Summary:AtomicStructureand

ChemicalBonding
Atom:composedofanucleus(neutron+proton)
andorbitingelectronsaroundit.
Electronicorbitalsarequantizedandgovernedby
thelawsofquantummechanics
Whentwoatomsarebroughttogether,depending
onfavourableenergetics,theymayformbondand
thetypesofbondisdecidedprimarilybytheatomic
structure(electronicconfiguration).
Howdothebondingatomsarrangein3D?
1
TetrahedronofMaterialsScience
Processing
Structure
Properties
Performance
Structure
AtomicStructure
andBonding
Structureof
crystallineSolids
Imperfections
StructureofCrystalline
Solids(Part1)
Textbook:Chapter3,FundamentalsofMaterials
ScienceandEngineering,Callister Jr.,5
th
edition,John
WileyandSonsInc
3
August12,2014
Lecture3
Basedontheregularitywithwhichatomsorionsarearranged
withrespecttooneanother,solidscanbeclassifiedas:
Crystalline
Atomsarepackedinperiodic array
Longrange orderexists
Noncrystalline (Amorphous)
Atomshavenoperiodicpacking
Shortrange orderexists
4
CrystallineSiO2 AmorphousSiO2
Si Oxygen
Examples: Metals
Ceramics
Polymers
(some)
Examples: Glasses
Polymers
Si Oxygen
TypesofSolids:BasedonAtomic
Arrangement
Idealcrystal:Definition
Anidealcrystalisaperiodicarray ofstructuralunits,such
asatomsormolecules.
Itcanbeconstructedbytheinfiniterepetitionofthese
identicalstructuralunitsinspace.
Crystalstructurecanbedescribedintermsofalattice,and
an/agroupofatom(s)attachedtoeachlatticepoint.The
/groupofatom(s)isthebasis.
CrystalStructure=Lattice +Basis
5
6
Lattice
Lattice
7
8
LatticeandUnitCell
Lattice:Aninfinitearrayofdiscretepointswithanarrangement
andorientationthatappearsexactlythesame,fromanyofthe
pointsthearrayisviewedfrom.
UnitCell:Thesmallestunitwhich,whenrepeatedinspace
indefinitelywillgeneratethespacelattice.
Primitivecell:A unitcellwhichmustcontainpreciselyonelattice
point.
9
CrystalStructure
Thestructureofallcrystalscanbedescribedin
termsofalatticeandan/agroupofatom(s)
attachedtoeverylatticepoint.
The/groupofatom(s)iscalledthebasis
10
Lattice Basis Crystalstructure
LatticeParametersofUnitCell
11
Aunitcellcanbecompletely
describedby:
Thelengthsa,b andc ofthree
noncoplanarvectorsa,b,andc.
Theangles,,and between
thevectors
AthreedimensionalBravais lattice
consistsofallpointswithposition
vectorsR thatcanbewrittenasa
linearcombinationofprimitive
vectors.Theexpansioncoefficients
mustbeintegers.
R =n
1
a +n
2
b +n
3
c
12
SevenCrystalSystems
FourteenBravaislattice
13
CubicCrystalStructure:HardSphereModels
14
Eachatomissharedby8
unitcells.
Shareofeachcorneratom
toaunitcell=
1
8
Numberofatomsperunit
cell=8
1
8
= 1
15
SimpleCubicStructure:Numberofatoms/unitcell
Shared by 8
unit cells
CoordinationNumber:
Numberofnearestneighbour
ortouchingatoms
Closedpackeddirectionsare
thedirectionsalongwhich
thehardspherestouch.For
simplecubicstructure,closed
packeddirectionisalongthe
edgeoftheunitcell.
Example:
Polonium
16
SimpleCubicStructure:CoordinationNumber
AtomicPackingFactor(APF)isthefractionofsolidsphere
volumeinaunitcell,assuminghardspheremodel
17
SimpleCubicStructure:AtomicPackingFactor
APF =
Iolumc o otoms in o unit ccll
Iotol :olumc o unit ccll
=
Numbc o] utoms unt ccII voIumc o] onc utom
1otuI oIumc o] unt ccII
=
N
4
3
n
3
u
3
=
N
4
3
n(0.5u)
3
u
3
=
1
4
3
n(0.5u)
3
u
3
= u.S2
PrincipalMetallicCrystalStructures
CrystalStructureofelementalmetals
About90%ofelementalmetalcrystallizesinoneofthe
threedenselypackedstructures:(a)bodycentered
cubic(bcc),(b)phasecenteredcubic(fcc)and(c)
Hexagonalclosepacked(hcp)
Thesepackingallowsenergyminimizationandmore
tightbondsdiscussedearlier
BodyCenteredCubicCrystalStructure
BCC:8nearestneighbors(CN)
Thismaybeacopyrightmaterial
20
BodyCentredCubic(BCC)Structure
Eachcorneratomissharedby8unitcells.
Thereisoneatomatthecentreoftheunitcell.
Numberofatomsperunitcell=
1
8
Coordinationnumber=8
Closedpackeddirectionisalongthebodydiagonals
BodyCenteredCubicCrystalStructure
3 4
4
,
3
a r
r
or a
=
=
Relationshipbetweenthelengthof
thecube,a andatomicradiusr:
No.ofatomsintheunitcell:
1
8 1 2
8
N = + =
Atomicpackingfactor(APF):
vol.of atoms in unit cell
100%
vol. of unit cell
= 68 %
APF =
BodyCenteredCubic
Metal a (nm) r (nm)
Cr 0.289 0.125
Fe 0.287 0.124
Mo 0.315 0.136
K 0.533 0.231
Na 0.429 0.186
Ta 0.330 0.143
BCCisnotaclosepackedstructure
Eachcorneratomissharedby8unitcells.
Eachfacecentredatomissharedbytwounitcells.
Numberofatomsperunitcell=
1
2
1
8
Closedpackeddirectionisalongthefacediagonals.
Coordinationnumber=12
23
FaceCentredCubic(FCC)Structure
Shared by 2 unit cells
FaceCenteredCubicCrystalStructure
2 4
4
,
2
a r
r
or a
=
=
Relationshipbetweenthelengthof
thecube,a andatomicradiusr:
1 1
8 6 4
8 2
N = + =
vol.of atoms in unit cell
100%
vol. of unit cell
= 74 %
APF =
No.ofatomsintheunitcell:
Atomicpackingfactor(APF):
FaceCenteredCubicCrystalStructure
Metal a (nm) r (nm)
Al 0.4050 0.143
Cu 0.3615 0.128
Au 0.4080 0.144
Pb 0.4950 0.175
Ni 0.3520 0.125
Pt 0.3930 0.139
FCCisaclosepackedstructure
Numberofatomsperunitcell=3+(2x)+(12x1/6)=6
Coordinationnumber=12
Atomicpackingfactor=0.74
26
HexagonalClosePacked(HCP)Structure
Whatistheidealc/aratioinanidealHCPstructure???
Metalliccrystals
Denselypacked
Typicallyforpuremetals,onlyoneelementis
present
Metallicbondingisnondirectional
Nearestneighbourdistancestendtobesmallto
lowerthebondenergy
Metalshavesimplestcrystalstructure
Crystalstructureandperiodictable
Atomicradiiofcommonmetals
Densitycomputationofmetals
Ceramiccrystals
Ceramicsarecomposedofatleasttwoelements.
Atomicbondingrangefrompurelyionictopurely
covalent.
Degreeofioniccharacterforatwoelement
ceramicdependsontheelectronegativities (X
A
and
X
B
)oftheatoms
100
2
- exp - 1 character ionic %
2

(
(

|
.
|

\
|

=
B A
X X
Ioniccrystals
Consistsofpositivelychargedcationsandnegatively
chargedanions.
Crystalstructureisinfluencedbytwofactors:
Magnitudeofelectricchargeoneachcomponentions
Relativesizesofthecationsandtheanions
Crystalmustbeelectricallyneutral
Stablecrystalsformwhenanionssurroundingacation
areallincontactwiththecation.
Ioniccrystals:NaCl structure
NumberofCl

ions/unitcell:(8x
1/8)+(6x1/2)=4
NumberofNa
+
ions/unitcell:1+(12
x)=4
Total+ve charge=4
Totalve charge=4
Totalcharge=4 4=0
TwointerpenetratingFCClattices(oneforNa
+
ions,
otherforCl

ions);withoneofthemshiftedby(,0,0)
4Cl

:(000),(0),(0),(0)
4Na
+
:(),(00),(00),(00)
r
Na+
/r
Cl
=0.54 6foldcoordination
Ioniccrystals
CsCl structure
r
Cs+
/r
Cl
=0.91
Ioniccrystals
CaF
2
structure
r
Ca2+
/r
F
=0.73
Exception
39
ZnS structure
r
Zn2+
/r
S2
=0.48
Whensignificantcovalentcharacterispresent
Satoms:(000)(0.50.50)(0.50
0.5)(00.50.5)
Znatom:(.250.25.75)(0.75
.250.25)(.25.75.25)(.75.75
.75)
87%covalency
Similarstructure:CdS,InAs,
InSb,ZnSe
PerovskiteStructure
ABO
3
Structure
Thisisacopyrightmaterial
Interstitialvoids
Voidsarecommoninalltypesofstructuresi.ealsoinclosepacked
structurelikefccandhcp
1. Tetrahedral
2. Octahedral
OctahedralVoids
Intheoctahedralsite,therearesix
nearestneighbors(ions/atoms)
equidistantfromthecenterofthe
void
Thissiteiscalledoctahedralsincethe
atomsorionssurroundingthesite
formsaeightsidedoctahedron
InFcc structure,thereisone
octahedralsiteatthecenterofthe
cellandthereisoneoctahedralsite
oneachcubeedgeofthecell
Therefore,fcc cellhastotal4
octahedralsitesoroneoctahedral
site/atom
Thisisacopyrightmaterial
43
Thisillustrationshowsthe
octahedralsiteinanfcc lattice
bottom.Wehave12/4+1=4
positionsperunitcell.
Herewehaveoctahedralsitesin
thebcc lattice.Wehave12/4+6/2
=6 positionsperunitcell
Sizeofthelargestspherethatcan
fitinanoctahedralvoidis0.414r,
whereristheradiusofthespheres
oftheclosepackedarray.
TetrahedralVoids
In the tetrahedral site, there are four nearest atoms/ions
equidistant from the center of the tetrahedron
A regular tetrahedron is formed when the centers of the four
atoms surrounding the void are joined
In fcc cell tetrahedral sites are located at (0.25, 0.25, 0.25
positions)
There are eight tetrahedral sites in fcc cell ie 2 voids/atom
Size of largest sphere that can fit into the tetrahedral void of
a close packed structure = 0.225 r, where r is the radius of a
sphere of the close packed structure.
45
Theconfigurationontopisthe
tetrahedralpositioninthefcc
lattice.Theblackcirclesdenote
latticepoints,theredcirclemarks
oneofthe8 thetetrahedral
position.
Thepictureonthebottomshows
thetetrahedralconfigurationfor
thebcc lattice.Wehave(64)/2=
12 positionsperunitcell.