(1) Atomic Structure and Interatomic Bonding

orbital electrons: n = principal quantum number 2 1 n=3

BOHR ATOM
Adapted from Fig. 2.1, Callister 6e.

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

2

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

4p 4s 3s 2s 1s 3p 2p

3d

Adapted from Fig. 2.5, Callister 6e.

STABLE ELECTRON CONFIGURATIONS

Stable electron configurations...
have complete s and p subshells tend to be unreactive. Z 2 10 18 36 Element Configuration He 1s2 Ne Ar Kr

Adapted from Table 2.2, Callister 6e.

1s22s 22p6 1s2 2s22p63s23p6 1s2 2s22p63s23p63d10 4s24p6

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 ... 18 Argon ... ... 36 Krypton
Electron configuration 1s1 1s2 (stable) 1s22s1 1s22s2 Adapted from Table 2.2, 1s22s22p1 Callister 6e. 1s22s22p2 ... 1s22s22p6 (stable) 1s22s22p63s1 1s22s22p63s2 1s22s22p63s23p1 ... 1s22s22p63s23p6 (stable) ... 1s22s22p63s23p63d104s246 (stable)

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

5

THE PERIODIC TABLE

give up 1e give up 2e give up 3e accept 2e accept 1e inert gases
He O S F Ne
Adapted from Fig. 2.6, Callister 6e.

Columns: Similar Valence Structure

Metal Nonmetal Intermediate

Li Be

Na Mg

Cl Ar

K Ca Sc Rb Sr Cs Ba Fr Ra Y

Se Br Kr Te I Xe

Po At Rn

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

Electronegative elements: Readily acquire electrons to become - ions.

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METALS

CERAMICS

POLYMERS

SEMICONDUCTOR

ELECTRONEGATIVITY
Ranges from 0.7 to 4.0, Large values: tendency to acquire electrons.
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 Fe 1.8 Ni 1.8 Zn 1.8 As 2.0 F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 He Ne Ar Kr Xe Rn -

Smaller electronegativity

Larger electronegativity
7

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.

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

EXAMPLES: IONIC BONDING

Predominant bonding in Ceramics NaCl MgO CaF2 CsCl
Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8 As 2.0

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

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

Acquire electrons
9

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.

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

CH4
H C

shared electrons from carbon atom

H shared electrons from hydrogen atoms

Adapted from Fig. 2.10, Callister 6e.

10

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 Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8 Ga 1.6

column IVA

H2O C(diamond) SiC

F2
He O 2.0 F 4.0 Cl 3.0 As 2.0 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

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.

GaAs

Molecules with nonmetals Molecules with metals and nonmetals Elemental solids Compound solids (about column IVA)

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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

12

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

SECONDARY BONDING

- 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

Adapted from Fig. 2.14, Callister 6e.

H Cl

H Cl

Adapted from Fig. 2.14, Callister 6e.

secon dary b ond ing

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SUMMARY: BONDING
Type
Ionic

Bond Energy
Large! Variable large-Diamond small-Bismuth Variable large-Tungsten small-Mercury smallest

Comments
Nondirectional (ceramics) Directional semiconductors, ceramics polymer chains)

Covalent

Metallic

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

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Secondary

PROPERTIES FROM BONDING: TM

Bond length, r
F

Melting Temperature, Tm
F

Energy (r)

r Bond energy, Eo Energy (r)

unstretched length ro

ro r smaller Tm r larger Tm Tm is larger if Eo is larger.

Eo= bond energy

15

PROPERTIES FROM BONDING: E

Elastic modulus, E
length, Lo cross sectional area Ao

Elastic modulus
F (L =E Ao Lo

undeformed
(L

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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PROPERTIES FROM BONDING: E

Coefficient of thermal expansion, E
length, Lo

coeff. thermal expansion (L (L = E(T2-T1) Lo

unheated, T1

heated, T2

E ~ symmetry at ro Energy ro larger E smaller E

17

E is larger if Eo is smaller.

SUMMARY: PRIMARY BONDS

Ceramics
(Ionic & covalent bonding):

Large bond energy

large Tm large E small E

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate E

Polymers
(Covalent & Secondary):
secon dary b ond ing

Directional Properties
Secondary bonding dominates small T small E large E

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 Non dense, random packing

ENERGY AND PACKING Energy

typical neighbor bond length typical neighbor bond energy r

Dense, regular packing

Energy typical neighbor bond length

typical neighbor bond energy

Dense, regular-packed structures tend to have lower energy.

2

MATERIALS AND PACKING

Crystalline materials... atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers

crystalline SiO2
Adapted from Fig. 3.18(a), Callister 6e.

Noncrystalline materials... atoms have no periodic packing occurs for: -complex structures -rapid cooling "Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.18(b), Callister 6e. 3

METALLIC CRYSTALS
tend to be densely packed. have several 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.

have the simplest crystal structures. We will look at three such structures...

SIMPLE CUBIC STRUCTURE (SC)

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

(Courtesy P.M. Anderson) 5

ATOMIC PACKING FACTOR

APF = Volume of atoms in unit cell* 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. 3.19, Callister 6e.

APF =

volume atom 4 T(0.5a)3 1 3 a3 volume unit cell

6

BODY CENTERED CUBIC STRUCTURE (BCC)

Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

Coordination # = 8

Adapted from Fig. 3.2, Callister 6e. (Courtesy P.M. Anderson) 7

ATOMIC PACKING FACTOR: BCC

APF for a body-centered cubic structure = 0.68 Close-packed directions: length = 4R = 3a Unit cell contains: 1 + 8 x 1/8 = 2 atoms/unit cell a

R
Adapted from Fig. 3.2, Callister 6e.

atoms volume 4 3 T( 3a/4) 2 unit cell atom 3 APF = volume 3 a unit cell
8

FACE CENTERED CUBIC STRUCTURE (FCC)

Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

Coordination # = 12

Adapted from Fig. 3.1(a), Callister 6e. (Courtesy P.M. Anderson) 9

ATOMIC PACKING FACTOR: FCC

APF for a body-centered cubic structure = 0.74 Close-packed directions: length = 4R = 2a Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell a
Adapted from Fig. 3.1(a), Callister 6e.

atoms volume 4 T( 2a/4)3 4 unit cell atom 3 APF = volume a3 unit cell
10

FCC STACKING SEQUENCE

ABCABC... Stacking Sequence 2D Projection A B B C A B B B A sites C C B sites B B C sites A B C

FCC Unit Cell

11

HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)

ABAB... Stacking Sequence 3D Projection A sites B sites A sites
Adapted from Fig. 3.3, Callister 6e.

2D Projection Top layer Middle layer Bottom layer

Coordination # = 12 APF = 0.74

12

STRUCTURE OF COMPOUNDS: NaCl

Compounds: Often have similar close-packed structures. Structure of NaCl Close-packed directions
--along cube edges.

(Courtesy P.M. Anderson)

(Courtesy P.M. Anderson) 13

THEORETICAL DENSITY, V
# atoms/unit cell Atomic weight (g/mol)

V! nA VcNA Volume/unit cell

(cm3/unit cell)

Avogadro's number (6.023 x 10 23 atoms/mol)

Example: Copper

Data from Table inside front cover of Callister (see next slide): crystal structure = FCC: 4 atoms/unit cell atomic weight = 63.55 g/mol (1 amu = 1 g/mol) atomic radius R = 0.128 nm (1 nm = 10 -7cm) Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Result: theoretical VCu = 8.89 g/cm3 Compare to actual: VCu = 8.94 g/cm3
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Characteristics of Selected Elements at 20C

At. Weight Element Symbol (amu) Aluminum Al 26.98 Argon Ar 39.95 Barium Ba 137.33 Beryllium Be 9.012 Boron B 10.81 Bromine Br 79.90 Cadmium Cd 112.41 Calcium Ca 40.08 Carbon C 12.011 Cesium Cs 132.91 Chlorine Cl 35.45 Chromium Cr 52.00 Cobalt Co 58.93 Copper Cu 63.55 Flourine F 19.00 Gallium Ga 69.72 Germanium Ge 72.59 Gold Au 196.97 Helium He 4.003 Hydrogen H 1.008 Density (g/cm3) 2.71 -----3.5 1.85 2.34 -----8.65 1.55 2.25 1.87 -----7.19 8.9 8.94 -----5.90 5.32 19.32 ----------Crystal Structure FCC -----BCC HCP Rhomb -----HCP FCC Hex BCC -----BCC HCP FCC -----Ortho. Dia. cubic FCC ----------Atomic radius (nm) 0.143 -----0.217 0.114 Adapted from -----Table, "Charac-----teristics of 0.149 Selected 0.197 Elements", inside front 0.071 cover, 0.265 Callister 6e. -----0.125 0.125 0.128 -----0.122 0.122 0.144 ----------15

DENSITIES OF MATERIAL CLASSES

Vmetals Vceramics Vpolymers Why?
Metals have...
close-packing (metallic bonding) large atomic mass
30 20
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Metals/ Alloys

Graphite/ Ceramics/ Polymers Semicond

Composites/ fibers

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

Ceramics have...

V (g/cm3)

less dense packing (covalent bonding) often lighter elements

5 4 3 2

PTFE Silicone PVC PET PC HDPE, PS PP, LDPE

Polymers have...
poor packing (often amorphous) lighter elements (C,H,O)
1

Glass fibers GFRE* Carbon fibers CFRE* Aramid fibers AFRE*

Composites have...
intermediate values

0.5 0.4 0.3

Wood Data from Table B1, Callister 6e. 16

CRYSTALS AS BUILDING BLOCKS

Some engineering applications require single crystals:
--diamond single crystals for abrasives
(Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission.)

--turbine blades
Fig. 8.30(c), Callister 6e. (Fig. 8.30(c) courtesy of Pratt and Whitney).

Crystal properties reveal features of atomic structure.

--Ex: Certain crystal planes in quartz fracture more easily than others.
(Courtesy P.M. Anderson)

17

POLYCRYSTALS
Most engineering materials are polycrystals.
Adapted from Fig. K, color inset pages of Callister 6e. (Fig. K is courtesy of Paul E. Danielson, Teledyne Wah Chang Albany)

1 mm

Nb-Hf-W plate with an electron beam weld. Each "grain" is a single crystal. If crystals are randomly oriented,
overall component properties are not directional.

Crystal sizes typ. range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).
18

SINGLE VS POLYCRYSTALS
Single Crystals
-Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron:
E (diagonal) = 273 GPa
Data from Table 3.3, Callister 6e. (Source of data is R.W. Hertzberg, Deformation and Fracture Mechanics of Engineering Materials, 3rd ed., John Wiley and Sons, 1989.)

Polycrystals
-Properties may/may not vary with direction. -If grains are randomly oriented: isotropic.
(Epoly iron = 210 GPa)

E (edge) = 125 GPa

200 Qm

-If grains are textured, anisotropic.

Adapted from Fig. 4.12(b), Callister 6e. (Fig. 4.12(b) is courtesy of L.C. Smith and C. Brady, the National Bureau of Standards, Washington, DC [now the National Institute of Standards and Technology, Gaithersburg, MD].)

19

X-RAYS TO CONFIRM CRYSTAL STRUCTURE

Incoming X-rays diffract from crystal planes.
1
de te c
ys -ra X

to r

extra distance travelled by wave 2

Measurement of:
Critical angles, Uc, for X-rays provide atomic spacing, d.

1 g in 2 m co ys in -ra X

g in o tg ou U

reflections must be in phase to detect signal

Adapted from Fig. 3.2W, Callister 6e.

spacing d between planes

x-ray intensity (from detector)

d=nP/2sinUc

U Uc
20

SCANNING TUNNELING MICROSCOPY

Atoms can be arranged and imaged!
Photos produced from the work of C.P. Lutz, Zeppenfeld, and D.M. Eigler. Reprinted with permission from International Business Machines Corporation, copyright 1995.

Carbon monoxide molecules arranged on a platinum (111) surface.

Iron atoms arranged on a copper (111) surface. These Kanji characters represent the word atom.
21

DEMO: HEATING AND COOLING OF AN IRON WIRE

Demonstrates "polymorphism"
Temperature, C 1536 1391
longer heat up
FCC Stable Liquid BCC Stable

The same atoms can have more than one crystal structure.

914
Tc 768

BCC Stable

cool down

shorter! longer! magnet falls off shorter

22

SUMMARY
Atoms may assemble into crystalline or amorphous structures. We can predict the density of a material, provided we know the atomic weight, atomic radius, and crystal geometry (e.g., FCC, BCC, HCP). Material properties generally vary with single crystal orientation (i.e., they are anisotropic), but properties are generally non-directional (i.e., they are isotropic) in polycrystals with randomly oriented grains.
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