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SPRAY PYROLYSIS

To
Dr. Harpreet Singh
Assistant Professor (SMMEE)
Prepared By
Patel A. R.
Research Scholar
SCHOOL OF MATERIALS, MECHANICAL AND ENERGY ENGINEERING
INDIAN INSTITUTE OF TECHNOLOGY ROPAR
Nangal Road, RUPNAGAR-140001
PUNJAB
1echnlque baslcally conslsL of aLomlzaLlon of a salLconLalnlng
llquld Lhe LransporL of spray dropleLs and pyrolysls of Lhe
salL on Lhe subsLraLe Lo form Lhe Cxlde coaLlng ceramlc
coaLlng and powder producLlon
vA8lCuS 1LCPnlCuLS
CLASSlllCA1lCn
atom|c |ayer ep|taxy
2
W 1echnlque Lo prepare dense and porous oxlde fllms ceramlc coaLlngs and nm
slzed powders
W Spray pyrolysls represenLs a very slmple and relaLlvely cosLeffecLlve meLhod
especlally regardlng equlpmenL cosL
W Spray pyrolysls does noL requlre hlgh quallLy subsLraLes or chemlcals
W 1he meLhod has been employed for Lhe deposlLlon of dense fllms porous fllms
and for powder producLlon
W Lven mulLllayered fllms can be easlly prepared uslng Lhls versaLlle Lechnlque
W Spray pyrolysls has been used for several decades ln Lhe glass lndusLry 1 and
ln solar cell producLlon Lo deposlL elecLrlcally conducLlng elecLrodes 2
SALlLn1 lLA1u8LS
LCulMLn1 8LCul8Lu
W An aLomlzer
W recursor soluLlon
W SubsLraLe heaLer and
W 1emperaLure conLroller
3
W recursor soluLlon prepared
W Slurry of soluLlon and powder made
W ALomlzaLlon of slurry
W PeaLlng of subsLraLes
W Spraylng of aLomlzed parLlcles over Lhe surface
W yrolysls of salL ln Lhe soluLlon
W lormaLlon of Lhe Lhln oxlde layers
W osL processlng of Lhe surface layer
S1LS
ALlCA1lCnS
W Solar cells (Lhln fllm deposlLlon)
W AnLlreflecLlon coaLlngs
W Solld oxlde fuel cells
W owder producLlon
W Cas sensors
W PumldlLy sensors eLc
4
1Pln llLM uLCSl1lCn
W Spraylng a meLal + salL soluLlon onLo a heaLed subsLraLe
W uropleLs lmpacL on Lhe subsLraLe surface
W Spread lnLo a dlsk shaped sLrucLure and
W undergo Lhermal decomposlLlon
W (1he shape and slze of Lhe dlsk depends on Lhe momenLum and volume of Lhe
dropleL and subsLraLe LemperaLure 1he fllm ls usually composed of overlapplng dlsks
of meLal salL belng converLed Lo oxlde on Lhe heaLed subsLraLe)
roducLlon of LransparenL and conducLlng oxlde fllms as wlndows ln solar cells by spray
pyrolysls
3
W MgC Lhln fllms are commonly used as buffer layers 1hln unlform and homogeneous
layers of MgC were deposlLed on Sl (100) fused slllca and sapphlre 3 1hese Lhln fllms
(01 Lo 03 urn Lhlck) are used as buffer /oyers for depositinq fi/ms of ?8a
2
Cu
3
0
7

W lm eL al have sLudled Lhe lnfluence of addlLlves on Lhe properLles of MgC fllms


deposlLed by elecLrosLaLlc spray deposlLlon 4 A large number of separaLed parLlcles
were observed on Lhe surface of MgC fllms when pure LeLrahydrofuran (1Pl) was used
as a solvenL Powever smooLh and parLlcle free MgC fllms were deposlLed when 1
buLyl alcohol or 1ocLyl alcohol was added Lo 1Pl le Lhe o/coho/s effective/y restroin
MqO nuc/eotion resulLlng fromLhe vaporlzaLlon of dropleLs
W ue SlsLo eL al deposlLed 02 pm Lhln alumlna fllms by spray pyrolysls uslng aqueous
aceLlc acld soluLlon of Al aceLylaceLone 3 Al
2
C
3
ls used ln elecLronlc devlces as a Lhln
lnsulaLlng layer 1here was no volLage breakdown observed up Lo 10 v of applled
poLenLlal lllms obLalned by Lhermal decomposlLlon of alumlnlum lsopropoxlde led Lo
volLage breakdowns aL 4 v lL was concluded LhaL Al
2
0
3
fllms deposlLed uslng spray
pyrolysls exhlblL hiqh quo/ity ond hiqher breokdown vo/toqes Lhan Lhose prepared by
oLher Lechnlque
1Pln llLM 8CuuC1lCn
AppllcaLlons
6
W Lven beLLer quallLy lnsulaLlng aCr203 layers wlLh breokdown vo/toqes hiqher Lhan 20
v were formed on slllcon subsLraLes 6
W ?LLrlasLablllzed zlrconla (?SZ) ls Lhe mosL commonly used e/ectro/yte moterio/ in so/id
oxide fue/ ce//s 1hln ?SZ fllms have already been deposlLed by spray pyrolysls on glass
7 8 alumlnlum 9 sLeel 10 porous La(Sr)Mn0
3
caLhode 11 12 and porous
La(Sr)Co0
3
caLhode 13 as subsLraLe
W 1erbladoped yLLrlasLablllzed zlrconla Lhln fllms have been deposlLed uslng
elecLrosLaLlc spray deposlLlon 14 1hls maLerlal exhlblLs mlxed elecLronlclonlc
conductivity ot hiqh oxyqen portio/ pressures and Lherefore can be used as SClC
elecLrode
W uense cell conLalnlng Lhe ?SZcoaLed cerla elecLrolyLe wlLh cracks exhlblLs a hiqher
open circuit vo/toqe Lhan Lhose wlLh cerla alone 13
W 1lLanla fllms have been deposlLed on sLeel to prevent corrosion uslng LlLanlum
lsopropoxlde as Lhe precursor 16
1Pln llLM 8CuuC1lCn
AppllcaLlons
7
CWuL8 8CuuC1lCn
W uurlng synLhesls Lhe soluLlon ls aLomlzed Lo dropleLs
W uslng carrler gas Lhe dropleLs are passed Lhrough a dlffuslon dryer for solvenL
evaporaLlon precursor preclplLaLlon and drylng
W AfLer Lhls Lhermolysls reacLor where dry parLlcles decomposes and form ln Lo a
mlcroporous parLlcle
W llnally parLlcles send Lo a calclnaLlon furnace for geLLlng slnLered
(roperLles of Lhe soluLlon and Lhe precursor can sLrongly lnfluence Lhe parLlcle
morphology spray pyrolysls resulLs ln parLlcles wlLh morphologles from solld Lo
hollowand porous and even flbers can be obLalned)
LnLrapped salL
Messlng eL al have revlewed Lhe spray pyrolysls Lechnlques ln Lerms of process parameLers
LhaL conLrol Lhe formaLlon of powders 17
8
CAS SLnSC8S
W Some semlconducLlng meLal oxldes LhaL changes Lhelr elecLrlcal conducLance ln Lhe
presence of carbon monoxlde eg hydrocarbons
W Such sensors Lyplcally conslsLs of an Lhln oxlde semlconducLor fllm on an lnsulaLlng
subsLraLe wlLh Lwo meLal elecLrodes aLLached
W 1hln oxlde fllms on glass subsLraLes as sensors for CP
2
Cl
2
ln oxygen 18
W Snu
2
fllms for nC
2
sensors uslng Lhe spray pyrolysls Lechnlque 19
W LaCClSn0
2
fllms produced by spray deposlLlon Lechnlque for senslng CC
2
ln alr 20
W orous Sn02 and Sn0
2
Mn
2
0
3
fllms for P
2
sensor by spray deposlLlon Lechnlque 2122
1he Sn0
2
Mn
2
0
3
(101) mlxed oxlde fllms showed a senslLlvlLy Lo hydrogen
W Some meLal oxlde sensors show senslLlvlLy Lo humldlLy 1he Sn0
2
le
2
0
3
fllms has been
lnvesLlgaLed for Lhls appllcaLlon 23
1he naLure of Lhe lron salL lnfluenced Lhe humldlLy senslLlvlLy of Lhe samples 1he fllms
deposlLed from an alcohol soluLlon conLalnlng le
2
(C
2
0
4
)
3
exhlblL hlgher senslLlvlLy Lhan a
soluLlon conLalnlng le(nP
4
)(S0
4
)
2
1hls ls due Lo Lhe hlgher poroslLy of Lhe sLrucLure
obLalned from lron oxalaLe because durlng Lhe oxalaLe pyrolysls a loL more gaseous
decomposlLlon producLs are released compared Lo Lhe sulphaLe precursors
9
W 1he spreadlng behavlor of dropleLs ls due Lo surface Lenslon and roughness of Lhe
coaLed subsLraLe poroslLy of subsLraLe also lnfluences Lhe morphology of a fllm 23
W lllms wlLh low poroslLy were produced when uslng a solvenL wlLh a hlgh bolllng polnL
24 23 26 uue Lo slower evaporaLlon of solvenL durlng Lhe dropleL LransporL and
spreadlng
W 8y addlng aceLlc acld Lo Lhe precursor soluLlon Lhe morphology of 1l0
2
fllms change
froma cracked Lo a crackfree reLlcular sLrucLure 27
W MeLalorganlc compounds are more favorable compared Lo nlLraLes due Lo Lhelr
volaLlllLy and lower decomposlLlon LemperaLures 28
llLM MC8PCLCC?
l) dense ll) dense wlLh lncorporaLed parLlcles lll) porous Lop layer wlLh dense boLLom layer
and lv) fracLalllke porous SubsLraLe LemperaLure ls Lhe maln parameLer governlng fllm
morphology lollowed by concenLraLlon of Lhe precursor soluLlon buL only aL hlgh salL
concenLraLlons whlch produces rough fllms 24
WlLh lncrease ln 1emperaLure
10
/ectrostotic otomiter
W SLrong local elecLrlc forces aL a charged llquldgas lnLerface Lo generaLe flne dropleLs
W varlous spraylng modes can be formed dependlng on Lhe elecLrlc poLenLlal applled Lhe
llquld flow raLe Lhe elecLrlcal conducLlvlLy and Lhe surface Lenslon of Lhe llquld 3
W 1he cone[eL mode provldes a spray wlLh flne monoslzed dropleLs A broad dropleL slze
dlsLrlbuLlon can be expecLed from mulLl[eL mode operaLlon
ir b/ost otomiters
W Plgh speed alr Lo produce Lhe aerosol 1
W 1he llquld ls lnLroduced lnLo an alr sLream and aLomlzed lnLo drops by Lhe energy of Lhe
gas sLream
A1CMlZL8
LLLC18CS1A1lC v/S Al8 8LAS1
referred dropleL lmpacL fashlon
onLo a heaLed subsLraLe
11
LSu AA8A1uS
a hlgh uC volLage power supply (30 kv) a
hollowmeLal needle and a subsLraLe holder
1he llquld feedlng unlL or syrlnge pump a
glass syrlnge and a flexlble Lube of vlLon
maLerlal
PeaLlng plaLe and elLher an l8 pyromeLer and
a conLacL Lhermo elemenL (l8 for conLacLless
and Lhermo elemenL for meLalllc subsLraLes
LemperaLure measuremenL
1echnlcal speclflcaLlons of LqulpmenLs
1hls spraylng unlL lncludes
1lp Lo heaLlng plaLe
LemperaLure dlsLrlbuLlon
12
ulsks of 33 mm ln dlameLer and 73 m ln Lhlckness of lnconel 600 (Coodfellow u) were
consldered as subsLraLes for experlmenLaLlon 1hls nlckel alloy (nl
72
/Crl
6
/le
8
) was chosen as
subsLraLe maLerlal due Lo lLs oxldaLlon reslsLance and has a shlny appearance wlLh a Lyplcal
surface roughness LhaL observed ln a rolllng operaLlon
Surface morphology of Lhe uncoaLed lnconel 600 subsLraLe 31
8ASlC Su8lACL
13
Su8S18A1L 1LML8A1u8L
Surface morphologles of ?SZ fllms deposlLed uslng Lhe LSu Lechnlque aL dlfferenL
LemperaLures (for 1 hour) 200C 230C 300C and 330C (from lefL) recursor soluLlon
0083 mol/l Zr(C3P
7
0
2
)
4
+ 0013 mol/l ?Cl
3
xP
2
C eLhanol (30 vol) + buLyl carblLol (30 vol)
AL 200HC dropleL sLlll reach ln solvenL Lhln weL layer
AL 230HC [usL dry surface and some chances of Lrace of weL layer
AL 300HC fasL drylng resulLs ln sLresses and subsequenL cracklng
AL 330HC dropleLs are dry dlscreLe parLlcles on surface and producLlon of rough surface
280 HC + 30 HC ls besL
for dense fllms
ln case of Su fllm was cracked aL 200C and dense AL 230HC hardly any parLlcles on Lhe
surface Whlle morphology of Lhe fllm aL 330C sLlll of Lype l
ence it fo//ows thot better quo/ity fi/ms con be deposited usinq the P5u setup
14
SCLu1lCn lLCW 8A1L
Surface morphologles of ?SZ fllms
deposlLed uslng LSu seLup aL 323C
for 2 h wlLh dlfferenL flow raLes 14
and 42 ml/h (from lefL) recursor
soluLlon 017 mol/l ZrCu + 003
mol/l ?Cl
3
xP
2
C eLhanol (30 vol) +
buLyl carblLol (30 vol) soluLlon
fllms deposlLed wlLh Lhe low precursor flow raLe conLaln less agglomeraLes and look
denser Lhan LhaL deposlLed wlLh Lhe hlgh flow raLe uslng LSu
ln case of Su has hlgher flow raLes around 30 ml/h Lo 120 ml/h WlLhln Lhls range of
flow raLes no slgnlflcanL change ln Lhe morphology ls observed
Powever lL should be noLed LhaL Lhe probablllLy of fllm cracklng ls much hlgher when
Lhe precursor soluLlon ls supplled aL a flow raLe of 120 ml/h
13
Surface morphology of ?SZ fllms
deposlLed uslng LSu seLup aL 323C for
2 h wlLh soluLlons of dlfferenL chlorlde
concenLraLlons (a) 02 mol/l and (b)
01 mol/l recursor soluLlon ZrCl
4
+
?Cl
3
xP
2
0 eLhanol (30 vol) + buLyl
carblLol (30 vol) soluLlon
Morphology 1ype ll for boLh
1?L Cl SAL1 Chlorlde
AdvanLages hlgh solublllLy ln eLhanol (more Lhan 03 mol/l) and low prlce
ulsadvanLage exLremely chemlcally aggresslve cause corroslon of Lhe seLup
chlorlne lmpurlLles hlnder Lhe crysLalllzaLlon of Lhe lnlLlally amorphous Lhln fllm
More agglomeraLes and sllghLly larger parLlcles are presenL ln Lhe fllm deposlLed uslng Lhe
02 mol/l soluLlon compared Lo Lhe 01 mol/l soluLlon
Spreadlng of dropleLs and lncrease ln parLlcle slze responslble for Lhls
8esulL ln more roughness
CuallLaLlvely Lhe spreadlng raLe decreases wlLh lncreaslng vlscoslLy (02 ml/l) 1hls resulL ln
more rough surface
8oughness also lncreases wlLh lncrease ln salL concenLraLlon ln Lhe precursor soluLlon
16
Surface morphology (Lwo magnlflcaLlons) of
an ?SZ fllm deposlLed uslng LSu seLup aL
323C for 2 h and nlLraLe soluLlon of 01
mol/l nlLraLe recursor soluLlon
ZrC(n0
3
)2aq + ?(n0
3
)36P
2
0 eLhanol (30
vol) + buLyl carblLol (30 vol) soluLlon
1?L Cl SAL1 nlLraLes
8esulL Lo a porous Lype lll fllm or a fracLalllke Lype lv morphology lL seems LhaL landlng
dropleLs already conLaln preclplLaLed parLlcles
AL low LemperaLure Lhe fllm was
cracked AL hlgher LemperaLure Lhe
fllm was crackfree and was of Lype l
morphology no solld parLlcles are
presenL on Lhe fllm surface
1hls ls because alr blasL aLomlzer generaLes larger dropleLs Large dropleLs evaporaLe slowly
and consequenLly preclplLaLlon of Lhe soluLe ls hlndered durlng aerosol LransporL 1herefore
dropleLs arrlvlng aL Lhe subsLraLe dld noL conLaln any preclplLaLes
9

17
lnfluence of Lhe deposlLlon Llme for Lhe
fllm deposlLlon uslng Lhe Su seLup
lllm morphology afLer 60 mln (a) and
300 mln (b) 1he lnfluence of Lhe
deposlLlon Llme on Lhe fllm morphology
deposlLed aL 230C 8oLh fllms belong Lo
Lhe Lype l morphology lndlcaLlng LhaL Lhe
deposlLlon Llme does noL have a
remarkable effecL on Lhe fllm
morphology
lnfluence of Lhe deposlLlon Llme for Lhe
1aylorcone mode spraylng uslng Lhe LSu
seLup lllm morphology afLer 43 mln (a)
and 300 mln (b) Layer wlLh LSu looks
dense wlLh many parLlcles on Lhe surface
Lype ll morphology lncreaslng Lhe
deposlLlon Llme Lo 300 mlnuLes shlfLs Lhe
morphology Lo Lype lv (porous wlLh
agglomeraLes of small parLlcles)
1hls ls due Lo effecL of dropleL spreadlng MosL of Lhe dropleLs arrlvlng aL Lhe subsLraLe are
nearly dry and spread slowly hence dlscreLe parLlcles are formed on Lhe surface Lhls glves
more rough surface 1hls enhances preferenLlal landlng and agglomeraLlon 24 17


9 9
uLCSl1lCn 1lML
18
SLM lmage of crosssecLlon of an ?SZ fllm
deposlLed on Sl wafer ln Lwo hours aL 280C
by Su Lechnlque recursor soluLlon 0083
mol/l Zr(C
3
P
7
0
2
)
4
+ 0013 mol/l ?Cl
3
xP
2
0
eLhanol (30 vol) + buLyl carblLol (30 vol)
soluLlon nozzle Lo subsLraLe dlsLance 44 cm
Alr pressure 073 bar SoluLlon flow raLe 30
ml/h
ueposlLlon Llme versus Lhlckness for ?SZ fllm
deposlLed aL 280C by Lhe Su Lechnlque
recursor soluLlon 0083 mol/l Zr(C
3
P
7
0
2
)
4
+
0013 mol/l ?Cl
3
xP
2
0 eLhanol (30 vol) +
buLyl carblLol (30 vol) soluLlon nozzle Lo
subsLraLe dlsLance 44 cm Alr pressure 073
bar SoluLlon flow raLe 30 ml/h
uLCSl1lCn 8A1L
9
9
19
lnfluence of Lhe alr pressure on Lhe dropleL
slze dlsLrlbuLlon recursor soluLlon flow raLe
30 ml/h
Mean dropleL dlameLer and dropleL
number fracLlon of Lhe pressurlzed spray
wlLh respecL Lo Lhe radlal dlsLance llow
raLe 30 ml/h dlsLance Lo subsLraLe 210
mm
9
9
S8A? ulS18l8u1lCn
20
WAceLaLe nlLraLe and oxalaLe precursors for ?8CC have been
spray pyrolyzed under dlfferenL condlLlons
WShelled and nonhollow mlcroparLlcles were obLalned from
aceLaLe and nlLraLe precursors and
WnonhollowagglomeraLes were obLalned from Lhe oxalaLe
Wsuspenslon
?8CC owder roducLlon
AALomlzer ACAlr
Compressor AlAlr
lllLers lnlurnace
lPlllLer PeaLer
PreheaLer
llnsulaLlon
lowder lllLers
erlsLalLlc ump
1he model shows Lhe absorbed
radlaLlon heaL by Lhe parLlcles
from Lhe furnace walls ls
slgnlflcanL ln heaLlng Lhe gas
1he gas and Lhe parLlcle
LemperaLures are falrly close due
Lo Lhe effecLlve heaL Lransfer Lo
Lhe parLlcles 32
AL furnace LemperaLures of 700
C Lhe maxlmum predlcLed
parLlcle LemperaLure ls abouL
300HC
1hls explalns Lhe lncompleLe
reacLlons obLalned under Lhese
condlLlons Above 900C Lhe
reacLlons are predlcLed Lo be
compleLe wlLhln Lhe flrsL half of
Lhe furnace leavlng sufflclenL
resldence Llme for parLlal
converslon lnLo ?8CC
CCuarLz 1ube 8eacLor
88oLameLers 8C8egulaLor S
SoluLlon 11hermocouples
vvalves
21
CL8AMlC CCA1lnC
Advance ceramlc coaLlng Lo replace an exlsLlng ceramlc plpe sub[ecLed Lo Lhe severe
chemlcal condlLlons le operaLed ln hlLemperaLure and corroslve envlronmenL
A recLangular plece ls coaLed wlLh speclal aLLachmenL over an lron base sLrucLure uslng
yLLrlum alumlnum garneL (?AC) whlch ls havlng hlgh sLrengLh low creep raLes aL hlgh
LemperaLure anLlcorroslve hlsLablllLy agalnsL alkallvapor
@echnico/ 5pecificotions
W Ceramlc coaLlng was formed uslng
1800 plasma Lechnlque wlLh
spraylng condlLlons of Ar gas flow
raLe 301 l/mln P
2
gas flow raLe 14
l/mln currenL 600 A powder feed
raLe 16 g/mln nl20Cr and Al
2
C
3
feed sLock
W ?AC coaLlng was made from nl
20Cr and 33?
2
C
3
+ 63 Al
2
C
3
mlxed powder
W Speed of Cun scannlng 230 mm/s
33
22
uL18ASCnlC S8A? ?8CL?SlS
ulLrasonlc spray pyrolysls of precursor drops recursor concenLraLlon plays a predomlnanL
role ln deLermlnaLlon of producL parLlcle slze
1he ?SZ parLlcle dlameLers were much smaller Lhan Lhose predlcLed by Lhe oneparLlcle
perdrop mechanlsm
unlform dense spherlcal nanoparLlcles of 73nm dlameLer were produced by spray
pyrolysls Lhrough Lhe use of unlform precursor drops (3 8m dlameLer) and a low
precursor concenLraLlon (001 wL)
@echnico/ 5pecificotion
recursor zlrconlum hydroxyl
aceLaLe concenLraLlon 001
wL spray pyrolysls aL 730C
uslng precursor drops 38 m
ln dlameLer by an ulLrasonlc
nebullzer aL 266 MPz
?leld oolfotm JeoseJ spbetlcol
?SZ parLlcles 73 nm ln dlameLer
measured by SLM 34

23
S18Cn1luM 1l1AnA1L llLMS
1valve 2flowmeLer 3aerosol generaLor 4
soluLlon 3aerosol 6subsLraLe 7heaLlngplaLe
8valve and 9valve
ueposlLlon parameLers such as soluLlon concenLraLlon Llme and LemperaLure of deposlLlon
and flow raLe of carrler gas were opLlmlzed Lo obLaln dense fllms wlLhouL cracks repared Lhln
fllms were homogeneous well crysLalllzed wlLh unlform graln slze 333 nm and 441 nm and
Lhlckness 129 nm and 212 nm for 60 and 120 mln deposlLlon Llme resp
AdvanLage onesLep slmple cheap equlpmenL unlversal precursors (lnorganlc organlc or
meLalorganlc compounds) easy and preclse composlLlon conLrol (d) varlous fllm morphologles
posslble and (e) accuraLe conLrol of Lhe deposlLlon klneLlcs 33
60 mln
m|n
24
1LCPnlCAL SLClllCA1lCnS
23
1LCPnlCAL SLClllCA1lCnS
26
8LlL8LnCLS
1 J.M. Mochel, US Patent 2,564,707, "Electrically Conducting Coating on Glass and other Ceramic
Bodies", 1951.
2 J.E. Hill and R.R. Chamberlin, US Patent 3,148,084, "Process for Making Conductive Film", 1964.
3 W.J. DeSisto and R.L. Henry, "Deposition of (100) oriented MgO thin films on sapphire by a spray
pyrolysis method", Applied Physics Letters, 56(25), p. 2522-2523, 1990.
4 S.G. Kim, K.H. Choi, J.H. Eun, H.J. Kim and CS. Hwang, "Effects of additives on properties ofMgO thin
films by electrostatic spray deposition", Thin Solid Films, 377, p. 694-698, 2000.
5 W.J. DeSisto, Y.T. Qian, C Hannigan, J.O. Edwards, R Kershaw, K. Dwight and A. Word, "Preparation
and Characterization of Alumina Films Prepared by a Novel Spray Pyrolysis Method", Materials
Research Bulletin, 25(2), p. 183-189, 1990.
6 Y.T. Qian, R. Kershaw, K. Dwight and A. Wold, "Preparation and Characterization of Chromium(III)
Oxide Films by a Novel Spray Pyrolysis Method", Materials Research Bulletin, 25(10), p. 1243-
1250,1990.
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