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Apart from the effortsof myself,the success ofanyprojectdepends largely on the encouragement andguidelines ofmany others. Itakethisopportunityto expressmy gratitudetothepeoplewhohavebeeninstrumentalinthesuccessfulcompletionofthis project.
Firstofall,IwouldliketothankmysupervisorsGisbertRiessandWolfgangKernfortheir guidanceandtheirpersistenthelpduringdifficultphasesofthisproject.Withouttheir supportthefinalisationofthisthesiswouldnothavebeenpossible.
AtthispointIwanttothankmybachelorstudentsRainerPuchleitnerandMartinSpörkfor theirthoroughwork.IwanttoexpressspecialthankstoAndreasKaufmannforhisworkin thefieldofmontmorilloniteactivation.Iamparticularlygratefulfortheassistancegivenby myformerstudentassistantsRebeccaKramerandKatharinaKoschell.
IwouldliketoexpressmygratitudetoMariaSchmuckandManfredKriechbaumforsharing their expertiseconcerning XͲrayscatteringmethodsandfor the pleasant timeat the InstituteofBiophysicsandNanosystemsresearchinGraz.FurtherthanksgoestoBernhard SartoryoftheMaterialsCenterLeobenforhispatienceduringtheelectronmicroscope measurements and his perfectionism concerning the sample preparation and imaging techniques. My appreciation goes toAnton HuberfortheGPCmeasurementsatthe UniversityofGrazandThomasMeiselsfortheXRFmeasurementsattheUniversityof Leoben.
IreceivedgeneroussupportfromSandraSchlöglandhergroup,DietmarLenko,Jakob ManhartandEvelynSattlerandIwanttothankthemforthepleasantworkingenvironment inourlab.SpecialthanksgoestoClaudiaWieserandEvaEmmersdorferfortheirpersistent supportandhelpwithbureaucratichurdles.
Lastbutnotleast,Iwanttothankmyfamilyfortheircontinuoussupportofmyworkand theirstronginterestinmyresearchtopics.
Theuseofenvironmentallybenigncoatingsandresistmaterialshascometoattentioninthe pastdecades.Besidesestablishedpolymericmaterialspoly(vinylalcohol)isofmajorinterest, asthispolymeriswatersolubleandregardedassafeforpackagingtechnologiesaswellas forbiomedicalapplications.
NewmethodsforthecrosslinkingofPVAbyradiationwereinvestigatedinthiswork,with emphasisonnonͲtoxicityandbiocompatibilityoftheemployedcrosslinkingagentsand cleavage products. Additionally a number of functionalised particles such as cation exchangedmontmorilloniteswerepreparedandcharacterised.Theaimwastoimmobilise functionalgroupsatthesurfaceofinorganicparticlesthatcapableofinitiatingcrosslinking reactions. Furthermore these additives were employed to prepare organicͲinorganic compositematerialswithpoly(vinylalcohol)asmatrixpolymer.
Thedistributionofthemodifiedparticleswasinvestigatedbymicroscopicmethods,while opticalspectroscopywasemployedtoobservecovalentcrosslinkformation,duetoheat treatmentofUVlightexposure.AdditionallycovalentcrosslinkformationandpolymerͲfiller interactionswereinvestigatedbydeterminationoftheswellingbehaviourindeionised water.
DieVerwendungumweltfreundlicherBeschichtungenundResistmaterialienistfürzahlreiche technische Anwendungen relevant. Neben bewährten Polymersystemen ist Poly(vinylalkohol)aufgrundseinerWasserlöslichkeitvongrößtemInteresse.Einweiterer VorteilistdieBiokompatibilitätundphysiologischeUnbedenklichkeitdiesesPolymers,das fürAnwendungenimBereichderVerpackungstechnologienundfürmedizinischeProdukte zugelassenist.
In der vorliegenden Arbeit wurden alternative Methoden für die Vernetzung von Poly(vinylalkohol)durchStrahlung(eͲBeam,UV)untersucht.DerSchwerpunktwurdeaufdie UnbedenklichkeitdereingesetzenVernetzungchemikalienundderenSpaltproduktegelegt.
ZusätzlichwurdeeineVielzahlanfunktionalisiertenanorganischenPartikeln,wiekationenͲ getauschteSchichtsilikate,hergestelltundcharakterisiert.DasZielwardieImmobilisierung funktioneller Gruppen an der Oberfläche von anorganischen Partikeln, um VernetzungsreaktionenderPolymermatrixzuinitiieren.Zusätzlichwurdendiemodifizierten anorganischen Komponenten zur Herstellung von Kompositmaterialien mit Poly(vinylalkohol)alsMatrixpolymereingesetzt.
Die Verteilung der modifizierten Partikel wurde mittels mikroskopischer Methoden untersucht,währendspektroskopischeMethodenzurUntersuchungderAusbildungvon Vernetzungsstellen (z.B. durch UV Bestrahlungoder thermische Reaktionen) eingesetzt wurden. Quellversuche in deionisiertem Wasser wurden durchgeführt, um zusätzliche Informationen über die Wechselwirkungen zwischen Matrix und Polymer, und die AusbildungvonVernetzungsstellenzuerhalten.
Iherebyconfirm thatmy thesis entitled“Alternative methods for the crosslinking of poly(vinylalcohol)bytheuseoffunctionalisedinorganicparticlesͲAwaterͲbasedapproach towardsenvironmentallybenigncoatingmaterials”istheresultofmyownwork.Ididnot receiveanyhelporsupportfromcommercialconsultants.Allsourcesand/ormaterials appliedarelistedandspecifiedinthethesis.
Furthermore,Iconfirmthatthisthesishasnotyetbeensubmittedaspartofanother examinationprocessneitherinidenticalnorinasimilarform.
Leoben,August2013 JörgGuidoSchauberger
I. IN
II. ST
1. Pol
S
1.1
C
1.2 1.2 1.2
2. Azo
2.1 2.1
3. Fun
3.1 3.1 3.1 3.1
S
3.2
4. Org
III. O
1. Alte
1.1
A
1.2
2. Fun
C
2.1 2.1
S
2.2
3. Org
IV. M
TRODUCT
TATEOFTH
y(vinylalcoho Synthesisand Crosslinking..
Acidcat
.1
Radiatio
.2
osulphonates
Stateof
.1
Decomp
.2
nctionalisatio Montmorillon
Activati
.1
MetalͲc
.2
Organo
.3
Surfacefunct
ganicͲinorgan
OBJECTIVE
ernativemeth Radiationassi Azosulphonat
nctionalisatio Cationexchan
Intercal
.1
Surfacefunct
ganicͲinorgan
MATERIAL
TION...
HEART:A
ol)(PVA)...
dproperties...
...
talysedmetho oninducedcro
...
ftheart...
positionmech
nofinorganic nite...
on...
cationexchang modification ionalisation...
iccomposite
ES...
hodsofcross istedmethod tedopedPVA
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ationoforgan ionalisation...
iccomposites
LSANDME
...
LITERATU
...
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ods...
osslinking...
...
...
hanismofarom
cparticles...
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ge...
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3. Exp 3.1
3.1 3.1 3.1 3.1 3.1 3.2
3.2 3.2 3.2 3.2 3.2 3.2 3.3
3.3 3 3 3 3 3.3
3 3 3 3.4
3.4 3 3 3 3.4
3 3 3
O
3.5 3.5
3 3
perimental....
NeatPVA–re
Determ
.1
Prepara
.2
Optical
.3
Therma
.4
Solubilit
.5
Investigation
Doping
.1
Sample
.2
Exposur
.3
Change
.4
Determ
.5
Photolit
.6
Preparationo
Synthes
.1
Sy
3.3.1.1
St
3.3.1.2
Ph
3.3.1.3
Th
3.3.1.4
Prepara
.2
A
3.3.2.1
U
3.3.2.2
In
3.3.2.3 Functionalisat
Prepara
.1
Ac
3.4.1.1
Tr
3.4.1.2
A
3.4.1.3
Prepara
.2
Su
3.4.2.1
D
3.4.2.2
Ch
3.4.2.3 OrganicͲinorg
PVAͲFe3
.1
Sa
3.5.1.1
In
3.5.1.2
...
eferencemate inationofstru ationofsolutio methods...
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3 3 3.5
3 3 3 3.5
3 3 3.5
3 3 3
V. RE
1. Nea
1.1
O
1.2
T
1.3
S
1.4
2. Alte
2.1
2.1 2.1 2.1 2.2
2.2 2.2 2.2 2.2
C
2.3
A
2.4 2.4
2 2
Sa
3.5.2.1
Co
3.5.2.2
UseofU
.3
Sa
3.5.3.1
D
3.5.3.2
Co
3.5.3.3
VinylͲm
.4
Sa
3.5.4.1
Ef
3.5.4.2
Improve
.5
Sa
3.5.5.1
D
3.5.5.2
In
3.5.5.3
ESULTSAN
atPVA–refe Determinatio Opticalmetho Thermalanaly Solubility...
ernativemeth EͲbeamcross
Doping
.1
Radiatio
.2
Determ
.3
UVcrosslinkin
Investig
.1
UVexpo
.2
Determ
.3
Photolit
.4
Conclusion....
Azosulphonat
Synthes
.1
Sy
2.4.1.1
St
2.4.1.2
ampleprepara ompositecha UVreactivepa ampleprepara etermination ompositecha modifiedpartic ampleprepara ffectsofeͲbea ementofsolv ampleprepara
etermination nvestigationo
NDDISCUSS
rencemateria nofstructura ods...
ysis...
...
hodsforthec linkingofPVA ofPVA...
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gationofUVͲr osure...
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ation...
racterisation. articlesforthe ation...
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ation...
amexposure.
entresistance ation...
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SION...
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ructuralchang ellingbehavio ...
esponse...
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alproperties.
stance...
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2 2.4
2 2 2 2 2.4
S
2.5
3. Fun
3.1
3.1 3.1 3.1 3.2
3.2 3.2 3.2
4. Org
4.1
4.1 4.1 4.1 4.1 4.1
C
4.2 4.2 4.2 4.2 4.2 4.3
4.3 4.3 4.3
V
4.4 4.4 4.5
Th
2.4.1.4
Charact
.2
A
2.4.2.1
Ph
2.4.2.2
In
2.4.2.3
Ph
2.4.2.4
Conclus
.3
Summary...
nctionalisatio Preparationo
Activate
.1
Transiti
.2
Aminoa
.3
Preparationo
Surface
.1
Investig
.2
Conclus
.3
ganicͲinorgan UVreactiveP
Investig
.1
Nanoco
.2
Determ
.3
Photolit
.4
Conclus
.5
Compositem
Determ
.1
Particle
.2
Investig
.3
Conclus
.4
UseofUVrea
Investig
.1
Compos
.2
Conclus
.3
VinylͲmodifie
Crosslin
.1
Improvement
hermolysis...
terisationofa nnealing...
hotolysis...
nvestigationo hotolithograp sions...
...
nofinorganic ofcationexcha edmontmoril
onmetalcatio acidintercalat ofsurfacefunc silanisation..
gationofthep sions...
iccomposite
VA–Fe3+ͲMM
gationofUVͲr ompositechar inationofswe thographicpa sions...
aterialscomp inationofthe distribution..
gationofheat sions...
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sitecharacter sions...
dparticlesfor nkformation..
tofsolventre
...
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fswellingbeh phicpatterning
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angedmontm lonite...
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acterisation..
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4.5
VI. O
1. Alte
2. Fun
3. Org
4. Out
VII. R
VIII. A
1. Tab
2. Figu
3. Figu
A
3.1 3.1 3.1
S
3.2 3.2 3.3
4. Cur
Conclus
.4
OVERALL
ernativemeth nctionalisedin ganicͲinorgan
tlook...
REFERENC
APPENDIX
bleHeadings.
ureCaptions.
ures...
Azosulphonat
Anneali
.1
Photoly
.2
Surfacefunct
Photoly
.1
UseofUVrea
rriculumvitae
sions...
CONCLUSI
hodsofPVAc norganicpart iccomposite ...
CES...
X...
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...
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tedopedPVA ng...
ysis...
ionalisedpart ysis...
activeparticle
e...
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IONS...
crosslinking...
ticles...
materials...
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ticles...
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Abbreviation Description
DSC Differentialscanningcalorimetry
EDX EnergydispersiveXͲrayspectroscopy
EVOH Poly(ethyleneͲcoͲvinylalcohol)
FTIRspectroscopy Fouriertransforminfraredspectroscopy
GCͲMS Gaschromatography–massspectrometer
GPC Gelpermeationchromatography
LOD Limitofdetection
LS Lightscatteringdetector
MAXS MediumangleXͲrayscattering
MMD Molarmassdistribution
MMT Montmorillonite
Mn Numberaveragemolecularweight
Mw Weightaveragemolecularweight
NMRspectroscopy Nuclearmagneticresonancespectroscopy
PDI Polydispersityindex
phr Perhundredpartsofrubber
PVA Poly(vinylalcohol)
RI Refractiveindexdetector(GPC)
RT Roomtemperature
SEC Sizeexclusionchromatography
SEM Scanningelectronmicroscope
TGA Thermogravimetricanalysis
UV/Visspectroscopy Ultraviolet/visiblelightspectroscopy
XNBR Carboxylatednitrilebutadienerubber
Symbol Unit(s) Meaning
D kGy Radiationdose(eͲBeam)
Mn gmolͲ1 Numberaveragemolecularweight
Mw gmolͲ1 Weightaveragemolecularweight
nD Ͳ RefractiveindexatsodiumDͲline
PDI Ͳ Polydispersityindex
RT °C Roomtemperature(23±2°C)
T °C Temperature
wd g,mg Drysampleweight
wi g,mg Initialsampleweight
ws g,mg Swollensampleweight
Ș mPas Viscosity
Ȝ nm,(Å) Wavelengthofvisible/UVͲlightor(XͲrays)
ʆ cmͲ1 Wavenumber
I. INTRODUCTION
Intherecentdecadesenvironmentalcompliancebecameofgrowingimportanceinthe packagingindustryandfortheapplicationofchemicaltechnologies.Hencethecriticalvalues fororganicsolventsinsewagewaterandinexhaustairgottighter,productionprocesses have to beadaptedtorecirculatesolvents and process chemicals.Thisbroughtforth reducedemissionsandwatercontamination.1
Asanexample,thefoodpackagingindustrywouldbenefitfromtheemploymentofwater basedcoatingsystems.Astheguidelinesandregulationsinthefieldofpackagingregarding themigrationoforganicsubstances(e.g.diͲisobutylphthalate)intopackagedgoodssuchas foodgetmoreandmoretight,theneedarisestodevelopwaterͲbasedcoatingmaterialsand barrierfilmstopreventmigrationofsuchsubstances.2–7Greateffortisdevotedtothe researchinsuchmaterials,whichhavetobeenvironmentallybenignandrecyclableaswell.8 Moreover,waterͲbasedcoatingsandresistmaterialsmayfindapplicationinthefieldof printedcircuitboards.Furthermorethepreparationofphotoresistmaterialsthatarewater solubleandthereforecanbedevelopedbywatercouldprovideanalternativetocommon resisttechnologiesforthepreparationofflexiblepolymerwaveguidesandholographic recordingmaterials.9–11
Theimmobilisationoffunctionalgroupsontoinorganicsurfaces(e.g.silicondioxide)bearing hydroxylgroups,providesawaytopreventleachingoutoftheactivesubstancesoforganicͲ inorganiccompositematerials.Thisalsoprovidesthepossibilitytoemploynewclassesof materialsinthefieldofbiomedicaltechnologiesandwaterpurification(e.g.removalof heavymetalcationsanddyes).4,12,13
ThesubstitutionofestablishedprocessesandchemicalsbywaterͲbasedsystemswouldpose alternatives that are environmentally benign as well as lead to cost reduction after implementation.Hencenoadditionalsafetymeasuresandclosedloopprocessconduction havetobeemployed.
Themajorgoalsofthisworkaretheinvestigationofalternativewaysforthecrosslinkingof poly(vinylalcohol)bytheemploymentofradiationandthermallyinducedmethods.Onthe
otherhand,newclassesoffunctionalisedfillermaterialshavebeenenvisaged,byeither cationexchangereactionstoobtainmodifiedlayeredclaysaswellassurfacemodificationof inorganicparticlessuchassilica.Theseparticleshavebeenassessedasfunctionaladditives forbothcovalentandphysicalcrosslinkingoforganicͲinorganiccompositematerialswith PVAasmatrixpolymer.
II.
1.
1.1
Poly(vin poly(vin chemica degree PVA is process agenta coatings biomed Further polyme oxygen strongh bonding propert In orde crosslin catalyse
1.2
1.2.1 Acidca crosslin concept withPV
STAT POLY
SYNTH
nyl alcohol) nyl acetate
alandphys ofpolymer employed sing3,16,for anddispersi s in conta icalapplica morePVA rchains,w andnonͲp hygroscopy g network, ties.25,26 er to prev
kingreacti ed.
CROSS
Acidcat atalysedcro kingagents tsthatare VAleadtoth
TE OF T (VINYLA
HESISAND
) (PVA) is ),which h icalpropert isationasw as adhesi watersolu ingaid.19D ct with fo tions.20–22
isableto whichleads olarsubsta ,theabsor
resulting
ent this a ons arew
SLINKING
talysedme osslinkingo s,butthem depictedin heformatio
THE AR ALCOHO
DPROPE
usually p hasbeen p
tiesofthew wellasbyth
ive for pa blegluesa Duetoitsb
oodstuff an
formanin tooutstan ancesasthe
ptionofae in swelling
dverse eff well describ
G
ethods ofPVAcan majorityofth
nFig.1.Asa onofstable
RT: A L OL)(PV
ERTIES
repared by polymerised watersolub hedegreeof
ckaging ap andmodelli iocompatib nd suitable
ntricatene ndingbarrie epolymer
rialhumidit g of the p
fect, crossl edinthe
nbeperfor hesereactio aldehydesa acetaland
ITERA VA)
y polymer d by free blepolymer
fsaponifica pplications17 ingmateria bilitythispo
for the p
etworkofh erpropertie itselfishig tyleadsto polymeran
inking has literature
rmedwith onsareperf arehighlyr
unstableh
TURE R
analogous radical pol arestrongl tion.15,16
7, as sizing als18aswe olymerisre preparation
hydrogenb esofthed hlypolar.23 deterioratio d diminish
to be ac andarein
anumber formedina reactive,cro
emiacetals
27,28
REVIEW
s saponifica lymerisation lyinfluence
g agent fo ellasencap egardedas n of hydro
bondsbetw rypolymer
3,24AsPVA onoftheh hing ofthe
chieved. Nu nmanycas
ofmultifu accordance osslinkingr structures,o
W
ation of n.14 The edbythe
or paper psulation safefor gels for
weenthe ragainst exhibits ydrogen e barrier
umerous sesacid
unctional tothree eactions ofwhich
employ esterbo duetow By the formati theform reporte process
Fig.1:
Analte utilisatio prepara betwee 1.2.2 Poly(vin rays,re
mentofdif onds,which wateruptak addition o onofano mationofs danddem ses.31–35
Overview ernativeto
onofpolym ationofcro nPVAandt Radiatio nylalcohol)
sultinginst
functionala hpreventsw ke.22,29,30 of multifun
rganicͲinorg ilicananop monstrated
wofacidca theemplo merswithc
osslinkedh thefreecar oninduced
canbecros tatisticform
acids,sucha wellingand
nctional sila ganichybrid
articlesdue byBandyo
talysedcro oymentof carboxylicm hydrogelm
rboxylicacid dcrosslink
sslinkedby mationoffr
asadipicac dthusfurth
anes, such dnetwork etoacidin opadhyay,
sslinkingm lowmolec moietiessuc membranes
dgroupsof king
exposuret eeradicals
idoroxalic erdeterior
as tetraet isdescribe ducedhydr Sarkarand
echanisms cularcross chaspoly(a
byuseof gelatin.30,36
oionisingr andtheirs
acidleadst ationofthe
thyl orthos dbyaseri rolysisofth
Bhowmick
forpoly(vin linkingage acrylicacid) acidcatal
6
adiationsu ubsequent
totheform ebarrierpr
silicate(TEO esofautho heethoxyg
kbyinͲsitu
nylalcohol).
entswould ).Paldescr lysedester
chasɴ/ɶͲra recombina
mationof roperties
OS), the ors.Also groupsis usolͲgel
.
be the ribesthe rification
aysorXͲ tion.29,37
Anumb blendsw crosslin Amore such as photose wellͲkno recordin whicha Maniva dopedP toradic theseU andnon itiscon PVA.48–5 Anothe moietie as 2Ͳh German samples
2.
2.1.1 Labilea traditio used as derivati inthe macroin
berofautho withchitos kingagents econvenien s iron chlo ensitisingo
own gelati ngmateria arehazardo nnan,Kunc PVAandfo calformatio UVcrosslink nlinearopti nsideredenv
51
rapproach esattached ydroxyͲ2Ͳm ny),UVindu sthatarein
AZOSU
Stateof azofunction ninthefie s initiators vesthemo mainchain nitiatorsfor
orsreportt anorgelat s.38–40 ntmethodt
oride or c ofthepolym
ne/dichrom ls.Butith ustotheen cserandFi
undthatph onandreco kingexperim
ics.AsFeCl3
vironmenta
htoattain tothepoly methylpropio
ucedcrossli nsolubleind
ULPHON
f theart nalitiesbea eldofpolym s for free ostwellͲkno
norsideg rthesynthe
thationising tineinorde
tocrosslink chromates mer.Them mate system
astobest nvironment
lotihavein hotoreduct ombination, mentswas
3isemploy allybenigna
UVcurabl ymerbackb
ophenone nkingviafre deionisedw
NATES
ringaliphat merchemist
radical po wnexampl groupsthat esisofblock
gradiation ertoprepar
kPVAisth such as p mechanism
ms in the tatedthat tandcarcin nvestigated ionoftheF ,thusleadin theprepar edasfloccu andposesa
lePVAist one.Bythe (Irgacure®
eeradicalr water.52–55
ticormixed try.Therma lymerisatio esofthiscl tcanbeth kandgraftp
canbeemp rehydroge
edopingw potassium
ofcrosslink fieldof p chromates ogenicasw themecha Fe3+ionsto ngtocrossl rationofho ulationage analternati
thegraftin eadditiono
® 1173; B eactioncan
daliphatica allycleavab
n, with 2, lass.56,57Als hermallyd polymers.58–
ployedforc lswithoutt
withtransiti dichromate kingcanbe hotographi
arehighly well.41–43
anismofcr oFe2+takes
linkformati olographicr ntforwast vewaytoc
gofcopoly ofaradical
BASF Gmb nbeperform
aromaticm bleazocom
2’Ͳazoisobu sopolymers ecomposed
–60
coͲcrosslink theadditio
ionmetalc e, which l ecompared
cand holo ytoxiccom
rosslinking splace,whi ion.44–48Th recordingm tewatertre
chromated
ymerswith photoinitia bH; Ludwig med,which
moietieshav mpoundsare
utyronitrile swithazof dareempl
kingPVA nofany
chlorides eads to dtothe ographic mpounds,
forFe3+
chleads eaimof materials eatment, opingof
hacrylic torsuch gshafen;
leadsto
vealong ewidely and its unctions oyedas
Thepre suchas field of prepara UVirrad 2.1.2 The ph Nuyken depend ofthea uponfu prevale thepre formati lead to environ
Fig.2:
eparationof azosulpho f photores ationandch
diationhas Decomp hotolysis be andVoitin ingonthe azosulphona urtherexpo
nt,leading esenceofa onofphen o formatio
ment.57,61,6
Decomp thechem
fphotolabil natesanda sist materi
haracterisat beenrepor positionme
ehaviour o ntheearly
chemicalen ateisrearr osure(seeF totheform alcohols,a nylgroups.
on of nit
6
ositionme micalenviro
eandtherm azophospho
als, laser tionofpoly rtedbyMat
echanismo f aromatic
1990s.Itw nvironment
angedtoth Fig.2).Inth mationofhy
radicalclea DuetoUV trogen gas
chanismof onmentasp
mallystable onatescam
ablation a ymersand tusche,Nuy ofaromati c azosulpho wasfound,
t.Asaresu heunstable hepresence ydroxyphen avagemech inducedde s, showing
farylazosu publishedby
elowmolec etointere and record
copolymers kenandTro icazosulph onate com
thatthem ltofUVirra ecisͲform,w eofwatera nylresidue
hanismisd ecompositio g no dep
ulphonatec yNuyken,V
culararoma st,forthee ding mater
sthatcanb ogisch.60,64,6 honates
pounds wa echanismo adiation,th
whichleads anionicscis groups.On dominant,w on,thedesc pendence
compounds VoitandRie
aticazocom employmen rials.61–63 A
bedecomp
65
as investig ofdecompo
establetra stodecom ssionmech ntheother whichlead cribedmec on the c
sindepend ess.57,61
mpounds ntinthe Also the posedby
ated by ositionis ansͲform mposition anismis hand,in stothe chanisms chemical
denceof
3.
3.1
Thesm general structur surface cations increasi exchang layer d montmo asthick
Fig.3:
Avariet thema attain o retarda compos
FUNCT
MONT
mectiteͲgrou compositi reconsistin chargesbe (seeFig.3 ingthelaye gedwithot distance an
orilloniteis eningagent
Triplelay platelets tyofcation reemploye organophili
nts; active sitesaswel
TIONAL
MORILLO
upmineral ion [Si8]IV[A ngoftwote etweenthe
).Theabso erͲtoͲlayer thermetalc nd thus im soneofthe
tforaqueo
yeredstruc s,waterand nexchange
edtoincor c behaviou e filler ma
lincreaset
LISATIO
ONITE
montmoril Al4оxMgx]VIO etrahedral eclayplate orptionofw
distance.T cationsorw mprove th emaincom ussuspensi
ctureofas dinterlayer
reactionsc rporatenon ur. Such m terials tha thegasbarr
NOFIN
llonite(MM O20(OH)4(Mx
sheetssand eletsexist, waterleads Thereforeth withorganic e exfoliati mponentsof ionsorforg
odiummon cations.(©A canbeperf
nͲpolaram modified m t enhance rierpropert
ORGAN
MT)isala
x/n)n+ͼyH2O.6 dwichingo thatareb stoswellin heinterlaye ccationsto
on behavi fdrillingmu
geotextiles.
ntmorillonit AndreasTre ormedonm moniumsa aterials ma
the mech tiesofanu
ICPART
yeredalum
7,68 Due to neoctahed alancedby gofthelay ercationsc ofurtherinc our and d udsandcan
69–71
teaggregat epte).
montmorillo alts,bearing ay find ap hanical str umberofpo
TICLES
mosilicatew o its speci dralsheet, yCa2+,Mg2+
yeredsilica canbemor creasethe dispersibilit nalsobeem
econsisting
onites,the gtallowgr pplication a rength of
olymericco
withthe ial layer negative
+orNa+ ate,thus reeasily layerͲtoͲ y. Neat mployed
goftwo
mostof roupsto as flame polymer omposite
materia polyolef 3.1.1 Thetrea nitricac mineral toarise ofthes tothea sites.77 Aseries whichd triplela takesp theMM Acidact acylatio materia Tyagian technol 3.1.2 Asthe reaction ofthep statehe acetalis Theimm clays,w
als.Thema finssuchas Activati atmentofm cidleadsto
sandbiolo eofthesurf surfacearea activations
sofauthor doesnoton ayerstructu lace,which MTplatelets tivatedmon onreactions alsanddyes ndChudasa ogyandin
MetalǦca interlayer nstoimmo particularm eterogenic
ationando mobilisation whichmaya
inaimiso sPEandPP
ion
montmorillo oavolume ogicalconta faceacidity aofthemo
tepadditio
rsreportth lyleadtod
reofthepa hisaleadt
areconver ntmorillonit s76,andthe sfromaque amareport
beveragea ationexch cationsof bilisetrans metalsalt.I catalysts,fo oxidationre
nofzincca alsofindap
ftentofac andtoena
oniteclaysw increaseof minants.73,7 yaswellas
ontmorillon onalsilanol
heactivatio elamination articles.Iti hatalumin rsedbythe teclaysmay eirsuitabilit
eoussolutio ttheemplo
ndfoodstuf ange
montmoril itionmetal tisreporte oraserieso
actions.80,84 ationsinth pplicationas
ilitatethec blemeltpro
withminera ftheMMT
74Thefirst topartiald niteandint groupsare
onofmont nofthepla sfoundtha iumions,w acidtreatm yfindapplic tyasadsorb onhasbee oymentof ffapplicatio
lonitecan ionscanbe edthatthe
ofreaction
4–86
einterlaye scrosslinki
compatibilit ocessingof
alacidssuc aswellast stepofthe elamination roducespe formed,w
tmorillonite telets,buta attheforma whicharelo ment.78–80
cationasso bentsforhe eninvestiga
themodifie ons(e.g.fin
beleached eperforme
semodified typesinclu
rgalleriesl ngagentsf
tyofthela theobtaine
hashydroc todecompo eacidtreatm
n.75Thisre ermanentm whichactas
eclaysusin alsotoade ationofalu ocatedatth
olidcatalyst eavymetals tedaswell edclaysin ingagentfo
douteasily dbythead dMMTsare udingesteri
leadstoan forXNBRla
ayeredsilica edcomposi
chloric,sulp ositionofa
mentproce esultsinan mesoporosit shydrogen
ngphospho ecompositio uminiumph hebrokene
tsforalkyla s,radioactiv l.81–83Furth thefieldo orwine).75
y,catione dditionofa eoutstand ification,al
ntimicrobial atticesassu
atewith ites.70,72
phuricor ccessory essleads increase ty.76Due bonding
oricacid, onofthe hosphate edgesof
tionand vewaste hermore ofpaper
xchange nexcess ingsolid kylation,
lyactive ubstitute
forcom exhibit exchang product Gerstle suchpr stateca toemp basedra 3.1.3 Thehyd tallowg section theinte Due to immobi perform multipo fordye establis Theimm studied, conden increase Organoc metalio
81,105,105–
claymin
mmoncross strong aff gedMMTsc tionofhydr etal.report reparedmo atalysts.92–96 ploythispa adicalphot
Organo drophobisa groupsisw
issetonth erlayergalle
o their hi lisation of medwithou orousstruct sfromaqu hedmetho mobilisatio ,howevert sates.101–104 eofthelaye
clayswithi onsfromwa
–107Asthio neralsmay
slinkingche finity to m canbeemp rogenperox tthatthein ontmorillon
6AstheFe3 articularmo
oinitiator.11 modificati tionofmo wellknown
heimmobil eriesofthe ghly polar amino co utdifficulty.
ture,theyc ueoussolut dtodeterm nofthea thisismost
4Theadso erͲtoͲlayer immobilised astewater olsareemp
beemploy
emicalssuc montmorillo ployedasen xideaswell
ntercalation ite,which
3+cationca ontmorillon
1
ionofmon ontmorillon anddescr lisationoff layeredclay r and neg ompounds
.Asmontm canbeemp
tions.83Fur minethesur
minoacid lyemploye rptionofo distanceas dthiolmoie
byformatio ployedforp yedassolid
chasZnO.8 onite, while nvironment ashydroxy nofFe3+io maybeem anbereduc niteasan
ntmorilloni nitebyinte ribedbyse functionalg yusingpola gatively ch by means morillonite ployedforf
rthermoret rfaceareao glycinein dasprecur organicsub wellastod etiesmayf onofcoord photochem statecross
87–89
Abollin e Hothi st
tallycompli ylamine.90,91 nsleadsto mployedas cedbyUVl
ovelenviro
ite
ercalationo everalautho
groupsbyc armodificat harged inte
of cation claysexhib filtrationpr
theabsorp ofclaymine
theinterla rsorforthe bstancesby
delaminatio findapplica inationcom icalcrosslin slinkingaid
noreports ates that iantsolidst
1
enhanced environme ightexposu onmentally
ofaminoco ors.70,72,98,99
cationexcha tionreagent erlayer ga
exchange bitalarges
ocessesas tionofme eralsandso ayergallerie
preparatio montmori onofthecla
tionforthe mplexeswith nkingofNR
s,withthe
thatMn2+
manganese tatecatalys
catalyticac entallybeni ure9,97,itis benignan
ompounds
9Thefocus angereacti
ts.
llery surfa reactions surfaceare
wellasabs ethyleneblu
ilsamples.1 esofMMT
noflonger illonitelead ayplatelets eremovalo he.g.Hg2+a RandXNBR
advantage
+cations e cation tforthe
ctivityof ignsolid possible dwater
bearing softhis onsinto
ace, the can be eaanda sorbents ueisan
100 Tiswell
peptide dstoan
.
ofheavy andCd2+
R89,such thatno
