Hyb ids based on laye ed
Silica es
Disse a ion
zu E langung des akademischen G ades
eines Dok o s de Na u wissenscha en (D . e . na .)
im P omo ionsp og amm Polyme Science
an de Bay eu he G aduie enschule
ü Ma hema ik und Na u wissenscha en (BayNAT)
de Uni e si ä Bay eu h
Vo geleg on
S ephan Weiß
gebo en in Cobu g
Bay eu h, 2013
Die o liegende A bei wu de in de Zei on Janua 2009 bis Feb ua 2013 in Bay-
eu h am Leh s uhl Mak omolekula e Chemie II un e Be euung on He n P o . D .
Axel H. E. Mülle ange e ig .
Volls ändige Abd uck de on de G aduie enschule BayNAT de Uni e si ä Bay-
eu h genehmig en Disse a ion zu E langung des akademischen G ades eines Dok-
o s de Na u wissenscha en (D . e . na .).
P omo ionsgesuch einge eich am: 02.05.2013
Zulassung du ch das Lei ungsg emium: 07.05.2013
Wissenscha liches Kolloquium: 11.06.2013
Am ie ende Di ek o :
P o . D . F.X. Schmid
P ü ungsausschuß:
P o . D . Axel. H. E. Mülle (E s gu ach e )
P o . D . Ad eas Fe y (Zwei gu ach e )
P o . D . Raine Schobe (Vo si z)
P o . D . Jose B eu
Fü meine wunde olle Familie.
»Nich s schockie mich. Ich bin Wissenscha le .«
Indiana Jones
»Wha su p ises me mos o all in mankind, is ha man will lose hei heal h in o -
de o ge money and hen hey lose ha money in o de o eco e hei heal h. A
he same ime while wo ying abou he u u e, hey o ge o li e he p esen , his
way hey end up li ing in nei he he p esen no he u u e. They li e as i hey a e
ne e going o die and hey die as i hey ha e ne e li ed.«
Buddha

Table o Con en s
Table o Con en s
SUMMARY .............................................................................................................................. 1
GLOSSARY .............................................................................................................................. 5
1 CHAPTER 1: INTRODUCTION ......................................................................... 7
1.1 Laye ed silica es ........................................................................................................................ 7
1.1.1 Na u al mon mo illoni e ....................................................................................................... 9
1.1.2 Syn he ic hec o i e (Na- luo ohec o i e) ............................................................................. 10
1.1.3 Na u al kaolini e .................................................................................................................. 11
1.2 O ganic/ino ganic hyb id nanopa icles .................................................................................. 12
1.2.1 Clay based hyb id nanopa icles .......................................................................................... 13
1.2.2 Pa chy nanopa icles ........................................................................................................... 14
1.2.3 Janus nanopa icles ............................................................................................................. 14
1.3 (Clay ein o ced) nanocomposi es .......................................................................................... 16
1.3.1 Nanocomposi es based on homopolyme s ......................................................................... 17
1.3.2 Nanocomposi es based on polyme blends ........................................................................ 17
1.4 Mo i a ion and objec i e o his hesis ................................................................................... 18
2 CHAPTER 2: EXPERIMENTAL PART AND METHODS ............................................ 20
2.1 Ma e ials ................................................................................................................................ 20
2.2 Ins umen a ion ...................................................................................................................... 21
2.2.1 Nuclea magne ic esonance spec oscopy (NMR) ............................................................. 21
2.2.2 Size exclusion ch oma og aphie (SEC) ................................................................................. 22
2.2.3 T ansmission elec on mic oscopy (TEM) ........................................................................... 22
2.2.4 Scanning elec on mic oscope (SEM) .................................................................................. 22
2.2.5 The mog a ime ic analysis (TGA) ...................................................................................... 22
2.2.6 Dynamic ligh sca e ing ...................................................................................................... 22
2.2.7 S abili y measu emen s (LUMiFuge®) ................................................................................. 23
2.2.8 Cha ge i a ion s abili y analysis (S abisize ®) ................................................................... 23
2.2.9 Dynamic-mechanical analysis (DMA) and ensile es s ....................................................... 23
2.2.10 Powde X- ay di ac ion (PXRD) ..................................................................................... 24
2.2.11 Fou ie - ans o m in a ed spec oscopy (FT-IR) ............................................................ 24
2.2.12 Speci ic su ace a ea measu emen s .............................................................................. 24
Table o Con en s
2.3 Tailo ing o s acks heigh and s i ness o luo ohec o i e ....................................................... 24
2.4 Syn hesis o he copolyme s o su ace modi ica ion ............................................................ 25
2.4.1 Syn hesis o he ca echol-modi ied PMMA copolyme (PCM) ............................................ 25
2.4.2 Syn hesis o poly(2-(2-b omoisobu y yloxy)e hyl me hac yla e)-s a -(2-
dime hyl(amino)e hyl me hac yla e) (MI) ia Re e sible Addi ion-F agmen a ion Chain T ans e
(RAFT) polyme iza ion ....................................................................................................................... 26
2.4.3 Syn hesis o poly(2-(dime hylamino)e hyl me hac yla e) (PDMAEMA) based diblocks ia
RAFT ............................................................................................................................................. 27
2.5 Clay su ace modi ica ion ........................................................................................................ 28
2.5.1 Su ace modi ica ion o K- luo ohec o i e and su ace-ini ia ed A om T ans e Radical
Polyme iza ion (si-ATRP) o me hyl me hac yla e (MMA) ................................................................ 28
2.5.2 Su ace modi ica ion o mon mo illoni e (MMT) ................................................................ 29
2.5.3 Su ace modi ica ion o kaolini e ........................................................................................ 30
2.6 P epa a ion o clay/polyme nanocomposi es ........................................................................ 31
2.6.1 Embedding o K- luo ohec o i e/PMMA hyb id pa icles (hyb id-hec ) in o a PMMA Ma ix
o ensile es ing ............................................................................................................................... 31
2.6.2 P epa a ion o hyb id-clay/polys y ene (PS)/PMMA nanocomposi e samples o TEM
analysis ............................................................................................................................................. 31
2.6.3 P epa a ion o hyb id-MMT/PS/PMMA nanocomposi e samples o DMA ........................ 32
3 CHAPTER 3: HYBRID MICA-LIKE PARTICLES BASED ON HIGH ASPECT RATIO
FLUOROHECTORITE ............................................................................................................. 33
3.1 P epa a ion o ailo ed mica-like K- luo ohec o i e/PMMA hyb id pa icles .......................... 33
3.1.1 Tailo ing o a high aspec a io mica-like nano ille ............................................................ 33
3.1.2 Selec i e su ace modi ica ion o he mica-like nano ille .................................................. 34
3.1.3 Su ace-ini ia ed ATRP o MMA ........................................................................................... 38
3.2 Mechanical p ope ies o he clay/PMMA nanocomposi es .................................................... 44
3.3 Conclusion .............................................................................................................................. 46
4 CHAPTER 4: PATCHY HYBRID PARTICLES BASED ON POLYMER GRAFTED
MONTMORILLONITE (MMT) ............................................................................................. 47
4.1 P epa a ion o pa chy hyb id pa icles based on MMT ........................................................... 47
4.1.1 Syn hesis o DMAEMA based diblock copolyme s ia sequen ial RAFT polyme iza ion ..... 48
4.1.2 Solu ion beha iou o he diblock copolyme s .................................................................... 52
4.1.3 Modi ica ion o he basal planes ......................................................................................... 54
Table o Con en s
4.2 Mechanical p ope ies o he clay/PMMA/PS nanocomposi es .............................................. 57
4.2.1 P epa a ion o clay/PS/PMMA blends ................................................................................. 57
4.2.2 DMA o he blends ............................................................................................................... 60
4.3 Conclusion .............................................................................................................................. 61
5 CHAPTER 5: HYBRID JANUS PARTICLES BASED ON POLYMER MODIFIED
KAOLINITE ............................................................................................................................. 62
5.1 P epa a ion o hyb id janus pa icles based on kaolini e ........................................................ 62
5.1.1 Syn hesis o he copolyme s PCM and D16-b-S115 ................................................................ 64
5.1.2 Modi ica ion o he kaolini e basal planes .......................................................................... 66
5.2 TEM Analysis o he mo phology o he hyb id-kaolini e / PMMA/ PS nanocomposi es ......... 72
5.3 Conclusion .............................................................................................................................. 75
6 CHAPTER 6: REFERENCES ......................................................................................... 76
ACKNOWLEDGEMENTS .................................................................................................. 82
Chap e 1
7
1 Chap e 1: In oduc ion
1.1 Laye ed silica es
In mankind's ea ly his o y, he u iliza ion o new ma e ials lead o majo
echnological p og ess, om he s one- o e he b onze- o he coppe -age, he new
ma e ials enabled be e ools, be e hygiene and be e p o ec ion and also o en
decided he a e o ci iliza ions. Mode n socie y in con as needs highly specialized
ma e ials, o en ailo ed o a single ask, o ace he challenges o i s apidly
ad ancing echnological sec o s like au omo i e, ae ospace, hygiene, ene gy and
enginee ing. Li ing in he age o polyme s, he e is al eady a la ge supply o basic and
ad anced ma e ials o choose om, bu he in oduc ion o nano echnology, and
wi h i nanopa icles, opened up a as ange o possibili ies o be e and no el
ma e ials, whe e e en he cheapes basic polyme s, which make up mos o he
daily-use i ems a ound he wo ld, can be mixed wi h a small amoun o nanosized
objec s o enhance and al e hei p ope ies signi ican ly1.
Clay mine als ha e been used since housands o yea s by cul u es wo ldwide as
ce amics, bu due o hei mani old o he p ope ies, e.g. high wa e adso p ion,
capaci y o ca ion exchange, non-New onian luid beha io hey ound hei way
in o mode n applica ions, like il a ion, pu i ica ion, encapsula ion o was es, d illing
and ga dening. A ecen ly ad anced opic and one o g owing in e es is hei use in
polyme ic ma e ials as cheap and e sa ile nano ille s o enhance hei oughness,
lame e a dency and gas ba ie p ope ies. All o hese p ope ies a e a di ec
esul om hei unique laye ed shee -like s uc u e a e which hey a e named and
classi ied.
Ga y W. Beall and Clois E. Powell ask as an in oduc o y ques ion o hei book2: „Can
one imagine he u ili y o a dispe sed-phase ein o cemen o polyme s ha has a
hickness o 1 nm, a pla e-like mo phology wi h minimal dimensions o 150 o 200
nm, obus wi h a modulus o 180 GPa, non- oxic [...], a su ace a ea in excess o 750
m²/g, a cha ge sui able o al e ing i s hyd ophilic balance a will, and a e ac i e
index simila o polyme so ha he nanopa icle will appea anspa en in he

In oduc ion
8
polyme composi e? How di icul would i be o p epa e such a pa icle?” As he
au ho s a e discussing na u ally occu ing laye ed silica es, his he o ical ques ion
ampli ies he po en ial which lies in hese clay mine als ound all o e he wo ld in
sedimen a y ocks like ben oni es o kaoline.
Laye s a e held oge he by an-de -Waals o ces, hyd ogen bonds and elec os a ic
in e ac ions o ming la ge s acks ( ac oids) in he d y s a e. Each laye is oughly 1
nm in heigh and is made up om wo di e en basic building blocks3, namely [TO4]-
e ahed a and [M(O,OH)6]-oc ahed a. Mos commonly e ahed al ca ions a e Si4+,
Al3+ and Fe3+, while oc ahed a ea u e Al3+, Fe3+, Mg2+, Fe2+ o Li+. Each co ne o one
polyhed on is occupied by O2-, OH- o F- anions. Te ahed a a e connec ed ia h ee
sha ed co ne s and o m a wo-dimensional hexagonal la ice s uc u e (Figu e 1.1).
The ou h apical co ne ac s as connec ion o he oc ahed al laye . Oc ahed a a e
connec ed o each o he by sha ed edges and he uppe and lowe iangula sides o
all e ahed a lie in plane espec i ely.
Figu e 1.1 Schema ic ep esen a ion o a 2:1 laye ed Silica e. T= Te ahed on, O=oc ahed on.
Rep in ed wi h pe mission om e e ence [4].
The e a e wo impo an ypes o laye ed silica es, in bo h cases each lamella
consis s o one oc ahed al laye connec ed ei he on one side o a e ahed al laye
(named 1:1 laye ed silica e, e.g. kaolini e, chap e 1.1.3) o sandwich-like on bo h
sides (called 2:1 laye ed silica e, e.g. mon mo illoni e o hec o i e, chap e 1.1.1 and
Chap e 1
9
1.1.2). This has a majo in luence on he way how each silica e compensa es i s laye
cha ge esul ing om isomo phous subs i u ion.
Any ca ion in he e ahed al o oc ahed al laye which is eplaced by a ca ion o
lowe alency will con ibu e o a pe manen ne laye cha ge, ζ, which is
compensa ed by coun e -ions close o he laye . The amoun o (exchangeable)
coun e -ions is deno ed as ca ion exchange capaci y (CEC). In he case o 2:1 silica es
he ca ions eside on he ex e nal basal planes and in he in e laye spaces. The
in e laye dis ance a ies wi h he ca ion species and i s deg ee o hyd a ion
be ween 9.1 Å and 18.0 Å. A 1:1 silica e does no ha e any ca ions in i s in e laye
space and compensa es i s cha ge only a he ex e nal e ahed al laye .
In he case whe e he open spaces o all oc ahed ons a e illed wi h ca ions he laye
is called ioc ahed al o b uci ic (e.g. hec o i e, see chap e 1.1.2), while an
occupa ion o only 2/3 is named dioc ahed al o gibbsi ic (e.g. mon mo illoni e and
kaolini e, chap e 1.1.1 and 1.1.3) (Figu e B7c). As a esul ca ions o highe alency
(Al3+ s. Mg2+) a e inco po a ed in o dioc ahed al s uc u es o compensa e o he
laye cha ge.
Wi h na u al silica es a ying deg ees o isomo phous subs i u ion occu in each
laye , depending on he condi ions unde which hey we e o med.
1.1.1 Na u al mon mo illoni e
Mon mo illoni e (MMT) is a na u al 2:1 laye ed silica e om he smec i e g oup wi h
he dioc ahed al s uc u e (Na, Ca)0.3(Al, Mg)2(Si4O10)(OH)2·nH2O. I is ound all o e
he wo ld5. I is an al e a ion p oduc o olcanic u and ash, o ming ben oni e
beds, and o wall ocks bo de ing hyd o he mal mine al deposi s. I o ms unde
alkaline condi ions o poo d ainage, wi h Mg, Ca, Na, and K emaining in he soil. As
i is a na u al p oduc i con ains impu i ies, mos commonly eldspa , qua z, mica,
ca bona e and hyd oxyca bona e, which ha e o be emo ed p io o comme cial
applica ion. Fu he mo e, all o i s p ope ies depend on he condi ions i was
o med unde , a ying wi h i s o igin. E.g. he CEC eaches om 90 up o 150
meq/100g as he nega i e cha ge is dis ibu ed inhomogenously inside each laye
and be ween laye s, esul ing in inhomogeneous su ace co e age wi h coun e ions,
In oduc ion
10
some imes esul ing in clus e s o ming a ound spo s wi h high densi y o
isomo phous subs i u ion6, 7. Coun e ions usually a e hyd a ed sodium o calcium
ca ions, and inc easing hyd a ion os e s desagg ega ion o ac oids and pa ial
ex olia ion. Delamina ion in o singula laye s o 1 nm heigh is only obse ed a e
ion exchange wi h Li and emo al o amo phous binde s. Combined wi h a la e al
dimension o up o o e 300 nm, hey can each aspec a ios, α, o up o 300 in
heo y. Though, hese single shee s lose hei in insic s i ness and s a o cu l and
b eak unde shea (e.g. du ing mixing), hei p ac ical aspec a io a e p ocessing is
usually no highe han 1008.
Ne e heless, due o i s easy mining and p ocessing MMT apidly became he
comme cially mos a ac i e clay as an addi i e o polyme ic ma ices in he las
decades and he e is a ange o companies, supplying MMT wi h di e en g ades o
pu i y, dimensions and CEC. In i s p is ine o m i is only miscible wi h hyd ophilic
polyme s, such as poly(e hylene oxide) and poly( inyl alcohol)9, 10. To ende MMT
miscible wi h hyd ophobic polyme s, alkali coun e ions classically a e exchanged
wi h ca ionic-o ganic su ac an s, such as alkylammonium sal s11, 12.
1.1.2 Syn he ic hec o i e (Na- luo ohec o i e)
Hec o i e is a 2:1 laye ed silica e commonly o he s uc u e Na0.3(Mg,Li)3Si4O10(OH,
F)2. Na u al hec o i e belongs o he smec i e g oup as well and is ela ed o
mon mo illoni e, bu has a ioc ahed al s uc u e.
I s na u al a ian su e s om he same impu i ies and inhomogeni ies desc ibed in
1.1.1. To omi hose disad an ages, classical solid-s a e eac ions and mel syn hesis
ha e been used o p oduce a i icial hec o i e. High empe a u es lead o s a is ical
dis ibu ion o isomo phous subs i u ion, gene a ing a homogeneous laye cha ge.
Un il ecen ly his p ocedu e has been e y expensi e and indus ially inapplicable.
De elopmen o a new syn he ic ou e in powe ul high equency u naces by
Hussein Kalo a he depa men o Ino ganic Chemis y I o Uni e si y o Bay eu h
unde supe ision o P o . B eu allows o p oduc ion quan i ies o kilog ams wi h a
p ice o 18 €/kg. Bu p ice is no he only bene i ; by syn hesis i is possible o c ea e
much la ge pla ele s, leading o huge p ac ical aspec a ios α o up o 20000 in case
Chap e 1
11
o Li- luo ohec o i e o annealed Na- luo ohec o i e (hec o i e whe e pa o he
oc ahed al O-a oms ha e been eplaced by F-a oms is called luo ohec o i e). Wi h
homogenei y in su ace cha ge and a less impu i ies han na u al clay13 i is possible
o con ol al e na ion be ween a highly hyd a ed ‘shea -labile’ s a e and a
nonhyd a ed ’shea -s i ’, mica-like s a e by simple ca ion exchange. This ansi ion
be ween hyd a ion s a es canno be obse ed o na u al MMT due o he e ogenei y
o cha ge densi y and lowe laye cha ge. Ca ion exchange owa d Mg-
luo ohec o i e gi es a highly hyd a ed and he e o e ‘shea -labile’ s a e, enabling
ex olia ion by applica ion o shea o ces in a s i ed media mill14. A subsequen
ca ion exchange wi h K+ ions yielded a collapsed non-swollen, ‘shea -s i ´, mica-like
ma e ial. Powde x- ay di ac ion (PXRD) measu emen s showed ha collapsed
s acks will no exchange in e laye ca ions and hus eac i i y is es ic ed o ex e nal
basal planes. This p e en s he cu a u e obse ed in delamina ed single shee s and
should subs an ially inc ease po en ial ein o cemen e ec s15.
These unique p ope ies ha e led o a enewed academic in e es o de elop hyb id
ma e ials based on syn he ic hec o i e o indus ial applica ions.
1.1.3 Na u al kaolini e
Kaolini e is a 1:1 silica e, wi h he o mula uni o Al2Si2O5(OH)4. Tac oid heigh
anges om 70 nm o 100 nm and la e al ex ension a ies be ween 500 nm and 15
µm, depending s ongly on i s o igin. Kaolini e has se e al ea u es no ound in 2:1
silica es. Single lamellae in ac oids a e no held oge he by an-de -Waals o ces
bu by s ong hyd ogen bonds be ween µ-hyd oxide-g oups o he oc ahed al laye
and he silicon ne wo k o he e ahed a (Figu e 1.2)16, esul ing in much smalle
in e lamella dis ances o 7.2 Å. This makes in e cala ion di icul and es ic s i o
only a small ange o neu al molecules wi h high dipola momen s like Dime hyl
sul oxide (DMSO)17 and N-Me hyl o mamide (NMF)18.
In oduc ion
12
Figu e 1.2 Schema ic ep esan a ion o 1:1 laye ed silica e (kaolini e). OS= Oc ahed al su ace,
TS= e ahed al su ace. Rep in ed wi h pe mission om e e ence [14].
The mos in e es ing ea u e in he pa icle a chi ec u e is he p ese a ion o i s
pola lamella s uc u e h oughou he ac oid, which means each pa icle has wo
chemically dis inc su aces, which can also be selec i ely a ge ed o modi ica ion
o c ea e Janus s uc u es (see chap e 1.2.3).
A combina ion o bo h ea u es (no in e cala ion and chemically dis inc ex e nal
su aces) leads o he in e es ing ac ha he nega i e cha ge gene a ed by
isomo phous subs i u ion o Si4+ agains Al3+ in he e ahed al laye can only be
compensa ed by coun e ions a he e ahed al su ace (abb e ia ed TS), which
means he ou e mos e ahed al laye o a ac oid19, 20. Na u al coun e ions a e
sodium and calcium, which a e easily eplaced by o he ions espec i e o hei
compa a i ely low CEC, which lies a ~2.6 meq/100g.
Recen s udies show ha he oc ahed al laye can be selec i ely add essed by
molecules bea ing a ca echol moie y21. Those g oups mos likely will unde go a
condensa ion eac ion and bind co alen ly o he µ-hyd oxide g oups o he
oc ahed al su ace (called OS), simila o wha was obse ed wi h alcohols and
s uc u ally ela ed aluminum oxide su aces22, 23.
1.2 O ganic/ino ganic hyb id nanopa icles
Nanoma e ials ha e, by de ini ion, a leas one dimension in he nanome e scale
(<100 nm) and show no el p ope ies s ongly in luenced by he la ge su ace o

Chap e 1
13
olume a io. The syn hesis, cha ac e iza ion, and applica ions o nanopa icles a e
among he mos impo an sec ions o he wide ange o nano echnology. In ecen
yea s, nanopa icles ha e gained emendous a en ion as he ansi ion om
mic opa icles o nanopa icles was seen o lead o immense changes in he physical
and chemical p ope ies o a ma e ial. Due o he as inc ease in su ace a ea o
olume a io gained om his s ep down in leng h scale, su ace a oms and hei
e ec s now play a dominan ole o e bulk a oms. Especially when in oduced in o
composi es, he huge speci ic in e phase a ea al e s he p ope ies o he ma ix
conside ably.
Resea ch s a ed in he 1980s wi h nanopa icles made om one ma e ial24-26, bu i
was quickly disco e ed, ha adding a shell a ound he co e pa icle gi es ise o new
ma e ials only possible by combina ion o bo h p ope ies27-29. The name
“co e/shell” pa icles was adop ed o ma e ials consis ing o a ino ganic/o ganic
co e o di e en shapes and an ino ganic o o ganic shell. Applica ions a e
mani old30 and ad ances in su ace modi ica ion echniques allow o e e new
combina ions o co e p ope ies and shell p ope ies. A ecen example o he
mul i unc ionali y o ino ganic co e/ polyme ic shell hyb ids a e supe pa amagne ic
and luo escen CdSe(ZnS) nanopa icles coa ed wi h p o ec i e silica and bea ing a
polyme ic he mo- esponsi e poly(N-isop opylac ylamide) shell31.
1.2.1 Clay based hyb id nanopa icles
Clay pa icles a e well sui ed ino ganic co es o he c ea ion o hyb id pa icles. E en
he symme ical 2:1 s uc u e o smec i es al eady p o ides wo chemically di e en
eac i e si es o a aching a shell: basal su aces and edges. The p e iously
desc ibed inhe en nega i e laye cha ge o laye ed silica es enables acile
modi ica ion o he basal su ace and in e laye spaces wi h o ganic molecules
bea ing a posi i ely cha ged g oup by simple ca ion exchange. Modi ica ion o edge
loca ed silanol g oups wi h silicon halides, acid halides o silazanes leads o s onge
co alen bonds. Bo h si es can be accessed o go beyond simple alkyl ammonium
su ac an modi ica ion by a aching polyme s wi h ailo ed p ope ies ia con olled
polyme iza ion o sui able monome s and chain leng h. Classically smec i e-based
In oduc ion
14
hyb id nanopa icles a e implemen ed in o polyme ic ma e ials o enhance
oughness, lame e a dancy and gas ba ie p ope ies.
1.2.2 Pa chy nanopa icles
Fo mix u es o polyme species o di e en pola i y i is ene ge ically a ou able o
seg ega e and o m domains o hei single polyme species, espec i ely. I bound o
an in lexible co e, comple e phase seg ega ion becomes inhe en ly di icul and
o ma ion o compa men alized (pa chy) shells can be obse ed.
The e has been a ecen b eak h ough in c ea ion o mul icompa men micelles by
hie a chical sel -assembly o ABC iblock e polyme s32 and pa chy wo mlike
c ys alline co e micelles made om ABC iblocks wi h c ys allisable co e33. These
g oups epo on he po en ial o pa chy pa icles o hie a chical s ep-g ow h
polyme iza ion o mul icompa men micelles in o “mic on-scaled segmen ed
sup acolloid polyme s”32 and hei use as supe su ac an s close o pu e Janus
colloids in su ace ac i i y, while usually being less complica ed o p oduce.
On he co e/shell pa icle side he e a e ew examples u ilizing he p omising
po en ial o a pa chy shell. Fu he mo e, mos o he p oduced pa chy pa icles a e
sphe ical in na u e34.
As shown by Schmelz e al. pa chy pa icles made om iblock e polyme s wi h
c ys allized middle block ac as gian su ac an s in mix u es o immiscible luids,
educing he su ace ension wi h an e ec compa able o ha o Janus cylinde s35.
In his hesis we use disc-like mon mo illoni e 2:1 laye ed silica es as co e o
in es iga e he in luence o a pa chy shell on i s in e acial beha io in an immiscible
polyme blend.
1.2.3 Janus nanopa icles
Pa icles which embed exac ly wo dis inc sides o su aces o di e en chemical
p ope y and/o pola i y in o one s uc u e a e called Janus pa icles, named a e
he Roman god Janus wi h wo aces and whose name is used symbolically o
en i ies showing cha ac e o beha io o wo incompa ible sides. This non-
cen osymme ic appea ance leads o a unique se o cha ac e is ics ega ding
Chap e 1
15
ma e ial p ope ies and sel -assembly beha io 36. A whole spec um o di e en
Janus pa icle a chi ec u es is known. Janus pa icles can be ca ego ized acco ding o
hei dimensions. The e a e h ee-dimensional sphe ical pa icles, wo e sions o
wo-dimensional disc-like s uc u es and wo di e en one-dimensional cylinde s.
While hei o e all geome y can be simple and symme ic, he lack o chemical
cen osymme y p o ed o be he bigges challenge in hei p epa a ion.
The pionee s in he ield o Janus pa icles we e Casag ande and Veyssié. They
embedded hal o a mesoscopic glass bead in o a subs a e and hen silyla ed he
o he hal . As he amoun o pa icles p oducible by hose syn heses was e y
limi ed, all hei me hods had he majo d awback ha hey we e no applicable on a
la ge scales37, 38. Recen ly he applica ion o pho opolyme iza ion and
pho oli hog aphic polyme iza ion o mic o luidic de ices enabled an e en highe
deg ee o con ol and s uc u al a ie y. The mic o luidic de ice sends a wo-phase
s eam in o a channel. The e i is cu in o d ople s by an aqueous c oss low,
con aining su ac an s o s abilize he esul an pa icles. Then a
pho opolyme iza ion locks he shape o he biphasic pa icles. Un o una ely his
me hod is no able o c ea e pa icles wi h submic on dimensions ye 39. Ano he
in e es ing app oach was de eloped by Mülle and cowo ke s36 , using he sel -
assembly beha io o iblock e polyme s. T iblock polyme s wi h phase-sepa a ing
ou e blocks will unde go sel -assembly upon ilm cas ing and o m nanome e -
scaled bulk s uc u es, which can be locked by c osslinking he inne pa (in his case
polybu adiene). Upon dissolu ion o he polyme , he c osslinked pa will p ese e
i s bulk shape and hus will yield non-cen osymme ic pa icles. By de ined
enginee ing o he e polyme composi ion he bulk s uc u e and hus he esul ing
pa icle shape and size can be con olled.
All hese app oaches ha e in common, ha hey s a wi h symme ical sys ems and
b eak hose apa in o non-symme ical pa icles o complica edly syn hesize non
symme ical building blocks o s a wi h ins ead o applying in insically pola
pa icles like kaolini e. As desc ibed in chap e 1.1.3 i is possible o add ess each
side indi idually in solu ion, acili a ing he c ea ion o disc-like Janus pa icles based
on a laye ed silica e, e en in la ge quan i ies.
In oduc ion
16
Se e al ields o applica ion esul om he unique s uc u al p ope ies o Janus
pa icles. They ha e e oked g ea academic in e es , as hey ep esen a class o
pa icles wi h ex ao dina y sel -assembly beha io . Fundamen al unde s anding o
sel -assembly p ocesses is a ibu ed wi h he possibili y o c ea e new
unc ionali ies no p esen in he indi idual building blocks by assembling hem in o
hie a chical supe s uc u es. Thei eno mous su ace ac i i y pu s hem in o he
ocus o indus ial applica ions as supe -su ac an s and s uc u ing agen s in
polyme blends. Fu he mo e he aniso opic cha ac e o single Janus pa icles is
used o op ical and analy ical p obes in con ined space 40, 41, medical senso s o cell
a ge ing42 and swi chable elec o-op ical de ices39.
.
1.3 (Clay ein o ced) nanocomposi es
The comme cial b eak h ough o clay ein o ced nanocomposi es happened in he
ea ly 1990´s when Toyo a esea che s published hei wo k on nylon-6-clay
he moplas ic nanocomposi e echnology43, 44. The key aspec was a undamen al
imp o emen o p ope ies a minimal loading. A only 4.2 w % clay he modulus
doubled, s eng h inc eased by 50 % and he hea dis o ion empe a u e (HDT)
inc eased by 80 °C compa ed o nea polyme . Toyo a s ill holds a b oad ange o
pa en s in his echnological ield. Ne e heless academic and indus ial in e es is
s ill s ong and esea ch and de elopmen o clay ein o ced nanocomposi es is
g owing.
Fo mos applica ions i is necessa y o o ganophilize he clay su ace o inc ease he
compa ibili y wi h he ma ix and enable a good dispe sabili y. A well known
comme cial b and o o ganophilized MMT is he Cloisi e p oduc amily by Rockwood
Addi i es, which has been op imized o applica ion in alipha ic polyme ma ices.
On hei p oduc webpage i is claimed ha hei clay based p oduc s can ac as a
new lame e a dan app oach, inc ease modulus and ensile s eng h, imp o e
ba ie p ope ies, inc ease dimensional s abili y, a e he moplas ic ecyclable,
imp o e cla i y, inc ease HDT, ein o ce and lowe densi y45, while a a much lowe
loading (3-5 w %) compa ed o con en ional ille s (20-60%). Howe e , as mos o
Chap e 2
23
2.2.7 S abili y measu emen s (LUMiFuge®)
The s abili y measu emen s we e pe o med in a LUMiFuge® 114 (LUM) wi h a
a iable o a ion equency o 300, 600, 900 pm ( ounds pe minu e) and di e en
ime in e als o 200 s, 300 s, and 900 s, espec i ely. Kaolini e suspensions (0.25
w %) in THF and wa e we e placed in ubes in ho izon al posi ions on he disc o he
LUMiFuge®. Du ing he ho izon al o a ion o his disc he anspa encies o he
suspensions we e measu ed in he a ea be ween he menisci and he sedimen . The
mean anspa ency o he whole a ea was de e mined. The anspa ency was
measu ed in ime in e als o 10 s while inc easing o a ion speed s epwise. High
u bidi y, e en a e applying cen i ugal o ces indica es a s able suspension.
2.2.8 Cha ge i a ion s abili y analysis (S abisize ®)
De e mina ion o poin o ze o cha ge o he clay pla ele s was done using a
S abisize ® (Pa icle Me ix GmbH). The e o e he mic oionic clouds o localized
pa icles a e displaced by low induced ia a pis on. The gene a ed po en ial is
measu ed and used o moni o ing i a ion wi h mono- and polyca ionic species.
A e comple e eplacemen o displaceable sodium ions by immobile ca ions he
poin o ze o cha ge is eached. Fou sepa a e solu ions con aining he polyca ionic
MI solu ion (1 g/l) in deionized wa e (DI) we e p epa ed wi h di e en pH alues
using ace ic acid (100 %) in o de o p o onize he amine unc ions. The poin o ze o
cha ge o he clay basal su ace was measu ed using a cha ge i a ion s abili y
analyze .
2.2.9 Dynamic-mechanical analysis (DMA) and ensile es s
Dynamic-mechanical analysis (DMA) expe imen s a e ca ied ou in he ension
mode a a cons an o ce o 5 N and a empe a u e ange om 30 o 140 °C using a
Me le Toledo DMA/STDA 861e. The hea ing a e is 5 °C/min and he es specimens
is app oxima ely 25 mm in leng h, 6 mm in wid h and 1 mm in hickness.
Tensile modulus, ensile s eng h and elonga ion a b eak we e measu ed using a
Uni e sal Tensile Tes e acco ding o ISO 527 applying a s ain a e o 1 mm/min. Fo

Expe imen al Pa and Me hods
24
each ma e ial a leas 8 samples we e es ed. The elonga ion a b eak was
de e mined by a mac o-displacemen - ansduce .
2.2.10 Powde X- ay di ac ion (PXRD)
The powde X- ay di ac ion (PXRD) pa e ns we e eco ded in e lec ion mode using
nickel il e ed Cu-Kα adia ion λ =1.54187 Å on a B agg-B en ano-geome y
di ac ome e (PANaly ical Xpe -P o) equipped wi h an X′Cele a o Scien i ic RTMS
de ec o .
2.2.11 Fou ie - ans o m in a ed spec oscopy (FT-IR)
The pa icles powde s o un ea ed and ea ed clay we e cha ac e ized wi h a
Nicole FTIR 460 (The mo Nicole Co p.). The ansmi ance abso p ion spec a we e
scanned 64 imes a 4 cm-1 spec al esolu ion a oom empe a u e.
2.2.12 Speci ic su ace a ea measu emen s
The speci ic su ace a ea o a eeze-d ied K-hec sample was calcula ed om he N2
adso p ion/deso p ion iso he ms using he B unaue -Emme -Telle (BET) equa ion.
Measu emen s we e ca ied ou on a Quan ach ome No a 2000e analyze .
2.3 Tailo ing o s acks heigh and s i ness o luo ohec o i e
The aqueous dispe sion o syn he ic Na-hec was ans e ed o a highly hyd a ed
‘shea -labile’ s a e by exchanging he in e laye Na+ wi h Mg2+ ca ions (Mg-hec ). The
aqueous dispe sion o Mg-hec was p ocessed in a s i ed media mill (LabS a LS1)
o 60 minu es in o de o ex olia e he ac oid s acks by applying shea o ces. The
deg ee o ex olia ion was con olled by he numbe o milling passages14.
Subsequen ly, he clay was ans e ed in o a collapsed and non-swollen ‘shea -s i ’
mica-like ma e ial (K-hec ) wi h no in ac ys alline eac i i y by exchanging Mg2+ wi h
K+ ca ions56. All exchanging p ocedu es we e ollowed by washing se e al imes wi h
wa e o emo e chlo ine ions.
Chap e 2
25
2.4 Syn hesis o he copolyme s o su ace modi ica ion
2.4.1 Syn hesis o he ca echol-modi ied PMMA copolyme (PCM)
3,4-Dibenzoxybenzoic acid 1 and 3-hyd oxyp opylbenzoa e 2 we e p epa ed
ollowing li e a u e p ocedu es (scheme 5.1).57
3-Me hac yloyloxyp opyl-3,4-dibenzoxybenzoa e 3
Compound 2 (2.11 g, 5.38 mmol) was dissol ed in d y DCM (20 ml) and cooled in an
ice ba h. E 3N (1.12 ml, 8.07 mmol) and me hac yloyl chlo ide (626 µl, 6.47 mmol)
we e added and he eac ion mix u e was s i ed a oom empe a u e o 3 h. A e
washing wi h wa e he aqueous phase was ex ac ed wi h DCM and he combined
o ganic phases we e d ied o e Na2SO4, il e ed and concen a ed in acuum. The
esidue was pu i ied by column ch oma og aphy (silica gel 60, e hyl ace a e/n-
hexane 1:2, / ). Yield: 1.64 g (3.57 mmol, 67%); colo less oil; R = 0.63 (e hyl
ace a e/n-hexane 1:2); νmax (ATR)/cm-1: 3032, 2963, 1711, 1636, 1599, 1510, 1454,
1427, 1380, 1321, 1266, 1204, 1163, 1130, 1104, 1038, 1006, 944, 815, 761, 734,
695; 1H NMR (300 MHz, CDCl3):  1.92 (3 H, s), 2.0-2.2 (2 H, m), 4.28 (2 H, , 3J 6.3 Hz),
4.36 (2 H, , 3J 6.3 Hz), 5.18 (2 H, s), 5.21 (2 H, s), 5.5-5.6 (1 H, m), 6.0-6.1 (1 H, m),
6.91 (1 H, d, 3J 9.0 Hz), 7.3-7.5 (10 H, m), 7.6-7.7 (2 H, m); 13C NMR (75.5 MHz, CDCl3):
 18.3, 28.2, 61.3, 61.4, 70.8, 71.2, 113.2, 115.6, 123.0, 124.0, 125.6, 127.1, 127.4,
127.9, 128.0, 128.5, 128.6, 128.9, 136.2, 136.5, 136.8, 148.3, 153.0, 166.1, 167.3;
m/z (%) 461 (13) [M+], 460 (47) [M+], 369 (6), 317 (8), 225 (17), 181 (27), 127 (12), 91
(100).
Copolyme PCBM 4
Me hyl me hac yla e (650 mg, 6.52 mmol), compound 3 (100 mg, 0.22 mmol) and
dodecane hiol (26 mg, 0.13 mmol) we e dissol ed in d y THF (3 ml) unde a gon
a mosphe e and AIBN (10 mg) was added o he eac ion mix u e, which was s i ed
unde e lux o 5 h. The solu ion was pou ed in o cyclohexane (100 ml) and he
appea ing colo less p ecipi a e was collec ed and p ecipi a ed once mo e om an
ace one/cyclohexane mix u e. Yield: 710 mg; colo less solid; νmax (ATR)/cm-1: 2996,
Expe imen al Pa and Me hods
26
2952, 1722, 1601, 1484, 1448, 1432, 1385, 1363, 1268, 1241, 1189, 1144, 989, 965,
911, 842, 761, 748, 698; 1H NMR (300 MHz, ace one-d6):  0.8-1.0 (33 H, m), 1.8-2.0
(24 H, m), 3.61 (30 H, s), 4.1-4.2 (2 H, m), 4.3-4.4 (2 H, m), 5.2-5.3 (4 H, m), 7.1-7.7
(13 H, m).
Copolyme PCM 5
Compound 4 (580 mg) was dissol ed in dioxane/me hanol (40 ml, 1:1), lushed wi h
a gon and 10% Pd/C (80 mg) was added. The a gon a mosphe e was eplaced by
hyd ogen gas and he eac ion mix u e was s i ed a oom empe a u e o 5 h. The
suspension was il e ed o e celi e and he il a e was concen a ed in acuum. The
oily esidue was i u a ed wi h n-hexane and d ied in acuum. Yield: 500 mg; o -
whi e solid; νmax (ATR)/cm-1: 3392, 2996, 2950, 1725, 1605, 1480, 1444, 1386, 1270,
1239, 1191, 1146, 1121, 988, 965, 889, 873, 842, 765, 750; 1H NMR (300 MHz,
DMSO-d6):  0.5-0.9 (33 H, m), 1.6-2.0 (24 H, m), 3.55 (30 H, s), 4.0-4.1 (2 H, m), 4.2-
4.3 (2 H, m), 6.81 (1 H, d, 3J 7.9 Hz), 7.2-7.4 (2 H, m), 9.32 (1 H, s), 9.81 (1 H, s); 13C
NMR (75.5 MHz, DMSO-d6):  16.1, 18.4, 27.5, 43.9, 51.6, 53.7, 60.8, 115.2, 116.3,
120.5, 121.8, 145.0, 150.4, 165.5, 176.2, 176.9, 177.3.
2.4.2 Syn hesis o poly(2-(2-b omoisobu y yloxy)e hyl me hac yla e)-s a -
(2-dime hyl(amino)e hyl me hac yla e) (MI) ia Re e sible Addi ion-
F agmen a ion Chain T ans e (RAFT) polyme iza ion
To a 100 ml ound bo om lask, equipped wi h ubbe sep um, 1.7 g (6.1 mmol) o
BIEM, 6.7 g (42.8 mmol) o DMAEMA, 270 mg (1.2 mmol) o 2-cyano-2-p opyl
benzodi hioa e (CPBT), 100 mg (0.6 mmol) o AIBN, 40 ml o DMSO as sol en and 2
ml o anisole as in e nal s anda d we e added. A e h ee eeze-pump- haw cycles
he eac ion was placed in o an oil ba h a 70 °C o 4 h o each a con e sion o 54%
as de e mined by 1H NMR spec oscopy. The esul ing polyme solu ion was cooled
down, exposed o ai and dialysed agains dioxane un il no monome ela ed peaks
a 5.8-6.4 ppm we e de ec ed by NMR spec oscopy. Mn = 9000 g/mol and Mw =
16000 g/mol was de e mined ia SEC wi h DMAc as eluen and a DMAEMA
calib a ion. The inal polyme is om he e on e e ed o as maco-ini ia o (MI). 1H
Chap e 2
27
NMR (300 MHz, CDCl3, δ in ppm): 4.4 – 4.1 (R-C(-CH3)-COO-CH2-CH2-OOC-C(CH3)2-B ),
4.0 (R-C(-CH3)-COO-CH2-CH2-N-(CH3)2), 2.6 (R-C(-CH3)-COO-CH2-CH2-N-(CH3)2), 2.2 (R-
C(-CH3)-COO-CH2-CH2-N-(CH3)2), 1.9 (R-C(-CH3)-COO-CH2-CH2-OOC-C(CH3)2-B ), 1.8 (R-
C(-CH3)-COO-CH2-CH2-N-(CH3)2).
2.4.3 Syn hesis o poly(2-(dime hylamino)e hyl me hac yla e) (PDMAEMA)
based diblocks ia RAFT
All polyme iza ions we e ca ied ou a 80°C in sep um sealed lasks. De ailed
amoun s o eac an s a e lis ed in Table 1. In each case DMAEMA p ecu so s we e
p epa ed by placing 1,4-dioxane, DMAEMA, AIBN, he chain ans e agen (CTA), 2-
cyano-2-p opyl benzodi hioa e, and 1,3,5- ioxane in he eac ion lask. Ni ogen
low was es ablished o 20 min a oom empe a u e and hen he polyme iza ion
was ini ia ed by hea ing he lask in an oil-ba h. The p ecu so solu ion was
ans e ed o a degassed and hea ed solu ion o 1,4-dioxane, second monome and
1,3,5- ioxane a e 4h a a ypical con e sion o DMAEMA o abo e 90 %. The
eac ion was e mina ed by cooling in an ice ba h and exposu e o a mosphe ic
oxygen. The polyme s we e pu i ied by p ecipi a ion in o a non-sol en (isop opanol
o PS con aining diblocks and cyclohexane o PMMA con aining diblocks) and
eeze-d ied om 1,4-dioxane. Final polyme s a e abb e ia ed D17-b-M300 in he case
o poly(2-(dime hylamino)e hyl me hac yla e)17-block-poly(me hyl me hac yla e)300
and D17-b-S360 in he case o poly(2-(dime hylamino)e hyl me hac yla e)17-block-
polys y ene300.
Table 1 Applied amoun s o chemicals in he p epa a ion o he PDMAEMA-mac o-CTA and
he diblock-copolyme s in 1,4-dioxane .
Fo mula a
DMAEMA /
mg, mmol
CTA / mg,
mmol
AIBN / mg,
mmol
Monome / g,
mmol
Sol en /
ml
D17-b-M300
380; 2.5
54; 0.25
15; 0.09
12.0; 120
30
D16-b-S360
1083; 6.9
149; 0.67
38; 0.24
35.2; 338
30
D16-b-S115
1402; 9.1
100; 0.45
26; 0.18
18.8; 181
30
a epea ing uni s o DMAEMA calcula ed by sub ac ing he molecula weigh o CPBDT (221.00 g/mol)
and di iding by he molecula weigh o DMAEMA (157.21 g/mol), epea ing uni s o he second block
Expe imen al Pa and Me hods
28
we e calcula ed by sub ac ing he molecula weigh o DMAEMA block, ac onyms: D: DMAEMA, , S:
s y ene, M: MMA
Figu e 3.1 a) Syn hesis o he s a is ical copolyme (PDB) and cha ac e iza ion ia b) 1H-NMR
spec um and c) SEC ace wi h DMAc as an eluen .
2.5 Clay su ace modi ica ion
2.5.1 Su ace modi ica ion o K- luo ohec o i e and su ace-ini ia ed A om
T ans e Radical Polyme iza ion (si-ATRP) o me hyl me hac yla e
(MMA)
The ex e nal su ace o K-hec (10 g) was modi ied wi h he MI (320 mg) in DI wa e
a pH=6.8. Subsequen ly, he loccula ed hyd ophobic nanopla ele s (O-hec ) we e
cen i uged and edispe sed in THF. The g a ing o MMA was ini ia ed om O-hec
ia a coppe media ed ATRP in he p esence o EBiB as a ee sac i icial ini ia o . All
expe imen s we e pe o med unde ine a mosphe e in a con en ional un
p ocedu e58, 59; A dispe sion o he O-hec (10 g; calcula ed 390 µmol o ini ia ing
4 3 2 1 0
chemical shi [ppm]
20 22 24 26 28 30 32 34
elu ion olume [ml]
b)
c)
a)

Chap e 2
29
si es) in 400 ml THF, MMA (164.5 g; 1.462 mol) and EBiB (19 mg; 97.5 µmol) we e
added o a lask and sealed wi h a ubbe sep um. The eac ion mix u e was
degassed h ee imes by eeze-pump- haw cycles and illed wi h a gon. In a
sepa a e lask a s ock solu ion o PMDETA, Cu(I)Cl and Cu(II)Cl2 (338 mg; 975 µmol,
115.8 mg; 1.17 mmol and 39.2 mg; 292.5 µmol) in 20 ml anisole was degassed o 30
min unde a gon. Finally, 10ml o he s ock solu ion was in oduced o he eac ion
lask by a sy inge. The eac ion lask was imme sed in an oil ba h a 80 °C. Samples
we e wi hd awn a a ious imes o moni o he eac ion kine ics and i was s opped
a e 300 min by cooling and exposing o ai . The inal hyb ids o K-hec wi h a
polyme ic shell o PMMA chains wi h an a e age DP o 380 (hyb id-hec (DP 380))
we e cen i uged and washed se e al imes wi h THF.
As a e e ence a nano ille wi h a comme cial su ac an , dodecylamine, was used
a e p o ona ion using one equi alen o HCl (0.1 mol). S anda d p ocedu es we e
used o exchange he K+ ca ions wi h he o ganic ca ion (C12 ammonium chlo ide)60.
A e ion exchange, he modi ied nanopla ele s (C12-hec ) we e cen i uged and
washed se e al imes wi h DI wa e , e hanol, and THF.
2.5.2 Su ace modi ica ion o mon mo illoni e (MMT)
The diblock copolyme solu ions o D17-b-M300 and D17-b-S360 o su ace modi ica ion
o MMT we e p epa ed in wo di e en ways:
1. Solu ions wi h p e- o med micelles o D17-b-M300 and D17-b-S360 we e p epa ed by
dissol ing he polyme in THF and adding wa e (pH=6.5) d opwise un il u bidi y
occu ed.
2. Molecula ly dispe sed solu ions we e p epa ed by adding he eeze d ied polyme
in o THF and s i ing un il no solids we e isible anymo e and he anspa en
solu ion had a sligh ly pink colou .
The polyme solu ions (30 mg, 1 mg/mL) we e added o a dispe sion o MMT in
wa e (100 mg, 5 mg/mL, pH=6.5) using a cannula and s i ed o e nigh . Final
MMT/PS/PMMA hyb id pa icles (hyb id-MMT) we e pu i ied by emo ing non-
ancho ed polyme ia cen i uga ion a 4000 pm, decan a ion o he supe na an
and edispe sion in wa e (1x) and THF (3x) using ul asonica ion.
Expe imen al Pa and Me hods
30
2.5.3 Su ace modi ica ion o kaolini e
I is possible o modi y each side, he e ahed al su ace and he oc ahed al su ace
(TS and OS), o he kaolini e speci ically and indi idually wi hou in luencing he
o he side as shown in a p e ious publica ion21. The o de o modi ica ion chosen,
s a ing wi h D16-b-S115 has a pu ely p ac ical pu pose, as he DMAEMA block o he
D16-b-S115 is cha ged a pH 6 and hus kaolini e can be modi ied in aqueous
suspension whe e i is dispe sed bes . A e ca ion exchange he unila e ally
modi ied kaolini e can be dispe sed in THF mo e easily han unmodi ied kaolini e, as
seen in Fig. 5.4 (s abili y measu emen s). PCM is soluble in THF, bu no in wa e .
Ne e heless p is ine kaolini e can be modi ied by PCM as i s s ep as well, bu o
ha kaolini e has o be dispe sed in THF by igo ous s i ing i s .
Modi ica ion o TS
100 mg D16-b-S115 we e dissol ed in 30 ml THF. 400 mg o he kaolini e was
suspended in 30 ml o wa e (pH~ 5.5, deg ee o p o ona ion o he DMAEMA block
~80 %61). A e 20 min o s i ing a comple e loccula ion o he kaolini e was
achie ed and he suspension was washed en imes wi h THF o emo e he excess
o D16-b-S115. The hyb id was dispe sed and s o ed in THF o p e en d ying.
Modi ica ion o OS
100 mg o PCM was dissol ed in 20 ml d y THF unde a gon a mosphe e in a Schlenk
lask. 400 mg kaolini e (p is ine o al eady unila e ally modi ied hyb id) was
dispe sed in he PCM THF solu ion by igo ous s i ing o e nigh a 60 °C. A e he
eac ion he kaolini e was washed en imes wi h THF o emo e he excess o PCM
and hen dispe sed in THF o gi e hyb id-kaolini e.
Chap e 2
31
2.6 P epa a ion o clay/polyme nanocomposi es
2.6.1 Embedding o K- luo ohec o i e/PMMA hyb id pa icles (hyb id-hec )
in o a PMMA Ma ix o ensile es ing
Two di e en K- luo ohec o i e/PMMA hyb id nanopa icles we e e alua ed as
nano ille s in a PMMA ma ix: hyb id-hec (DP 380) and C12-hec we e mixed wi h a
solu ion o PMMA in THF (5 w . -% clay loading), espec i ely. To ensu e good
dis ibu ion o he clay in he polyme ma ix bo h dispe sions we e placed in an
o e head shake o e nigh . Bo h dispe sions we e ilm cas ed and d ied in a acuum
o en i s a 90 °C o 14 h ollowed by d ying a 140 °C o ano he 18 h. Nea PMMA
was ea ed in a simila way be o e mel compounding. The d ied nanocomposi e
ma e ials we e mel -compounded in a discon inuous coun e - o a ing win-sc ew
mic ocompounde (DSM Xplo e, 15 ml mic ocompounde ) a a empe a u e o 190
°C, a mixing speed o 210 pm and a mixing ime o 3 min. The ma e ial was added
s epwise o he unning mic ocompounde and du ing each cycle a ba ch o 7.5 g
was p ocessed. A e ex usion, he mel was injec ion-moulded wi h a mic oinjec o
(DSM Xplo e 12 ml injec ion moulding machine; mel empe a u e: 190 °C; mould
empe a u e: 40 °C; injec ion p essu e: 8 ba ) in o dumbbell specimens (75 mm × 5
mm × 2 mm) o ensile es ing.
2.6.2 P epa a ion o hyb id-clay/polys y ene (PS)/PMMA nanocomposi e
samples o TEM analysis
PS and PMMA in he a io o 1:2 we e dissol ed in THF. The polyme con en o he
solu ions was 10 w %. 50 mg o hyb id-clay (hyb id-MMT o hyb id-kaolini e) was
suspended in 10 ml o he PS/PMMA solu ions by 15 minu es o s ong shea ing
(Heidolph Silen C ushe , 16.000 pm) a 30 °C, esul ing in 5 w % hyb id-clay in he
inal, d y blend.
A ilm was cas by le ing he sol en e apo a e slowly om he mix u e in a glass
ial. The esul ing d y ilm was cu wi h an ul amic o ome and examined ia TEM.
Expe imen al Pa and Me hods
32
2.6.3 P epa a ion o hyb id-MMT/PS/PMMA nanocomposi e samples o
DMA
The PS/PMMA ma ix con aining he hyb ids is cas in o glass pe i dishes and d ied
in a acuum o en. The polyme is c ushed and mel p essed in o DMA mould
samples using ho pla es om P/O/Webe co. (Ge many). The samples a e mel ed a
200 °C wi hou p essu e o abou 6 minu es, emo ing las aces o THF, hen hea
p essed o 5 minu es using 70-75 kN and inally cold p essed o 3 minu es using 30-
40 kN.
Chap e 3
39
clay su ace. The ATRP echnique allows o p epa a ion o polyme s wi h na ow
molecula weigh dis ibu ions and p ecise con ol o e he a chi ec u e. Table 3.1
gi es he numbe and weigh a e age molecula weigh s Mn and Mw, espec i ely, o
he ee PMMA g own in solu ion de e mined by SEC as a unc ion o eac ion ime.
The di e ences be ween heo e ical and expe imen al alues can be a ibu ed o an
ini ia ion e iciency o less han 100%.
Table 3.1 Molecula weigh s o he ee PMMA chains as a unc ion o polyme iza ion ime in
THF [MMA] : [PMDETA] : [EBiB/MI] : [Cu(I)Cl] : [Cu(II)Cl2] (3000 : 2 : 0.2/0.8 : 1.2 : 0.3)
Reac ion ime (min)
Con .a (%)
DP a
Mn a
(kg/mol)
DP b
Mn b (kg/mol)
Mw b (kg/mol)
PDI b
10
1
36
3.5
84
8.4
10.0
1.2
20
2
72
7.2
100
10.0
13.0
1.3
30
4
120
12.0
150
15.0
17.0
1.1
60
5
143
14.3
190
19.0
23.0
1.2
120
7
203
20.3
310
31.0
36.0
1.2
300
9
263
26.3
380
38.0
50.0
1.3
a de e mined by 1H NMR spec oscopy. b de e mined by SEC wi h THF as eluen and PMMA s anda d
calib a ion.
The eac ion shows a con olled cha ac e wi h a e y good polydispe si y index. Fig.
3.6 (le ) shows i s -o de kine ic o ln[M0]/[M] as a unc ion o ime, whe eas,
polyme iza ion a e slowed down a e 120 min. This indica es ha he numbe o
he ini ia ing species emained app oxima ely cons an up o 120 min eac ion ime
and hen s a ed o dec ease. Fu he mo e, by plo ing he molecula weigh e sus
con e sion as in Fig. 3.6 ( igh ), a linea inc ease asce ained he con olled
beha iou o he eac ion. Based on a su ace a ea o 68 m²/g o K-hec we can
calcula e a g a ing densi y o 0.08 chains pe nm² using he ollowing o mula:

Hyb id mica-like pa icles
40
Whe e 𝜌 is he g a ing densi y (chains pe nm2), MP is he mola amoun o PMMA
chains wi h a DP o 380, NA is he A ogad o cons an and SA is he su ace a ea in
m2/g.
Figu e 3.6 (▲) Fi s -o de kine ic plo o he polyme iza ion o PMMA. (■) E olu ion o he
molecula weigh wi h con e sion o PMMA.
Fo a quali a i e analysis o he g a ed polyme hyb id, FT-IR spec a o nea PMMA
and hyb id nano ille wi h g a ed PMMA chains a e compa ed in Fig. 3.7.
Cha ac e is ic CH ib a ions (2800-3000 cm-1), C=O ib a ion (1727 cm-1) and C-O
ib a ion (1263 cm-1) con i m he p esence o PMMA on he su ace e en a e
ex ensi e washing wi h THF.
Chap e 3
41
Figu e 3.7 FT-IR spec a o nea PMMA (black), su ace modi ied O-hec ( ed) and hyb id
nano ille (blue).
The amoun o su ace g a ed PMMA was examined by TGA (Fig. 3.8). As expec ed,
nanocomposi es wi h longe polyme chains showed a highe weigh loss o o ganic
ma e ial. O-hec was ound o ha e 3.1 % loss o ola ile ma e ials a e hea ing up
o 400 °C ( he weigh loss p io o 100 °C is neglec ed due o he aces o sol en ).
The g a ed hyb ids showed a weigh loss o 15.2 % and 32.4 % o g a ed PMMA
chains wi h a DP o 150 and 380, espec i ely.
Hyb id mica-like pa icles
42
100 200 300 400 500 600 700
0
20
40
60
80
100
hyb id (DP 150)
nea PMMA
hyb id (DP 380)
weigh (%)
empe a u e (°C)
O-hec
Figu e 3.8 TGA measu emen s showing weigh loss e sus empe a u e o O-hec ( ed),
hyb id wi h PMMA DP 150 (blue), hyb id wi h PMMA DP 380 (g een) and nea
PMMA (black).
Powde X- ay di ac ion (PXRD) was used o ack any changes in he in e lamella
spacing du ing p epa a ion o he hyb id nano ille . The PXRD pa e ns o ex olia ed
K-hec and he hyb id nano ille a e shown in Fig. 3.9.
Chap e 3
43
5 6 7 8 9 10
in ensi y (a.u.)
2 (°)
d (001): 1 nm
Figu e 3.9 PXRD pa e ns o he (001) peak o K-hec (─), C12-hec (∙∙∙) and o hyb id nano ille
(DP 380) (---).
The eco ded PXRD pa e ns showed no shi ing o he cha ac e is ic (001) sha p
e lec ion a d001= 9.9 Å which is ypical o non-hyd a ed mica-like clay. This
obse a ion assu es ha all ea men s including su ace g a ing do no ha e any
in luence on he in e lamella s uc u e. The mo phological changes o he clay’s
ex e nal su ace we e analyzed using scanning elec on mic oscopy (SEM). In Fig.
3.10 a) a high aspec a io o K-hec can be seen a e ex olia ion, ha ing a la ge
la e al ex ension and smoo h su ace. In compa ison o O-hec (Fig. 3.10 b), he
su ace g a ed hyb id nano ille has a oughe and coa se su ace (Fig. 3.10 c). The
pa e n is ypical o collapsed PMMA chains in a d ied s a e o ming mush oom-like
s uc u es, as expec ed o he achie ed g a ing densi y.
Hyb id mica-like pa icles
44
Figu e 3.10 SEM images o a) ex olia ed K-hec , b) su ace mo phology p io o O-hec c) Su ace
o hyb id nano ille co e ed wi h collapsed polyme chains abo e en anglemen
leng h. *(A ows indica e clay agmen s om milling ea men , ac ual polyme s a e
he smalle s uc u es on he su ace).
3.2 Mechanical p ope ies o he clay/PMMA nanocomposi es
The mechanical p ope ies o nea PMMA and PMMA/clay nanocomposi es
de e mined by ensile e alua ion es s a a 5 w % clay loading a e p esen ed in Fig.6.
Wi h inco po a ion o hyb id clay pa icles he ensile modulus o PMMA/clay
nanocomposi es showed a signi ican enhancemen compa ed o nea PMMA. The
imp o emen o C12-hec is al eady 45 % and hyb id-hec (DP 380) almos doubled
he ensile modulus wi h an imp o emen o 84 %. The addi ion o he nanopla ele s
has no signi ican in luence on he ensile s eng h. The elonga ion a b eak is
educed by 35% in case o C12-hec and on he con a y shows an inc ease o 18%
o he hyb id-hec (DP 380).

Chap e 3
45
Figu e 3.9 Young’s modulus (o ange, s iped), ensile s eng h (g ey) and elonga ion a b eak
(blue) o nea PMMA and wo di e en clay/PMMA nanocomposi es.
The inco po a ion o high aspec a io nanopla ele s in o a PMMA ma ix al eady
leads o a signi ican ein o cemen e ec compa ed o nea PMMA as demons a ed
by Fische e al. in 201269. The op imiza ion o he p epa a ion me hod h ough
solu ion blending elimina es any agglome a es o med in a no mal mel blending
p ocess, which usually a e he cause o a signi ican educ ion in he ensile
s eng h70. The absence o such agglome a es educes any local s ess concen a ion
in he ma ix and hus he ensile s eng h o he composi e is no a ec ed by he
addi ion o he nano ille .
Signi ican shi s in he elonga ion a b eak beha iou we e obse ed depending on
he ype o nano ille . Usually, he addi ion o igid nano ille s o a b i le ma ix
leads o an inc ease in modulus a he expense o s eng h, s ain and oughness as
emb i lemen akes place71.
This beha iou was obse ed o he inco po a ion o C12-hec , which inc eased he
modulus by 45 %, bu educed he elonga ion a b eak by 35 %. The clay ac s as a
ba ie and hus es ic s he sliding o polyme chains among each o he . On he
con a y a signi ican inc ease in modulus and elonga ion a b eak was obse ed o
Hyb id mica-like pa icles
46
he no el hyb id nano ille , which emphasizes he impo ance o he addi ion o
polyme ic chains ma ching he pola i y o he ma ix on o he hyb id’s su ace. This
leads o a be e adhesion o he nano ille o he ma ix, which gene a es an
e ec i e s ess ans e om he ma ix o he nano ille while s ill pa icipa ing in
he sliding o polyme chains among each o he and consequen ly leads o a
signi ican inc ease in bo h, he modulus and elonga ion a b eak wi hou sac i icing
ensile s eng h.
3.3 Conclusion
Su ace-ini ia ed ATRP was success ully employed o g a PMMA chains om he
ex e nal basal planes o a shea -s i , mica-like K-hec o c ea e no el hyb id
nano ille . The employed syn he ic luo ohec o i e was cha ac e ized by a high
aspec a io and homogenei y o laye cha ge, while he mul iple ancho ing g oups
o he syn hesized mac oini ia o enabled a s ong adhesion o he clay’s su ace.
The kine ic s udy o si-ATRP o PMMA con i med a con olled polyme iza ion in a
linea a ia ion. Fu he mo e, g a ed polyme chains allow o s able dispe sions o
he hyb ids in a ious o ganic sol en s. The ob ained hyb id nano ille shows a
s ong ein o cing e ec a e being compounded in o a PMMA ma ix due o he
syne gis ic e ec o inhe en shea s i ness and huge la e al ex ension o he clay
i sel and he op imized in e ace be ween he hyb id nano ille and he ma ix
h ough addi ion o a ailo ed polyme ic shell.
Chap e 4
47
4 Chap e 4: Pa chy hyb id pa icles based on poly-
me g a ed mon mo illoni e (MMT)
4.1 P epa a ion o pa chy hyb id pa icles based on MMT
To compa ibilize an immiscible bina y polyme blend, a hyb id clay pa icle wi h
homogeneous shell as used in he las chap e is no pe ec . Based on he
assump ion, ha a pa icle wi h a bina y polyme shell should be d awn owa ds he
in e ace i placed in o a mix u e o wo immiscible componen s (polyme s in a blend
o liquids o di e en pola i y) by he Picke ing e ec , we c ea ed disc-like pa icles
wi h compa men alized su ace, bea ing pa ches o polyme , each ma ching one o
he componen s o an immiscible blend (Figu e 4.1). We hypo hesize, ha he
ac ion o polyme chains wi h un a ou able in e ac ions would collapse and s ay
close o he solid su ace o he hyb id disc, whe eas polyme chains wi h a ou able
in e ac ion would p o ude in o he ma ix.
Fig. 4.1 Gene al app oach o pa chy hyb id nanodiscs ia g a ing o diblock copolyme s on o
clay su ace and selec i e collapse o chains a an in e ace.
Pa chy Hyb id Pa icles
48
4.1.1 Syn hesis o DMAEMA based diblock copolyme s ia sequen ial RAFT
polyme iza ion
Fig. 4.2 RAFT-polyme iza ion o DMAEMA using 2-cyano-2-p opyl benzodi hioa e (CPBDT) as
chain ans e agen
As shown in chap e 3 and in li e a u e, posi i ely cha ged poly(2-
(dime hylamino)e hyl me hac yla e) (PDMAEMA) can i mly a ach o nega i ely
cha ged su aces, like hose o laye ed silica es o colloidal silica64, 72. In his chap e ,
p o ona ed PDMAEMA is inco po a ed in o a diblock copolyme and, as i can be
cha ged posi i ely depending on he pH o pe manen ly by qua e niza ion, is used as
a lexible ca ionic ancho ing g oup o equip clay pa icles wi h a polyme ic shell. The
polyme o DMAEMA is easily accessible ia RAFT polyme iza ion and can unde go
copolyme iza ion wi h a ange o di e en monome s g ea ly con ibu ing o he
lexibili y o modi ying clay su aces wi h polyme s o di e en pola i ies,
esponsi eness and sensi i i ies. I se ed as an ancho o he MMT ex e nal planes
ia ca ion exchange. The block-leng h was kep sho and s ayed in he ange o 14
o 20 epea ing uni s o all diblock-copolyme s, as wi h inc easing leng h o chain i
becomes mo e likely o c osslink se e al pla ele s by he same ancho ing block.
Con olled adical polyme iza ion by he RAFT-p ocess gua an ees low
polydispe si ies o he ob ained polyme s which is a p econdi ion o gene a e well
de ined mic ophase-sepe a ed solu ions and hus con ol o e pa ch size. Also RAFT
polyme iza ion is applicable o a ious monome s and he syn hesis o block-
copolyme s is acile.
Chap e 4
55
Fig. 4.8 SEM images o hyb ids based on hec o i e (le ) and MMT ( igh ) modi ied wi h a 1:1
(mola ) mix u e o D17-b-M300 and D16-b-S360 in THF
By his app oach i was possible o modi y se e al ypes o clay ( o kaolini e see
chap e 5): The small pa icle ( ac oid) size and agglome a ion in o band-like
s uc u es o sel -suppo ing clay ilms upon d ying makes i di icul o isualize he
success ul g a ing and i s pa chiness in gene al on he su ace o MMT. Since no
indi idual pla ele s a e isible, bu a he agglome a es o se e al µm in diame e , i
is impossible o dis inguish polyme om pla ele s. As a p oo o p inciple la ge and
s i e syn he ic clay was used. The same shea -s i K- luo ohec o i e om chap e 3
was modi ied ia “g a ing on o”. Quali a i e analysis o SEM images showed less
g a ing densi y and mo e inhomogeneous su ace co e age (Fig. 4.8) as compa ed
o expe imen s wi h polyme ic shells a ached ia a “g a ing om” echnique (Fig.
3.10).
While SEM analysis o he syn he ic clays deli e ed e idence o success ul g a ing
o polyme on o he clay su ace, i was no possible o p o e g a ing o bo h
polyme species in his way. 1H-NMR analysis was used o de e mine whe he
p e e en ial adso p ion o ei he o he polyme s occu ed. Ra ios be ween peaks o
he 5 a oma ic p o ons in he PS block (δ=6.4-7.2 ppm) and he 3 p o ons o he CH3-
O- es e g oup o he PMMA block (δ=3.6 ppm) whe e compa ed, be ween he
solu ion used o modi y he clay and he supe na an a e cen i uga ion o he i s

Pa chy Hyb id Pa icles
56
ime. Bo h a ios o PS o PMMA we e oughly he same be o e and a e
modi ica ion (de ia ion o less han 10%), which leads o he assump ion ha
adso p ion is p ima ily con olled by he PDMAEMA block, which is o compa able
leng h in all cases, and he e is no signi ican p e e en ial adso p ion depending on
he species o he second block wi h he gi en species.
-100 0 100 200 300 400 500 600 700 800
80
85
90
95
100
Weigh [%]
Tempe a u e [°c]
Fig. 4.9 TGA esul s showing he empe a u e dependen weigh s o di e en hyb id
pa icles: unmodi ied MMT (solid g ay), D16-b-S360 modi ied MMT (solid black), D17-b-
M300 modi ied MMT (s iped g ay), pa chy hyb id MMT modi ied wi h bo h
a o emen ioned diblock copolyme s (solid ed)
To quan i y he amoun o su ace-bound polyme a he mog a ime ic analysis
(TGA) was pe o med (Fig. 4.9): unmodi ied MMT showed a o al mass loss o 2 %,
while all hyb ids showed a mass loss o a ound 12-15 % in he mos ele an egion
(200-500 °C), which gi es a calcula ed g a ing densi y o 0.5 uni s o DMAEMA pe
nm² o comple ely ex olia ed MMT using he ollowing o mula:
Whe e; ρ is he g a ing densi y (ini ia o pe nm2), MD is he a e age mola amoun
o DMAEMA uni s pe g o hyb id, NA is he A ogad o cons an and SA is he su ace
Chap e 4
57
a ea o 68 m2/g. The calcula ed alue is a ound hal o he ca ion exchange capaci y
(CEC) alue p o ided by he company o he employed MMT (PGV) in a heo e ical
delamina ed s a e and. The disc epancy can be explained by incomple e ex olia ion.
4.2 Mechanical p ope ies o he clay/PMMA/PS nanocomposi es
4.2.1 P epa a ion o clay/PS/PMMA blends
Dually modi ied PS/PMMA-pa chy hyb id pa icles, wi h he polyme pa ches on
each side should be able o selec i ely collapse o ex end o ma ch he su ace
ension o he polyme phase hey eside in, we e es ed as compa ibilize s in ilms
o PS/PMMA blends cas om THF, a good sol en o bo h polyme s and a good
dispe san o he hyb ids. Loca ed a an in e ace, each side should collapse he
incompa ible polyme chains and ex end he compa ible ones in o he ma ix,
o ming a Janus-like s uc u e.
Fo compa ison and o be able o es ima e he e ec o he pa chy cha ac e
addi ional blends wi h homogeneously modi ied clay (ei he PS o PMMA as shell)
and blends wi h unmodi ied MMT we e p epa ed by sol en cas ing unde he same
condi ions. A PS/PMMA a io o 1:2 (w /w ) was chosen. The Flo y-Huggins
pa ame e o a blend o his molecula weigh is χSM = 0.041 a 20 °C74 indica ing i s
incompa ibili y.
The samples o ansmission elec on mic oscopy (TEM) we e p epa ed by cas ing
he polyme solu ion wi h dispe sed clay in o a glass ial ollowed by slow d ying and
mic o ome cu ing. The di e ence be ween PS and PMMA is clea ly isible in he
TEM images (Fig. 4.9) e en wi hou selec i e s aining. Da k g ey a eas esul om
s onge elec on con as o PS and ligh g ey a eas om PMMA, which is mo e
easily damaged by he elec on beam. The clay pa icles appea e en da ke , almos
black, and hei p o ile shapes a e clea ly isible due o hei s ong con as , he
comple ely whi e egions a e holes in he ilm in oduced du ing ul a mic o ome
cu ing.
Pa chy Hyb id Pa icles
58
We a e awa e o he ac ha sol en e apo a ion will ap he sys em in a
me as able s a e and such p epa ed ilms can only show a quali a i e aspec o
compa ibiliza ion achie ed by ou hyb id pa icles. Fo pu e PS/PMMA blend ilms o
compa able molecula weigh wi hou compa ibilize , i is known, ha la ge (se e al
µm in diame e ) sphe ical domains o he mino i y phase inside a ma ix o med by
he majo i y phase esul om phase seg ega ion51. F om li e a u e on classical
o ganoclays (e.g. Cloisi e 20A), i is known, ha modi ica ion wi h simple alkyl chains
will lead o dispe sion only in he PMMA phase o a PS/PMMA blend and o ma ion
o clus e s in PS homopolyme blends.75 Analysis o blends mixed wi h PS-g a ed
MMT (modi ied wi h D16-b-S360) showed ha he hyb ids wi hou excep ion s ay in
he PS phase o assemble a he in e ace, hough no s ong endency o in e acial
in e ac ion is obse ed (Fig. 4.10 a). Simila esul s a e ob ained o hyb ids based on
PMMA-g a ed MMT (modi ied wi h D17-b-M300). Bo h hyb ids s ay in he phase o
he polyme hei su ace is modi ied wi h. Though being he mino i y phase, we can
ind p ominen ly huge domains o PMMA, illed wi h andomly o ien ed hyb id
pla ele s (Fig. 4.10 b). The obse ed polygonal shape o polyme domains can be
a ibu ed o inc eased iscosi y o he ille - ich phase a he han in e acial
ac i i y, as he e a e only a ew pla ele s di ec ly assembled a he in e ace.
Fig. 4.10 TEM images o 2:1 (w /w ) PS/PMMA blend ilms a) showing D16-b-S360 modi ied
hyb ids in he PS phase only, b) D17-b-M300 modi ied hyb ids in PMMA phase. The
ac ion o he added hyb id is 5 w % and he scale ba ep esen s 1 µm.
b
)
a
)
Chap e 4
59
Blends compa ibilized wi h pa chy hyb id pa icles (shell based on modi ica ion wi h
a 1:1 (mola ) mix u e o D16-b-S360 and D17-b-M300) show a comple ely di e en
s uc u e. Hyb ids a e andomly o ien ed and dis ibu ed o e he whole blend in
bo h phases and he in e ace (Fig. 4.11 a). The domain size is educed compa ed o
blends compa ibilized wi h unmodi ied and single-polyme -species modi ied clay.
Domain shapes a e comple ely i egula (Fig. 4.11 b), ollowing he shape o pla ele s
whe e hey eside in he in e ace. As no all o he in e acial a ea is co e ed, he
hyb ids ac as a physical ba ie and inc ease iscosi y, p e en ing he o ma ion o
la ge sphe ical domains (Fig. 4.11 b). Rega ding he s uc u e o he polyme ic shell
o he pa chy hyb ids, we expec h ee di e en cases: a hyb id esiding in he PS
phase will ha e i s PMMA chains collapsed nea he clay su ace, sc eened by
ex ended PS chains, in e ac ing wi h he ma ix. Hyb ids in he PMMA phase will
show opposi e beha iou , whe e PMMA chains a e ex ended and PS chains a e
collapsed. In an in e ace, a hyb id would show bo h a o emen ioned beha iou s a
once, acco ding o he polyme phase he espec i e side is acing.
Fig. 4.11 TEM images o 2:1 (w /w ) PS/PMMA blend ilms a) showing pa chy hyb ids wi h
PMMA and PS shell in he PS phase, he PMMA phase and he in e ace, b) close up.
The ac ion o he added pa chy hyb ids is 5 w % and he scale ba ep esen s 1
µm.
As he blend mo phology is c ea ed unde in luence o THF as a sol en and is ixa ed
only a e slow e apo a ion o he sol en , he shell o each hyb id has enough ime
a
)
b
)
Pa chy Hyb id Pa icles
60
and is lexible enough o ex end and collapse i s polyme chains o ma ch he
in e acial ension / su ace ene gy o he polyme phase i esides in. Compa ed o a
pu e Janus o Picke ing pa icle i can ind i s ene ge ic minimum no only a an
in e ace, bu inside one o he phases as well.
4.2.2 DMA o he blends
F om he a ie y o DMA da a, he s o age modulus, E', is plo ed in dependence o
he hea ing empe a u e, T. (Fig. 4.12).
20 40 60 80 100 120 140 160
-0,5
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
S o age Modulus E' [GPa]
Tempe a u e [°C]
Fig. 4.12 DMA esul s showing he empe a u e dependend s o age moduli o 2:1 PS:PMMA
blends: uncompa ibilized pu e blend (solid black), blend compa ibilized wi h 5 w %
alkylammonium-modi ied PGV (do ed g ay) and compa ibilized wi h pa chy hyb ids
o PGV (solid ed).
The s o age modulus o a pu e, uncompa ibilized 2:1 PS/PMMA blend is 3.2 ±0.1 GPa
a 35 °C, compa ibiliza ion wi h a C12-alkylammonium modi ied MMT esul ed in a
s o age modulus inc ease o ~7 % o 3.4 ±0.1 GPa, while compa ibiliza ion by a
pa chy hyb id esul ed in an inc ease o 17 % o 3.9 ± 0.1 GPa (Fig. 4.12). Thus, a
signi ican ly highe deg ee o ein o cemen is obse ed by compa ibilizing he blend
wi h pa chy hyb ids han wi h simple o ganoclay.

Chap e 4
61
4.3 Conclusion
The expe imen al da a p esen ed con i m he success ul g a ing o di e en pa ches
o wo diblock copolyme species on o he su ace o clays om he smec i e g oup,
c ea ing no el pa chy hyb id pa icles. We used a e sa ile and simple app oach o
syn hesize unc ional diblock copolyme s which consis o a sho ancho ing block o
a ach o he clay su ace and a longe block adding he desi ed pola i y o
unc ionali y. A combina ion o wo o mo e o di e en diblock copolyme s g a ed
on o clay can lead o a dynamic shell which is able o adap o en i onmen s o
di e en pola i y and e en show in e acial ac i i y in immiscible polyme blends.
The dispe sion in bo h phases and he in e ace o an immiscible polyme blend
indica es he ele ance o he heo e ical concep o selec i e polyme chain collapse
and ex ension in he polyme ic shell o he pa icles and leads o a ein o cing e ec ,
shown in an inc ease o up o 17 % in Young’s-modulus.
While he p esen ed me hod did no lead o Janus- ype beha iou , cha ac e ized by
p e e able p esence in he in e ace, he me hod should allow u he in e es ing
combina ions o di e en diblock copolyme s o unc ionalize he pa chy shell o he
hyb id pa icles, opening up new ields un eachable wi h homogeneously modi ied
pa icles.
Hyb id Janus Pa icles
62
5 Chap e 5: Hyb id Janus pa icles based on polyme
modi ied kaolini e
This chap e is he esul o he coope a ion wi h Dunja Hi seman and majo pa s o
his chap e we e published in Polyme 2013, 54, 1388-1396 unde he i le: “Hyb id
Janus pa icles based on polyme -modi ied kaolini e” by S ephan Weiss, Dunja
Hi semann, Be nha d Bie sack, Mazen Ziadeh, Axel H.E. Mülle , Jose B eu, Tex and
espec i e igu es a e adap ed and ep in ed wi h pe mission. Copy igh 2013
Else ie
5.1 P epa a ion o hyb id janus pa icles based on kaolini e
The in es iga ions o andomly compa men alized, pa chy hyb id pa icles based on
MMT showed in e acial ac i i y oo low o a ach o he in e phase be ween PS and
PMMA in an immiscible blend o bo h. One o he easons we ound was he
lexibili y o he pa icle shell, wi h immiscible pa ches collapsing and miscible
pa ches ex ending in o he ma ix, hus keeping he hyb id pa icle lexible enough
o adap o i s su oundings, independen o whe e i was loca ed. The nex logical
s ep was o c ea e disc-like Janus hyb id pa icles, wi h a shell comp ised o exac ly
wo chemically dis inc , opposi ely loca ed compa men s, inc easing in insic
pola i y o he hyb id and a ge ing he in e phase o he blend as he ene ge ically
mos a ou able loca ion. 2:1 Smec i es, like hec o i e and mon mo illoni e a e no
well sui ed o c ea e Janus pa icles, as i is e y edious o selec i ely add ess each
o hei ex e nal basal planes indi idually. Howe e , due o i s pola c ys al s uc u e,
he wo opposing ex e nal basal planes o kaolini e, TS and OS a e unca ed by
dis inc unc ional g oups and may selec i ely be modi ied by simple ca ion exchange
and co alen g a ing ia ca echol g oups, espec i ely, making i he pe ec base o
a disc-like hyb id Janus pa icle. As an example we chose poly((2-
dime hylamino)e hyl me hac yla e)-block-polys y ene (D16-b-S115) and poly(3-(2,3-
dihyd oxy-benzoyloxy)p opyl me hac yla e)-s a -(me hyl me hac yla e)) (PCM).
Chap e 5
63
HO OH
O
O
OO
*3
O
N
O20
O O
*
90
s a
block
*
115
H
(H2C)3
Fig. 5.1 S uc u e o poly(3-(2,3-dihyd oxybenzoyloxy)p opyl me hac yla e)-s a -(me hyl
me hac yla e) (PCM) ( op) and poly(2-(dime hylamino)e hyl me hac yla e)-block-
polys y ene (D16-b-S115) ca ions (bo om).
PCM is a s a is ical copolyme , while D16-b-S115 is a block copolyme (Fig. 5.1).
Consequen ly, bo h modi ie s in e ac wi h he kaolini e basal planes in a di e en
manne (Fig. 5.2). PCM will likely be close o he OS, o ming sho loops o lying la .
In con as , he polys y ene block migh a ange b ush-like on he TS o he kaolini e.
The esul ing Janus pa icles a e ailo ed o compa ibilizing PS-PMMA o indus ially
mo e ele an PPE–SAN (poly(2,6-dime hyl-1,4-phenylene e he ) (PPE), poly(s y ene-
co-ac yloni ile) (SAN)) blends50, 51.
Hyb id Janus Pa icles
64
Fig. 5.2 Schema ic pic u e o a) p is ine kaolini e, b) modi ied wi h D16-b-S115 on he
e ahed al su ace (TS), c) u he modi ied wi h PCM on he opposi e oc ahed al
su ace (OS) and d) embedding o he inal hyb id pa icle a he in e ace in a PS-
PMMA blend.
5.1.1 Syn hesis o he copolyme s PCM and D16-b-S115
Syn hesis o he ca echol-modi ied poly(me hyl me hac yla e) copolyme (PCM)
Ini ially, a sui able ca echol modi ied me hac yla e monome was p epa ed o
copolyme iza ion wi h me hyl me hac yla e (MMA). 3,4-Dibenzoxy-(3-
hyd oxyp opyl)benzoa e 2 was ob ained om 3,4-dibenzoxybenzoic acid 1.57
Reac ion o 2 wi h me hac yloyl chlo ide ga e he mixed dies e 3 (Scheme 5.1).
OBn
OBn
CO2H
OBn
OBn
O O OH
OBn
OBn
O O O O
12 3
(i) (ii)
Scheme 5.1 Syn hesis o he ca echol monome . Reagen s and condi ions: (i) SOCl2, CH2(CH2OH)2,
E 3N, THF / DCM, . ., 5 h, 51%; (ii) CH2C(CH3)COCl, E 3N, DCM, . ., 3 h, 67%.
Monome 3 was copolyme ized wi h a 30- old excess o MMA by ee adical
polyme iza ion using AIBN as ini ia o and dodecane hiol as ans e agen o gain
con ol and educe molecula weigh , gi ing copolyme 4. 1H NMR spec oscopy and
Chap e 5
71
he s a is ical copolyme PCM s ays compa a i ely close o he su ace. Mo eo e ,
he hyd a ed ino ganic ca ions esiding a unmodi ied TS con ibu e o an e icien
elec os a ic s abiliza ion o PCM-kaolini e in wa e . Al e na i ely, he s abili y o
PCM-kaolini e migh be explained by he o ma ion o sandwich s uc u es as
depic ed in Fig. 6a (blue amed inse ). Fo such sandwich s uc u es only he
hyd ophilic TS a e exposed o he aqueous media. Such polyme -b idged sandwich
s uc u es would no be expec ed o D16-b-S115-kaolini e because he long PS-
b ushes will hampe dime - o ma ion s e ically.
In THF (Fig. 5.6b) bo h, he PCM-kaolini e (Fig. 5.6b, blue) as well as he D16-b-S115-
kaolini e (Fig. 5.6b, ed), showed good s abili y which in u n is compa able o ha o
he dually modi ied D16-b-S115/PCM-kaolini e (Fig. 5.6b, black). This sugges s ha
e en he sho PCM loops a he OS we e able o assu e a good s abili y in THF and
expec edly he longe chains pe o m as well. Mo eo e , i would be expec ed ha
sandwich s uc u es o D16-b-S115- and PCM-kaolini e a e o med (Fig. 5.6b, ed and
blue squa es).
Fig. 5.6 In eg a ed anspa ency o 0.25 w % suspensions in a) wa e and b) THF o p is ine
kaolini e (pink), PCM-kaolini e (blue), D16-b-S115-kaolini e ( ed) and D16-b-S115/PCM-
kaolini e (black) unde ime dependen cen i ugal o ces o 300 pm, 600 pm, and
900 pm.
In summa y, he s abili ies in wa e - and THF-suspensions obse ed o he di e en
kaolini e samples a e in line wi h a speci ic modi ica ion o TS and OS by D16-b-S115
and PCM, espec i ely, and s ongly suppo he Janus cha ac e o D16-b-S115/PCM-
kaolini e.

Hyb id Janus Pa icles
72
5.2 TEM Analysis o he mo phology o he hyb id-kaolini e / PMMA/
PS nanocomposi es
Dually modi ied D16-b-S115/PCM-kaolini e, whe e he su ace ensions o he
opposing basal su aces a e ine- uned o ma ch PS and PMMA, espec i ely, was
es ed as compa ibilize in ilms o incompa ible PS-PMMA blends cas om THF,
simila o he p ocess used in chap e 4.3.4. Fo compa ison and o be able o
es ima e he e ec o he Janus cha ac e in excess o he pu e Picke ing e ec
addi ional blends wi h unila e ally modi ied and blends wi h unmodi ied kaolini e
we e p epa ed by sol en cas ing unde he same condi ions. A PS/PMMA a io o
1:2 (w /w ) was chosen.
The samples o ansmission elec on mic oscopy (TEM) we e p epa ed by cas ing
he polyme solu ion wi h dispe sed clay in o a glass ial ollowed by slow d ying and
mic o ome cu ing. All images a e uns ained. Da k g ey a eas esul om s onge
elec on con as o PS and ligh g ey a eas om PMMA. The kaolini e pa icles
appea e en da ke , almos black, and hei shapes a e clea ly isible due o hei
s ong con as , he comple ely whi e egions a e holes in he ilm, in oduced du ing
ul a mic o ome cu ing.
Simila o wha was he case wi h expe imen s conduc ed in chap e 4.3.4 we a e
awa e o he ac ha sol en e apo a ion will ap he sys em in a me as able s a e
and such p epa ed ilms can only show he quali a i e aspec o compa ibiliza ion
achie ed by ou hyb id pa icles. To de e mine indus ially ele an quan i a i e
e ec s, like mechanical p ope ies o compa ibilized blends, i is necessa y o
conduc ex usion expe imen s and mechanical es s.
Fo pu e PS/PMMA blend ilms o compa able molecula weigh ha con ain no
compa ibilize s, i is known, ha la ge (se e al µm in diame e ) sphe ical domains o
he mino i y phase inside a ma ix o med by he majo i y phase esul om phase
seg ega ion.51
Wi h unmodi ied kaolini e we obse e mac ophase sepa a ion (Fig. 5.7a). No
dispe sion is achie ed, only la ge agg ega es o clay pa icles can be ound,
sepa a ing om he ma ix, apped inside he polyme phase whe e hey happen o
be upon d ying (Fig. 5.7a). This beha iou is expec ed due o he clay’s hyd ophilic
Chap e 5
73
na u e (cha ged on one side and pola hyd oxy g oups on he o he side) and he
ac ha i does no o m s able dispe sions in THF (and hus is ha d o dispe se in
he Polyme mix u e o s a wi h). In ano he expe imen we modi ied he TS o
kaolini e wi h dodecylamine, which is compa able in s uc u e o he alkyl
ammonium sal s used o p epa e comme cial o ganoclay like he widely used Cloisi e
20A. He e we can obse e clus e ing in he PMMA phase (Fig. 5.7b). Like in he
Lumi uge expe imen s we expec he kaolini e o o m sandwich s uc u es wi h he
alkyl chains o he o ganophilized TS agg ega ed ia hyd ophobic in e ac ions in he
inside and he pola OS a he ou side o he o he way ound. In none o he cases
we could ind a su ace which has high compa ibili y wi h any o he polyme phases
and hus is no dispe sed homogeneously. This obse a ion is in good ag eemen
wi h li e a u e abou o he o ganoclay (e.g. Cloisi e 20A), which dispe ses only in he
PMMA phase o a PS/PMMA blend and o ms s ong clus e s in PS homopolyme
blends.75 Ob iously modi ica ion o one side is no su icien o align he pa icles a
he in e ace unde hese condi ions.
Hyb id Janus Pa icles
74
Fig. 5.7 TEM images o 3:7 (w /w ) PS/PMMA blend ilms. a) wi h p is ine kaolini e, b) wi h
unila e ally o ganophilized kaolini e, c) wi h D16-b-S115/PCM-kaolini e, and d) close
up a an in e - ace. The ac ion o he clay is 5w % and he scale ba ep esen s 500
nm.
In con as , in he ilm p epa ed wi h he Janus- ype D16-b-S115/PCM-kaolini e (Fig.
5.7c, d) he kaolini e pa icles a e assembled exac ly a he in e ace be ween bo h
polyme phases. A nea ly ull co e age o he in e ace by compa ibilize is ealized.
Due o he Janus cha ac e o he modi ied kaolini e he in e acial ension o he
pla ele s in he blend in e ace should be e y low. The e o e, he assembly o he
pa icles a he in e ace is ene ge ically highly a o ed. As a consequence, he PS
domains a e no longe sphe ical bu appea polygonal ollowing he shape o he clay
pla ele s (Fig. 5.7c, d).
Chap e 5
75
5.3 Conclusion
A synopsis o all expe imen al da a p esen ed con i ms ha he ex e nal basal planes
o kaolini e pla ele s can be selec i ely add essed by polys y ene and PMMA, simila
o wha has been s udied in de ail o he molecula modi ica ion wi h Ru(bpy)32+ and
a phospho ous-labelled ca echol (3-Diphenylphosphinyloxyp opyl-3,4-
dihyd oxybenzoa e) in li e a u e21. Janus- ype D16-b-S115/PCM-kaolini e pla ele s
ob ained by dual modi ica ion showed in e acial ac i i y in a sol en -cas PS/PMMA
blend ilm. Ob iously, blend p epa a ion ia mel ex usion would be ad an ageous.
Wo k in ha di ec ion is on he way bu he esul s ob ained by sol en -cas ing
al eady gi e a s ong indica ion on he e iciency o he hyb id Janus pa icles as
blend compa ibilize s.
While he p esen ed wo k ep esen s a p oo o p inciple, he app oach is, o cou se,
highly modula and should allow o acile and a o dable ine- uning o app op ia e
compa ibilize s o a b oad ange o blend sys ems.
The in insically pola s uc u e o kaolini e se es as e sa ile co e o hese Janus
pla ele s. Adjus men o he su ace ensions o bo h basal planes can easily and
selec i ely be ailo ed o each speci ic blend composi ion. Mo eo e , pa icle size
dis ibu ion and mo phology (aspec a io) may be a ied o e a wide ange by he
choice o he kaolini e sou ce. Fu he mo e, ha concep is no es ic ed o
kaolini e bu can be ans e ed o any o he ino ganic ma e ial which possesses a
pola c ys al s uc u e and whe e opposing c ys al aces a e unca ed by chemically
di e en unc ional g oups, pa ing he way o selec i e modi ica ion.
An addi ional ad an age o he concep should be an inhe en ein o cemen o he
blend by he ino ganic ille , which, mo eo e , is concen a ed a he blends
in e aces. This should c ea e a syne gis ic e ec s e ching a beyond a pu e
Picke ing e ec and should boos he mechanical p ope ies o he blend.
Re e ences
76
6 Chap e 6: Re e ences
1. Hussain, F.; Hojja i, M.; Okamo o, M.; Go ga, R. E., Jou nal o Composi e
Ma e ials 2006, 40, (17), 1511-1575.
2. Ga y W. Beall, C. E. P., Fundamen als o Polyme -Clay Nanocomposi es.
Camb idge Uni e si y P ess: 2011.
3. B iga i, M. F.; Galan, E.; Theng, B. K. G.; Fayza Be gaya, B. K. G. T. a. G. L.,
Chap e 2 S uc u es and Mine alogy o Clay Mine als. In De elopmen s in Clay
Science, Else ie : 2006; Vol. Volume 1, pp 19-86.
4. B eu, J., Tone und Tonmine ale. Uni e si ä Bay eu h: 2007.
5. Ralph, J., h p://www.minda .o g/min-2821.h ml. In 14.12.2012.
6. J. B eu, N. R., C. R. A. Ca low, J.Chem.Soc.Dal on T ans. 1999, 835-845.
7. J. B eu, N. R., C. R. A. Ca low, in Na u al Mic opo ous Ma e ials in;
En i onmen al Technology , V., (Eds.: P. Misaelides, F. Macasek, T.; Pinna aia, C. C.,
Kluwe Academic Publishe s, Do d ech 1999, p. pp.; 85-99.
8. Sa o, H.; Yamagishi, A.; Kawamu a, K., The Jou nal o Physical Chemis y B
2001, 105, (33), 7990-7997 .
9. S awhecke , K.; Manias, E., Chem. Ma e . 2000, 12, 2943.
10. Vaia, R.; Vasude an, S.; K awiec, W.; Scanlon, L. G.; Giannelis, E. P., Ad .
Ma e . 1995, 7, 154.
11. Alexand e, M.; Dubois, P., Ma e ials Science and Enginee ing: R: Repo s
2000, 28, (1-2), 1-63.
12. Schmid , D.; Shah, D.; Giannelis, E. P., Cu en Opinion In Solid S a e &
Ma e ials Science 2002, 6, (3), 205-212.
13. Kalo, H.; Mölle , M. W.; Ziadeh, M.; Dolejs, D.; B eu, J., Applied Clay Science
2010, 48, (1-2), 39-45.

Re e ences
77
14. Weiss, S.; Hi semann, D.; Bie sack, B.; Ziadeh, M.; Mülle , A. H. E.; B eu, J.,
Polyme 2013, (0).
15. Che igny, C.; Jouaul , N.; Dalmas, F.; Boue, F.; Jes in, J., Jou nal o Polyme
Science Pa B: Polyme Physics 2011, 49, (11), 781-791.
16. Nede , R. B.; Bu ghamme , M.; G asl, T.; Schulz, H.; B am, A.; Fiedle , S., Clays
and Clay Mine als 1999, 47, (4), 487-494.
17. Wada, K., Ame ican Mine alogis 1961, 46, (1-2), 78-91.
18. Komo i, Y.; Sugaha a, Y.; Ku oda, K., Jou nal o Ma e ials Resea ch 1998, 13,
(4), 930-934.
19. B ady, P. V.; Cygan, R. T.; Nagy, K. L., Jou nal O Colloid And In e ace Science
1996, 183, (2), 356-364.
20. Sch o h, B. K.; Sposi o, G., Clays and Clay Mine als 1997, 45, (1), 85-91.
21. Hi semann, D.; Shylesh, S.; De Souza, R. A.; Dia -Bake ly, B.; Bie sack, B.;
Muelle , D. N.; Ma in, M.; Schobe , R.; B eu, J., Angewand e Chemie In e na ional
Edi ion 2012, 51, (6), 1348-1352.
22. Inoue, M.; Kominami, H.; Inui, T., Jou nal Chemical Socie y Dal on
T ansac ions 1991, (12), 3331-3336.
23. Inoue, M.; Kondo, Y.; Inui, T., Ino ganic Chemis y 1988, 27, (2), 215-221.
24. Henglein, A., Chemical Re iews 1989, 89, (8), 1861-1873.
25. Spanhel, L.; Welle , H.; Henglein, A., Jou nal o he Ame ican Chemical Socie y
1987, 109, (22), 6632-6635.
26. Youn, H. C.; Ba al, S.; Fendle , J. H., The Jou nal o Physical Chemis y 1988,
92, (22), 6320-6327.
27. Hoene , C. F.; Allan, K. A.; Ba d, A. J.; Campion, A.; Fox, M. A.; Mallouk, T. E.;
Webbe , S. E.; Whi e, J. M., The Jou nal o Physical Chemis y 1992, 96, (9), 3812-
3817.
28. Honma, I.; Sano, T.; Komiyama, H., The Jou nal o Physical Chemis y 1993,
97, (25), 6692-6695.
Re e ences
78
29. Zhou, Z. H.; Gun e , W. D., Clays and Clay Mine als 1992, 40, (3), 365-368.
30. Ho man-Ca is, C. H. M., New Jou nal o Chemis y 1994, (18), 1087.
31. Ruhland, T. M.; Reichs ein, P. M.; Majewski, A. P.; Wal he , A.; Mülle , A. H., J
Colloid In e ace Sci 2012, 374, (1), 45-53.
32. G öschel, A. H.; Schache , F. H.; Schmalz, H.; Bo iso , O. V.; Zhulina, E. B.;
Wal he , A.; Mülle , A. H. E., Na Commun 2012, 3, 710.
33. Schmelz, J.; Ka g, M.; Hellweg, T.; Schmalz, H., ACS Nano 2011, 5, (12), 9523-
9534.
34. Pawa , A. B.; K e zschma , I., Mac omolecula Rapid Communica ions 2010,
31, (2), 150-168.
35. Schmelz, J., Disse a ion, Uni e si y o Bay eu h, 2012.
36. Wal he , A.; Mulle , A. H. E., So Ma e 2008, 4, (4), 663-668.
37. Casag ande, C.; Veyssié, M., C.R. Acad. Sci. (Pa is) 1988, Se II, (306), 1423.
38. Casag ande, C.; Veyssié, M.; Fab e, P.; Raphael, E., Eu ophys. Le . 1989, 9,
(3), 251-255.
39. Nisisako, T.; To ii, T.; Takahashi, T.; Takizawa, Y., Ad anced Ma e ials 2006,
18, (9), 1152-1156.
40. Beh end, C. J.; Anke , J. N.; McNaugh on, B. H.; Kopelman, R., Jou nal o
Magne ism and Magne ic Ma e ials 2005, 293, (1), 663-670.
41. Anke , J. N.; Beh end, C. J.; Huang, H.; Kopelman, R., Jou nal o Magne ism
and Magne ic Ma e ials 2005, 293, (1), 655-662.
42. Yoshida, M.; Roh, K.-H.; Mandal, S.; Bhaska , S.; Lim, D.; Nandi ada, H.; Deng,
X.; Lahann, J., Ad anced Ma e ials 2009, 21, (48), 4920-4925.
43. Kojima, Y.; Usuki, A.; Kawasumi, M.; Okada, A.; Fukushima, Y.; Ku auchi, T.;
Kamigai o, O., Jou nal o Ma e ials Resea ch 1993, 8, (5), 1185-1189.
44. Okada, A.; Usuki, A., Ma e ials Science and Enginee ing: C 1995, 3, (2), 109-
115.
Re e ences
79
45. Rockwood, h p://www.nanoclay.com/bene i s2.asp. In 14.12.2012.
46. Sho , G. J.; Guild, F. J.; Pa ie , M. J., Composi es Science and Technology
2001, 61, (14), 2075-2086.
47. Ruckdäschel, H.; Sandle , J. K. W.; Al s äd , V.; Re ig, C.; Schmalz, H.; Abe z,
V.; Mülle , A. H. E., Polyme 2006, 47, (8), 2772-2790.
48. Binks, B. P.; Lumsdon, S. O., Langmui 2001, 17, (15), 4540-4547.
49. Nes e o , A. E.; Lipa o , Y. S., Polyme 1999, 40, (5), 1347-1349.
50. Kha ua, B. B.; Lee, D. J.; Kim, H. Y.; Kim, J. K., Mac omolecules 2004, 37, (7),
2454-2459.
51. Li, Y.; Shimizu, H., Polyme 2004, 45, (22), 7381-7388.
52. Li, Y. Q.; Zhang, G.; Nu mikko, A. V.; Sun, S. H., Nano Le e s 2005, 5, (9),
1689-1692.
53. Ammann, L.; Be gaya, F.; Lagaly, G., Clay Mine als 2005, 40, (4), 441-453.
54. Cai, Y.; A mes, S. P., Mac omolecules 2004, 38, (2), 271-279.
55. Kelle , W., Applied Clay Science 2008, 5, 123-133.
56. Mölle , M. W.; Handge, U. A.; Kunz, D. A.; Lunkenbein, T.; Al s „d , V.; B eu, J.,
Acs Nano 2010, 4, (2), 717-724.
57. Wang, W.-L.; Chai, S. C.; Ye, Q.-Z., Bioo ganic & Medicinal Chemis y Le e s
2009, 19, (4), 1080-1083.
58. Bo che , H.; Hallensleben, M. L.; Nuá, S.; Wu m, H.; Baue , J.; Beh ens, P.,
Jou nal o Ma e ials Chemis y 2002, 12, (5), 1351-1354.
59. Ma yjaszewski, K.; Mille , P. J.; Shukla, N.; Imma apo n, B.; Gelman, A.;
Luokala, B. B.; Siclo an, T. M.; Kickelbick, G.; Vallan , T.; Ho mann, H.; Pakula, T.,
Mac omolecules 1999, 32, (26), 8716-8724.
60. Ca ado, K. A.; Deca eau, A.; Pe i , S.; Be gaya, F.; Lagaly, G.; Be gaya, F.;
Benny, K. G., Chap e 4 Syn he ic Clay Mine als and Pu i ica ion o Na u al Clays. In
Re e ences
80
De elopmen s in Clay Science Handbook o Clay Science, Else ie : 2006; Vol. 1s ed.,
pp 115-139.
61. Plampe , F. A.; Ruppel, M.; Schmalz, A.; Bo iso , O.; Ballau , M.; Mülle , A. H.
E., Mac omolecules 2007, 40, (23), 8361-8366.
62. O al, A.; Shahwan, T.; Gule , C., Jou nal o Ma e ials Resea ch 2008, 23, (12),
3316-3322.
63. Wang, B. X.; Zhao, X. P., Jou nal o Ma e ials Chemis y 2003, 13, (9), 2248-
2253.
64. Hwang, S. J.; Chen, C. Y.; Zones, S. I., Jou nal O Physical Chemis y B 2004,
108, (48), 18535-18546.
65. Yamamo o, S.; Ejaz, M.; Tsujii, Y.; Fukuda, T., Mac omolecules 2000, 33, (15),
5608-5612.
66. Madejo a, J.; Keckes, J.; Paalko a, H.; Komadel, P., Clay Mine als 2002, 37,
(2), 377-388.
67. Ejaz, M.; Tsujii, Y.; Fukuda, T., Polyme 2001, 42, (16), 6811-6815.
68. Husseman, M.; Malms ”m, E. E.; McNama a, M.; Ma e, M.; Mece eyes, D.;
Benoi , D. G.; Hed ick, J. L.; Mansky, P.; Huang, E.; Russell, T. P.; Hawke , C. J.,
Mac omolecules 1999, 32, (5), 1424-1431.
69. Fische , B.; Ziadeh, M.; P a , A.; B eu, J.; Al s „d , V., Polyme 2012, 53, (15),
3230-3237.
70. Liaw, J. H.; Hsueh, T. Y.; Tan, T. S.; Wang, Y.; Chiao, S. M., Polyme
In e na ional 2007, 56, (8), 1045-1052.
71. Meneghe i, P.; Qu ubuddin, S., The mochimica Ac a 2006, 442, (1–2), 74-
77.
72. Shin, Y. W.; Robe s, J. E.; San o e, M., Jou nal o Colloid and In e ace Science
2001, 244, (1), 190-199.
73. A i a, T.; Buback, M.; Vana, P., Mac omolecules 2005, 38, (19), 7935-7943.