UNI

T-3

MATERI ALSCI ENCEANDENGI NEERI NG 7+5hrs

I
II-
A:Nanomat eri
als:I
ntroduct i
on, Preparati
onofCar bonNanoTubes( CNTs)by
ArcdischargeandChemi cal VaporDeposi t
ionMet hods.
Full
erenes: Preparat
ion, Properti
esandAppl i
cations;
Chemi calSynthesisofNanomat erials:Sol-
gelmet hod,Applicat
ionsofNanoMat er
ial
s
i
nWast ewatertreatmentandMedi cine.
I
II-
B:Gr eenChemi str
y:I ntroducti
on,Pr incipl
esofGr eenChemi stryandEngi neeri
ng
Appli
cat i
onswi thacasest udy
BandTheor yofSol i
ds:Int roducti
on–Expl anationofConduct or
s,Semi conductor
sand
I
nsulators by Band Theor y.Superconduct ors:Ty pes-
Preparation,Propert
ies and
Appli
cat i
ons.
NanoMat
eri
als:

I
NTRODUCTI
ON

Inrecenty ears,nanoscalescienceandt echnol

ogyhav egr ownr apidly.
Nanochemi str
y,in
parti
cul ar pr esenta uni que approach to bui
lding dev i
ces wi th a mol ecular-
scale
precision.Onecanseet headv antagesofnanodevicesinmedi cine, computing,scientif
ic
explorat i
on, andel ect
ronics,
wher enanochemistr
yof f
erst hepr omi seofbui l
dingobj ects
atom byat om. The main challengest ofulluti
li
zati
on ofnanochemi st
rycent eron
under standingnew r ul
esofbehav ior
,because nanoscal esy stem l i
eatt het hreshold
betweencl assi calandquantum behav i
orthatdonotexi stinlar gerdev i
ce.
DEFI
NITI
ONS

Nanochemistryisthesci
enceoftool
s,t
echnologi
es,andmet
hodol
ogi
esforchemi
cal
synt
hesis,anal
ysi
s,andbiochemi
caldi
agnost
ics,perf
ormedi
nnanoli
tr
etofemtol
i
ter
domains.

Nanopar
ti
cesar
ethepar
ti
ceswi
thi
nthesi
zer
angi
ngf
rom 1-
50nm

Nanomat
eri
alar
ethemat
eri
alshav
ingcomponent
swi
thi
nsi
zel
esst
han100nm atl
east
i
nonedi
mensi
on.

● Nanomat
eri
alsi
nonedi
mensi
onar
elay
ersl
i
ket
hinf
il
msorsur
facecoat
ings.

● Nanomat
eri
alsi
ntwodi
mensi
onsar
etubesl
i
kenanot
ubesandnanowi
res.

● Nanomat
erialsint
hreedi
mensi
onsar
epar
ti
clesl
i
kepr
eci
pit
ates,col
l
oidsand
quant
um dots.

CARBONNANOTUBES(
CNT’
S)

Thet
erm nanowasdi
scov
eredbyNor
iot
ani
guchi
in1974.

Carbonnanot ubesarelong,t hi
ncy
li
nder
sofcar bonandweredi
scover
edin
1991byS.Iij
ima.
Thesear elargemacr o mol ecul
est
hatareuniqueforthei
rsi
ze,shapeand
remarkabl
ephy sical
proper
ties.
Carbonnanotubesar eal
lot
ropeofcar
bonwithnanostr
uct
ure.

Theyareconsideredasasheetofgr aphi
teroll
edintoacy l
inderthuscar
bon
tubesareext
endedtubesofrol
ledgraphi
tesheets.
Nano tubes haveav erybroad range ofelectr
onic,t
hermal,and str
uct
ural
proper
ti
esthatchangedependi
ngont hedif
fer
entkindsofnanotubes.

TYPESOFCARBONNANOTUBES(
CNT’
S):
-
 Carbonnanot
ubesarelat
ticeofcar
bonatoms,hav
ingeachcarboniscov
alent
ly
bondedtothr
eeothercar
bonatoms.
Dependi
nguponthewayofar r
angement,
theyar
etwotypesofCNT’S.
1.Singl
eWalledNanoTubes(SWNT) .

2.Mul
tiWal
l
edNanoTubes(
MWNT)
.

SINGLEWALLEDNANOTUBES:Si nglewall
ednanotubeshav eadiameterofcloseto
1nm andl engthismanymil
l
iont
imesoflonger
.Thestructureofsingl
ewallednano
tubesobtainedbywrappi
ngaoneatom t
hickl
ayerofgraphit
ecall
edgrapheneint
oa
seamlesscy l
inder
.

Therear ethreet ypesofSWNTS based on t hewayt hegr aphenesheeti s

wrapped.Gr aphenesheeti srepresent edbyapai rofindices( n,m)calledthe
chir
alvector
.
Ifm=0,thenanot ubesarecall
ed“ zig-zag”.Thelinesofcar bonbondsar edown
thecentre.
Ifn=m, t
henanot ubesarecall
ed“ armchai r
”.Thelinesofhexagonsar eparal
l
elto
theaxisofthenanot ubes.
Otherthantwof unctionst
heyar ecalledchi r
al.I
thasat wistorspi r
alaroundthe
nanotubes.

MULTI-
WALLED NANOTUBES( MWNT) :Multiwal
lednanotubesconsistofmult
ipl
e
r
oll
edlayer
sofgraphi
te.Theint
erl
ayerdi
stanceinmultiwal
l
ednanotubesiscl
oseto
o
t
hedist
ancebet
weengr aphenel
ayer
singraphit
eis3.3A.

I
texhi
bitbot
hmetall
i
candsemiconductingpr
oper
ti
es.Therear
etwomodel
s
whi
chcanbeusedtodescr
ibet
hest
ruct
uresofmul
tiwal
lednanot
ube.

I
ntheRussi
andol
lmodel
,sheet
sofgr
aphi
tear
ear
rangedi
nconcent
ri
ccy
li
nder
s.

I
nthepar
chmentmodel
looksl
i
kear
oll
ednewspaper
.
PROPERTI
ESOFCARBONNANOTUBES(
NANOMATERI
ALS)

Mechani
cal
Proper
ti
es:

1.Strengt h:
Thest rengt hoft hesp2 car bon- carbonbondgi vescar bonnanot ubesamazi ng
mechani calproper ti
es.
Car bonnanot ubesar ethest rongestandst i
ffestmat er ialsi ntermsoft ensil
e
strengt handel asticmodul usrespect i
vel
y.
Thist ypeofst rengthr esultsfrom t hecovalentSP2 bondsf ormedbet weent he
i
ndi v i
dual atoms.
2.Har dness:
Dur i
ngsy nthesisofcar bonnanot ubeofsuperhar dmat erialbycompr essing
abov e24GPa( Gigapascal )atroom t emperature.
Thehar dnessoft hi
smat erialwasmeasur edwi thananoi ndent er
.(
verysmal l
dev icest ransferdat aov eranet wor k.t
emp,humani ty,gaseousf umeset c.)
3.Elect r
icalPr operti
es:Car bonnano t ubecanbemet alli
corsemiconduct ing
dependi ngont heirstructure.
Forgi v
en( n,m)nanot ubes, i
fn=m, t
henanot ubesmet al
lic, i
fn- mi smultipl
eof3,
thennanot ubesi ssemi conduct or.
Allar mchai rformsnanot ubesar emet al
li
cand( 10,1),( 4,1)et cnanot ubesar e
semi conduct ors.

Engi
neer
ingAppl
i
cat
ionofCar
bonNanoTubes

1.InFuelCel
ls:
Hydrogencanbest oredinthecarbonnanotubes,
whichi
stur
nusedf ort
hef
uel
cel
ls.SWNTmor eeff
ecti
veinthi
scase.
Carbonnanot ubesreplaceplat
inum asthecatal
ystint
hefuelcel
l
s.Theyare
 r
esi
stanttocorr
osi
on
2.I
nCatalysi
s:
Acat
alysthavi
ngCNTsmakesar
eact
ionmi
l
der
,saf
erandmor
esel
ect
ive.
Oxidi
zedCNTswi thphosphor
ousaddedar
esel
ect
ivecat
aly
stsf
ort
heoxi
dat
ive
dehydrogenat
ionofbut
anetobut
adi
ene.

3.I
nMedici
ne:
Car
bonnanotubesar
ebei
nghi
ghl
yusedi
nthef
iel
dsofef
fi
cientdr
ugdel
i
ver
y.

Usedadr
ugdel
iv
eryofcancercell
s.Itat
tacksonl
yatcancerspot
sdoesnothar
m
heal
thy cel
l
sandsigni
fi
cant
lyreducessi
deef f
ect
s.

SYNTHESISOFCARBONNANOTUBES:Thef ol
l
owi
ngar
emet
hodst
opr
oducecar
bon
nanot
ubes
ARCdischarge
Chemi
cal vapourdeposi
ti
on(
CVD)
.

ARCDI
SCHARGE:
-

Thismet hodcr eatescarbonnanot ubesthroughar cvapor i

zationoft wocarbon
rodsplacedendt oend,separatedbyapproximately1mm, inanencl osur
et hati
s
usual
lyfil
ledwithinertgasatl owpressur
e.
A dir
ectcur rentof50t o 100A dri
venbyappr oximately20vcr eatesahi gh
temperaturedischargebetweent hetwoelectrodest hi
sdi schargevaporizesone
ofcarbonr odsandf ormsasmal l
rodshapeddeposi tont heot herr
od.
CHEMI
CALVAPOURDEPOSI
TION(
CVD)
:-

I
nt hi
smet hodacarbonsourceli
kemethaneandacety
leneusedasi nthegas
phaseand an ener
gysour ceneed totr
ansf
erenergyt o agaseouscarbon
molecul
e.
Theenergysour
ceisusedtocrackthemol
ecul
eint
oreacti
veatomiccar
bon.
Iti
stwostepprocessesin1ststepcatalystpr
eparat
ionstepgener all
ytransit
ions
metalsusedassuppor t
edcat al
y sti
nsecondst epchemi caletchingort hermal
anneal
ingtakesplace,i
ncaseofchemi calet
chingNH3 usedaset chantor650-
O
900Ct emperatur
eshouldmaint aini
nthermalanneali
ngpr ocess.
 ProcessstepsinCVD
1.
Transportofreact
antsviaforcedconv ect
iontor eacti
onr
egion
2.
Transportofreact
antsviadiff
usiont owafersur f
ace
3.
Adsor breact
antsonsurface.
4.
Surfaceprocesses:chemicaldecomposi t
ion,surfacemigrat
ion,
sit
eincor
por
ati
on,
etc.
5.
Desorpti
onofbypr oductsfrom surface.
6.
Transportofbyproductsthroughboundar ylayer.
7.
Tranportofbyproductsawayf rom depositi
onr egion

Substr
ate=carbon
Catalyst
=ni,
co,fe
Pr
ecursor=acet
ylene,ethy
lene,
Carr
iergas=ammoni a,
N2,hydrogen
FULLENES:Ful
ler
enesareaf amilyofcar
bonallotr
opes,mol
ecul
esent
ir
elycomposed
ofcarbon,
int
heform ofhol
l
ow, spher
e,el
l
ipsoi
d,tubeorpl
ane.

Full
ereneswerediscov
ered asanunexpected surpr
isedur
ing l
aserspect
roscopy
experi
mentsatri
ceuniversi
tyi
nsept
ember1985. The1996Nobelprizei
nchemi st
ry
wasawar dedf
ort
heirdi
scovery
Ful
l
erenesar
efol
l
owi
ngt
ypes

1.SphericalFull
erenes.
2.Cyli
ndricalFul
lerenes.
3.PlanarFuller
enes.

Spher
ical
Ful
l
erenes:
Theyl
ookl
i
keasoccerbal
l
,of
tencal
l
edBuckybal
l
s.
Cyli
ndricalFul
lerenes: Thesearecall
edcarbonnanotubes.
PlanarFull
erenes: Graphenei sanexampleofplanarfull
erenesheet
.
Preparati
on
Full
erenesar eprepar edbyv apori
zi
ngagr aphit
er odinahel i
um atmosphere.Mixtures
offull
ereneslikeC60,C70,et
c.aref
ormedwhi chareseparatedbysolventextr
acti
on.C60is
i
solated from thismi xtur
ebycol umnchr omatographyusing al
umi na/
hexaneasa
solventsystem.

St
ruct
ure:
Full
erenesareacl assofcl osed-
cagecarbonmolecul
econtai
ning12pentagons
andv ari
abl
enumber( 20)ofhexagons.
C60isasphericalcrystalofcarbonat omswit
hanarrangementofeven number
2
ofsp atomsov erthesur faceofclosedhol
lowcage.

St
ruct
ureofC60

TheC60mol
ecul
ehast
runcat
edi
cosahedr
onsst
ruct
ure.
 Anicosahedronsisapol y
gonwith60vert
icesand32f aces,12ofwhi
chare
pentagonal
and20hexagonal.
A carbonatom ispresentateachver
texthevalencesofeachcarbonat
om
sati
sfi
edbytwosingl
eandonedoublebond.

Pr
oper
ti
es:
Iti
smust
ardcol
our
edsol
i
d.
C60 ispoorconductorofelectr
ici
ty.Whenf ul
l
erenesreactswithgoodelect
ron
donorsli
keal kal
imet
als,
itsconducti
vi
tyincr
eases.
I
tismoder atel
ysol
ubl
eint hecommonor gani
csolvents,especi
all
yinar
omat i
c
hydrocarbons.
I
tisv er
yt oughandhi
ghtensil
est r
ength.
Itcanbecompressedt
olose30% ofi
tsv
olumewi
thoutdest
roy
ingi
tscage
str
uctur
e.
Iti
sther
mall
yst
abl o600oC.
eupt

SuperConduct
ingFull
erenes:
C60 i
spoorconduct orofel
ectr
ici
ty.Whenfull
erenesreact
swi thgoodel
ectr
on
donorsl
ikealkal
imet al
s,i
tsconducti
vi
tyi
ncreases.Al
kalif
ull
erenesar
esuchas
K3C60ar
esuperconduct i
ng.

Engi
neer
ingAppl
i
cat
ionofFul
l
erenes:
Ful
l
erenescaneasi
l
yacceptel
ect
rons,
ther
efor
etheymaybeusedaschar
gecar
ri
eri
nbat
ter
ies.
Al
kal
imet
alf
ull
eri
desar
esuper
conduct
ors.
I
tsspher
ical
str
uct
uremakesi
tsui
tabl
efort
heuseasl
ubr
icant
.
I
tcanbeal
sousedassof
tfer
romagnet
.
Researcher
shavefoundthatwat
ersol
ubl
ederi
vat
ivesoff
ull
erenesi
nhi
bitt
heHI
V-Ipr
oteaseand
ther
eforeusef
uli
nfight
ingtheHI
Vthatl
eadst
oAIDS.

Ful
l
erenesar
epower
ful
oxi
dant
s.

Gener
alMethodsofPrepar
ati
on:Ther
ear
ebasi
cal
l
ytwomaj
ort
ypesofappr
oachf
or
t
heprepar
ati
onofnanomateri
als.

1.Top–downappr oach:Inthismet hodbul

kmat eri
alsar
econv er
tedtopowder
andthentonanoparti
clesbymakinguseofli
thographi
cmethods.Thi
smethodis
usedinthemicr
oelectr
onicindust
ry.

Bottom –upapproach:I
nt hi
smethodverysmal
lpart
icl
esli
keindi
vi
dualmolecul
esor
atomsareassembledtogetclust
erswhi
chintur
nareaggregat
edtogetnanopart
icl
es.
Thismethodisusedtoprepar
eanewclassofnanomater
ial
s.Exampl
es:Ful
ler
enesand
polymernanocomposit
es
Sol
gel
Met
hod
Sol -gelmet hodi sbot t
om- upappr oachf ort hesy nthesisofnanomat erial
sandi tisvery
l
ongknowsi nce1980s.Thev ersat i
li
tyoft histechni chasbeenr edi scov eredint heear l
y
1970swhengl asswer epr oducedwi thouthi ght emper aturemel ti
ngpr ocesses.Asoli s
acol loi
dal ormol ecularsuspensi onofsol idpar t
iclesofionsi nasol vent.Agel isasemi
-regidmasst hatformswhent hesol ventf rom thesolbegi nstoev apor ateandpar ti
cles
ori onsleftbehi ndbegi ntoj oint ogetheri nacont inuousnet wor ki.e.,gel .Met aloxides
ormet alchloridesunder gohy drolysi
sandpol ycondensat i
onreact iont of orm acol l
oid
whi chissy stem composedofnanopar ticlesdisper sedinsol vent .Thesol v
entev olves
towar dst hef ormationofani nor ganiccont i
nuousnet workcont ainingal i
quidphase.
For mationofamet aloxi dei nvolvesconnect ingt hemet alcenter swi thoxo[ M-O-M]or
hy droxo[M-OH- M]br idgesgener ating met al-
hydroxopol ymersi nt hesol ut
ion.Af t
era
dr yi
ngpr ocesst heliquidphasei sr emov edf rom thegelandcal cinat i
oni sper formedi n
or dertoenhancet hemechani cal propert
ies.Al cohol i
susedasasol vent .
Advantagesofsol-gelmethod:
1.Abletogetuniform andsmal l
sizepowder.
2.Cangetnewmi crostr
uctureandcomposit
ionatl
owt
emper
atur
e.
3.Canpr oduceunifor
m mul t
icomponentsystems.
4.Bett
ercont r
oloverthereacti
on.

GREENCHEMI
STRY

Hi
stor
yofGr
eenChemi
str
y
Theideaofgr eenchemi str
ywasi nit
iall
ydevelopedasar esponsetot hePolluti
on
Prevent
ionActof1990, whichdecl aredthatU.S.nat ionalpoli
cyshouldel i
minat e
poll
uti
onbyi mpr oveddesign(includingcost-effectivechangesinpr oducts,processes,
useofrawmat erial
s,andrecycli
ng)i nsteadoft reatmentanddi sposal. Al
thought he
U.S.Envi
ronment alProtect
ionAgency( EPA)isknownasar egulat
oryagency ,itmoved
awayf r
om the“ commandandcont rol”or“endofpi pe”approachinimpl ement i
ngwhat
wouldev ent
uall
ybecal ledits“greenchemi stry”pr ogram.  

By1991,
theEPAOf
fi
ceofPol
l
uti
onPr
event
ionandToxi
cshadl
aunchedar
esear
ch
grantpr
ogram encour
agi
ngredesignofexi
sti
ngchemi calpr
oduct
sandprocessesto
reducei
mpact sonhumanhealthandtheenvi
ronment. TheEPA,i
npart
nershipwit
hthe
U.S.Nat
ional
ScienceFoundat
ion(NSF),t
henproceededtofundbasi
cresearchi
ngreen
chemist
ryintheearl
y1990s.
  

Theintr
oductionoftheannualPr
esidenti
al Gr
eenChemist
ryChallengeAwardsin1996
drewattenti
ontobothacademicandi ndustri
algr
eenchemist
rysuccessstori
es.
 The
Awardspr ogr
am andthetechnol
ogiesithighl
ight
sarenowacor nerst
oneofthegreen
chemistryeducat
ionalcur
ri
cul
um.  

Themi d-
to-
lat
e1990ssawani ncreasei
nthenumberofinternat
ionalmeeti
ngsdevoted
togreenchemist
ry,
suchastheGor donResear
chConferencesonGr eenChemistr
y,and
greenchemist
rynetwor
ksdevelopedintheUni
tedSt
ates,theUnitedKingdom,Spai
n,
andItal
y.
  

The12Principl
esofGreenChemistr
ywerepubli
shedi
n1998,prov
idi
ngthenewf i
eld
wit
haclearsetofguidel
inesforf
urt
herdev
elopment.
 In1999,
theRoyalSoci
etyof
Chemi
strylaunchedi
tsjournal
 Gr
eenChemist
ry.
  

Inthelast10years,nationalnetworkshav eprol
if
erated,speci
ali
ssuesdevotedtogreen
chemistryhaveappear edinmaj orj
ournals,andgreenchemi st
ryconcept
shav e
conti
nuedt ogai
nt r
act i
on. Aclearsignoft hi
swaspr ovidedbythecit
ati
onforthe2005
NobelPr i
zeforChemi stryawardedt oChauv i
n,Grubbs,andSchrock,whi
chcommended
thei
rwor kas“agreatst epforwardforgreenchemi stry”

Oneoft hemostimport
antnew aspectsofchemi st
ryi
st hedev el
opmentof
GreenChemist
ry.GreenChemi
str
yist
hedesi gnofchemicalpr
oductsandpr ocesses
t
hatreduceoreli
minatet
heuseandgenerat
ionofhazardoussubstances.
 GREENCHEMI
STRY

I
ntr
oduct
ion:Gr
eenchemi
str
yisal
socal
l
edassust
ainabl
echemi
str
y.I
tisa
phi
l
osophyofchemi
calr
esear
chandengi
neer
ingwhi
chencour
agest
hedesi
gn
ofpr
oduct
sandpr
ocessest
hatmi
nimi
zet
heuseandgener
ati
onofhazar
dous
subst
ances pot
ent
ial
l
ydanger
ous t
oli
fe on ear
th.The conceptofgr
een
chemi
str
y(Env
ironment
all
ybeni
gnsy
nthesi
s)wascoi
nedbyPaulAnast
asof
Amer
ica.Heenunci
ated12pr
inci
plesofGr
eenchemi
str
yin1994t
owar
dsi
deal
sy
nthet
icmet
hodst
osav
enat
ural
resour
ces.
“
Green chemi
str
yist
he use of chemi
str
yfor pol
l
uti
on pr
event
ion by
env
ironment
all
y–consci
ousdesi
gnofchemi
calpr
oduct
sandpr
ocessest
hat
r
educeorel
i
minat
etheuseorgener
ati
onofhazar
doussubst
ances”
.
Needf
orGr
eenChemi
str
y
The20th cent
urybr
oughtt
hehi
ghestsci
ent
if
icdev
elopmentwi
thr
espectt
o
v
ari
ousbenef
it
stot
hemanki
nd,
buti
ntur
nhasbeenr
esponsi
blef
oranumber
ofenv
ironment
alpr
obl
emsatl
ocalandgl
oball
evel
.Ourenv
ironmenti
stobe
pr
otect
edf
rom i
ncr
easi
ngchemi
cal
pol
l
uti
onassoci
atedwi
thcont
empor
aryl
i
fe
st
ylesandemer
gingt
echnol
ogi
es.Thi
sisessent
ial
forsur
viv
alofl
i
fesy
stems.
Gr
eenchemi
str
yisanessent
ialpi
eceofcompr
ehensi
vepr
ogr
am t
opr
otect
humanheal
thandenv
ironment
.Gr
eenchemi
str
yincl
udeschemi
calpr
ocessor
t
echnol
ogyt
hati
mpr
ovest
heenv
ironmentandt
husourqual
i
tyofl
i
fe.Gr
een

Non

Av
oid Env
ironment

Saf Gr
een Economi
c

At
om
Sust
ainabl

Si
mpl
chemi
str
yappl
i
esacr
ossl
i
fecy
cleofachemi
calpr
oducti
ncl
udi
ngdesi
gn,
manuf
act
ureanduse.

Gr
eenChemi
str
yisbasedonTwel
vePr
inci
ples.

1.Pr
eventi
on:(
ZWT)Iti
sbet
tert
opr
eventwast
ethant
otr
eatorcl
eanupwast
e
af
teri
thasbeencr
eat
ed.

2.At
om Economy:Synt
het
icmethodsshould bedesi
gned t
o maxi
mizet
he
i
ncor
por
ati
onofal
lmater
ial
susedi
ntheprocessi
ntot
hefi
nalpr
oduct
.
3.Less Hazardous Chemical Syntheses: Wher ever pr
acticabl
e,sy ntheti
c
methodsshouldbedesignedtouseandgener atesubstancest hatpossess
l
itt
leornotoxi
cit
ytohumanhealthandt heenv i
ronment.
4.Designi
ngSaferChemical
s:Chemi calproductsshouldbedesi gnedtoef f
ect
thei
rdesir
edfunct
ionwhil
eminimizingtheirt
oxici
ty.
5.SaferSolventsandAuxi li
ari
es:Theuseofauxi li
arysubst
ances(e.
g.,
solvents,
separat
ionagent s,etc.
)shouldbemadeunnecessar ywherev
erpossibl
eand
i
nnocuous whenused.
6.Designf orEner gyEf f
ici
ency:Energyr equi
rement sofchemicalprocesses
shouldber ecognizedf orthei
renv i
ronment alandeconomi cimpactsand
shouldbemi ni
mi zed.I
fpossible,sy
ntheticmet hodsshoul
dbeconduct edat
ambienttemper atureandpressure.

7.Use ofRenewable Feedst

ock’s:A raw mat
eri
alorfeedst
ock shoul
d be
renewablerat
herthan deplet
ing whenev
ertechni
cal
l
y and economical
l
y
pract
icabl
e.

8.ReduceDer
ivat
ives:
Unnecessar
yder
ivat
izat
ionshoul
dbemi
nimi
zed.

9.Cat alysi
s: Catal yti
cr eagent s(assel ectiveaspossi ble)ar
esuper i
orto
stoichiomet ricr eagent s.
10.Desi gnf orDegr adat i
on: Chemi cal pr oduct sshouldbedesignedso
thatatt heendoft heirfunctiont heybr eakdowni ntosafe
degr adat i
on.
11.Real -
timeanal ysisf orPol l
utionPr ev ention:Analyt
icalmethodologiesneedt o
bef ur
therdev elopedt oallowf orreal -ti
me,i n-
processmoni tor
ingandcont r
ol
pr i
ortot hef ormat ionofhazar doussubst ances.
12.I nherent l
y (existi
ng as an essent i
al consti
t )Saf
uent erChemi stryf orAcci dent
Pr evention:Subst ancesandt hef or m ofasubst anceusedi nachemi cal
pr ocessshoul dbechosent omi nimi zet hepotenti
alforchemi calacci
dents,
includingr el
eases, explosions, andf i
res.
Appli
cat
ionofgr eenchemistr
y
1.r
educeairpoll
utant
semi ssi
on.
2.r
emoveni t
rogenoxides,
Sulphur
oxi
des.

r
3.emov
eai
rpol
l
utant
sli
kev
ehi
cleexhaust
inggases.
t
4.oel
i
minat
ewast
eandr
educeconsumpt
ionofor
gani
c
sol
vent
s.
5.5.
greenbui
l
dingandcl
eani
nguppol
l
utedwast
esi
tes.
CaseStudies:UseGreenEngi
neer
ingi
ntheDesi
gnandOper
ati
onof
I
ndustr
ialProcesses
Gree
ne ngineeri
ngisbei
ngi nc
orporate
dac rossthec hemicalpr
ocessi
ngindustryto
l
owe rri
sk,re
duc ewaste
, andimprovethee conomi c
sof c
he mical
manufacturi
ng.
Towardthate f
fort
,EPA’
sGr ee
nEnginee r
ingPr ogramprovidescasest
udiesthatcan
beusedase xamplesintheappli
cati
onof thegr ee
ne ngi
nee r
ingpri
nci
plesto
i
ndus t
ri
alprocesses.

The
sec
ases
tudi
esar
eme
antt
obe
:

● Steppi
ngs t
onesforthose 
withinteres
tsinthechemicalproces
singi
ndustr
yto
useindevelopi
ngt hei
rownindus t
ry-spe
c i
fi
cscenari
os.
● Awayt oimprove 
ac r
ossgovernme ntandnon-governme nte
ntiti
esthe
knowledgeand broadappli
cationoftheninePrinci
plesofGreenEngine
eri
ng.

Casest
udies:Gr
eenengi
neer
ingi
nindust
ri
alpr
ocesses
Onthi
spage:

● React
ivedis
til
lat
ion
● Automobil
ee mis
s i
ons
● Hazordouschemicals
● Mist

React
ivedi
sti
ll
ati
on
Pr
of e
ssorsM.DohertyandM. Mal
oneof t
heUni v
e rs
ityofMassachuset
tsDepartment
ofChemicalEngi
neeringexpl
oredthetopi
c"Re c
e ntAdvancesinReacti
veDisti
ll
ati
on."
I
nc omparingtr
adit
ionalvers
usreact
ivedis
til
lat
ionme thods,suchasinthe
pr
oduc t
ionofme t
hyl ace
tate
,thelat
termethodshav etheadvantageofbeingableto:

● I
mpr ovese
lecti
vi
ty
o Reducerawmat e
rial
sus
age
o Reducebyproduct
sprev
entpol
lut
ion
● Reduceenergyuse

● Handledi
ffi
cultseparat
ions
o Avoidseparati
ngr e
actants
o Eli
minate/reducesolv
e nt
s
● Enhanceoverall
rates
● "Beat
"lowe quil
ibri
umc onstants
Example:Gr
aphi
ccompar
isonofpr
oduct
ionofmet
hylacet
ateusi
ngt
radi
ti
onalandr
eact
ive
di
sti
ll
ati
onmethods.

Tr
adi
ti
onal
produc
tion
(
Cli
ckt
oenl
argei
mage
.)
 Reac
tivedi
sti
ll
ati
on(
Agr
eda
andPart
en,1984)
(Cl
ic
ktoenl
argei
mage
.)

Topof
Page
Reduci
ngaut
omobi
leemi
ssi
onsandsav
ingener
gy
Wil
li
amObe nchai
nandMar cel
vanSchaikoft
heAme ri
canIr
onandSteelI
nst
it
ute,and
Pet
ePeter
sonof t
heU.S.Steel
Groupconductedacasest
udyontheUltr
aLi
ghtSteel
Aut
oBody-AdvancedVehi
c l
eConcept
s(ULSAB-AVC)
,inwhic
hreduct
ionsi
n
aut
omobil
ee miss
ionsandimprovementsi
ngasmi l
eagewereobs
ervedasares
ultof
usi
ngli
ght
we i
ghtsteel
intheconst
ruc
tionofcars
.

TheUL SAB-AVCi sacompletec onceptualdesi

gnf ors
teeli
ntensiv
ec ompactandmid-
si
zes e
dans .Thede si
gnswe r
ede v
elopedbyac ons or
ti
umof 33s t
eelmakersfr
om
aroundt heworld.Thede s
ignss peci
fygasoli
neanddi esel
powe redmodels;i
ntheU.S.
combine ddrivi
ngc yc
lethemi d-si
zeds edanwil
l achi
eve52mi l
espergall
onwhe n
powe r
edwi thagas ol
ineengineand6 8mi l
espergall
onifequippedwithadiesel
engine.Thisequatestoonly0.32(diesel
)-0 .
38(gasol
ine)l
bsof CO2 
permil
e .
ULSAB-
AVC:Compar
isonofmi
l
eageandCO2 
emi
ssi
ons

U.
S.C.A.
F.E. ULSAB-AVC ULSAB-
ABC
 
st
andard Gasol
ine Di
esel

U.
S.combi
ned 27.
5 52 68
[
mpg]
 U.
S.C.A.
F.E. ULSAB-AVC ULSAB-
ABC
 
st
andard Gasol
ine Di
esel

CO2 
emi
ssi
on
204 108 92
[
g/km]

CAF
E=Cor
por
ateAv
erageF
uel
EconomySt
andar
dsf
oraut
omobi
le
sandt
ruc
ks

Topof
Page
Mi
nimi
zinghazar
douschemi
cal
sint
hepaperi
ndust
ry
CarlHoutmanof theU.S.Depart
mentofAgri
culture(
USDA) Fores
tPr oductServi
ce
andof theUniv e
rsit
yof Wis
consi
natMadisonconduc te
dac asestudyonmi ni
mizi
ng
theuseof hazardousche mic
alsi
nthepaperindustry
.Toe l
iminat
et heus eofand
exposuretohaz ardouschemical
sint
hebl e
achingprocess,
ane wde lignif
ic
ati
onagent
(apolyoxomet al
ate,orPOM)isusedtoprovi
det hebasi
sforclose
d-mi llbl
eachi
ng
technology.

Thist
echnologyeli
minatestheuseof ahazardousc
hemic
al whi
lemai
ntai
ning
ef
fect
ivel
igninremoval.Thetwoflowc hart
sbe l
owcomparethetr
adi
ti
onalbl
eac
h
proce
ssandt henew" gr
e en"pr
oce s
sus i
ngPOM.
Gr
aphi
ccompar
isonofl
i
gni
nremov
alf
rom wood 
usi
ng 
tr
adi
ti
onaland"
green"met
hods.
 
Tr
adit
ionalbleac
hproc es
sforl
igni
nremoval
fromwood(
del
igni
fi
cat
ion)-DEop
Pr
ocess 
(Cl
icktoenl
argeimage.
)

"Gr
een"pr
oces
sforl
igni
nremoval
fromwoodvi
apol
yoxomet
alat
e(POM)
 (
Cli
ck
toe
nlar
gei
mage.
)

Whil
ethisdelignif
ic
ationprocessc
ompletel
yeli
minatesbeachplantef
fl
uent ,
it
re
quir
esinc r
eas edste
amande ner
gyusageaswe l
lasnewc api
talequi
pme nt.As
demonstratedinthetablebelow,thet
rade-
off
sarethatthePOMpr ocessr
e quir
es
hi
gherprocessf l
owtempe rat
ureandhasahighsteamr e
quirementtorunthe
oxi
dati
ver e
ac tor
.

F
urt
hermore,
theinc
rease
dc api
tal
costinmill
sal
readybuil
tpr
ohibi
tsimmedi
ate
i
mplement
ati
on.Thechal
lengewil
lbetoreducepr
oc es
stemperat
ureandt
o
e
li
minat
etheoxi
dati
vereactort
odecreasest
eamre qui
rement
s.
Paperbl
eachi
ng:compar
isonofpr
ocessst
ream andener
gyi
nput
s

  Pr
ocessSt
ream I
nput
s Ener
gyI
nput
s

Steam
H2SO Elect
ri
cit
y
  NaOH O2 CI
O2 H2O2 POM (kg/MT
4 (kW-hr/
MT)
)

POM   137       0.
27 277 2,
858

DEop 24 5 5 18.
3 6   281 1,
693

POM=pol
yox
ome
tal
atepr
oce
ss,
use
snoCl
O2 
orNaOH,
 
DEop=t
radi
ti
onal
met
hodof
ble
achi
ng

Mi
nimi
zingwor
kerexposur
etomi
sti
ntheaut
oindust
ry
Exposuretomis tf
rommac hiningflui
dsc ancauses erioushe alt
hpr obl
ems ,i
ncl
uding
cancer,
respi
ratoryproblems,andal l
ergicre
actions .
Tol imite xpos
urefrominhalat
ion
ofthi
smi s
t,Professor
sMank e,Gulari
,andSmol insk i
of theWay neStat
eUni v
ers
ity
Departmentof ChemicalEngi
ne er
ingandMat er
ialsSc iencete s
tedtheeffe
ctofadding
polymerstobot hwater-
basedands t
raight
-oil
mac hiningfluids.

Acost-ef
fect
ivemethodof r
educi
ngmi s
tfromoil-
basedfluidshasalr
eadybeenwide
ly
i
mpl e
me ntedintheautoindust
ry.
Forwate r
-bas
edfluids
, however,t
heeconomic
sof
mistsuppress
iontechni
quesarenotyetasfavor
able
, ande ngi
neerscont
inuet
olook
f
orpractic
alwaystome etthi
schal
lenge.

Forst
raightoilf
lui
ds ,
polyi
sobuty
lene(PIB)canbeadde dt ocontr
olmi s
t.Anaddit
ion
of70ppmof PIBresult
sina40percent 
reductioninaveragemistl
e v
elsanda6 7
perce
nt reducti
oninpe akmistl
evel
s.Thisaddi t
ivehasbeenusede xt
ensive
lyinauto
manufacturingfac
il
iti
es.It
scost
sarerelati
velylowandonl yweeklyrepl
aceme nti
s
requi
red.
Gr
aphi
cshowi
ngi
nfl
uenceofpol
ymer
sonat
omi
zat
ionofmachi
nef
lui
ds.

Char
tshowi
ngr
educt
ionofmi
stofmachi
ningf
lui
dsusi
ngPI
Baddi
ti
ve.

-70ppmofPIBaddedtomac hini
ngoil
-40%reduct
ioninaver
agemi s
tlevel
s
-67%reduct
ioninpeekmistl
evels
-24hourspl
usservi
celi
fe 

Tocontr
olmistfromwater
-base
dmac hi
ningfl
uids,
engi
neer
sareexplor
ingtheuseof
poly
ethyl
eneoxide(PEO)f
orthi
spur
pose.Theresul
tsar
epromisi
ng.Howe ve
r,hi
gh
tr
eatmentle
velsareneede
d(upto500pm) ,
thepolymeri
srel
ati
vel
ycostly
,anddail
y
r
epl
ace
menti
sre
qui
red.

Toi
mpr ovetheeconomicsof
tre
atmentforwat
er-
basedfl
uids
,re
s e
arc
hersare
i
nvest
igati
ngoptimiz
ati
onofpolyme
r-s
ur f
acei
nte
rac
tionsandsynt
hesi
sof"desi
gne
r"
ant
imist
ingsyst
ems .

BandTheor
yOfSol
i
ds
Thebandt heoryofsol
idsisdi
ffer
entfr
om theother
sbecausetheat
omsar earranged
veryclosetoeachothersuchthatt
heenergylev
elsoftheout
ermostorbi
tal
electrons
areaffect
ed.Buttheenergyl
evelofthei
nnermostelect
ronsi
snotaff
ectedbythe
neighbori
ngatoms.

I
n-bandt
heoryofsol
id,
ther
ear
emanyener
gybandsbutt
hef
oll
owi
ngar
ethet
hree
mostimpor
tantener
gybandsi
nsol
i
ds:

1.Val
enceband
2.Conducti
onband
3.For
biddenband

Valenceband:
 Theenergybandthatconsistsofv
alenceelectr
onsenergylev
els,
is
knownast hevalenceband.Thevalencebandispresentbelowtheconducti
onband
andt heel
ect
ronsoft hi
sbandarelooselyboundtothenucleusoftheatom.

Conduct
ionband: 
Theenergybandt hatconsi
stsoff
reeel
ectr
onsenergyl
evel
s,i
s
knownast heconduct
ionband.Forelectr
onstobefr
ee,ext
ernalener
gymustbe
appl
iedsuchthattheval
enceelect
ronsgetpushedtotheconducti
onbandandbecome
fr
ee.

Forbi
ddenband: 
Theenergygapbet weenthevalencebandandt heconduct
ionbandi s
knownast hefor
biddenbandwhi chi
salsoknownast heforbi
ddengap.Theelectr
ical
conduct
ivi
tyofasolidi
sdeterminedfrom t
heforbiddengapandal sot
heclassif
icati
on
ofthemateri
alsasconductor
s,semiconductor
s,andi nsul
ator
s.

Whati
sBandTheor
yofSol
ids?
Thistheor
yexplainst
hequantum st
atethatanel
ect
rontakesi
nsidemet
alsol
i
d.Ever
ymolecul
e
compr i
sesvari
ousdiscr
eteener
gylevel
s.Thewayelect
ronsbehavei
nsi
deamolecul
eiswel
l
explai
nedthroughthi
stheor
y.

● I
nat
oms,
elect
ronsar
efi
l
ledi
nrespect
iveener
gyor
bit
sfol
l
owi
ngPaul
i
’sexcl
usi
onpr
inci
ple.
● I
nmol
ecul
es,
Twoat
omi
cor
bit
alscombi
net
ofor
m amol
ecul
aror
bitwi
tht
wodi
sti
nct
ener
gyl
evel
s.
● I
nsol
i
ds,
1023 
stackedupl
i
nesconf
inedi
nat
inyspacewoul
dlookl
i
keaband.Ther
eby
f
ormi
nganener
gycont
inuum cal
l
edener
gybands.
● Thi
stheor
yhel
pst
ovi
sual
i
zet
hedi
ff
erencebet
weenconduct
or,
 
semi
conduct
or,
andan
i
nsul
ator
 bypl
ott
ingav
ail
abl
eener
giesf
oranel
ect
roni
namat
eri
al.
Di
ff
erences Bet
ween Conduct
ors,Semi
conduct
ors&
I
nsul
ators:
Char
act
eri
sti
cs Conduct
or Semi
conduct
or I
nsul
ator

Asemiconduct
or
Aninsulatorisa
Aconductorisamat er
ial isamat er
ial
mater
ialthat
thatal
lowstheflowof whoseconducti
vit
y
Def
ini
ti
on doesnotal l
ow
chargewhenappliedwith li
esbetween
t
heflowof
av ol
tage. conductor&
cur
rent.
i
nsulat
or

Ther esistanceof
asemi conduct or
I
nsulatorhasv er
y
Theresi
stanceofa decreasewi t
h
hi
ghr esi
stance
Temperatur
e conductorincreases i
ncreasesi n
buti
tstil
l
Dependence wit
hani ncreasein t
emper at ure.Thus
decreaseswi t
h
temperature. i
tact sasan
temperature.
insulatorat
absol utezer o.

They
hav eintermedi ate
Theyhav e
Theconduct or
shave conduct i
vity(10-
(
7 verylow
veryhigh Ʊ/ mt o10-13Ʊ
-
7 conduct i
vit
y(10-
Conduct
ivi
ty conducti
vit
y(10 Ʊ /m) ,thustheycan 13
Ʊ/ m) ,t
hus
/
m) ,t
hustheycanconduct acts as i
nsu l
ato r&
t
heydonotal l
ow
el
ectri
calcurr
enteasi
l
y. conduct orat
currentfl
ow.
diff
erent
conditi
ons.

Theconducti
onin
Theconduct i
oni
n Therearenof ree
semiconduct
oris
conductorsisduetothe elect
ronsor
Conduct
ion duetothe
f
reeelectronsinmetal holesthus,t
her e
movementof
bonding. i
snoconduct ion.
elect
ron&holes.

Therei
snoorl owener gy Thebandgapof Thebandgapi n
gapbetweent he semi conduct ori
s insul
atorishuge
conducti
on&v alanceband greate rthanthe (+5e V)
,w hich
Bandgap conduct orbut needan
ofaconductor.Itdoesnot
needextr
aener gyf ort
he smal lerthanan enormous
conduct
ionst ate. i
nsulat ori.
e.1eV. amountofener gy
Thei relectr
ons li
keli
ghtningto
 needal i
tt
le pushelect
rons
ener
gyfor i
ntothe
conducti
on conduct
ionband.
st
ate.
Nor
mal(10- VeryHigh
Resi
sti
vi
ty 10-5Ω/
Low( m) 5 5 5
Ω/
mto10 Ω/m) (10 Ω/
m)

Thecoef fi
cientof
It resist
ivityofan
I
thasnegativ
e
Coeff
ici
ent haspositi
vecoeffi
cientof insulatoris
coeff
ici
entof
of resi
sti
vi
tyi.
e.i
tsresi
stance alsonegat i
vebut
resi
sti
vit
y.
Resi
sti
vit
y incr
easewithtemperatur
e i
thasv eryhuge
resistance.

Somespeci al conduct
ors Thei nsul
ator
’s
The
turnintosuper conduct
ors r
esist
ance
semi conduct
ors
Absol
uteZer
o whensuper cool eddownto increasewhen
t
urninto
absolut
ezer owhi l
eother cooleddownt o
insulat
orat
havef i
nit
er esist
ance. absolut
ezero.
absolutezero.

8Valence
ValenceEl
ectr
on 1Val
enceel
ect
roni
nout
er 4Valenceelect
ron
el
ect
roninouter
inOuterShel
l shel
l
. i
nout ershel
l
.
shel
l.

Silicon,
Ger mani um,
Seleni um, Rubber,Glass,
Gol
d,Copper
,Sil
ver
, Anti
mony ,Gall
ium Wood,Air
,Mi ca,
Exampl
es
Aluminum et
c Arsenide( known Pl
ast
ic,Paper
assemi etc.
i
nsulator )
,Bor
on
et c.

Semi conduct ors

Thei nsulators
areusedev ery
areusedf or
Themet alslikeir
on& dayel ectr
oni c
protection
copperetc.thatcan dev i
cessuchas
againsthi gh
conductelectri
cit
yare cell
phone,
Appl
i
cat
ion voltages&
madeintowiresandcable comput er
, solar
prev enti
onof
forcarr
yingelectri
c panel etcas
electricalshort
current. switches,ener gy
betweencabl es
conv er
ter ,
i
nci rcuits.
ampl i
fier
s, et
c.
t
heexpul
sionofmagnet
icf
luxwhenamat
eri
albecomessuper
conduct
ingi
namagnet
icf
iel
d.
SUPERCONDUCTORS
 Asolidwhichof fer
snor esistancetothepassageofelect
ri
citythroughitis
cal
ledsuperconductors.Superconduct ivi
tyi
sexhi
bitedbysever
almetals,butonl
yat
l
ow t emperature.The t emper ature at which the normalmet alpasses i nto
superconducti
ng statei s cal
led t he super
conducti
ng t
ransi
ti
on temper at
ure or
cri
ti
caltemperatur
e( Tc)
Resi
sti
vi
ty-
Temperatur
ebehav
iorof
super
conductor
s
Typesofsuper
conductor
s:Super
conduct
orsar
edi
vi
dedi
ntot
wot
ypesbasedon
thei
rmagnet
icr
esponse.

1.Ty
pe-
I(or
)Ideal
super
conduct
ors.
2.Ty pe-
II(
or)Hardsuper conductor s.
Type-Isuperconductors:Those whi ch become compl etel
y diamagnet i
ci nthe
superconducti
ng state.Thesemat erialsar eexhibi
t‘Mei ssnereffect’.Theseare
perf
ectsuperconductors.Thesear ealsocal ledassoftsuper conductors.Eg:Pb,Sn,
Hg,&et c.
Type-I
Isuperconductors:Thosei nwhi cht heidealbehav i
ori sseenupt oal ower
cri
ti
calmagnet icf i
eld beyond which t he magnet i
zation gradual
lychanges and
att
ainszeroatanuppercr it
icalmagnet icfiel
d.Thesear emi xedbehavior.I
tdoesnot
exhibi
tcomplete‘Meissnereffect
’.
Thesear eal
socalledashardsuper conduct ors.Eg:Nb-Zr,Nb-Pb,Nb-La&et c.
Sy
nthesi
sofaSuper
conduct
or

The1-
2-3super
conduct
ormaybesy
nt zed[4]bymi
hesi xi
ng0.
60gofy
ttr
ium oxi
de

wih"
t stoi
chi
ometri
cquantit
ies"(
seebel
ow)ofbar
ium per
oxi
deandcopper(
II
)oxi
de
accor
dingt
otheequat
ion:

2Y2O3+8BaO2+12CuO→4YBa2Cu3O6+5O2(
1)(
1)2Y2O3+8BaO2+12CuO→4YB
a2Cu3O6+5O2

TheYBa2Cu3O7-xisprepar
edbygr indi
ngt hereact
ant stoget
her, st
ronglyheat i
ng" cal
cinat
ing"
at900–950° Cf or8-12hour
s, pell
eti
zi
ngt hepowdermi xt
ure,heat i
ngor"sintering"the
pel
letat950°Cf or12ormor ehours,thenmai nt
ainingtheproductat500° Cf or12- 16hours.
Onslowcool i
ngi noxygenatmospher e,YBa2Cu3O6i sconvertedt ononstoichiomet ri
c,
[5]
superconduct
ingYBa2Cu3O7-xformsbyupt akeandl ossofoxy gen .
Pr
oper
ti
esofsuper
conduct
ors:
1.Superconducti
ngmat eri
alsar
egeneral
lybri
ttl
enatur
e.
2.Atroom temperature,
theresi
sti
vi
tyofsuperconduct
ingmat
eri
ali
sgr
eat
er
thanotherelements.
3.Asuper conduct
orexhibi
tperf
ectdiamagneti
sm.
4.Thermoelect
ri
ceffect
sofmater
ial
sdisappeari
nthesuperconduct
ingst
ate.
5.I
nsuf f
ici
entl
ystr
ongmagneti
cfiel
disappli
edbelowTcit
ssuperconduct
ing
proper
tyisdest
royed.

Appl
icat
ionsofsuper
conduct
ors:
1.Super
conductor
scanbeusedtoperf
orml ogi
candstoragefuncti
onsin
computer
s.
2.Powercanbet r
ansmi
tt
edthr
oughsuperconduct
ingcablewithoutl
oss.
3.TheyareusedforMRIi
nthemedical
fiel
dasadiagnostict
ool .
 4.Superconducti
ngmagnet sareemployedforoperati
ngfri
cti
onl
ess,
highspeed,l
evi
tati
ngtrains.
Thesearedevi
cesthatmakeuseofst rong,super
conductors-
der
ivedmagneti
c
fi
eldst
ocreateafast,
high-i
ntensit
yelectr
omagnet i
cpulse(EMP)todisabl
ean
enemy’
selectr
onicequipment.Whi chi
scalled“E-
BOMB” .