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Atomic structure

3 basic subatomic particles: Proton, electrons and neutrons

Atomic structure
What is atom? Basic structural unit of all engineering materials Atoms = Nucleus (protons+neutrons) + electrons

Electrons: Smallest mass (1/1836 of proton) compare to neutrons (1.675x10-24g) and protons (1.673x10-24g). Determine most of the electrical, mechanical, chemical and thermal properties of the atoms.

Alkali (s1)

The Periodic Table

Inert Gas (s2p6) Halogen (s2p5)

Alkaline Earth (s2)

Transition Metals (incomplete d subshell)

Foundation of materials science and engineering,William F. Smith,McGrawHill, 2004, pg19-58

Atomic Bonding

Valence Electrons
Valence electrons are the electrons that occupy the outermost filled shell.
These electrons are extremely important as they participate in the bonding between atoms to form atomic and molecular aggregates. Most of the electrical, mechanical, chemical and thermal properties of the atoms of solids are based on these valence electrons.

Types of Bonding
Primary Atomic Bonds

1. Ionic Bonding 2. Covalent Bonding 3. Metallic bonding

Secondary Atomic Bonds

1. Permanent dipole bonds 2. Fluctuating dipole

Occurs in compounds that are composed of both metallic

and nonmetallic elements which are in the horizontal extremities of the periodic table

Ionic Bonding

Ionic Bonding
Metallic elements transfer the valence electrons to nonmetallic atoms To produce ions that are bonded together by coulombic forces
(attraction of positively and negatively charged ions).

In the process, all the atoms acquire stable or inert gas


Ionic bonding is termed strong and nondirectional, i.e. the

magnitude of the bond is equal in all directions around an ion

Ionic Bonding
Examples: NaCl, MgO The properties of ionic materials are: i. hard and brittle ii. electrically and thermally insulative

Foundation of materials science and engineering,William F. Smith,McGrawHill, 2004, pg19-58

Ionic Bonding
N aC l M gO C aF 2 C sC l
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

He O F 3.5 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 Ne Ar Kr Xe Rn -

Give up electrons

Acquire electrons

Ionic materials are poor electrical conductors

When voltage is applied to an ionic material, the entire ions must move to cause a current flow. However, the ion movement is slow and therefore, the electrical conductivity is poor.

Covalent Bonding
similar electronegativity share electrons bonds determined by valence s & p orbitals dominate bonding Example: CH4

C: has 4 valence needs 4 more


CH 4

shared electrons from carbon atom

H: has 1 valence e-, needs 1 more Electronegativities are comparable.

shared electrons from hydrogen atoms

Adapted from Fig. 2.10, Callister & Rethwisch 8e.


Metallic Bonding

Occurs in the solid metals and alloys.

In solid state, atoms are packed relatively close together in a systematic pattern or crystal structure.
The valence electrons of metallic materials are not bound to any particular atom in the solid and are more or less free to drift throughout the entire metal.

Valence electrons belong to the metal as a or forming a sea of electrons.


Metallic Bonding

Metals have low ionization energies, thus they do not have a tight hold on their valence electrons. These outer electrons easily move around, as they do not "belong" to any one atom, but are part of the whole metal crystal

The remaining non-valence electrons and atomic nuclei form ion cores, which possess a net positive charge equal in magnitude to the total valence electron charge per atom.

The metallic bonding is also nondirectional. Metallic bonding may be strong or weak. The properties of metallic materials are: i. Good ductility ii. Good electrical conductivity iii.Lustrous iv.Malleable

(a) Atomic arrangement in metallic copper crystal. Each copper atom is coordinated with 12 other copper atoms, producing a crystal structure called face-centered-cubic. (b) Two dimensional schematic diagram of metallically bonded atoms. The circles with the inner positive ion cores, and the charge clouds around the iron cores represent the dispersed valence electrons.
Foundation of materials science and engineering,William F. Smith,McGrawHill, 2004, pg19-58

Summary: Bonding

Bond Energy

Nondirectional (ceramics)


Variable large-Diamond

Directional (semiconductors, ceramics polymer chains)


Variable large-Tungsten Nondirectional (metals)

Secondary smallest Directional inter-chain (polymer) inter-molecular


Materials Structure and Bonding

Crystal Structure of Metals

Long-range order (LRO) of the positions of the atoms.

Short-range order (SRO) of the positions of the atoms. Random orientation of particles.

The constituent atoms, molecules, or ions are packed in a regularly ordered. Examples: Metals, alloys, minerals, sand, clay, limestone, carbon, and salts (NaCl, KCl)

Examples: ceramic - common window glass, polymers polystyrene & plastic and food - cotton candy

Crystalline Solids
Volume Liquid


Quartz crystal
Properties: Relate to orientation and are dependent on the crystals axes (anisotropic).

Crystal Tm Temperature

Single crystals Poly-crystals

Crystals become liquids at a specific temperature (melting point)

Amorphous Solids
Volume Softening Liquid

Amorphous solid

Tm Wax Properties: Identical in all directions along any axis (isotropic). A relatively wide temperature range for the melting point. Soften gradually when they are heated.


The orderly arrangement of atoms in three dimensional space. Space lattice -infinite 3D array of points. -repeating unit cells

Each point in the space lattice has identical surroundings. Size & shape of unit cell can be described by 3 lattice vectors (a,b,c). Lattice constants: Axial lengths (a,b,c) Interaxial angles (,,).

The arrangement of the atoms is called crystalline structure

Space Lattice

Unit cell

7 different types of unit cells (specify the lattice constants): 1. Cubic 2. Tetragonal 3. Orthorhombic 4. Rhombohedral 5. Hexagonal 6. Monoclinic 7. Triclinic

14 standard unit cells (Bravais)

4 basic types of unit cells: 1. Simple 2. Body-centered 3. Face-centered 4. Base-centered

14 Bravais Conventional Unit Cell

The Structure of Metal

What is metal?

What makes metals immediately recognizable?

What are the properties of metals that make

them such useful materials?

What simple experiments can be carried out to

distinguish metals from other materials?

The Structure of Metal

Why are some metals hard and other soft? Why some metals can withstand high temperatures, while some others not?

Structure - arrangement of atoms

Influence the behavior and structure

Metallic Crystal Structures


Products: Solid state devices Turbine blades


Lattice imperfections Dislocations


Products: Paper clips, bolts, springs, aircraft fuselage

Grain boundaries Plastic deformation Anisotropy

Metallic Crystal Structures

Metals crystallize in the dense-packed structures because energy is released. (atoms come close together & bond more tightly with each other)

Body centered cubic (BCC)

Face centered cubic (FCC)

Hexagonal centered cubic (HCP)


The cube side of the unit cell of BCC iron at room temperature is 0.287nm. If unit cells of pure iron are lined up side by side, in 1mm there will be:
1mm x 1 unit cell = 3.48 x 106 unit cells 0.287nm x 10-6mm/nm

Metallic Crystal Structure

3 densely packed crystal structures:

Body centered cubic (BCC)

Face centered cubic (FCC)

Hexagonal centered cubic (HCP)

Simple Cubic Structure (SC)

Rare due to low packing density (only Po Close-packed directions are cube edges.

has this structure)

Coordination # = 6 (# nearest neighbors)

Click once on image to start animation (Courtesy P.M. Anderson)


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 volume atoms a R=0.5a 4 unit cell APF = a3 volume unit cell 1 p (0.5a) 3 atom

close-packed directions contains 8 x 1/8 = 1 atom/unit cell

Adapted from Fig. 3.24, Callister & Rethwisch 8e.


Body Centered Cubic (BCC)

Atomic-site unit cell

Hard-sphere unit cell

Isolated unit cell

How many atoms ?

1(at the center)+ 8 x 1/8 = 2 atoms per unit cell

Prove the relation between the lattice constant a and the atomic radius R..

Prove it!

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68


Close-packed directions:
Adapted from Fig. 3.2(a), Callister & Rethwisch 8e.

R a 4 2 3

length = 4R =


unit cell APF =

p ( 3 a/4 ) 3

volume atom volume unit cell



Face Centered Cubic (FCC)

Atomic-site unit cell

Hard-sphere unit cell

Isolated unit cell

How many atoms ?

6 x + 8 x 1/8 = 4 atoms per unit cell



Prove it?

Atomic Packing Factor: FCC

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


4 atoms/unit cell

unit cell APF = 4

4 3

p ( 2 a/4 ) 3

volume atom volume


unit cell

Hexagonal Close-Packed (HCP)

Atomic-site unit cell

Hard-sphere unit cell

Isolated unit cell

How many atoms?

6 x + 2 x 6 x 1/6 + 2 x 1/2 = 6 atoms per unit cell


Atomic-site unit cell

Base of Hcp unit cell

Triangle ABC removed from base of unit cell

The ratio of the height c to its basal a called c/a ratio Ideal c/a ratio consisting of uniform spheres: 1.633

Problem: Calculate the volume of the zinc crystal structure unit cell by using the following data; pure zinc has the Hcp crystal structure with lattice constants a = 0.2665 nm and c= 0.4947 nm.

From Fig. c Area of triangle ABC = 1 2 base height o 1 2 a a sin60 = From Fig. b Total area of Hcp base = 6 1 2 a2 sin60o = 3 a2 sin60o

From Fig. a 2 o Volume of zinc Hcp unit cell = 3 a sin60 c = 3 0.265 nm 2 0.8660 0.4947 nm = 0.0913 nm3

Comparison of FCC, HCP & BCC Crystal Structures.

Crystal Structure Atom position BCC Atoms are positioned at each corner of the cube and one at the center of the cube 0.68 FCC (close packed) Atoms are positioned at each corner of the cube and one at the center of each cube face 0.74 HCP (close-packed) Atoms are positioned at each corner of the hexagon and 3 at the center of the cube 0.74

Atomic Packing Factor =volatoms/volunit cell


Iron, tungsten, chromium, molybdenum, vanadium

Aluminum, copper, lead, nickel, and iron (at 9121394oC)

Cadmium, zinc, magnesium, cobalt, zirconium, titanium, beryllium

Theoretical Density, r
Density = r =

Mass of Atoms in Unit Cell Total Volume of Unit Cell

r = nA VC NA


n = number of atoms/unit cell A = atomic weight VC = Volume of unit cell = a3 for cubic NA = Avogadros number = 6.022 x 1023 atoms/mol


Theoretical Density, r
Ex: Cr (BCC) A = 52.00 g/mol R = 0.125 nm n = 2 atoms/unit cell
Adapted from Fig. 3.2(a), Callister & Rethwisch 8e.

a = 4R/ 3 = 0.2887 nm

atoms g

unit cell

2 52.00


rtheoretical ractual

= 7.18 g/cm3 = 7.19 g/cm3

unit cell


6.022 x 1023


In general r r r metals > ceramics > polymers Why?


Densities of Material Classes

Metals/ Alloys
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Graphite/ Ceramics/ Semicond


Composites/ fibers

Metals have...

close-packing 10 (metallic bonding) often large atomic masses

r (g/cm3 )

B ased 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).

Al oxide Diamond Si nitride Glass -soda Concrete Silicon G raphite

Ceramics have...
less dense packing often lighter elements

5 4 3 2

Glass fibers PTFE Silicone PVC PET PC H DPE, PS PP, LDPE GFRE* Carbon fibers CFRE * A ramid fibers AFRE *

Polymers have...

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

Composites have...
intermediate values

0.5 0.4 0.3


Data from Table B.1, Callister & Rethwisch, 8e.


Single Crystals

Single vs Polycrystals E (diagonal) = 273 GPa

Data from Table 3.3, Callister & Rethwisch 8e. (Source of data is R.W. Hertzberg, Deformation and Fracture Mechanics of Engineering Materials, 3rd ed., John Wiley and Sons, 1989.)

-Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron:

E (edge) = 125 GPa

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

200 mm

-If grains are textured, anisotropic.

Adapted from Fig. 4.14(b), Callister & Rethwisch 8e. (Fig. 4.14(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].)


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. 8.33(c), Callister & Rethwisch 8e. (Fig. 8.33(c) courtesy of Pratt and Whitney).

Properties of crystalline materials often related to crystal structure.

-- Ex: Quartz fractures more easily along some crystal planes than others.

(Courtesy P.M. Anderson)


Most engineering materials are polycrystals.


Adapted from Fig. K, color inset pages of Callister 5e. (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 grains are randomly oriented,
Grain sizes typically range from 1 nm to 2 cm


overall component properties are not directional.

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

Polymorphism / Allotropy
Elements and compounds which exist more than one crystalline form under different conditions of temperature and pressure Examples: iron, titanium and cobalt (at elevated temp. and atmospheric pressure).
Temperature Alpha iron -273-912oC Crystal structure BCC

Gamma iron
Delta iron



Materials Structure and Bonding

Deformation and Strength of Single Crystal

Deformation and Strength of Single Crystal

Elastic deformation
The lattice structure is shifted, stretched, and distorted but returns to the materials original shape when force removed.

Plastic deformation

Atoms change positions and slip past one another because the atomic bond is broken material does not return to original shape when force removed

Metallic bonding allows for slip, the basic mechanism by which metals deform plastically when subjected to high stresses The properties of materials are a function of their: 1. Atomic Structure 2. Bonding Structure 3. Crystal Structure 4. Imperfections If these various structures are known then the properties of the material can be determined.

Crystalline Imperfections
Crystals contain various types of imperfections and defects that affect their physical and mechanical properties. Crystal lattice imperfections are classified according to their geometry and shape. Strength of a material also depends on crystal imperfections, alloying agents, and impurities.

Crystalline Imperfections
May be intentional or unintentional. May be present because of an added alloy. Steel is an alloy of Iron (Fe) and Carbon (C). Carbon atoms are much smaller than the iron atoms and appear as interstitial.

Types of Imperfections in the Crystal Structure

1. Zero dimensional / Point defects

e.g.: vacancy, interstitialcy (atom or impurity) 2. One dimensional / Line defects e.g.: dislocations 3. Two dimensional / Planar defects e.g.: grain boundaries, twin boundaries, low

4. Three dimensional macroscopic / Volume or bulk

angle boundaries, high angle boundaries, twists, and stacking faults.

imperfection e.g.: voids or inclusion (nonmetallic such as oxide,sulfide and silicates)

1. Point Defects
Vacancy Missing atoms Produced during solidification as a result of: local disturbances during crystal growth Atomic rearrangements in an existing crystal due to atomic mobility. Additional vacancies in metals: Plastic deformation Rapid cooling from higher temperature to lower temperature to entrap vacancies

Defects in a Single-Crystal Lattice

Schematic illustration of types of defects in a single-crystal lattice: self-interstitial, vacancy, interstitial, and substitutional.

Self-Interstitial Extra" atoms positioned between atomic sites. Impurities A foreign atom that has replaced an atom of the pure metal.

2. Line defects
Dislocations Rows of unit cells that become shifted and upset the orderly arrangement. Types of dislocations: Edge Screw Mixed All crystalline materials contain dislocations introduced during: Solidification Plastic deformation As a consequence of thermal stresses resulting from rapid cooling.

Types of dislocations in a single crystal: (a) edge dislocation; and (b) screw dislocation.

Movement of an Edge Dislocation

Movement of an edge dislocation across the crystal lattice under a shear stress. Dislocations help explain why the actual strength of metals is much lower than predicted by theory.

Dislocations cause slip between crystal plane when they move. They produce permanent (plastic) deformation.

(a) Plastic deformation of a single crystal under a tensile load. Note that the slip planes tend to align themselves in the direction of the pulling force. This behavior can be simulated using a deck of cards with a rubber band around them. (b) Twinning in a single crystal in tension.

Elastic deformation Plastic deformation

Plastic deformation of a single crystal subjected to a shear stress: (a) structure before deformation; and (b) permanent deformation by slip. The size of the b/a ratio influences the magnitude of the shear stress required to cause slip.

3. Planar Defects
Boundaries having two dimensions and separate regions of materials having different crystal structure and/or crystallographic orientations. Twin boundaries Occur when two crystals of the same type intergrow, so that only a slight misorientation exists between them. Twin results from atomic displacements produced from mechanical shear force (mechanical twin, found in BCC & HCP) or annealing heat treatment (annealing twin, found in FCC). Responsible for many of the changes that occur in cold work of metals with limited slip systems or at very low temperatures.

Twin plane or boundary and the adjacent atom positions.

Atoms on one side of a plane (called the twinning plane) are shifted to form a mirror image of the other side

Twinning, involving the formation of an atomic mirror image (i.e., a "twin") on the opposite side of the twinning plane: (a) before, and (b) after twinning

4. Volume Defects
Form when a cluster of point defects join to form a 3D void or pore. Introduced during processing and fabrication steps.

Deformation may be elastic or plastic.

Elastic Deformation - lattice structure is distorted but reorients. Plastic Deformation occurs by slip along lattice where atomic bonds are broken.

A way of explaining two key observations about the plastic deformation of crystalline material: i. The stress required to plastically deform a crystal is much less than the stress one calculates from considering a defect-free crystal structure ii. Materials work-harden: when a material has been plastically deformed it subsequently requires a greater stress to deform further A dislocation in a 2D close-packed plane can be described as an extra 'half-row' of atoms in the structure.


Explain how plastic deformation of materials occurs through the mechanism of slip. Slip involves dislocation glide on particular slip planes Slip occurs when the shear stress acting in the slip direction on the slip plane reaches some critical value. This critical shear stress is related to the stress required to move dislocations across the slip plane. When a single crystal is deformed under a tensile stress, it is observed that plastic deformation occurs by slip on well-defined parallel crystal planes. Sections of the crystal slide relative to one another, changing the geometry of the sample as shown in the diagram.

The tensile yield stress of a material is the applied stress required to start plastic deformation of the material under a tensile load.

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