bonding may be weak or strong; energies range
from 68 kJ/ mol (0.7 eV/ atom; m.p., –390C ) for mercury to
850 kJ/ mol (.8 eV/ atom; m.p., 34100C ) for tungsten.

18
19
 atmos ： C

atmos ： C bonding ： covalent and van der

bonding ： covalent Waals

coordination ： coordination ： sp2 ， planar ， 2-
sp3 ， tetrahedral ， 3-D D
CN ： 4 CN ： 3
20
21
D. Mixed bonding
• Mixed bonding between primary bonds
• Mixed bonding between primary and secondary bonds

D-1. Mixed bonding between primary bonds

(a bond with characteristics of two different
primary bonds)
(a) Ceramics:

Many ceramics contain primary bonds with mixed

ionic/covalent characteristics.
◎ Classification of the bonds
– qualitative Classification:

◎ A bond is considered predominantly ionic when Δx >

1.7 and predominantly covalent if Δx <1.7 Ceramics 22
- Quantitative classification:
The percent ionic character of a bond between elements A
and B ( A being the most electronegative ) may be
approximated by the expression % ionic character =
( 1-e –(0.25)(XA-XB)2 ) 100
where xA and xB are the electro negativities for the
respective elements.
T 12.1

e.g., SiO2 : Si atom, EN (XB ) = 1.9 ; O atom, EN

(XA )= 3.44,ΔEN(ΔX)= 1.54
the Si-O bond is ~45% ionic and ~55% covalent.

23
(b) Elements in same row of periodic table
In the Group IA metals, moving from left to right in the
periodic table, bonds begin to take on some covalent
characteristics. F 2.7
The increase in covalent characteristic is part of the
reason the density of metals generally decreases as one
moves to the right in the periodic table in a given row.
(c) Intermetallics, e.g., AlLi, Ni3Al, Al3V, AlSb, CuZn, and
Ti3Al, exhibit either mixed metallic/covalent or mixed
metallic/ionic bond characteristics.
They are more brittle, stiffer and lighter than metals
because of possessing ceramic properties.
These materials often have good high-temperature
resistance and a high strength-to weight ratio. (As a
result, Ni3Al and Ti3Al are finding usage in the aerospace
industry) intermetallic
24
D-2. Mixed bonding between primary
and secondary bonds
◎ Another type of “mixed” bonding occurs in
materials having both primary and secondary
bonds.
◎ Many materials properties are determined by
the secondary bonding:
- melting point (sublimation temp, glass
transition temp)
- mechanical strength
- ductility
(Bonds to be broken for melting or softening or
sublimation: secondary bonds.) 36 52
F 2.9-1 F 13.19 F 3.14 54 77
25
E. SECONDARY BONDS
(or van der Waals, or physical bonds)
◎ bonding energies are typically on the order of 10 Kj/mol
( 0.1 ev/ atom).
◎ Secondary bonds are fundamentally different from primary
bonds in that they involve neither electron transfer nor
electron sharing.
Instead, attractive forces are produced when the center of
positive charge is different from the location of the center of
negative charge.
The resulting electric dipole can be either temporary,
induced, or permanent and can occur in atoms or molecules

F 2.27 F 2.13 F 2.14 F 2.12

26
◎ Two major types of secondary bonds
• dipoles (or van der Waals bonding) ← ordinary dipoles
• hydrogen bonding ← strong dipoles
(A) Bonding by dipoles
(a) Temporary dipole
(or van der Waals bonding, <4KJ/mol)
Fluctuating induced (temporary) dipole bonds
·Temporary dipole is responsible for the
condensation of noble gases at low temperatures
·The strength of the van der Waals bond generally
increases as the number of atoms in the
compound increases. This phenomenon explains
why the melting temperatures and also b.p. of
the hydrocarbons with chemical formulas CnH2n+2
increase as n increases. 27
F 2.13
 atmos ： C

atmos ： C bonding ： covalent and van der

bonding ： covalent Waals

coordination ： coordination ： sp2 ， planar ， 2-
sp3 ， tetrahedral ， 3-D D
CN ： 4 CN ： 3
28
29
 (b) Permanent dipoles: formed between polar molecules,
generally stronger than van der Waals bonds.
F 2.13
(c) Polar molecule — induced dipole bonds.
(B) Hydrogen bond (8-40 KJ/mol) F 2.14
·occurs whenever a hydrogen atom can be shared
between two strongly electronegative atoms such as
N, O, F, or C1.
·Hydrogen bonds hold the wood fibers in a sheet of
paper together. F 2.15
◎ Secondary bonds control properties such as melting point
and elastic modulus in solids where primary bonds do not
form a three-dimensional (3-D) network.
30
◎ Classification of Crystals (solids) according to bonding

Properties (e.g., melting point, strength) are

existing determined by primary bonding

3-D network of covalent bonding - Covalent crystals (solids)

F 12.15
Primary ionic bonding - ionic crystals (solids)
F 2.9-2
Bonding metallic bonding - metallic crystals (solids)
F 13.2
F 2.11

non existing Properties are determined by secondary

bonding molecular crystals
F 2.9-1 (solids)
hydrogen bonding–hydrogen bonded crystals
F 13.17 (solids): e.g., water, ice.

F 13.18
van der Waals forces–van der Waals crystals (solids)
e.g., dry ice.
31
VI. Influence of Bonding on Material Properties

Many materials properties are determined by the atomic

scale structure (bonding) alone.

A. Ductility and Brittleness

A-1.Metallic Bonded Materials

◎ Atoms in the metal can slip and slide past one another
with regard to applied force and thus absorb the
impact without breaking. This phenomenon is called
ductile.(A large extent of deformation can occur.) F 2.4-5
32

◎ Examples ： most metals.

 A-2. Ionic Bonded Materials
◎ In an ionic solid, each ion is surrounded by oppositely
charged ions. Ionic slip may lead to like charges moving
adjacent positions, causing Coulombic repulsion.
This makes slipping much more difficult to achieve and
the material responds by breaking. Such behavior is
known as brittle.(Little deformation can occur.)
◎ Examples ： most ceramics.
F 2.4-5

A-3. Covalent Bonded Materials

◎ Covalent bonds are directional bonding, thus are not flexible.
Such materials are therefore brittle. (Little deformation can occur.)
◎ Example ： diamond.
36 33
 B. Electrical Conductivity F 2.11 39 F 2.9

◎ Electrical conductivity of materials depends on ：

(1) the type of charge carrier in the materials ：
electrons or ions (Holes in semiconductors are also
considered as a type of change carriers.)
(2) the spatial density of charge carriers
(3) the charge carrier mobility.
Present consideration: electrons as change carriers
mobility determined by type of bonding
• Very high mobility: free electrons(electrons can move freely)
• Very low mobility: no free electrons(electrons are held tightly
by atoms or between atoms)
◎ Metallic bonded materials (metals) :
The combination of high mobility and high concentration free electrons of
charge carriers ＝＞ high electrical conductivities for most metals. F 2.10
◎ Ionic and covalent bonded materials (e.g., ceramics and polymers) :
36
no free electrons ＝＞ electrical insulators
F 13.17
34
C. Stiffness and Elastic Modulus
◎ The slope of the bond force curve, ( F/ χ ), at χ 。 is a
measure of the force required to displace atoms from their
equilibrium positions. Usually
F   or F  aE (χ≡r ，≡  r) (2.5-1)

Where a is a geometric factor and E is a materials property

known As Young’s modulus. Young’s modulus (stiffness) is a
measure of the resistance of the material to elastic deformation
(or microscopically, relative atomic separation) The steeper the
slope (I.e., the higher the value of E), the greater the force
required to move the atoms from their equilibrium positions.
Materials with large values of E are stiff.
78

＃70 ＃71 ＃72 ＃73 ＃74 F 2.8 F 2.5-1 F 6.7

35
D. Bond Energy and Bond Length
◎The bond-energy curve

Several important macroscopic materials properties directly

from the bond-energy curve, e.g., bond energy, average
bond length, elastic modulus and coefficient of thermal
expansion.

◎ Bond Energy and Bond Length

The depth of the energy well (at r ) is the strength of the bond,
0

i.e., bond energy. The equilibrium separation

F 2.8 distance, r ° ,
corresponds to the bond length. 36
◎ Elastic (young’s) Modulus

As discussed previously
U  F and 2U 2  F  (2.5-2)
U   a (2.5-3)

  F  x
  E F / x  aE
(microscop ic property)
 / E
(interatio mic bonding)
(macroscop ic property)
(bond force curve)

37
 E. Coefficient of thermal expansion, αth
Definition of αth
macroscopic description
Over a limited temperature range, increase of gross material
dimension due to temperature
(L - L0) / L0 = αth(T-T0) Increase.
L0(T0)
L0: length at reference temperature T0
L: length at temperature T
αth: thermal expansion coefficient (i.e, L(T)
coefficient of linear expansion.)
microscopic interpretation
microscopic illustration:
(χ - χ0) / χ0 = αth ( T –T0) increase of equilibrium
interatomic distance
due to temperature increase
χ ： the equilibrium spacing at temperature T ，
χ0 ： the equilibrium spacing at reference temperature T0 ，
αth ： the coefficient of linear expansion.
X(T)

F 2.5-2 38

(T0)
◎ As temperature increases, the atoms gain energy and
are able to “ move up “ the sides of the energy well , i.e.,
the average atomic-separation distance increases as
the temperature increases.
◎ The magnitude of α th increases as the bond-energy curve
becomes more asymmetric. Deeper energy wells tend to be
more symmetric, materials with high bond energies- those
with deep and symmetric wells-- should have low α th
values .

Thermal expansion coefficient Atomic scale structure

αth (interatomic bonding)
L↑ T↑ (bond energy curve)
(macroscopic property) Bond length↑ potential energy↑ T↑
(microscopic property)

39
F 2.5-3 F 2.5-1 F 2.5-2 F 13.17
 Thermal Shock Resistant Materials ：
low thermal expansion coefficient material F 2.5-2

 symmetric energy well ： deep energy well →

strong bonding → high latent heat → high m.p.
(covalent > ionic > metallic)
 low density ： low CN→less No. of bonding
covalent <ionic <metallic F 12.15 F 12.10

strong covalent bonded materials

T 2.5-1 T 4.3 T 4.3-1 F 4.4

Thermal shock : uneven thermal expansion

very quick change (or contraction) within the cracking
of themperature material
strong
Thermal shock A material, low thermal
which does not expansion covalent
resistant material
crack under a coefficient bonded
thermal shock material materials 40
F. Others

Latent heat of fusion(△Hf)

Melting temperature (mp) Bonding Energy

Coefficient of thermal expansion

△Hf↑ higher bond energy mp↑ deeper energy well α th↓

(stronger bonding) &
steeper bond
energy curve

T 2.3 T 2.5-1 41
◎ The relationships between the bond-energy curve and
macroscopic properties developed in this section show
general trends. The constants in the corresponding
equations are not known with sufficient accuracy to
facilitate calculation of the absolute values of bond
length , bond energy, modulus of elasticity, and
coefficient of thermal expansion. The values of these
properties for engineering materials are usually directly
measured in the laboratory.

42
 atmos ： C

atmos ： C bonding ： covalent and van der

bonding ： covalent Waals

coordination ： coordination ： sp2 ， planar ， 2-
sp3 ， tetrahedral ， 3-D D
CN ： 4 CN ： 3
43
metallic bonding covalent bonding
mixed bonding
(high density) (low density)
increasing covalent characteristics
decreasing density

44
 neutral atoms

Microscopic illustration:
variation of
interatomic
separation

(covalent or metallic bonding)

macrosscopic description:
Elastic deformation:elongation
Bond Force Curve
Energy of independent(isolated)atoms
Is defined as zero.

ro: equilibrium distance

(≡bond length)

Eo: minimum energy

Energy well
(≡bond energy)

45
Bond Energy Curve
46
47
Na+, Cl-
Na, Cl

48
49
50
51
77
B. ELASTIC DEFORMATION ( 彈性變形 ) ＃ 27

B-1. Stress-Strain Behavior

(A) Tension
◎ For most metals at relatively low levels, stress and strain
are proportional to each other
  E (6.5) F 6.11

Hooke’s law;
the constant of proportionality E (GPa or psi):
Modulus of elasticity or Young’s modulus.
For most typical metals, E=45 GPa (6.5 x 106 psi) for Mg to 407
MPa (59 x 106 psi) for W.
T 6.1
78
 ＃ 27

◎ Engineering stress 
F
  (6.1)
A0
F ： the instantaneous load applied newtons (N) or pounds
force (lbf) ；
A0 ： original cross-sectional area (m2 or in.2) ； ：
engineering stress, MPa (SI) (where 1 MPa = 106
N/m2),
and pounds force per square inch, psi
(Customary U.S.).2
79
 ＃ 27

◎ Engineering strain 
li  l0 l
  (6.2)
l0 l0
l0 ： the original length ；
li ： the instantaneous length ；
Δl ＝ li - l0
Engineering strain, ： unitless (meters per meter
or inches per inch ; or a percentage)

80
＃ 27

81
 ＃ 27

( 𝜎)

Slope: stiffness

E:Young’s modulus

(𝜖 )
82
 metallic Metallic +
ionic or covalent
ionic or covalent
intermetallic
(compounds):
metals: Al, Ti, AlLi, Ni3Al, ceramics: Al2O3,
Li, Ni, Zn… Al3V, Ti3Al, ZrO2, SiO2, …
CuZn, …

ductile ductility ↓ brittle

electrically conductive electrical conductivity ↓ electrically insulation

low mechanical strength mechanical strength ↑ high mechanical strength

(low stiffness) density ↓ high stiffness
high density temp. resistance ↑ low density
low m.p.
high m.p.
strength to weight ratio ↑
(light, tough, hightemp 83
★
materials)
 water ice

O=C=O

O=C=O

O=C=O

dry ice
(m.p. =~ 1500℃)
(sublim Temp
<<0℃)
Bond Force Curve
(𝜎)

Slope: stiffness

E:Young’s modulus

(𝜖 )
corresponding
slope slope