Classification of Materials

1. Metals
2. Ceramics
3. Polymers
4. Composites
5. Advanced Materials (“Materials of the future”)
– Semiconductors
– Smart Materials
– Biomaterials
– Nanomaterials

Case Study – Materials Selection

Problem:
Select suitable material for bicycle frame and
bicycle forks.

Carbon fiber
Steel and Aluminum Ti and Mg
Wood Reinforced
alloys alloys alloys
plastic

Last submission date: 3rd March 2017

Chapter 2

Atomic Structure
and
Bonding

KIG 1004: Basic Materials for Mechanical

Introduction • In some instances. • Some important properties of materials depend on the geometrical atomic arrangements and the interactions among constituent atoms or molecules. atomic structure and the type of interatomic bonding in solids allow the understanding of a material’s properties. Example: Metals are relatively dense in comparison to polymers or ceramics due to highly ordered arrangement of their atoms KIG 1004: Basic Materials for Mechanical .

Neutrally Charged Nucleus Electron Cloud Diameter : 10 m –14 Mass : 9.602 x 10 –9 C Positive Charge Accounts for all volume Proton Mass : 1.602 x 10 –19 C Neutron Mass : 1.673 x 10 –24 g Charge : 1.675 x 10 –24 g Neutral Charge KIG 1004: Basic Materials for Mechanical . Structure of Atoms ATOM Basic Unit of an Element Diameter : 10 –10 m.109 x 10 –28 g Accounts for almost all mass Charge : -1.

neutrons. and electrons. .• Different types of atom have different numbers of protons.

• Isotope – Atoms of the same element that have different atomic masses. KIG 1004: Basic Materials for Mechanical . • Atomic mass = masses of protons + masses of neutron within the nucleus Example: Carbon has 6 Protons and 6 Neutrons. atomic mass = 12. Hence. Structure of Atoms • The mass of an atom is contributed by proton and neutron.

Structure of Atoms • Atomic number (Z) = the number of protons in the nucleus • Atomic mass (A) = masses of protons + masses of neutron • The number of protons is the same for all atoms. but the number of neutrons (N) may be variable . • Example: Carbon-12 (12C). Carbon-14 (14C) KIG 1004: Basic Materials for Mechanical . › isotopes. Carbon-13 (13C).

ions. The Periodic Table • Columns: Similar Valence Structure inert gases give up 1e give up 2e accept 2e accept 1e give up 3e H He Li Be O F Ne Adapted from Na Mg S Cl Ar Fig. 2. K Ca Sc Se Br Kr Rb Sr Y Te I Xe Cs Ba Po At Rn Fr Ra Electropositive elements: Electronegative elements: Readily give up electrons Readily acquire electrons to become + ions. KIG 1004: Basic Materials for Mechanical Engineer . to become . Callister 7e.6.

.

Bohr Atomic Model • Electrons are assumed to revolved around the atomic nucleus in discrete orbital • The position of any particular electron is more or less well defined in terms of its orbital. KIG 1004: Basic Materials for Mechanical Engineer .

Quantum Numbers • Principle Quantum Number (n) • Subsidiary Quantum Number l • Third Quantum Number ml • Electron spin quantum number ms KIG 1004: Basic Materials for Mechanical Engineer .

d and f. energy. • Each subshell have slightly different energy level n=1 s orbital n=2 (l=0) n=2 n=1 n=3 p Orbital (l=1) KIG 1004: Basic Materials for Mechanical . Quantum Numbers Principal Quantum Number (n) Subsidiary Quantum Number l • Represents main energy levels. • Larger the ‘n’ higher the • Range 0…n-1. (orbital). • Represented by letters s.p. • Represents sub energy levels • Range 1 to 7.

• No effect on energy. d. five and • Two electrons on same seven states exist orbital have opposite repectively. spins. & f • Values are +1/2 or –1/2. KIG 1004: Basic Materials for Mechanical Engineer . subshells. number ms. whereas for p. Quantum Numbers of Electrons of Atoms (Cont. atomic orbital. • Represents spatial • Specifies two directions orientation of single of electron spin.) Third Quantum Number Electron spin quantum ml.. three. • Directions are clockwise • For s subshell there is a or anticlockwise or up and single energy state down.

Relatives energies of the electrons for the carious shells and subshells KIG 1004: Basic Materials for Mechanical .

63 x 10-34 J. • Energy is absorbed to move to higher energy level. • Energy change due to transition = ΔE = hc  Absorb Emit h=Planks Constant Energy Energy = 6. • Energy is emitted during transition to lower level.s (Photon) (Photon) c= Speed of light λ = Wavelength of light Energy levels KIG 1004: Basic Materials for Mechanical Engineer . electron are permitted to have only specific values of energy. that is. Quantum Mechanic Principle • Energies of electron are quantized.

KIG 1004: Basic Materials for Mechanical Engineer . • Electron charge cloud surrounding the nucleus of a hydrogen atom in the ground state. The outer circle of r = 0.05nm corresponds to the radius of the first Bohr orbit (n = 1) and indicates the most probable region for finding the electron.

• b) An electron in a higher energy orbit dropping to a lower orbit. KIG 1004: Basic Materials for Mechanical . The Hydrogen Atom • a) The hydrogen electron being excited into a higher orbit. resulting in the emission of a photon of energy.

KIG 1004: Basic Materials for Mechanical .

6 (n=1. the energy of photon emitted is 13.If an electron undergoes transition from n=3 state to n=2 state.) principal quantum E  2 eV n numbers • Example:.6 13.89eV 3 2 • Energy required to completely remove an electron from hydrogen atom is known as ionization energy KIG 1004: Basic Materials for Mechanical Engineer . Energy in Hydrogen Atom • Hydrogen atom has one proton and one electron • Energy of hydrogen atoms for different energy levels is given by 13.2….6 E  2  2  1..

Hydrogen Energy Level • Energy level diagram for the line spectrum of hydrogen. KIG 1004: Basic Materials for Mechanical Engineer .

 Example :. • Electron Configuration lists the arrangement of electrons in orbital. Electron Configuration • Maximum number of electrons in each atomic shell is given by 2n2. Number of Electrons Orbital letters 1s2 2s2 2p6 3s2 Principal Quantum Numbers KIG 1004: Basic Materials for Mechanical . (n= Principal Quantum Number ) • Atomic size (radius) increases with addition of shells.

particularly when the atomic number is large and the d and f levels begin to fill. – Ex: iron (atomic number 26) 1s2 2s2 2p6 3s2 3p6 3d 8 but the actual structure however is 1s2 2s2 2p6 3s2 3p6 3d 6 4s2 • Valence electrons – The number of electron in an atom that participate in bonding or chemical reactions. the valence is the number of electrons in the outer s and p energy level ( valence also depends on the immediate environment surrounding the atom or the neighboring atoms available for bonding). Usually. Electron Configurations • The orderly building up of the electronic structure is not always followed. – example: C (atomic number = 6) 1s2 2s2 2p2 valence electrons KIG 1004: Basic Materials for Mechanical .

4.atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2 4d 4p N-shell n = 4 valence electrons 3d 4s Energy 3p M-shell n = 3 3s Adapted from Fig. 2p L-shell n = 2 2s 1s K-shell n = 1 KIG 1004: Basic Materials for Mechanical Engineer . 2. Electronic Configurations Eg: Fe . Callister 7e.

KIG 1004: Basic Materials for Mechanical .

Relative sizes of some atoms and ions in nm KIG 1004: Basic Materials for Mechanical .

most noble gasses (Ne. Give electrons during chemical reactions to form cations. Rn) are chemically very stable  All have s2 p6 configuration for outermost shell.  Helium has 1s2 configuration • Electropositive elements are metallic in nature. Kr. Ar. Xe.  Cations are indicated by positive oxidation numbers  Example:- Fe : 1s2 2s2 sp6 3s2 3p6 3d6 4s2 Fe2+ : 1s2 2s2 sp6 3s2 3p6 3d6 Fe3+ : 1s2 2s2 sp6 3s2 3p6 3d5 KIG 1004: Basic Materials for Mechanical Engineer . Electron Structure and Chemical Activity • Except Helium.

1 Electronegativity of Sodium is 1.1  Example :. • Some elements behave as both electronegative and electropositive. Na Te N O Fl Electro.Electronegativity of Fluorine is 4.) • Electronegative elements accept electrons during chemical reaction. • Electronegativity is the degree to which the atom attracts electrons to itself  Measured on a scale of 0 to 4. Electro- positive 0 negative K 1 W 2H Se 3 4 KIG 1004: Basic Materials for Mechanical . Electron Structure and Chemical Activity (Cont..

Smaller electronegativity Larger electronegativity Adapted from Fig. 2. Copyright 1960 by Cornell University. • Large values: tendency to acquire electrons. 2. KIG 1004: Basic Materials for Mechanical Engineer .7.0. 3rd edition. The Nature of the Chemical Bond.7 is adapted from Linus Pauling. Copyright 1939 and 1940. Callister 7e. 3rd edition. Electronegativity • Ranges from 0.7 to 4. (Fig.

KIG 1004: Basic Materials for Mechanical .

Summary of some electronic structure-chemical property relationships for metals and nonmetals KIG 1004: Basic Materials for Mechanical .

Atomic and Molecular Bonds Chemical Bond Primary Bond Secondary Bond Ionic Bonds Permanent Dipole Bonds Covalent Bonds Fluctuating Dipole Metallic Bonds Bonds KIG 1004: Basic Materials for Mechanical Engineer .

Electropositive Electronegative Electron Element Atom Transfer Electrostatic Cation Attraction Anion +ve charge -ve charge IONIC BOND KIG 1004: Basic Materials for Mechanical Engineer . • Strong atomic bonds due to transfer of electron. • It can form between metallic (highly electropositive) and nonmetallic elements (highly electronegative). • Electrons are transferred from electropositive to electronegative atoms. Ionic bonding is due to electrostatic force of attraction between cations and anions. Ionically Bonded Solids • Ionic bonding – the bond formed between two different atom species when one atom (cation) donates its valence electrons to the second atom (anion).

099nm) Chlorine Ion (Cl –)(0. Na (0.192nm) Sodium Ion (Na+)(0.181nm) KIG 1004: Basic Materials for Mechanical . Sodium Atom.095nm) Chlorine Atom (Cl) (0.

KIG 1004: Basic Materials for Mechanical Engineer . (Fig. Examples: Ionic Bonding • Predominant bonding in Ceramics NaCl MgO CaF 2 CsCl Give electrons Take electrons Adapted from Fig. 3rd edition. Callister 7e. 3rd edition. The Nature of the Chemical Bond.7. 2. 2.7 is adapted from Linus Pauling. Copyright 1960 by Cornell University. Copyright 1939 and 1940.

Fnet = Fattrative +Frepulsive Force versus separation Distance for a pair of oppositely charged ions Figure 2.11 KIG 1004: Basic Materials for Mechanical . Ionic Force for Ion Pair • Nucleus of one ion attracts electron of another ion. • The electron clouds of ion repulse each other when they are sufficiently close.

85 x 10 -12c2/Nm2) (n and b are constants) KIG 1004: Basic Materials for Mechanical . Ionically Bonded Solids Z1 and Z2 = number of electrons removed or added during ion formation e = Electron Charge a = Interionic separation distance ε = Permeability of free space (8.

181 nm = 2.85 x 10-12 C2/Nm2 a0 = Sum of Radii of Na+ and Cl.60 x 10-19 C ε0 = 8.76 x 10-10 m Na+ Cl- a0 KIG 1004: Basic Materials for Mechanical .095 nm + 0.ions? Z1 = +1 for Na+ Z2 = -1 for Cl- e = 1. Activity: Attractive Force in Ionically Bonded Solids Force of attraction between Na+ and Cl.ions = 0.

.

Ionic Bonding • Energy – minimum energy most stable – Energy balance of attractive and repulsive terms A B EN = EA + ER =   r rn Repulsive energy ER Interatomic separation r Net energy EN Adapted from Fig. Callister 7e. Attractive energy EA KIG 1004: Basic Materials for Mechanical Engineer . 2.8(b).

Interionic Energies for Ion Pairs

• Net potential energy for a pair of oppositely
charged ions =
2
Z Z e b
E  1
 2

4  a  a
net

0
2 n

Attraction Repulsion
Energy Energy

Energy Energy
Released Absorbed

• Enet is minimum when ions are at equilibrium
separation distance a0

KIG 1004: Basic Materials for Mechanical Engineer

KIG 1004: Basic Materials for Mechanical Engineer

Ion Arrangements in Ionic Solids

• Ionic bonds are non-directional
• Geometric arrangements are present in solids to
maintain electric neutrality.
 Example:- in NaCl, six Cl- ions pack around central Na+ Ions

Ionic packing
In NaCl
and CsCl
Figure 2.13

CsCl NaCl

• As the ratio of cation to anion radius decreases, fewer
anion surround central cation.

KIG 1004: Basic Materials for Mechanical Engineer

KIG 1004: Basic Materials for Mechanical .

• Lattice energy decreases when size of ion increases. Bonding Energies • Lattice energies and melting points of ionically bonded solids are high.  Example :- NaCl Lattice energy = 766 KJ/mol Melting point = 801oC CsCl Lattice energy = 649 KJ/mol Melting Point = 646oC BaO Lattice energy = 3127 KJ/mol Melting point = 1923oC KIG 1004: Basic Materials for Mechanical . • Multiple bonding electrons increase lattice energy.

KIG 1004: Basic Materials for Mechanical Engineer .

• Takes place between elements with small differences in electronegativity and close by in periodic table. a bond is formed between 2 atoms by sharing their 1s1 electrons Overlapping Electron Clouds . Covalent Bonding • In Covalent bonding. outer s and p electrons are shared between two atoms to obtain noble gas configuration. • In Hydrogen.

• Covalent bonds are very strong. • Since the valence electron are locked in bonds between atoms and are not readily available for conduction. covalently bonded materials are very hard and strong. KIG 1004: Basic Materials for Mechanical . which means they could be useful for high temperature application. • In order for the covalent bonds to be formed. • High melting point. So covalent bonding is a directional bonding. As a result. the atoms must ne arranged so the bonds have a fixed directional relationship with one another and form specific angles.

• The highest electron charge cloud density is in the region of overlap between the hydrogen atom nuclei Electron Pair H + H H H 1s1 Hydrogen Electrons Molecule KIG 1004: Basic Materials for Mechanical Engineer .

Potential energy vs separation distance for two hydrogen atoms • The equilibrium interatomic distance ao in the hydrogen molecule occurs at the minimum potential energy Emin KIG 1004: Basic Materials for Mechanical Engineer .

KIG 1004: Basic Materials for Mechanical .

2s2 2p4) atoms share two p electrons O + O O O O=O Bond Energy=28KJ/mol • Nitrogen (Outer orbital . O2 and N2. F + F F F F F H Bond Energy=160KJ/mol • Oxygen (Outer orbital .2s 2p ) atoms share three p electrons 2 3 HH N + N N N N N Bond Energy=54KJ/mol KIG 1004: Basic Materials for Mechanical . Covalent Bonding . covalent bonding is formed by sharing p electrons • Fluorine gas (Outer orbital – 2s2 2p5) share one p electron to attain noble gas configuration.Examples • In case of F2.

Result four sp3 orbitals. four covalent 1s bonds are 2p Four ½ filled sp3 orbitals formed KIG 1004: Basic Materials for Mechanical Engineer . Covalent Bonding in Carbon • Carbon has electronic configuration 1s 2 2s2 2p2 Ground State arrangement Indicates carbon Forms two 1s 2s 2p Covalent Two ½ filed 2p orbitals bonds • Hybridization causes one of the 2s orbitals promoted to 2p Indicates orbital.

Hybridization of carbon orbitals for the formation of single covalent bond KIG 1004: Basic Materials for Mechanical Engineer .

KIG 1004: Basic Materials for Mechanical Engineer .

Carbon Containing Molecules • In Methane. • Carbon also forms bonds with itself. Methane • Molecules are very weekly molecule bonded together resulting Figure 2. Carbon forms four covalent bonds with Hydrogen.  Examples:. • Molecules with multiple carbon bonds are more reactive.H H C C H C C H H H Acetylene Ethylene KIG 1004: Basic Materials for Mechanical Engineer .20 in low melting temperature (-183oC).

• Single and double bonds alternate between the atoms. Covalent Bonding in Benzene • Chemical composition of Benzene is C6H6. • The Carbon atoms are arranged in hexagonal ring. H H C H C C C C H H C Figure 2.23 H Structure of Benzene Simplified Notations KIG 1004: Basic Materials for Mechanical Engineer .

• Loosely bounded valence electrons are attracted towards nucleus of other atoms. called as free electrons. Metallic Bonding • Metallic bond defined as elements have electroposotive atoms that donate their valence electrons to form a “sea” of electrons surrounding the atoms. • Atoms in metals are closely packed in crystal structure. • These free electrons are reason for electric conductivity and ductility KIG 1004: Basic Materials for Mechanical Engineer . • The valence electrons are weakly bonded crystal.

the valence electrons move. metallic bonds are non-directional • Because their valence electrons are not fixed in any one position. • Relatively high Young’s modulus and good ductility. most pure metals are good electrical conductors. • Since outer electrons are shared by many atoms. causing a current to flow if the circuit is complete. KIG 1004: Basic Materials for Mechanical Engineer . Under influence of an applied voltage.

KIG 1004: Basic Materials for Mechanical Engineer .

Each copper atom is coordinated with 12 other copper atoms. The circle with the inner positive signs represent positive ion cores & the charge clouds around the ion cores represent the dispersed valence electrons KIG 1004: Basic Materials for Mechanical Engineer . • a) Atomic arrangement in a metallic copper crystal. • b) 2-D schematic diagram for metallicaly bonded atoms.

• This structure gives high hardness. high bonding strength (711KJ/mol) and high melting temperature (3550oC).19 KIG 1004: Basic Materials for Mechanical Engineer . Structure of Diamond • Four sp3 orbitals are directed symmetrically toward corners of regular tetrahedron.18 Figure 2. Carbon Atom Tetrahedral arrangement in diamond Figure 2.

• The equilibrium atomic separation distance ao is reached when the net potential energy is a minimum. KIG 1004: Basic Materials for Mechanical Engineer . Energy vs separation distance for a pair of metal atoms.

KIG 1004: Basic Materials for Mechanical Engineer .

bonding + - Adapted from Fig. Callister 7e. bonding • Permanent dipoles-molecule induced secondary -general case: + . SECONDARY BONDING Arises from interaction between dipoles • Fluctuating dipoles asymmetric electron ex: liquid H 2 clouds H2 H2 + . Callister 7e. 2.14. 2. H H H H secondary secondary bonding Adapted from Fig. secondary -ex: liquid HCl H Cl bonding H Cl secon -ex: polymer dary bond secondary bonding ing KIG 1004: Basic Materials for Mechanical Engineer .13. + .

• A secondary bond developed between atoms and molecules as a result of interactions between dipoles that are induced or permanent. • Relatively weak compare to primary bonding. • Dipole moment is defined as the charger value multiplied by the separation distance between positive and negative charge -q Dipole moment=μ =q. KIG 1004: Basic Materials for Mechanical Engineer . Secondary Bonding • Secondary bonds are due to attractions of electric dipoles in atoms or molecules.d q= Electric charge d = separation distance • There two types of bonds permanent and fluctuating.

The dipole moment is qd. • b) An electric dipole moment in a covalently bonded molecule. KIG 1004: Basic Materials for Mechanical Engineer . • a) An electric dipole.

• Weak secondary bonds in noble gasses.27 Asymmetrical distribution Distribution of electron charge (Changes with time) KIG 1004: Basic Materials for Mechanical Engineer . • Symmetrical Figure 2. • Dipoles are created due to asymmetrical distribution of electron charges. Fluctuating Dipoles • Electron cloud charge changes with time created fluctuation dipoles.

Permanent Dipoles • Dipoles that do not fluctuate with time are called Permanent dipoles.  Examples:- Symmetrical No Dipole CH4 Arrangement moment Of 4 C-H bonds Asymmetrical Creates CH3Cl Tetrahedral Dipole arrangement KIG 1004: Basic Materials for Mechanical Engineer .

28 Hydrogen H Bond KIG 1004: Basic Materials for Mechanical Engineer . dipole is created due to asymmetrical arrangement of hydrogen atoms. H 105 0 O Figure 2.  Example :-  In water.  Attraction between positive oxygen pole and negative hydrogen pole. Hydrogen Bonds • Hydrogen bonds are Dipole-Dipole interaction between polar bonds containing hydrogen atom.

a) Permanent dipole nature of the water molecule. b) Hydrogen bonding among water molecules due to permanent dipole attraction KIG 1004: Basic Materials for Mechanical Engineer .

KIG 1004: Basic Materials for Mechanical Engineer .

KIG 1004: Basic Materials for Mechanical Engineer .

KIG 1004: Basic Materials for Mechanical Engineer .

Summary: Bonding Type Bond Energy Comments Ionic Large! Non-directional (ceramics) Covalent Variable Directional large-Diamond (semiconductors. ceramics small-Bismuth polymer chains) Metallic Variable large-Tungsten Non-directional (metals) small-Mercury Secondary smallest Directional inter-chain (polymer) inter-molecular KIG 1004: Basic Materials for Mechanical Engineer .

What are percentage of Cu and Ni atoms in this alloy? Given:. Problem A 100 gram alloy of nickel and copper consists of 75 wt% Cu and 25 wt% Ni.75g Cu Atomic Mass 63.69 a) Number of gram moles of Cu b) Number of gram moles of Ni c) Atomic Percentage of Cu d) Atomic Percentage of Ni KIG 1004: Basic Materials for Mechanical Engineer .54 25g Ni Atomic Mass 58.

75g Number of gram moles of Cu =  1.4260mol 58.1803mol 63.5% (1.4260) Atomic Percentage of Ni = 0.54 g/mol Number of gram moles of Ni = 25 g  0.1803  0.1803 Atomic Percentage of Cu =  100  73.1803  0.5% (1.4260  100  26.4260) .69 g/mol 1.