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RichardE.Eitel
TeachingAssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
IntroductiontoMaterialsScience
andEngineering
2
Introductions
Coursestructure&learning
approachandobjectives.
Thisclassperiodwillservesasanintroductiontothecourse
andMaterialsScience&Engineeringdiscipline.
Exploringstructure
propertyrelationships.
vs
2
BorninClevelandOhio:
HOMEoftheBROWNSandtheRockandRollHallofFame!
Undergrad:AlfredUniversity(19941998)
B.S.inCeramicEngineering
SouthernTierofNewYorkState
HomeoftheSaxons
X
Nowhere
Alfred
3
PennState:19992006
MaterialsResearchInstitute
MaterialsResearchLaboratory
Foundedin1956:
1stInterdisciplinaryResearch
LabinMaterialsScience
Ph.D.inMaterialsScienceand
Engineering:
Thesis:
NovelPiezoelectricCeramics:
DevelopmentofHigh,
Temperature,High
PerformanceMaterialsonthe
BasisofToleranceFactor
UniversityofKentucky(20062013)
Teaching:
DepartmentofChemicaland
MaterialsEngineering
IntroductiontoMaterials
CeramicEngineering
MaterialsCharacterization
Threedifferentlabcourses
Research:
PiezoelectricMaterials
Microfluidics
MaterialsSynthesis
Sensing
Biofluidics
CellBasedSensors
4
Pastimes:AsinthingsusedtodobeforeIstartedteaching!
2015NYC
Marathon?
Yearsofeducationalresearchshowsthattheaverageanindividuals
averageattentionspaninapassivelectureisabout15minutes.
Learning howeverrequiresnotjustattentionbutactivethought!
After15minuteofLecture LearninginanActiveClassroom
5
TeambasedGuidedInquiry
9
1. Breakintogroupsof3or4.
2. Rearrangeseatsotheyoucantalk
comfortably.
3. Onestudentineachgrouplogonto:
m.socrative.com
4. Room#129851
GuidedInquiryI:Heat(10minutes)
UseFigure1.1.1toanswerthefollowingquestions(workasagroup
makesureeveryoneagreesbeforemovingtothenextquestion):
6
ConceptCheckI:
Ahotpieceofcopperisplacedincontactwithacoldbrick?
Ifthecopperloses5caloriesofenergy,howmuchenergy
doesthebrickgain?
Guided Inquiry II:
Heat and Work (10 Minutes)
Heat
Transfer of energy
when there is a
difference in
temperature.
Work
Transfer of energy
when there is no
difference in
temperature.
7
ConceptCheck:
AccordingtotheFirstLawofthermodynamics,
couldheatbetransferredfromacoldobjecttoa
hotobject,resultinginthehotobjectgetting
hotterandthecoldobjectgettingcolder'?
14
GuidedInquiryIII:ActiveLearning
(10minutes)
1
RichardE.Eitel
AssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
01 IntroductiontoMaterialsScience
andEngineering
Bytheendofthislectureyoushouldbeableto:
Theoverallobjectistointroducethefieldofmaterials
scienceandengineering.
Appreciatetheinterdependence
ofstructure,processing,
properties,andperformancefor
materialsdesignandselection.
Classifymaterialonthebasisof
structureandbonding.
Beabletopredictbondingand
materialpropertiesbasedonthe
atomicstructure.
2
Thegoalofmaterialsscienceandengineeringistodescribethe
structure,processing,andpropertiesrelationshipwhichdictatethe
performanceofamaterialforaspecificengineeringapplication.
Acompletestructuraldescriptionofanengineeringmaterial
mayspanlengthscalesfromthenano tothemacro.
AtomicStructure:
< 1u
-10
m
BondingandCrystalStructure:
1u
-10
-1u
-8
m
Macrostructure:
> 1u
-3
m
Microstructure:
1u
-7
-1u
-4
m
3
Materialspropertiesarecharacteristicswhichareintrinsic
tothematerialandformthebasisformaterialsselection.
PERFOMANCEREQUIREMENT:
Supporta6000poundtruck
TensileStrengthofHardenedSteel:
250,000PSI
Strcss
]uIuc
=
IooJ
Arco
Materialspropertiesareinputsinordertodesignacomponentto
achievesuitableperformanceinagivenapplication.
HighTensionWire:
PerformanceSpec:<0.02Ohms/km
MaterialsProperty:
TransparentArmor:
PerformanceSpec:>90%lighttransmission
MaterialProperty:
TotalHipReplacement:
PerformanceSpec:20yearlife
MaterialProperty:
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Processingincludestheentirehistoryofamaterialrequired
toforminintoacomponentwiththerequiredperformance.
ProcessingimpactBOTHtheSTUCUTREandthePROPERTIES
Theperformanceofamaterialinagivenapplicationisa
consequenceofcarefulmaterialsselectionandengineeringofthe
materialintoacomponent.
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Materialsclassificationmaydependonwhetherwearetryingto
developunderstandingofselectamaterialsforagivenapplication.
StructuralClassification ApplicationsBasedClassification
Structural
Classification
Ceramics
Polymers
Composites
Metals
Thetraditionalclassificationofmaterialintoceramics,polymers,
metals,andcompositionisprimarilyonthebasisofatomicbonding
andstructure.
Ceramics:
Inorganic,nonmetallicsolids
composedofasleastone
metallicandonenon
metallicatom.
Polymers:
Macromoleculesformedby
covalentbondingofsimpler
molecularrepeatunits.
Metals:
Pureandalloyedatomic
speciesheldtogetherby
metallicbonding.
Composites:
Twoormoreoftheabovecombined
toproduceanewmaterialwith
uniquepropertiesorcombinations.
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Metals
Consistofpureandalloyedatomsheldtogetherbydelocalizedelectronsthat
overcomethemutualrepulsionbetweentheioncores(MetallicBonding)
Excellentstructuralmaterials:
high strength, toughness
(resistance to impact)
Electrical,thermalconductors
Atomsarrangedinregularlydefined,
repeatingpositionsthroughoutstructure
Steel: An alloy of iron, containing various amounts of carbon,
manganese, and one or more other elements, such as sulfur,
nickel, silicon, phosphorus, chromium, molybdenum, and
vanadium. These elements, when combined with iron, form
different types of steels with varying properties.
Metals?
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CeramicsandInorganicGlasses
Inorganic,nonmetallicsolids,composedofacombinationofoneormoremetallic
andoneormorenonmetallicatoms:
Al
2
O
3
(alumina);
SiO
2
(quartz, glass)
Mixedatomicbonding(ionicandcovalent)
Highstrength(compression),butbrittle
Excellent(electrical)insulators
Highthermalresistance;resistancetochemicalattack
High-end application: ceramic
tiles for use as heat shield in
aerospace vehicles (> 1600C)
Ceramics?
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Polymers
Macromoleculesformedbycovalentbondingofsimplermolecular
repeatunits(mers)
Easilyprocessedtoawiderangeofshapes,dimensions
Moderatestrength;goodductility.Lightweight.
Usuallynotsuitableforhightemperatureapplications
(>100to200C)
polyethylene
polypropylene
polystyrene
PVC
Polymers?
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Composites
Twoormorematerialscombinedtoproduceanewmaterialwith
desiredproperties(newpropertiesareaveragedvaluesof
components)
Lowtechexamples:
plywood(panelcomprised
ofmultiplelayersofwood
veneer,plusadhesive;grain
laidat90 angles)
concrete(cement[binder]
plussandandgravel)
steelbeltedtires(steel
belts,polyestercord,
rubber)
Hightechexamples:
carbonfiberepoxy
composites
ceramicfibermetalmatrix
composites(SiC fibersinAl)
Innovation:
Boeings new 787 DREAMLINER is be
predominantly carbon fiber epoxy
laminate, yielding a savings of ~20% in
fuel costs owing to weight reduction.
Alternativelymaterialsmaybeclassifiedandselectedbasedon
theirfunctionorsuitabilitytoaparticularengineeringneed.
1
RichardE.Eitel
AssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
02 GuidedInquiryAtomicBonding
Bytheendofthislectureyoushouldbeableto:
Theoverallobjectiveofthesesessionistodescribehow
atomicstructureleadstobondinginmaterials.
DefineElectronegativity
Predictthedistributionof
electronsinabond.
Predictthetypesofbonds
formedindifferentatomsand
theirproperties
2
Thestructureofmaterialsandtheircorrespondingpropertiesarise
duetotheelectronicstructureoftheconstituentatoms.
Electronicstructure
inmetalsallows
planesofatomsto
slidepasteachother
Electronconfigurationina
hightemperature
superconductor.
In1913Bohrclarifiedthestructureoftheatombytheorizing
electronswereconfinedtospecificallowedstates(orbits).
Explainssimpleemissionspectraofgases.
Allowedenergylevelsina
hydrogenlikeatomarelimitedto
integralvaluesofn:
Where:
h PlanksConstant
m
c
massofanelectron
q fundamentalcharge
e
0
permittivityoffreespace
n n
th
energylevel(shell)
3
Electrontransitionsbetweenallowedstatesareaccompaniedby
theadsorptionoremissionofaquantaorpacketofenergy,for
exampleinthefromofaphoton.
E
nm
= E
m
-E
n
= bv
Ionizationenergy(IE)requiredto
removeaboundelectronintheE
n
stateyieldingafreeelectron(E

)
Allowedenergy
levelsinasingle
electronatomwith
effectiveatomic
numberZ:
E
n
= -
m
c
c
4
Z
2
8e
0
2
n
2
b
2
IE = E

-E
n
Atomswithmorethanhalffilledoutershellswill
tendtoATTRACTmoreelectronstocreateafull
outershell:Electronegative
Atomswithlessthanhalffilledoutershellswill
tendtogetridofouterelectrons:Electropositive
TheseouterVALANCEelectronsleadBONDING.
Emptyandcompletelyfilledshellshavelowerenergythanpartially
filledshells.ThusVALANCEelectronintheoutermostorpartially
filledshelltendtobeparticularlyactive.
4
Therelativetendencyofanelementtogainorlooseelectronsis
quantifiedaccordingtoitselectronegativity .
Atomswithrelativelyhighvaluesof_:__________________
Atomswithrelativelylowvaluesof_:__________________
Electronegativity=affinityofatomsforelectrons
Atomwithhigherelectronegativityhasastrongerpullonelectrons.
Electrons are closer to atom with higher electronegativity
GuidedInquiryI:Electronegativity
(10minutes)
m.socrative.comRoom#129851
5
A. FeBr
B. BrBr
C. KBr
D.CBr
E. Idontknow
ConceptCheck#1:
In which of the following bonds are the electrons
most strongly pulled to one of the atoms?
m.socrative.comRoom#129851
A. FeBr
B. BrBr
C. KBr
D.CBr
E. Noneoftheabove.
F. Idontknow.
ConceptCheck#2:
In which of the following bonds are the electrons
distributed evenly between the two atoms?
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GuidedInquiryII:TypesofBond
(12minutes)
A.Covalent
B. Ionic
C. Metallic
D.Idontknow
ConceptCheck#3:
What are the primary bonds in the compound
CaF
2
?
m.socrative.comRoom#129851
7
A.Covalent
B. Ionic
C. Metallic
D.Idontknow
ConceptCheck#4:
What are the primary bonds in the compound
GaN?
m.socrative.comRoom#129851
GuidedInquiryIII:BondCharacter(12minutes)
%IonicCharacter %IC :
OnlyConsidersIonicand
CovalentBonding
Type of Bond How do you know?
%IC = 1uu% 1 - exp
- _
A
-_
B
2
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ElectronegativityDifference
(EN):
EN = _
A
-_
B
BondTypeTriangle:
ElectronegativityDifferenceover
AverageElectronegativity
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A. 0%ionic
B. 22%ionic
C. 68%ionic
D. 100%Ionic
E. Idontknow
ConceptCheck#5:
What is the ionic character of the bond formed in
the compound FeBr
2
?
m.socrative.comRoom#129851
A. Ionic
B. Covalent
C. Metallic
D. Idontknow
ConceptCheck#6:
What is dominant primary bond type in the
compound FeBr
2
?
m.socrative.comRoom#129851
1
RichardE.Eitel
TeachingAssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
03 Crystallography:
lattices,directions&planes
Identifythesevencrystal
systems.
Distinguishbetweenacrystal
system,apointlattice,anda
crystalstructure.
Thegoalofthislectureistodeveloptheskillsrequiredto
describeanddefinethestructureofcrystallinesolids.
AssignMillerIndicesto
directions[UVW]and
planes(hkl).
Bytheendofthislectureyoushouldbeableto:
vs vs
2
Accuratelydescribingtheorderedstructureofcrystalline
materialsrequiresidentifyingseverallayersofstructure.
3
CrystalStructure spacefillingpolyhedra
PointLattice referencepointsdescribing
symmetricallyequivalentpositions
Basis Atomoratomiccomplex
CrystalStructure
lattice+basis
Therearesevenunique3Dcrystalstructureswhich
encompassallpossiblespacefillingpolyhedral.
4
6Latticeparameters:
Edges:a,b,c
Angles:obc, [oc, yab
NOPOINTSinacrystalstructure!
3
The14Bravais pointlatticesincludethelocationsofthe
symmetryequivalentpoints(referencepositions)within
thesevencrystalsystems.
5
Auguste Bravais
18111863
Latticepoints atoms
Primitivelattices(P)haveexactlyonelatticepointperunit
cell.
4
Nonprimitivelatticeshavemultiplepointsperunitcelland
mayincludebodycentered(I),facecentered(F),andend
centered(ABC)types.
PPrimitive
F FaceCentered I Body
Sincealllatticepointshaveidenticalsurroundingsthe
choiceoftheoriginisarbitrary.
5
Toconstructacrystalstructureamotifofbasisunitis
assignedtoeachlatticepoint.
Basis
Lattice Motif(Basis) CrystalStructure +
=
TheSAMEmotifmustbeassignedtoEVERYpointinthe
lattice.
BodyCenteredLatticewith
1AtomPerPoint
SimpleCubicLattice
With2AtomsPerPoint
VS.
6
Differentmotifscanproduceverydifferentcrystal
structuresfromthesamelattice.
Positions,directions,andplanesincrystalstructuresare
distinguishedbymaintainingaspecificconventionunique
toeach.
Positional
Coordinates:
,1,
Direction
Vectors:
UFW
hk|
Planar
Indices:
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Conventionistodefinearighthandedcoordinatesystemin
whicheachoftheunitcelledgesa,b,andchaveunit
length.
x
y
z
o
b
c
x
y
z
o
b
c
o = b = c
o = [ = y = 9u
o
o = b = c
o = [ = y = 9u
o
Specificpositionsaredesignatedusingthecoordinates h,k,
and l whereeachvaluerepresentsafractionofthelattice
parametera,b,andc,respectively.
Findthecoordinatesforthe
following:
PointD:
PointC:
PointH:
8
DirectionsarespecifiedbylowestintegersvaluesU,V,and
Walongunitvectorso,b,andc andenclosedinsquare
brackets uIw .
0 = ua +Ib +w = 111
Specifiesonlydirection
NOTmagnitude...
Assigningdirectionalindicescanbeperformedbyfollowing
theprocedure:
1. Usingarighthandedcoordinatesystem,determinethe
coordinatesoftwopointsthatlieonthedirection
2. Subtractthepositionofthetailpointfromthecoordinatesof
theheadpoint,toobtainthenumberoflatticeparameters
traveledineachdirection
3. Clearfractionsand/orreducethedifferences,togive(lowest)
integervalues.
4. Writeindicesinsquarebrackets[UVW](nocommas)
5. Indicatenegativevalueswithoverbar.
9
Practice:
Findthedirectionindicesfor
vectorEOatleft:
Findthedirectionalindicesfor
thefollowingvectors(atright):
VectorOA:
VectorOF:
VectorCB:
ImportantNotesaboutDIRECTIONS:
ADIRECTIONanditsnegative
areNOTthesame!

1 1

Multiplesofdirections
AREidentical!
(Reducebyconvention) 1 = 2
=
Certaingroupsor
familiesofdirections
andtheiroppositesare
equivalent.
Cubic 1 :
1 , 1 , 1 ,
1

, 1

, 1

,
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Millerindicesofplanesaredenotedbyintegersh,k,andl
enclosedinparenthesis hk| .
MillerPlanesaredeterminedusing
1. Chooseaplanethatdoesnotpassthroughtheorigin at:0,0,0
moveoriginifneeded.
2. Determinefractionalintercepts oftheplanewiththe
crystallographicaxesx,y,andz.
forplanesparalleltoanaxestheinterceptis
3. Takereciprocal oftheintercepts.
4. ClearfractionsbutDONOTREDUCEtolowestintegers.
5. Citeplaneswithparenthesis bkl
indicatenegativevalueswithoverbar.
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ExamplesandPracticewithPlanes:
ImportantNotesaboutMillerindicesforplanes.
Planesandtheir
NEGATIVES areidentical!
PlanesandtheirMULTIPLES
areparallelbutNOT
identical!
Equivalentfamiliesofplanes
areindicatedbyBraces
{hkl}:
1 = 1

2 = 1
Family 1 :
1 , 1

, 1 ,
1

, 1 , 1

1
RichardE.Eitel
AssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
04 CrystallineSolids
2
Thegoalofthislectureistodeveloptheskillstodescribe
andpredictbothstructureandpropertiesofcrystalline
materials.
Bytheendofthislectureyoushouldbeableto:
Describethecrystalstructuresof
severalcommonengineeringmetals
andceramics
Estimatedensitiesofbothmetal
andceramicmaterialsusingonly
theirknowncrystalstructure.
Useatomicradiitopredictthe
structureofsimpleionic
compounds.
2
1.Yes
2.No
3.Imnotsure
ConceptCheck:CanyouIdentifyCommonUnitCellsand
Calculatetheirassociatedproperties(latticeparameter,
mass,volume,density,etc)?
GuidedInquiryI:CrystalsandGlasses
(5minutes)
Hypotheticalarrangementofatomsinacrystalandaglass.
3
1.Itwouldbedifferent.
2.Itwouldbethesame.
3.Idontknow.
ConceptCheck:Aglassrodhasastiffnessof70GPa when
pulledalongitslength.Howwouldyouexpectthestiffness
tochangeifyoupulleditperpendiculartoitslength?
Crystalstructuresareusedtodescribethelongrange
periodicitypresentincrystallinematerials.
LongRangeOrder: ShortRangeOrder:
4
Crystallinematerialsrepresentthestablelowestenergy
stateofanysolid.
Dense,regular
packing
Typicalbondlength
Typicalbondenergy
Nondense,
random packing
Typicalbondlength
Typicalbondenergy
GuidedInquiryII:CrystalUnitCells
(10minutes)
SimpleCubic
(SC)
BodyCentered
Cubic
(BCC)
FaceCentered
Cubic
(FCC)
5
1. 1
2. 2
3. 3
4. 6
5. Idontknow.
ConceptCheck:Forthecrystalstructureshown,
howmanyblueatomsarethereperunitcell(i.e.,
withintheunitcell)?
1. 1
2. 2
3. 4
4. 8
5. Idontknow.
ConceptCheck:Forthecrystalstructureshown,
howmanygreenatomsarethereperunitcell(i.e.,
withintheunitcell)?
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TheUNITCELListhesmallestessentialunitofacrystalline
material.
UnitCellofCesiumChloride
Keycharacteristicsofaunitcell:
Dimensionsspecifiedbysixlattice
parameters (o, b, c, o, [, onJ y)
Basedononeofthe14Bravais
lattices
Includesexactlyonebasisateach
latticepoint
Repeatsindefinitelyinall
direction
Canbeusedtocalculatethe
densityofthecrystallinephase
Mostmetaltypicallyassumeoneofthreebasiccrystal
structures.
MetalswiththeBodyCentered
Cubic(BCC)structureinclude:
Tungsten,chromium,iron,
molybdenum,vanadium
MetalswiththeFaceCentered
Cubic(FCC)structureinclude:
aluminum,calcium,copper,gold,
lead,nickel,platinum,silver
MetalswiththeHexagonalClose
Packed(HCP)structureinclude:
Cadmium,Titanium,Zinc,
Magnesium,Cobalt
BCC
FCC
HCP
7
GuidedInquiryIII:AtomicPackingFactor
(10minutes)
= lattice
parameter
R = atomic
radius
SC BCC FCC
AtomicPacking
Factor(APF):
APF =
uu|ume u atumx |n un|t ce||
uu|ume u un|t ce||
A. 0.52
B. 0.68
C. 0.74
D. 1.00
E. Idontknow
ConceptCheck:Whatistheatomicpackingfactor
(APF)foraSCunitcell?
8
GuidedInquiryIV:Density
(10minutes)
SC BCC FCC
A. a = 2R
B. a = 2R 2
C. a = 4R 3
D. a = 4R 3
E. Idontknow
Concept Check: What is the
relationship between a and R for an
FCC unit cell?
FCC
9
Ceramiccrystalstructuresarebasedoneitherionicor
covalentbondingoftheconstituentspecies.
ConsiderCovalentbonding: Consideranionically bondedceramic
GuidedInquiryV:InterstitialSites
(10minutes)
10
A. Originalatoms
B. Interstitialatom
C. Idontknow
Concept Check: Basedontherelativesizesof
anionsandcations,ifthiswereanioniccompound,
whichatomswouldbetheanions;theoriginal
atomsatthecornersoftheunitcell,orthe
interstitialatomyouadded?
Consideringtheclosestpackingofatomsonly74%ofthe
spaceisoccupied,theseholesorintersticesoffersitesfor
additionalatoms...impurities,dopants,compounds...
11
Inionically bondedceramicsstablecrystalstructuresmust
balancetheelectrostaticinteractionsofoppositelycharged
ions.
+


+


Cations willsurroundthemselveswiththe
maximumnumberofoppositelycharged
anionspossible!
Radiusratioscanbeusedtopredictthenumberofnearest
neighbors(Coordinationnumber)ofvarioussizedcations.
12
GuidedInquiryVI:DensityofCeramics
(10minutes)
A. a = 2r
an|un
B. a = 2r
cat|un
C. a =
4r
an|un
2
D. a = 2r
an|un
+2r
cat|un
E. Idontknow
Concept Check: What is the general
formula for the lattice parameter of a
the rock salt structure?
1
RichardE.Eitel
AssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
05 StructureandProperties
ofPolymers
2
Thegoalofthisdiscussionistobeabletodescribethe
macromolecularstructureofpolymersandrelatethisto
theirengineeringproperties..
Bytheendofthisdiscussionyoushouldbeableto:
Describetheroleofpolymerchain
lengthonkeyengineering
properties.
Classifythebasicstructuresof
polymerchains.
Predicttrendsinthecrystallinity
andpropertiesofpolymerbasedon
theirmolecularweightandchain
structure.
2
Polymersaregiantmacromoleculesconsistingof10sto
many1,000sofcovalentlybondedrepeat(mer)units.
mer
GuidedInquiryI:AverageMolecularWeight
(10minutes)
m.socrative.comRoom#129851
3
A. 0.0012
B. 831.75
C. 832
D. 1,472,800
E. I don't know.
ConceptCheck:
What is the DP for polypropylene with a
molecular weight of 35,000 g/mol?
m.socrative.comRoom#129851
A. g
B. gmol
C. mol
D. It is unit less
E. I don't know.
ConceptCheck:
What are the units for DP?
m.socrative.comRoom#129851
4
Thechainlengthofpolymersischaracterizedbythedegree
ofpolymerization(DP)andthemolecularweight.
PolymersareALWAYSmixtureofmacromoleculesof
varyingmolecularweights
NumberAverageMolecularWeight(H
n
):
Where:
H

isthemedianmolecularweightofachaininthei
th
sizerange.
x

isnumberfractionofchainsinthei
th
sizerange
w

isweightfractionofchainsinthei
th
sizerange
m ismolecularmassoftherepeat(mer)unit
M
n
= x
|
M
|
M
w
= w
|
M
|
=
x
|
M
|
M
|
x
|
M
|
=
x
|
M
|
2
x
|
M
|
WeightAverageMolecularWeight(H
w
):
Degreeofpolymerization(DP):
Polydispersity Index(PDI):
DP =
M
n
m
PDI =
M
w
M
n
0
0.05
0.1
0.15
0.2
0.25
F
r
a
c
t
i
o
n
a
l

C
o
n
t
e
n
t
MolecularWeightRange(g/mol)
FractionalDistrubtionofMolecularWeights
WeightFraction(wi)
NumberFraction(ni)
GuidedInquiryII:MolecularWeightCalculations
(8minutes)
Considerasampleofplasticwhichyouknowis15mol%polymer
moleculeswithmolecularweight500,000g/mol,and85mol%
polymermoleculeswithmolecularweight150,000g/mol.
NumberAverageMolecularWeight(H
n
):
H
n
= x

WeightAverageMolecularWeight(H
w
):
H
w
= w

=
x

=
x

2
x

Degreeofpolymerization(DP):
P =
H
n
m
Polydispersity Index(PDI):
PI =
H
w
H
n
5
A. 119,600g/mol
B. 202,500g/mol
C. 280,000g/mol
D. Idontknow
ConceptCheck:
What is the number average molecular weight for
the above mixture?
m.socrative.comRoom#129851
A. 119,600g/mol
B. 202,500g/mol
C. 280,000g/mol
D. Idontknow
ConceptCheck:
What is the weight average molecular weight for
the above mixture?
m.socrative.comRoom#129851
6
A.Yes
B. No
C. H
w
isalwayslessthanH
n
.
D.Idontknow
ConceptCheck#3:
Can M
w
belessthanM
n
?Why?
m.socrative.comRoom#129851
Formanysimplelinearpolymers,materialpropertiesare
dictatedbychainlengthandweaksecondarybonding
betweenchains.
7
GuidedInquiryIII:MWandProperties.
(5minutes)
Considertwodifferentplatesofspaghetti.Oneinwhichallthe
strandsarethefulllengthandoneinwhichthestrandhavebeen
cutintoshortsegments.
A. 100,000 g/mol
B. 200,000 g/mol
C. Theyhavethesamestrength.
D. Idontknow
ConceptCheck#4:
Which has a higher strength; polyethylene of
100,000 g/mol or 200,000 g/mol?
m.socrative.comRoom#129851
8
ConceptCheck#5:
Which flows more easily; polyethylene of 100,000
g/mol or 200,000 g/mol?
m.socrative.comRoom#129851
A. 100,000 g/mol
B. 200,000 g/mol
C. Theyflowequally.
D. Idontknow
Polymersmayalsobecharacterizedbychainlengthand
meanendtoendDistance.
Total(stretchedout)chainlength(L):
I = N J sin
0
2
Meanendtoenddistance(r):
r = J N
Where:
d bondlength
N numberofbondsinchain
anglebetweenadjacentatoms
=109.5
o
forCC
L
9
Thepropertiesoflinearpolymerscanbemodifiedby
introducingbranchingorcrosslinking.
Linear
secondary
bonding
Branched
Cross-Linked Network
Likemetalsandceramicspolymersmayexhibithighly
orderedcrystallineregions.
10
GuidedInquiryIV:PolymerCrystallinity.
(10minutes)
a) Polyethyleneorpolystyrene.
b) Polyethylenewithmanylongbranchesorpolyethylene
withafewshortbranches.
c) Atactic polypropyleneorisotacticpolypropylene.
d) Polypropyleneorpoly(ethyleneterephthalate)(PET).
e) Polyethyleneorarandomcopolymerof50%ethylene
repeatunitsand50%propylenerepeatunits.
f) PETmeltedandrapidlycooledtoroomtemperatureor
PETmelted,cooledto150 C,heldtherefor1hour,and
thencooledtoroomtemperature.
Reportout:
Which of the following pairs is more crystalline?
m.socrative.comRoom#129851
11
Theproductionofmostpolymermacromoleculesfrom
theirmonomeroccursbyoneoftwopolymerization
routes.
Addition(Chaingrowth)
polymerization:
Condensation(stepreaction)
Polymerization
(byproductproducedoftenwater)
Initiator
monomer
Polyethylene:
Polyethyleneterephalate
Thermoplasticpolymersaretypicallylinearorslightly
branchedandsoftenonheatingallowingthemtobeeasily
(re)formedandreadilyrecycled.
12
Thermosetpolymersreactonmixingorunderactionof
heatformingextensivecrosslinks.
Example: Bakelitefirstcompletely
syntheticplastic,1907.
1
RichardE.Eitel
AssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
06 MaterialsCharacterization
Methods
Theoverallobjectivethislectureistogiveyoutheskillstoapply
severalofthemostwidelyusedmaterialscharacterization
methods:
Bytheendofthislectureyoushouldbeableto:
Calculateinterplanar spacings in
materialspossessingacubic
crystalstructure.
UseBraggsLawtorelate
experimentaldiffractiondata
tointerplanar spacing.
Calculatemeangraindiameter
andATSMgrainsizefrom
microstructureimages.
2
Diffractionistheapparentbendingofwavesaroundsmallobjects
andthespreadingoutofwavebeyondsmallopenings.
BeyondanOpening
AroundACorner
Theapparentspreadingduetodiffractiondependsonthe
wavelengthofthewaveorparticle.
SpreadingofWhiteLightSource
DispersionofSoundWaves?
3
Youngsdoubleslitexperimentrevealedunexpected
propertiesoflightandquicklymovingparticles.
https://www.youtube.com/watch?feature=player_detailpage&v=Iuv
6hY6zsd0
Theperiodicityofinterferencepatternsproducedby
diffractionexperimentsarerelatedtothegeometryofthe
slitorstructurecreatingthepattern.
4
GuidedInquiryI:BraggsLaw
(10minutes)
Ifconstructiveinterferenceoccursfromtwoplanesof
atomsforascatteringangle(theta)of20.0degrees
whatisthedistance(d)betweentheplanes,ifthethe
wavelengthofthewavesis0.154nm?
A. 0.450nm
B. 0.225nm
C. 0.119nm
D. 0.0843nm
E. Idontknow
ConceptCheck:
5
Theconditionforconstructiveinterferencefromequally
spacedlayersisgivenbyBraggsNoblePrizeWinningLaw.
ConstructiveInterferencefor
ABC=n*lambda
1912@21YearsOld!

d
WhataretheconditionsforwhichdiffractionOccurs?
nz = 2 J sin 0
Considern=1
z
2J
= sin 0
6
Whataretypicalspacings (dspacings)betweenatomic
planes?
SimpleRelationshipsexistdepending
onthecrystalsystemofthecrystal
structure:
General(othorhomic)
1
d
hk|
2
=
h
2
a
2
+
k
2
h
2
+
|
2
c
2
Cubic(a=b=c):
1
d
hk|
2
=
h
2
+ k
2
+ |
2
a
2
d
hk|
=
a
h
2
+ k
2
+ |
2
Tetragonal a = h = c :
1
d
hk|
2
=
h
2
+ k
2
a
2
+
|
2
c
2
GuidedInquiryII:Interplanar Spacings
(10minutes)
7
Diffractionexperimentscanbeusedtodescribethestructureand
atomicpositionsinbothsingleandpolycrystalmaterials.
PowderDiffractionwithArea
Detector
SingleCrystalDiffraction
Powderdiffractionisusedtocollectdataonthefullsetof
interplanar spacingbyequallysamplingallorientations.
PhotographicMethod DigitalMethod
8
GuidedInquiryIII:DiffractionExperiments
(10minutes)
Dependingonthecrystalstructurenotallsetofplanes
producediffractionevents.
9
Microscopyisusetorecordgeometricalstructureand
orientationofmaterialsatthemicroscopicscale(<1mm).
GrainSize&shape
PhaseContent&Arrangement
CompositionandOrientation
FractureSurfaceand
FailureAnalysis
Theabilitytoobservesmallfeaturesisdiffractionlimitedby
thewavelengthoftheradiationused.
DiffractionPatternProduce
byPointlightsource
Resolution(R)islimitedbythe
overlapbetweenAirydisks:
R =
o
2
=
u.61z
p sino
p = InJcx o Rcroction o mcJio
sino = lcns gcomctry
AiryDisk
10
Opticalmicroscopesusevisuallighttocreateimagesand
characterizetheopticalpropertiesofmaterials.
PracticalResolutionLimit:
~1micron
IdentificationofMineralsby
OpticalProperties:
BoneCancer
Cell
Image:Nikon
2012SmallWorld
Intransmissionelectronmicroscopyhighenergyelectrons
areusetoachieveatomicscaleimagesofthin(~10nm)
sectionsofmaterial.
ResolutioninaTEM:
HighEnergyElectrons:
z
c
-
1
E
@300KeV
z
c
~ 2.u pm
Schematic
Practical
Resolutionlimit:
0.08nm~1
11
TEMscanbelargebutarealwaysEXPENSIVE!
HVEMJEOL1.25MeV
FEITitan300KeV
>$3MILLIONUSD??
Scanningelectronmicroscopeelectronicallyacquireanimageby
scanning(rastering)afocusedbeamofelectronsacrossasample
surface.
Resolutionlimit:
ProbeSize
Interactionvolume
~1nm
12
Scanningelectronmicroscopesarehavebecometheworkhorse
microscopeofchoiceforroutinematerialscharacterization
MinimalSamplePrep
CompatiblewithSizeofFeatures
ReasonableCost:
$100K500K
Thechoiceofmicroscopicmethodsdependsonthescale
andtypeofinformationtheisneeded!
ThefollowingareimagesofCarbonnanotubes:
OpticalMicroscope(Fluorescence):
30Mnanotubefilamentusedfor
solarenergyharvesting
ScanningElectronMicroscope:
Bundlesofnanotubes.
TransmissionElectron
Microscope:
atomicspacinginasingle
multiwallnanotube
13
MicrostructureAnalysis

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