Classes of materials

POLYMERS DUCTILITY CONDUCTIVITY (ELECTRICAL & THERMAL) HARDNESS/STRENGTH CORROSION RESISTANCE STIFFNESS FRACTURE TOUGHNESS MACHINABILITY
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CERAMICS Poor Low Very high Good High Low Poor

METALS Good High Medium high Fair poor Fair High Good
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Varies Low Low medium Fair good Low Low medium Good
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Why study bonding?

Because the properties of materials (strength, hardness, conductivity, etc..) are determined by the manner in which atoms are connected. Also by how the atoms are arranged in space Crystal Structure .

What determines the nature of the chemical bond between atoms? Electronic structure (distribution of electrons in atomic orbitals) electronegativity (tendency for an Number of electrons and atom to attract an electron)
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BOHR ATOM
orbital electrons: n = principal quantum number 2 1 n=3

Adapted from Fig. 2.1,

Callister 6e.

Nucleus: Z = # protons = 1 for hydrogen to 94 for plutonium N = # neutrons Atomic mass A Z + N

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ELECTRON ENERGY STATES

Electrons... have discrete energy states
tend to occupy lowest available energy state.

Increasing energy

n=4 n=3 n=2 n=1

4s 3s 2s 1s

s, p,d and f signify the subshells which the 4p 3d electrons occupy.

3p 2p

Different types of subshells have different numbers of energy states Within each energy state there are two possible spin orientations

Remember that n is the principal quantum number

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Stable electron configurations... have complete s and p subshells are unreactive.

Element Configuration He 1s2 Adapted from Table 2.2, Callister 6e. 10 Ne 1s22s 22p6 18 Ar 1s2 2s22p63s23p6 36 Kr 1s2 2s22p63s23p63d10 4s24p6 Z 2

Valence electrons are the electrons that occupy the outermost filled shell.

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SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element Atomic # Hydrogen 1 Helium 2 Lithium 3 Beryllium 4 Boron 5 Carbon 6 ... Neon 10 Sodium 11 Magnesium 12 Aluminum 13 ... Argon 18 ... ... Krypton 36
Electron configuration 1s 1 (stable) 1s 2 1s 22s 1 1s 22s 2 Adapted from Table 2.2, 1s 22s 22p 1 Callister 6e. 1s 22s 22p 2 ... 1s 22s 22p 6 (stable) 1s 22s 22p 63s 1 1s 22s 22p 63s 2 1s 22s 22p 63s 23p 1 ... 1s 22s 22p 63s 23p 6 (stable) ... 1s 22s 22p 63s 23p 63d 10 4s 24 6 (stable)

Why? Valence (outer) shell usually not filled completely.

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Increasing Electronegativity

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give up 1e give up 2e give up 3e

Columns: Similar Valence Structure

Metal Nonmetal Intermediate

Li Be

Na Mg

K Ca Sc Rb Sr Cs Ba Fr Ra Y

Electropositive elements: Readily give up electrons to become + ions. MECH 221 PM Wood-Adams

Electronegative elements: Readily acquire electrons to become - ions.

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accept 2e accept 1e inert gases

He O S F Ne Cl Ar Se Br Kr Te I Xe Po At Rn

THE PERIODIC TABLE

ELECTRONEGATIVITY
Ranges from 0.7 to 4.0, Large values: tendency to acquire electrons.

Smaller electronegativity

Larger electronegativity

IONIC BONDING
Occurs between + and - ions. Requires electron transfer. Large difference in electronegativity required. Example: NaCl
Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable

Coulombic Attraction
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Cl (anion) stable

Stable because the s and p subshells are filled!

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EXAMPLES: IONIC BONDING

Predominant bonding in Ceramics

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7

Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9 Ti 1.5 Cr 1.6

NaCl MgO CaF2 CsCl

Fe 1.8 Ni 1.8 Zn 1.8 As 2.0

O F 3.5 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2

He Ne Ar Kr Xe Rn -

Give up electrons

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Acquire electrons

COVALENT BONDING
Requires shared electrons Example: CH4
C: has 4 valence e, needs 4 more H: has 1 valence e, needs 1 more

CH4
H

shared electrons from carbon atom H shared electrons from hydrogen atoms

Electronegativities are comparable.

Adapted from Fig. 2.10, Callister 6e.

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EXAMPLES: COVALENT BONDING

H2
H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9

column IVA

H2O

C(diamond) SiC
Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8 Ga 1.6

F2
He O 2.0 F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 Ne Ar Kr Xe Rn -

C 2.5 Si 1.8 Ge 1.8 Sn 1.8 Pb 1.8

Cl2

As 2.0

Molecules of nonmetals Molecules of metals and nonmetals Elemental solids (RHS of Periodic Table) Compound solids (about column IVA) It is possible for bonds to be partially covalent and partially ionic in nature. Look in Chapter 2 to see how to evaluate this aspect of bonds

GaAs

METALLIC BONDING
Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).

+ + +

+ + +

+ + +
Adapted from Fig. 2.11, Callister 6e.

Primary bond for metals and their alloys

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SECONDARY BONDING
Arises from interaction between dipoles Fluctuating dipoles ex: liquid H2 asymmetric electron H2 H2 clouds

- secondary +
bonding

H H

Adapted from Fig. 2.13, Callister 6e.

secondary bonding

H H

Permanent dipoles-molecule induced

-general case: -ex: liquid HCl -ex: polymer

secondary bonding secondary bonding

ondin

H Cl
secon d a ry b

H Cl

SUMMARY: BONDING
Type
Ionic Covalent

Bond Energy
Large!

Comments
Nondirectional (ceramics)

Directional Variable large-Diamond semiconductors, ceramics small-Bismuth polymer chains) Variable large-Tungsten small-Mercury smallest Nondirectional (metals) Directional inter-chain (polymer) inter-molecular
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Metallic Secondary

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Bonding Forces and Energies

Bond length, r
F

r
Net force is given by the sum of an attractive force and a repulsive force
repulsive, attractive, and net forces

Potential is given by the integral of the net force curve with respect to distance:

E = F dr

Note: equilibrium separation occurs where the net force = 0 and the energy is at a minimum.
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Bonding Forces and Energies

Bonding energy: Minimum of the potential vs. distance curve. Indicates how much energy must be supplied to completely disassociate the two atoms Depth of the potential well indicates bonding strength strongly bonded Deep well weakly bonded Shallow well

Energy (r)
unstretched length ro

Eo= bond energy

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PROPERTIES FROM BONDING: TM

Bond length, r
F

Melting Temperature, Tm
F

Energy (r) ro r smaller Tm

r

r Bond energy, Eo
Energy (r)
unstretched length ro

larger Tm Tm is larger if Eo is larger.

Eo= bond energy

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Example: Bonding energy and TM

Use the data below to estimate the bonding energy of copper which has a melting temperature of 1084C. E0, eV/atom TM, C

Hg Al Fe W
tungsten
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0.7 3.4 4.2 8.8

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-39 660 1538 3410

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Solution: Plot the data

4000
Melting Temperature (C)

3500 3000 2500 2000 1500 1000 500 0 -500 0 2 4 6 8 10

Bonding Energy (eV/atom)

E0=3.6 eV/atom

With this analysis we estimate E0 of copper = 3.6 eV/atom. The measured value is 3.5 eV/atom.

 Elastic modulus, E
length, Lo

PROPERTIES FROM BONDING: E

cross sectional area Ao

Elastic modulus
F L =E Ao Lo

undeformed deformed

E ~ curvature at ro Energy
unstretched length ro

E is larger if Eo is larger.

smaller Elastic Modulus larger Elastic Modulus

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 Coefficient of thermal expansion,

length, Lo

PROPERTIES FROM BONDING:

coeff. thermal expansion
L
unheated, T1

heated, T2

L Lo

= (T2-T1)

~ symmetry at ro Energy ro larger smaller

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is larger if Eo is smaller.

Bonding Types: Summary

A comparison of the type of bonding found in different materials: metallic For brass, the bonding is .. since it is a metal alloy. Van der covalent For rubber, the bonding is with some . Waals Rubber is composed primarily of carbon and hydrogen atoms
secon d a ry b ondin g

For BaS, the bonding is predominantly ionic (but with some covalent character) .. on the basis of the relative positions of Ba and S in the periodic table. For solid xenon, the bonding is Van der Waals since xenon is an inert gas. . Van der For nylon, the bonding is covalent with perhaps some .. Waals .. Nylon is composed primarily of carbon and hydrogen For AlP the bonding is predominantly covalent (but with some ionic character) on the basis of the relative positions of Al and P in the periodic table.
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SUMMARY: PRIMARY BONDS

Ceramics
(Ionic & covalent bonding):

Large bond energy

large Tm large E small

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate

Polymers
(Covalent & Secondary):
secon d a ry b ondin g

Directional Properties
Secondary bonding dominates small T small E large

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