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Tailored(Designed)MaterialAge
Todaysclass:
Atomicbondings Crystalstructures
Compositions Properties Atomic arrangements

Tailormaterialsfromatomicscaleupwardsto obtaindesiredproperties.
Chapter 2 - 11 Chapter 2 12

Composition DifferencesinAtomicStructures
Atomic Structure (Freshman Chem.)
atom electrons 9.11 x 10-31 kg protons 1.67 x 10-27 kg neutrons

ElectronicStructure
Electronshavewavelikeandparticulateproperties.
Thismeansthatelectronsareinorbitals definedbya probability. Eachorbitalatdiscreteenergyleveldeterminedby quantumnumbers. Quantum# n =principal(energylevelshell) l=subsidiary(orbital) #oforbitalseachsubshell ms =spin Designation K,L,M,N,O (1,2,3,etc.) s,p,d,f (0,1,2,3,,n 1) 1,3,5,7(lto+l) ,
14

atomic number = # of protons in nucleus of atom = # of electrons of ne neutral tral species A [=] atomic mass unit = amu = 1/12 mass of 12C Atomic wt = wt of 6.023 x 1023 molecules or atoms 1 amu/atom = 1g/mol C H 12.011 1.008 etc.
13

ElectronEnergyStates
Electrons...
have discrete energy states tend to occupy lowest available energy state.
4d 4p 3d 4s Energy 3p 3s 2p 2s 1s M-shell n = 3 Energy N-shell n = 4

ElectronicConfigurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2
4d 4p 3d 4s 3p 3s 2p 2s 1s M-shell n = 3

N-shell n = 4 valence electrons

L-shell n = 2 K-shell n = 1
16

L-shell n = 2 K-shell n = 1
15

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ElectronConfigurations
Valenceelectrons thoseinunfilledshells Filledshellsmorestable Valenceelectronsaremostavailablefor bondingandtendtocontrolthechemical properties
example: C (atomic number = 6) 1s2 2s2 2p2
valence electrons

Electronic configuration Valenceelectronsdetermineallofthe followingproperties

1) 2) 3) 4) Chemical Electrical Thermal Optical

Mostdifferentpropertiesresultfromdistinct electronicstructuresofmaterials.
18 17 Chapter 2 -

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element Hydrogen Helium Lithium Beryllium Boron Carbon ... Neon Sodium Magnesium Aluminum ... Argon ... Krypton Atomic # 1 2 3 4 5 6 10 11 12 13 18 ... 36
Electron configuration 1s 1 1s 2 (stable) 1s 2 2s 1 2 2 1s 2s 1s 2 2s 2 2p 1 1s 2 2s 2 2p 2 ... 1s 2 2s 2 2p 6 1s 2 2s 2 2p 6 3s 1 1s 2 2s 2 2p 6 3s 2 1s 2 2s 2 2p 6 3s 2 3p 1 ... (stable) ... 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable) 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)

ThePeriodicTable
Columns: Similar Valence Structure give up 1e give up 2e giv ve up 3e accept 2e accept 1e inert gases
He O S F Ne Cl Ar
Adapted from Fig. 2.6, Callister 7e.

Li Be

Na Mg

K Ca Sc Rb Sr Cs Ba Fr Ra Y

Se Br Kr Te I Xe

Po At Rn

Valence (outer) shell usually not filled completely.

19

Electropositive elements: Readily give up electrons to become + ions.

Electronegative elements: Readily acquire electrons to become - ions.

20

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

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

Cl (anion) stable

Smaller electronegativity

Larger electronegativity
21 Chapter 2 - 22

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Ionic bond metal

donates electrons

nonmetal
accepts electrons

Examples: Ionic Bonding

Predominant bonding in Ceramics NaCl MgO CaF 2 CsCl

Dissimilar electronegativities
ex: MgO Mg 1s2 2s2 2p6 3s2 [Ne] 3s2 O 1s2 2s2 2p4

Mg2+ 1s2 2s2 2p6 [Ne]

O2- 1s2 2s2 2p6 [Ne]

Chapter 2 - 23

Give up electrons

Acquire electrons
Chapter 2 - 24

Adapted from Fig. 2.7, Callister 7e. (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.

Covalent Bonding
similar electronegativity share electrons bonds determined by valence s & p orbitals dominate bonding. Bond is directional. shared electrons H Example: CH4 from carbon atom CH 4
C: has 4 valence e-, needs 4 more H: has 1 valence needs 1 more e-,
H H C H shared electrons from hydrogen atoms

Examples: Covalent Bonding

H2O C (diamond) SiC F2

GaAs Molecules with non-metals Molecules with metals and nonmetals Elemental solids (RHS of Periodic Table) Compound solids

Electronegativities are comparable.

Adapted from Fig. 2.10, Callister 7e.

Chapter 2 - 25

Chapter 2 -

SECONDARY BONDING
Arises from interaction between dipoles Fluctuating dipoles
asymmetric electron clouds

Summary: Bonding
Type Bond Energy
Large! Variable large-Diamond ll Bi th small-Bismuth Variable large-Tungsten small-Mercury smallest

Comments
Nondirectional (ceramics) Directional (semiconductors, ceramics l chains) h i ) polymer

ex: liquid H 2 H2 H2 H H
secondary bonding

Ionic Covalent

secondary bonding

H H

Adapted from Fig Fig. 2 2.13, 13 Callister 7e 7e.

Permanent dipoles-molecule induced

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

secondary bonding secondary bonding

Adapted from Fig. 2.14, Callister 7e.

Metallic

Nondirectional (metals) Directional inter-chain (polymer) inter-molecular

Chapter 2 - 28

H Cl

H Cl Secondary
secondary bonding
Chapter 2 - 27

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Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Large bond energy

large Tm large E small

Atomicarrangements:electronicstructuresof materialsaredeterminedbyinteractionsoftheirvalence electronswiththeirnucleiandcoreelectrons. Crystalstructures: atomsarrangedinregular,repeating manner,andthereisalongrangeorder.

Allcrystalshavediscretetranslational symmetry:Ifdisplaced byaproperlyselectedlatticevector,everyatommovestothe positionofanidenticalatominthecrystal. Acrystalcanbeconstructedbyrepeatingthebasisatevery Bravais latticepoint. Thebasisisthe``buildingblock"ofthecrystal,itmaycomprise of1ormoreatoms.
30

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate

Polymers
(Covalent & Secondary):

Directional Properties
Secondary bonding dominates small Tm small E large

Chapter 2 - 29

Crystal Systems
Unit cell: smallest repetitive volume which contains the complete lattice pattern of a crystal.
7 crystal systems
7 crystal systems

14 crystal lattices (b (bravais i lattices)

14 crystal lattices

a, b, and c are the lattice constants

32

Chapter 3 - 31

Metallic Crystal Structures

Tend to be densely packed. Reasons for dense packing:
- Typically, only one element is present, so all atomic radii are the same. - Metallic bonding is not directional. - Nearest neighbor distances tend to be small in order to lower bond energy. - Electron cloud shields cores from each other

Simple Cubic Structure (SC)

Rare due to low packing denisty (only Po has this structure) Close-packed directions are cube edges.
Coordination # = 6 (# nearest neighbors)

Have the simplest crystal structures. We will examine three such structures...

(Courtesy P.M. Anderson) Chapter 3 - 33 Chapter 3 - 34

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Atomic Packing Factor (APF)

Volume of atoms in unit cell* APF = Volume of unit cell *assume hard spheres APF for a simple cubic structure = 0.52 atoms unit cell R=0.5a
close-packed directions contains 8 x 1/8 = 1 atom/unit cell
Adapted from Fig. 3.23, Callister 7e.

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12 volume ol me atom (0.5a) 3 volume unit cell

Chapter 3 - 35 (Courtesy P.M. Anderson)

4 3

APF =

a3

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Chapter 3 - 36

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74 maximum achievable APF Close-packed directions: length = 4R = 2 a 2a Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms volume 4 ( 2a/4) 3 4 unit cell atom 3 APF = volume a3 unit cell
Chapter 3 - 37

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

Coordination # = 8

a
Adapted from Fig. 3.1(a), Callister 7e.

Adapted from Fig. 3.2, Callister 7e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

(Courtesy P.M. Anderson) Chapter 3 - 38

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

Theoretical Density,
Density = =
Mass of Atoms in Unit Cell Total Volume of Unit Cell

a =
2a

nA VC NA

Adapted from Fig. 3.2(a), Callister 7e.

Close-packed directions: length = 4R = 3 a

where

atoms volume 4 ( 3 a/4) 3 2 unit cell atom 3 APF = volume a3 unit cell

n = number of atoms/unit cell A = atomic weight VC = Volume of unit cell = a3 for cubic NA = Avogadros number = 6.023 x 1023 atoms/mol
Chapter 3 - 40

Chapter 3 - 39

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Densities of Material Classes

In general metals > ceramics > polymers 30 Why?
Metals have...
close-packing (metallic bonding) often large atomic masses
Metals/ Alloys
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Crystallographic Directions
Composites/ fibers

Graphite/ Ceramics/ Semicond

Polymers

Algorithm
1. Vector repositioned (if necessary) to pass through origin. 2. Read off projections in terms of unit cell dimensions a, b, and c 3. Adjust to smallest integer values 4. Enclose in square brackets, no commas

20

10

Based on data in Table B1, Callister *GFRE, CFRE, & AFRE are Glass, Carbon, & Aramid Fiber-Reinforced Epoxy composites (values based on 60% volume fraction of aligned fibers in an epoxy matrix).

y
Zirconia Al oxide Diamond Si nitride Glass -soda Concrete Silicon Graphite

(g/cm3 )

C Ceramics i have... h
less dense packing often lighter elements

5 4 3 2

x
PTFE Silicone PVC PET PC HDPE, PS PP, LDPE Glass fibers GFRE* Carbon fibers CFRE* Aramid fibers AFRE*

[uvw]

Polymers have...

low packing density (often amorphous) lighter elements (C,H,O)

ex: 1, 0, => 2, 0, 1 => [ 201 ] -1, 1, 1 => [ 111 ] where overbar represents a negative index

Composites have...
intermediate values

0.5 0.4 0.3

Data from Table B1, Callister 7e.

Wood

families of directions <uvw>

Chapter 3 - 42 Chapter 3 - 43

Crystallographic Planes

Crystallographic Planes
Miller Indices: Reciprocals of the (three) axial intercepts for a plane, cleared of fractions & common multiples. All parallel planes have same Miller indices. Algorithm
1. Read off intercepts of plane with axes in terms of a, b, c 2. Take reciprocals of intercepts 3. Reduce to smallest integer values 4. Enclose in parentheses, no commas i.e., (hkl)

Adapted from Fig. 3.9, Callister 7e. Chapter 3 - 44 Chapter 3 - 45

Crystallographic Planes
z
example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices a 1 1/1 1 1 (110) a 1/2 1/ 2 1 (100) b 1/ 0 0 c 1/ 0 0 b 1 1/1 1 1 c 1/ 0 0

Crystallographic Planes
z example 1. Intercepts 2. Reciprocals 3 3. 4. Reduction Miller Indices a 1/2 1/ 2 6 (634) b 1 1/1 1 3 c c 3/4 1/ 4/3 4 a x

c y a x c y a x
Chapter 3 - 46

b z

example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices

Family of Planes {hkl} Ex: {100} = (100), (010), (001), (100), (010), (001)
Chapter 3 - 47