Film o ming hyb id ac ylic/ZnO la exes wi h
excellen UV abso p ion capaci y
Mi en Agui e a, Ma iano Ba ado b, Maide I u ondobei ia c, Ana Oka iz d, Te esa
Gu aya c, Ma ia Paulis a, Jose Ramon Leiza a
a POLYMAT, Kimika Aplika ua saila, Kimika Zien zien Fakul a ea, Uni e si y o he
Basque Coun y UPV/EHU, Joxe Ma i Ko a Zen oa, Tolosa Hi ibidea 72, 20018
Donos ia-San Sebas ián, Spain
b SGIke , Uni e si y o he Basque Coun y UPV/EHU, Joxe Ma i Ko a Zen oa,
Tolosa Hi ibidea 72, 20018 Donos ia-San Sebas ián, Spain
c eMERGE and Depa men o Mining and Me allu gical Enginee ing and Ma e ials
Science, Uni e si y o he Basque Coun y UPV/EHU, P_ Ra ael Mo eno Pi xi xi, 3,
48013 Bilbao, Spain
d eMERGE and Depa men o Applied Physics I, Uni e si y o he Basque Coun y
UPV/EHU, P_ Ra ael Mo eno Pi xi xi, 3, 48013 Bilbao, Spain
Abs ac
Ac ylic/ZnO hyb id la exes we e syn hesized h ough a wo-s ep emulsion
polyme iza ion p ocess. Fi s , a hyb id seed was syn hesized by miniemulsion
polyme iza ion, which con ained all he hyd ophobically modi ied ZnO nanopa icles.
Subsequen ly, his hyb id seed was employed in a seeded semiba ch emulsion
copolyme iza ion yielding high solids con en hyb id la exes (40 w %). C yo-
ansmission elec on mic oscopy (c yo-TEM) demons a ed ha he dispe sion o he
ZnO nanopa icles in he ini ial miniemulsion was no homogeneous, which led o a
hyb id seed wi h wo popula ions, polyme pa icles con aining ZnO and p is ine polyme
pa icles. A e he second s ep o polyme iza ion ba ely he same mo phology was
ob ained. Ne e heless, i was p o ed by elec on omog aphy (3D-TEM) ha he ZnO
nanopa icles we e encapsula ed in he polyme pa icles. The hyb id ilms con aining
ZnO p esen ed a supe io UV abso p ion capaci y han hei coun e pa hyb id
ac ylic/CeO2 p epa ed ollowing he same s a egy.
This is he accep ed manusc ip o he a icle ha appea ed in inal o m in Chemical Enginee ing Jou nal 270 : 300-308 (2015), which has
been published in inal o m a h ps://doi.o g/10.1016/j.cej.2015.02.025. © 2015 Else ie unde CC BY-NC-ND license (h p://
c ea i ecommons.o g/licenses/by-nc-nd/4.0/)
1. In oduc ion
In he las wo decades he inco po a ion o nanosized ino ganic ma e ials in o o ganic
polyme ma ix has a ac ed he in e es o scien is s in academia and indus y. This is
mainly due o he syne ge ic e ec s obse ed when combining he p ope ies o he
ino ganic ma e ials (ine ness, chemical esis ance, empe a u e esis ance, wea he and
UV esis ance, ha dness..) wi h he polyme ic ones (p ocessabili y, lexibili y, oughness,
gloss, cu ing…) [1].
Miniemulsion polyme iza ion is a powe ul echnique o ob ain hyb id o ganic–ino ganic
ma e ials wi h encapsula ed mo phology. This mo phology is a ac i e due o he
ad an ages ha i p o ides o he inal hyb id ma e ial. Fo ins ance, be e dispe sion o
he ino ganic ma e ial in he polyme ic ma ix, imp o ed s abili y agains agg ega ion o
he nano ille s, p o ec ion o he ille om he ou side componen s (en i onmen ) o
imp o emen s in many p ope ies such as mechanical, op ical o ba ie [2], [3], [4], [5],
[6]. Howe e , he e a e h ee main aspec s o ake in o conside a ion when encapsula ing
ino ganic nanopa icles by miniemulsion polyme iza ion. The i s one is he we abili y
o he nanopa icles in he monome phase. This equi es he modi ica ion o he na u ally
hyd ophilic su ace o he ino ganic ma e ial. The second one is he emulsi ica ion
p ocess, which will de ine he size o he monome d ople s. And he las one, he aspec
a io and he size o he nano ille [7], [8], [9], [10], [11]. The encapsula ion o he
ino ganic ma e ial by miniemulsion polyme iza ion is no always achie ed; i s success
being go e ned by he modynamic and kine ic conside a ions [12], [13].
Recen ly, we ha e shown ha CeO2 nanopa icles we e success ully encapsula ed in o
high solids con en ac ylic la ex binde s by means o a wo-s ep semiba ch polyme iza ion
s a egy [14]. The i s s ep consis ed on he p oduc ion o a hyb id seed by ba ch
miniemulsion polyme iza ion using hyd ophobically modi ied CeO2 nanopa icles, and
he second s ep comp ised a seeded semiba ch p ocess whe e he eed was ei he a
p eemulsion o monome , o low CeO2 loadings [14], [15], o a hyb id miniemulsion,
o highe CeO2 loadings [16].
This wo-s ep semiba ch polyme iza ion s a egy can be used o encapsula e o he me al
oxides o ino ganic ma e ials wi h po en ial applica ions in ields ha include UV-
blocking clea coa s, sola cells and an ico osi e coa ings among o he s. Ano he
in e es ing me al oxide nanopa icle ha can be inco po a ed in o polyme ma ices is zinc
oxide (ZnO). ZnO nanopa icles p esen a wide band gap ene gy (3.4 eV) and la ge
exci a ion binding ene gy (60 mV), which make hem ideal o ca aly ic, op ical and
elec ical applica ions [17], [18], [19], [20], [21].
ZnO nanopa icles ha e been inco po a ed in o o ganic–ino ganic nanocomposi e
wa e bo ne dispe sions using di e en polyme iza ion s a egies and polyme ic ma ices
[19], [22], [23], [24], [25], [26] and o a wide ange o applica ions. Dhoke e al. [25]
di ec ly added a dispe sion o ZnO nanopa icles o an aqueous comme cial alkyd esin
dispe sion and obse ed ha small amoun s (0.01–0.03 w %) o ZnO nanopa icles
imp o ed co osion and mechanical p ope ies (sc a ch and ab asion esis ances). Xiong
e al. [26] blended s y ene/bu yl ac yla e la exes and nanoZnO dispe sions in subs an ially
highe amoun s (up o 9 w %) and analyzed he e ec o ZnO pa icle size on mechanical
and op ical (UV and NIR shielding) p ope ies. They ound ha he be e he dispe sion
o ZnO in he ma ix and he smalle he size o ZnO nanopa icles, he be e he
p ope ies achie ed by he hyb id composi e ma e ials.
O he au ho s used ZnO nanopa icles as Picke ing s abilize s in oil-in-wa e dispe sions.
Thus, Chen e al. [23] showed ha he mo phology o ZnO/PS hyb id dispe sions changed
depending on he hyd ophilici y o he ini ia o used (KPS s AIBN), esul ing in
Picke ing s abilized pa icles when AIBN was used. Upon d ying he hyb id la exes
showed a pH-bu e ing abili y. Also o pH-bu e ing applica ions Jeng e al. [24]
syn hesized oil-in-wa e Picke ing s abilized polyanyline dispe sions using THF o
Toluene as oil-phase.
Modi ied ZnO nanopa icles ha e been also inco po a ed in o polyme ic dispe sions
using miniemulsion polyme iza ion. Zhang e al. [22] used ZnO nanopa icles modi ied
wi h me hoxyp opyl silane (MPS) in he miniemulsion polyme iza ion o s y ene. Low
solids con en hyb id la exes wi h encapsula ed and homogeneous dis ibu ions o ZnO
in he polyme pa icles we e ob ained, when a high enough amoun o MPS was used o
modi y he ZnO. When lowe MPS amoun s we e used he nanopa icles emained a he
polyme pa icle-aqueous phase in e ace like in Picke ing s abilized sys ems. Bo h
mo phologies p esen ed luminescence p ope ies ha we e no p esen when ba e ZnO
nanopa icles we e dispe sed in a PS la ex.
Lu e al. [19] syn hesized also hyb id PS/ZnO la exes by miniemulsion polyme iza ion
using ac ylic acid as comonome and compa ibilize o he ZnO nanopa icles wi h he
PS. In e es ingly, he au ho s ound ha when he polyme iza ion was done in he
p esence o co on ab ic, he UV-blocking capaci y o he co on ab ic was subs an ially
imp o ed, wi h espec o blends o he ab ic and he hyb id la ex o he ab ic and ZnO
nanopa icles. The inc eased pe o mance was a ibu ed o he in e ac ion o he
ca boxylic g oups o he hyb id pa icles and he hyd oxyl g oups o he co on.
In his wo k hyd ophobically modi ied ZnO was inco po a ed in o a ilm o ming clea
coa ac ylic la ex binde by he wo-s ep seeded semiba ch polyme iza ion s a egy
de eloped ecen ly by ou g oup o CeO2. La exes wi h 40 w % solids con en we e
p oduced and he UV-blocking capaci y o he anspa en hyb id ilms cas ed was
assessed and compa ed wi h ac ylic/CeO2 ilms. Fu he mo e, he mo phology o he
hyb id pa icles was assessed by elec on omog aphy (3D-TEM) and unlike in p e ious
wo ks, i was unambiguously p o ed ha mos o he ZnO agg ega es we e encapsula ed
in he polyme pa icles.
2. Expe imen al
2.1. Ma e ials
The hyd ophobic ZnO nanopa icles dispe sion (in me hoxyp opyl ace a e) was kindly
supplied by Al ana (Ge many) wi h 40 w % o nanopa icles. The dispe sion was d ied
(a 60 °C o 2 days) and he esul ing powde g inded. Me hyl me hac yla e, MMA
(Quimid oga) and n-Bu yl ac yla e, BA (Quimid oga) we e used as ecei ed. Po assium
pe sul a e (KPS, Ald ich) ini ia o was used as supplied. Dodecyl diphenyloxide
disul ona e (Dow ax 2A1 45%, Dow Chemical) and n-Oc adecyl ac yla e (OA, 97%,
Ald ich) we e used as an anionic emulsi ie and as a co-s abilize , espec i ely. Deionized
wa e (MiliQ quali y) was used in he miniemulsions and hyd oquinone (Ald ich) was
used o s opping he eac ion in he samples wi hd awn om he eac o .
2.2. Cha ac e iza ion me hods
ZnO nanopa icle, polyme pa icle and monome d ople size dis ibu ions we e
measu ed by Dynamic Ligh Sca e ing (DLS) using a Ze asize Nano Se ies (Mal e n
Ins umen ). Fo his analysis, a ac ion o la ex (o miniemulsion) was dilu ed wi h
deionized wa e , whe eas in he case o he ZnO nanopa icles dispe sions hey we e
measu ed as ecei ed. The epo ed a e age pa icle size (d ople size) alues ep esen
an a e age o wo epea ed measu emen s. The s abili y o he miniemulsions was s udied
by measu ing he ligh backsca e ed a 60° in he Tu biscan Lab expe equipmen .
Con e sion was measu ed by g a ime ic analysis.
The mo phology and pa icle size dis ibu ion (PSD) o he la ex pa icles as well as he
mo phology o he ilms cas ed om he la exes we e analyzed by T ansmission Elec on
Mic oscopy (TEM), TECNAI G2 20 TWIN (FEI), ope a ing a an accele a ing ol age o
200 keV in a b igh - ield image mode. The samples we e dilu ed and d ied using a UV
lamp. The ilms cas ed a oom empe a u e we e immed using an ul amic o ome de ice
a −40 °C (Leica EMFC6) equipped wi h a diamond kni e. The ul a hin sec ions
(100 nm) we e placed on 300 mesh coppe g ids and we e obse ed wi hou u he
s aining. 500 polyme and ZnO pa icles we e coun ed and measu ed using a
comme cially a ailable so wa e (Image P o Plus 7.0).
The p epa a ion o he miniemulsion samples o c yo-TEM, in ol ed i s a i i ica ion
p ocedu e on a FEI Vi obo Ma k IV (Eindho en, The Ne he lands). One d op o he
sample solu ion (∼3 μL) was deposi ed in a coppe g id (300 mesh Quan i olis,
hyd ophilized by glow-discha ged ea men jus p io o use) wi hin he en i onmen al
chambe o he Vi obo and he excess liquid was blo ed away. The sample was sho
in o mel ing (liquid) e hane and ans e ed o a Single Til C yo-Holde . The C yo-
Holde was p e iously p epa ed by 655 Tu bo Pumping S a ion o main ain he sample
bellow – 170 °C and o minimize he he mal de i e. The sample was examined in he
TECNAI G2 20 TWIN (FEI) men ioned abo e, ope a ing a an accele a ing ol age o
200 keV in a b igh - ield and low-dose image mode.
In o de o assess he deg ee o encapsula ion o he ZnO, a 3D omog aphic
econs uc ion o a ep esen a i e a ea o he sample was ca ied ou using mic og aphs
acqui ed in a JEOL JEM-1230 he mionic emission TEM mic oscope a 100 keV wi h a
digi al came a in low dose condi ions. The il se ies was acqui ed om −60° o +60°
e e y 2°, a nominal magni ica ion o ×20 K and ×30 K. The images we e hen aligned
using he IMOD 4.3.4 so wa e package [27]; and he aligned il se ies we e
econs uc ed using he WBP econs uc ion algo i hm wi h he TOMO3D so wa e [28].
A e he econs uc ion, a pos -p ocessing o he images was ca ied ou in Fiji [27].
2.3. Miniemulsion p epa a ion and seeded semiba ch polyme iza ion
In a ypical o mula ion 8.7 g o ZnO dispe sion (5 weigh based on monome s pe cen ,
wbm%, o ZnO) was added o MMA (30 g), BA (30 g) and OA (2.47 g) o p oduce he
oil phase; i was s i ed o 15 min unde magne ic agi a ion. On he o he hand, he wa e
phase was p oduced by mixing 1.33 g o Dow ax 2A1 wi h 140 g o wa e . Then bo h
phases we e mixed o 15 min and soni ied o 15 min (ope a ing a 8-ou pu con ol and
80% du y cycle in an ice ba h and unde magne ic s i ing) o p oduce he miniemulsion.
The p e iously p epa ed 30 w % solids con en (SC) miniemulsions we e polyme ized
ba chwise in a 1 L glass jacke ed eac o i ed wi h a e lux condense , sampling de ice,
N2 inle and a s i e o a ing a 150 pm. The miniemulsion was cha ged in he eac o
and a e eaching he desi ed empe a u e (75 °C) a sho o KPS ini ia o (0.3 g) was
added. The eac ion was ca ied ou o hal an hou . Once he seed was p oduced, ano he
sho o KPS (1 g) was added o he eac o and he eeding o a p eemulsion (81.4 g
MMA, 81.4 g BA, 3.6 g Dow ax 2A1 and 187.2 g o wa e ) con aining he es o he
monome needed o each 40 w % SC was s a ed. The p eemulsion was ed o 4 h and
he eac ion mix u e was cooked o one mo e hou a 90 °C.
3. Resul s and discussion
3.1. ZnO nanopa icles we abili y
As i has been explained in he in oduc ion, he we abili y o he nanopa icles in he
monome mix u e is a key aspec a ec ing conside ably he inal mo phology o he
hyb id ma e ial. Fo ha , 1 wbm% o ZnO nanopa icles we e dispe sed in he monome
mix u e composed o MMA/BA (50/50 w %). Fig. 1 p esen s he hyb id dispe sion
ob ained.
Fig. 1. Dispe sion o he ZnO nanopa icles in MMA/BA 50/50 w % monome mix u e.
ZnO nanopa icles did no sedimen in he bo om o he lask, bu as i can be seen he
dispe sion was opaque. The eason can be ound in he ZnO pa icle size. Acco ding o
he DLS, he a e age diame e o he ZnO nanopa icles was 75 nm. Fig. 2 p esen s he
TEM mic og aphs o his dispe sion. The mic og aphs show ha indi idual ZnO
nanopa icles (25–35 nm) agg ega ed o o m la ge size en i ies in ag eemen wi h he
a e age alue measu ed by DLS.
Fig. 2. TEM mic og aphs o 1 w % ZnO nanopa icles in MMA/BA (50/50 w %).
3.2. Polyme iza ion o he hyb id la exes
The p e iously desc ibed wo-s ep seeded semiba ch emulsion copolyme iza ion s a egy
was applied o p oduce hyb id ac ylic/ZnO la exes. In o de o p oduce hyb id la exes
wi h he highes ZnO nanopa icle inco po a ion e iciency and he lowes coagulum
con en , se e al p ocess a iables we e a ied such as he way ZnO nanopa icles we e
inco po a ed (di ec ly as ecei ed; dispe sed in me hoxyp opyl ace a e o as powde a e
d ying ou o 2 days a 60 °C) o he emulsi ie amoun used in he seed polyme iza ion
(1 o 2 wbm%). The ob ained coagulum alues we e in good ag eemen wi h he
miniemulsion s abili y measu emen s (see Suppo ing In o ma ion), showing ha he
eac ion ca ied ou wi h 1 wbm% o Dow ax in he seed and adding he ZnO di ec ly as
ecei ed (in he dispe sion wi h me hoxyp opyl ace a e) p esen ed good miniemulsion
s abili y and no coagulum in he inal la ex.
The inal a e age polyme pa icle size o he hyb id la ex (measu ed by DLS) was
392 nm, almos 100 nm highe han he one ha should ha e been ob ained om an
homogeneous dis ibu ion o he ed monome among he seed pa icles (dpseed: 152 nm).
This is an indica ion o pa icle agg ega ion/coagula ion du ing he eeding s ep ha is
analyzed below wi h he help o TEM measu emen s. Ano he in e es ing esul was ha
he gel con en was 31% in he inal la ex. P e ious wo ks ha e shown ha o a ypical
seeded semiba ch emulsion polyme iza ion o mula ion o MMA/BA 50/50 w %, a e
he cooking pe iod he gel con en ha dly exceeds 10–15% [29], [30]. The highe gel
con en ob ained in his p ocess may be associa ed o he abo e men ioned pa ial
coagula ion o pa icles (i.e., la ge sizes o he polyme pa icles), which would inc ease
he a e age numbe o adicals pe pa icle, he p obabili y o bimolecula e mina ion
and hence o gel o ma ion [31].
3.3. Mo phology o he ac ylic/ZnO hyb id la exes
Fig. 3 p esen s he TEM mic og aphs o he polyme iza ion discussed abo e. The
mic og aphs p esen he hyb id MMA/BA/ZnO hyb id nanod ople dispe sion (a), he
seed hyb id la ex (b) and he inal hyb id la ex a e he semiba ch addi ion o he
p eemulsion (c).
Fig. 3. (a) C yo-TEM mic og aph o he ac ylic/ZnO hyb id miniemulsion, (b) TEM
mic og aph o he hyb id ac ylic/ZnO seed and (c) TEM mic og aph o he hyb id
ac ylic/ZnO inal la ex.
As i can be seen, he monome d ople size dis ibu ion was e y b oad (Figs. 3 and 4a).
O e all, 50% (see Fig. 3a) o he d ople s con ained ZnO nanopa icles o agg ega es.
ZnO nanopa icles appea ed agg ega ed as had al eady been seen in he monome mix u e
(see Fig. 2). The e o e he sonica ion p ocess led o a e y he e ogeneous dis ibu ion o
he ZnO agg ega es; bo h la ge and small d ople s can be iden i ied wi h and wi hou ZnO.
Bou gea -Lami e al. [32] obse ed a simila ype o dis ibu ion o silica nanopa icles
in MMA and BA monome s. They s a ed ha a d ople wi h nanopa icles can be
agmen a ed gi ing smalle d ople sizes, which some o hem migh con ain he
nanopa icles and o he s no . No e ha he p oduc ion o a nanod ople dispe sion wi h
each d ople con aining one nanopa icle o agg ega e o he ino ganic ma e ial is no an
easy ask. Ma ching he numbe o d ople s and he numbe o ino ganic nanopa icles
equi es an accu a e con ol o he size o he nanod ople s, which is con olled by a la ge
numbe o p ocess a iables (e.g., he ene gy applied o he coa se emulsion, he iscosi y
o he o ganic phase, he s abili y o he o med nanod ople s wi h espec o Os wald
ipening and coalescence ha depends on he composi ion o he o ganic phase (e.g.,
cos abilize and hyd ophobe used) and he su ac an amoun and ype) ha makes his
ask challenging in many ci cums ances. In compa ison wi h he mo phology o hyb id
miniemulsions p epa ed wi h CeO2 [33], [34], hese ob ained wi h ZnO showed a less
homogeneous dis ibu ion o he ZnO and a highe agg ega ion o he nanopa icles.
Fig. 4. PSD measu ed using TEM mic og aphs o he (a) miniemulsion d ople s, (b) seed
pa icles and (c) inal pa icles.
Fig. 3b p esen s he mo phology o he hyb id seed pa icles ob ained a e polyme izing
he miniemulsion o 30 min. Two main popula ions can be dis inguished, a popula ion
o la ge polyme pa icles con aining ZnO and a popula ion wi h smalle pa icles wi hou
ZnO. The compa ison o he miniemulsion d ople size dis ibu ion (Fig. 4a) and he PSD
o he seed la ex (Fig. 4b) indica es ha a subs an ial ac ion o small d ople s did no
nuclea e, bu deg aded (di using he monome o he exis ing pa icles) inc easing he
size o he exis ing polyme pa icles. The numbe o pa icles con aining ZnO was
smalle (33%) han he numbe o monome d ople s ha con ained ZnO, which is an
indica ion ha in addi ion o he ans e o monome om small d ople s o la ge ones
(due o Os wald ipening), he e was also coagula ion be ween d ople s con aining ZnO
agg ega es. Figs. 3c and 4c p esen he TEM mic og aph and PSD o he inal la ex. The
igu es clea ly indica e ha g ow h occu ed by polyme iza ion o he en e ing monome
in he seed pa icles and coagula ion/agg ega ion o he pa icles. The a e age pa icle
size was well abo e ha expec ed in absence o coagula ion and he TEM analysis (Fig.
4c) shows he p esence o e y la ge pa icles (600–1000 nm) con aining ZnO. The
pe cen age o hese polyme pa icles (21%) was sligh ly smalle han hose ound in he
seed pa icles p o ing ha he coagula ion among polyme pa icles con aining ZnO
occu ed.
The mo phology o he polyme pa icles con aining ZnO was analyzed in u he de ail
by using elec on omog aphy (3D-TEM). This assessmen will allow o unambiguously
de e mine he loca ion o he ZnO nanopa icle agg ega es in he inal la ex; namely, i
he agg ega es a e ully encapsula ed in he polyme pa icles o no .
Two di e en a eas o he hyb id la ex we e analyzed. In he i s one, a single polyme
pa icle was analyzed which con ained mo e han one ZnO nanopa icle (see Fig. 5a),
whe eas in he second egion nine polyme pa icles wi h ou ZnO agg ega es (Fig. 5b)
we e s udied. Each agg ega e has been numbe ed o simpli y he ollowing discussion.
Fig. 5. TEM mic og aphs o wo selec ed a eas o he hyb id ac ylic/ZnO la ex. (a)
Specimen wi h a single polyme pa icle con aining ZnO. (b) Specimen wi h nine polyme
pa icles and h ee o hem con aining ZnO.
Tomog aphic econs uc ions a e desc ibed in he OXYZ coo dina es (Fig. 6). The OZ
axis coincides wi h he di ec ion o he beam and he OX axis is he il ing axis. In o de
o isualize his 3D objec , di e en 2D sec ions a e ep esen ed in he Fig. 7, Fig. 8, Fig.
9, Fig. 10. Aiming a he de e mina ion o he loca ion o he ZnO nanopa icles inside
he polyme pa icle, hei posi ion in di e en 2D sec ions o planes, commonly known
as o hoslices was analyzed.
Fig. 6. Schema ic ep esen a ion o he X, Y and Z axis posi ion, elec on beam di ec ion,
he di ec ion in which he sample was il ed and he dimension o he chosen sample’s
a ea.
Fig. 7. O hogonal sec ions o he econs uc ed single pa icle o Fig. 5a. OXY sec ions
co esponding o he planes indica ed in he OYZ sec ion wi h whi e lines. (a) Z = 26 nm;
(b) Z = 86 nm; (c) Z = 156 nm; (d) Z = 229 nm; (e) Z = 298 nm; ( ) Z = 367 nm; (g)
Z = 420 nm.
Sci. 90 (2003) 1923–1931.
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