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Engineering Materials ENGG ZC232

Karthik Chethan V. and Ramesh Babu A. BITS Pilani, Hyderabad Campus 2014

Introduction to materials and atomic forces (different bonds such as metallic, ionic, covalent, secondary etc.). Crystallography and structures of various materials (metals, ceramics and polymers). X-ray diffraction (principle, instrumentation, materials characterization, indexing and determination of structures). Structural defects (imperfections). Phase transformations and Phase diagrams. Mechanical properties (stimulus and response) (various modes of testing-tensile, compressive etc.) (short-term, long-term, static and dynamic).

Ability to understand and focus on the self-explanatory language. Ability to question based on the language. Ability to visualize phenomena physically (cartoons and schematics). 1/4th electronic interaction (chat, email, phone etc.) 1/4th reading and assimilating course material 1/4th contemplating, questioning and expanding 1/4th creative discussions and revisions with instructor

Useful Guidelines
No strategies. Attend lectures as much as possible. Be consistent. Be conceptual and compartmentalize issues. Interact thoroughly with instructor and fellow students (if possible). Question and question some more and come up with hypothetical examples and case studies with schematics (you will be surprised). Get comfortable, clear doubts and alleviate your fear. Follow a real, physical, evidence-based problemsolving approach. Do not be unrealistic.

Engineering Materials
Materials Investigating materials and relationships that exist between the structure and properties of materials (chemistry and physics). Metals, ceramics, polymers, semi-conductors, pharmaceuticals, biomaterials (skin, bone, tissue) etc.

Engineering Materials
Engineering on the basis of these structureproperty correlations, designing or engineering STRUCTURES (bridge), DEVICES (sensor) or MACHINES (printing machine, windmill) of a material to produce a predetermined set of properties. Optical, electrical, mechanical, thermal, magnetic etc.

Atomic Structure and Bonding

Internal Structure - Atomic structure Bonding

Atomic Structure and Bonding

Sub atomic electrons and nuclei (protons and neutrons) (do not forget quantum mechanics) Atomic organization of atoms or molecules (crystal structure and clustering of the same) Microscopic groups of atoms or molecules that are normally agglomerated together Macroscopic viewable with the naked eye

What are they (composition) How heavy and how much space do they occupy (mass and volume) Physical appearance (size, shape and color) How and Why are they arranged (arrangement pattern and type of bonding) How and Why do they move (dynamics) How do they eventually interact How do they respond to various stimuli How is all of this related to properties

Material Selection Process in Industry

Pick Application: Determine required Properties Properties: mechanical, electrical, thermal, magnetic, optical, deteriorative. Properties: Identify candidate Material(s) Material: structure, composition. Material: Identify required Processing Processing: changes structure and overall shape ex: casting, sintering, vapor deposition, doping, forming, joining, annealing.



Aluminum oxide may be transparent, translucent, or opaque depending on the material structure.
polycrystal: low porosity polycrystal: high porosity

single crystal


Types of Materials
Metals: strong, ductile, tough, high density, conductors. Ceramics: strong, brittle, low density, insulators. Polymers: moderately strong, ductile, low density, insulators. Composites: strong, ductile, low density, conductors, insulators.

John Dalton (1766-1844) found the evidence of those "hooks in his quantitative chemical measurements, making the foundation of modern atomic theory of matter.


Bonds in Materials
Metals: valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the ions together. Strong, ductile, conduct electricity and heat well, are shiny if polished. Ceramics: atoms behave like either positive or negative ions, and are bound by Coulomb forces in addition to covalent bonding. They are usually combinations of metals or semiconductors with oxygen, nitrogen or carbon (oxides, nitrides, and carbides). Hard, brittle, insulators. Examples: glass, porcelain. Polymers: are bound by covalent forces and also by weak van der Waals forces, and usually based on C and H. They decompose at moderate temperatures (100 400 C), and are lightweight. Examples: plastics and rubber.

Structure of Atom


Structure of Atoms
The bonding mechanisms between atoms are closely related to the structure of the atoms themselves. Atoms = nucleus (protons and neutrons) + electrons Charges: Electrons and protons have negative and positive charges of the same magnitude, 1.6 10-19 Coulombs. Neutrons are electrically neutral. Masses: Protons and Neutrons have the same mass, 1.67 10-27 kg. Mass of an electron is much smaller, 9.11 10-31 kg and can be neglected in calculation of atomic mass.

Electronic Structure
Electrons have wavelike and particulate properties.
This means that electrons are in orbitals defined by a probability. Each orbital at discrete energy level determined by quantum numbers.
Quantum #
n = principal (energy level-shell) l = subsidiary (orbitals) ml = magnetic ms = spin

K, L, M, N, O (1, 2, 3, etc.) s, p, d, f (0, 1, 2, 3,, n -1) 1, 3, 5, 7 (-l to +l) , -
Chapter 2 - 18

Electron Energy States

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 N-shell n = 4

L-shell n = 2 K-shell n = 1
Chapter 2 - 19

Electron Configurations
Valence electrons those in unfilled shells Filled shells more stable Valence electrons are most available for bonding and tend to control the chemical properties
example: C (atomic number = 6) 1s2 2s2 2p2
valence electrons

Chapter 2 - 20

Types of Bonding
The electronic structure of atoms defines the character of their interaction among each other. Filled outer shells result in a stable configuration as in noble inert gases. Atoms with incomplete outer shells strive to reach this noble gas configuration by sharing or transferring electrons among each other for maximal stability. Strong primary bonding results from the electron sharing or transfer.

Types of Bonding-Primary
Primary bonding: electrons are transferred or shared Strong (100-1000 KJ/mol or 1-10 eV/atom) Metallic: the atoms are ionized, loosing some electrons from the valence band. Those electrons form a electron sea, which binds the charged nuclei in place. Ionic: Strong Coulomb interaction among negative atoms (have an extra electron each) and positive atoms (lost an electron). Example - Na+Cl Covalent: electrons are shared between the molecules, to saturate the valency. Example - H2

Types of Bonding-Secondary
Secondary Bonding: no e- transferred or shared Interaction of atomic/molecular dipoles Weak (< 100 KJ/mol or < 1 eV/atom) Fluctuating Induced Dipole Permanent dipole bonds (polar molecules - H2O, HCl...) Polar molecule-induced dipole bonds (a polar molecule induces a dipole in a nearby nonpolar atom/molecule) Dipole-dipole Dipole-ion


Primary Metallic Bonding

Valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the positive ions together. A metallic bond is non-directional (bonds form in any direction) atoms pack closely. The bonds do not break when atoms are rearranged metals can experience a significant degree of plastic deformation (WHY). Examples of typical metallic bonding: Cu, Al, Au, Ag, etc. Transition metals (Fe, Ni, etc.) form mixed bonds that are comprising of metallic bonds and covalent bonds involving their 3d-electrons. As a result the transition metals are more brittle (less ductile) that Au or Cu.


Metallic Bonding


Ionic Bonding
Ionic Bonding is typical for elements that are situated at the horizontal extremities of the periodic table. Atoms from the left (metals) are ready to give up their valence electrons to the (nonmetallic) atoms from the right that are happy to get one or a few electrons to acquire stable or noble gas electron configuration. As a result of this transfer mutual ionization occurs: atom that gives up electron(s) becomes positively charged ion (cation), atom that accepts electron(s) becomes negatively charged ion (anion). Formation of ionic bond: Ions are attracted by strong coulombic interaction Oppositely charged atoms attract each other An ionic bond is non-directional (ions may be attracted to one another in any direction)

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

Chapter 2 -


A strong electrostatic attraction between positively charged Na+ ions and negatively charged Cl- atoms along with Na+ - Na+ and Cl- - Cl- repulsion result in the NaCl crystal structure which is arranged so that each sodium ion is surrounded by Cl- ions and each Na+ ion is surrounded by Cl- ions. Any mechanical force that tries to disturb the electrical balance in an ionic crystal meets strong resistance: ionic materials are strong and brittle. In some special cases, however, significant plastic deformation can be observed, e.g. NaCl single crystals can be bent by hand in water.

Covalent Bonding
In covalent bonding, electrons are shared between the molecules. In this case the electrons are not transferred as in the ionic bonding, but they are localized between the neighboring ions and form directional bond between them. The ions repel each other, but are attracted to the electrons that spend most of the time in between the ions. Formation of covalent bonds: Cooperative sharing of valence electrons Can be described by orbital overlap Covalent bonds are HIGHLY directional (sharing) Bonds - in the direction of the greatest orbital overlap (electron density is highest) Covalent bond model: an atom can covalently bond with at most 8number of valence electrons


Covalent Bonding
similar electronegativity share electrons bonds determined by valence s & p orbitals dominate bonding Example: CH4
C: has 4 valence e-, needs 4 more H: has 1 valence e-, needs 1 more Electronegativities are comparable.

CH 4

shared electrons from carbon atom

H shared electrons from hydrogen atoms

Chapter 2 -

Secondary Bonding
Secondary = van der Waals = physical (as opposite to chemical bonding that involves e- transfer) bonding results from interaction of atomic or molecular dipoles and is weak, ~0.1 eV/atom or ~10 kJ/mol. Permanent dipole moments exist in some molecules (called polar molecules) due to the asymmetrical arrangement of positively and negatively regions (HCl, H2O). Bonds between adjacent polar molecules permanent dipole bonds are the strongest among secondary bonds. Polar molecules can induce dipoles in adjacent non-polar molecules and bond is formed due to the attraction between the permanent and induced dipoles. Even in electrically symmetric molecules/atoms an electric dipole can be created by fluctuations of electron density distribution. Fluctuating electric field in one atom A is felt by the electrons of an adjacent atom, and induce a dipole momentum in this atom. This bond due to fluctuating induced dipoles is the weakest (inert gases, H2, Cl2).


Arises from interaction between dipoles Fluctuating dipoles
asymmetric electron clouds

ex: liquid H 2 H2 H2 H H
secondary bonding

secondary bonding


Permanent dipoles-molecule induced

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

secondary bonding

H Cl

secondary bonding

H Cl
secondary bonding
Chapter 2 -

Hydrogen Bonding (different phases of ice/water)


Bond Energies


Summary: Bonding

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

Nondirectional (ceramics)

Directional (semiconductors, ceramics polymer chains)


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

Chapter 2 -


Bond Energies (potential energy-distance and attraction between atoms)

This is typical potential well for two interacting atoms. The repulsion between atoms, when they are brought close to each other, is related to the Pauli principle: when the electronic clouds surrounding the atoms starts to overlap, the energy of the system increases abruptly. The origin of the attractive part, dominating at large distances, depends on the particular type of bonding (depth and shape of the well, bond lengths and unit cells).


Bond Force
Forces can be calculated from the potential energy of interatomic interaction. For example, for a system of two atoms (e.g. a diatomic molecule), the potential depends only on the distance between the two atoms U(r12) Electron volt or joules is used


Bond Energy Expression

The net potential energy between two adjacent atoms or ions, EN, may be represented by, EN = EA (attractive potential) + ER (repulsive potential)

EN = - A/r + B/rn

Properties From Bonding: Tm

Bond length, r r Melting Temperature, Tm Energy

Bond energy, Eo
unstretched length ro

ro smaller Tm r larger Tm

Eo = bond energy

Tm is larger if Eo is larger.

Chapter 2 - 41

Properties From Bonding : a

Coefficient of thermal expansion, a coeff. thermal expansion length, L o
unheated, T1 heated, T 2


DL = a (T2 -T1) Lo

a ~ symmetry at ro
unstretched length ro

a is larger if Eo is smaller.


smaller a larger a
Chapter 2 - 42


Summary: Primary Bonds

(Ionic & covalent bonding):

Large bond energy

large Tm large E small a

(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate a

(Covalent & Secondary):

Directional Properties
Secondary bonding dominates small Tm small E large a

Chapter 2 - 43