Transcript (1) Atomic Structure and Interatomic Bonding BOHR ATOM orbital electrons: n = principal quantum number2 n=3 Adapted from Fig.

(1)
Atomic Structure and
Interatomic Bonding
BOHR ATOM
orbital electrons:
n = principal
quantum number
1
2
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
2
ELECTRON ENERGY STATES
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.
Adapted from Fig. 2.5,
Callister 6e.
3
STABLE ELECTRON CONFIGURATIONS
Stable electron configurations...
• have complete s and p subshells
• tend to be unreactive.
Adapted from Table 2.2,
Callister 6e.
4
SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Electron configuration
1s1
1s2
(stable)
1s22s1
1s22s2
Adapted from Table 2.2,
1s22s22p 1
Callister 6e.
1s22s22p 2
...
1s22s22p 6
(stable)
1s22s22p 63s1
1s22s22p 63s2
1s22s22p 63s23p 1
...
1s22s22p 63s23p 6
(stable)
...
1s22s22p 63s23p 63d 10 4s246
(stable)
• Why? Valence (outer) shell usually not filled completely.
5
THE PERIODIC TABLE
• Columns: Similar Valence Structure
Adapted
from Fig. 2.6,
Callister 6e.
Electropositive elements:
Readily give up electrons
to become + ions.
Electronegative elements:
Readily acquire electrons
to become - ions.
6
METALS
CERAMICS
POLYMERS
SEMICONDUCTOR
ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.
Smaller electronegativity
Larger electronegativity
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.
7
IONIC BONDING
•
•
•
•
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
8
EXAMPLES: IONIC BONDING
• Predominant bonding in Ceramics
NaCl
MgO
CaF2
CsCl
H
2.1
Li
1.0
Be
1.5
Na
0.9
Mg
1.2
K
0.8
Ca
1.0
Sr
1.0
Rb
0.8
Cs
0.7
Fr
0.7
Ti
1.5
Cr
1.6
Ba
0.9
Fe
1.8
Ni
1.8
He
O
3.5
Zn
1.8
As
2.0
F
4.0
Cl
3.0
Ne
-
Br
2.8
I
2.5
Kr
Xe
Rn
-
At
2.2
Ar
-
Ra
0.9
Give up electrons
Acquire 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.
9
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.
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
Sr
1.0
Ba
0.9
Fr
0.7
Ra
0.9
•
•
•
•
C(diamond)
SiC
Be
1.5
Mg
1.2
Ca
1.0
column IVA
H2O
Ti
1.5
Cr
1.6
Fe
1.8
F2
He
O
2.0
C
2.5
Ni
1.8
Zn
1.8
Ga
1.6
Si
1.8
Ge
1.8
As
2.0
Sn
1.8
Pb
1.8
F
4.0
Cl
3.0
Ne
-
Br
2.8
Ar
Kr
-
I
2.5
Xe
-
At
2.2
Rn
-
Cl2
GaAs
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.
Molecules with nonmetals
Molecules with metals and nonmetals
Elemental solids
Compound solids (about column IVA)
11
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
SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
Adapted from Fig. 2.13, Callister 6e.
• Permanent dipoles-molecule induced
-general case:
-ex: liquid HCl
Adapted from Fig. 2.14,
Callister 6e.
Adapted from Fig. 2.14,
Callister 6e.
-ex: polymer
13
SUMMARY: BONDING
Type
Bond Energy
Comments
Ionic
Large!
Nondirectional (ceramics)
Covalent
Variable
Directional
large-Diamond semiconductors, ceramics
small-Bismuth
polymer chains)
Metallic
Variable
large-Tungsten
small-Mercury
Nondirectional (metals)
smallest
Directional
inter-chain (polymer)
inter-molecular
Secondary
14
PROPERTIES FROM BONDING: TM
• Bond length, r
F
• Melting Temperature, Tm
F
r
• Bond energy, Eo
Tm is larger if Eo is larger.
15
PROPERTIES FROM BONDING: E
• Elastic modulus, E
Elastic modulus
F
L
=E
Ao
Lo
• E ~ curvature at ro
Energy
unstretched length
ro
r
E is larger if Eo is larger.
smaller Elastic Modulus
larger Elastic Modulus
16
PROPERTIES FROM BONDING: a
• Coefficient of thermal expansion, a
coeff. thermal expansion
L
= a(T2-T1)
Lo
• a ~ symmetry at ro
a is larger if Eo is smaller.
17
SUMMARY: PRIMARY BONDS
Ceramics
(Ionic & covalent bonding):
Metals
(Metallic bonding):
Polymers
(Covalent & Secondary):
Large bond energy
large Tm
large E
small a
Variable bond energy
moderate Tm
moderate E
moderate a
Directional Properties
Secondary bonding dominates
small T
small E
large a
18
ENERGY AND PACKING
• Non dense, random packing
• Dense, regular packing
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
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...
4
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 for a simple cubic structure = 0.52
Adapted from Fig. 3.19,
Callister 6e.
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
R
Adapted from
Fig. 3.2,
Unit cell contains:
1 + 8 x 1/8
= 2 atoms/unit cell
a
Callister 6e.
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
a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
Adapted from
Fig. 3.1(a),
Callister 6e.
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
• FCC Unit Cell
11
HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection
• 2D Projection
A sites
B sites
A sites
Adapted from Fig. 3.3,
Callister 6e.
• 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, 
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)
Result: theoreticalCu = 8.89 g/cm3
Compare to actual: Cu = 8.94 g/cm3
14
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/cm 3 )
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
-----------
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
metals• ceramics• polymers
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values
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.
1 mm
Adapted from Fig. K,
color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
• 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
Data from Table 3.3,
Callister 6e.
(Source of data is
R.W. Hertzberg,
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
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)
-If grains are textured,
anisotropic.
200 mm
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.
Adapted from Fig.
3.2W, Callister 6e.
• Measurement of:
Critical angles, qc,
for X-rays provide
atomic spacing, d.
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"
The same atoms can
have more than one
crystal structure.
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.
23