European Polymer Journal 45 (2009) 2487–2493

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Macromolecular Nanotechnology

Epoxy-nanocomposites containing exfoliated zirconium phosphate:

Preparation via cationic photopolymerisation and
physicochemical characterisation
R. Bongiovanni a, M. Casciola b,*, A. Di Gianni a, A. Donnadio b, G. Malucelli a
a
Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino c.Duca degli Abruzzi 24, 10129 Torino, Italy
b
Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, 06123 Perugia, Italy

MACROMOLECULAR NANOTECHNOLOGY
a r t i c l e i n f o a b s t r a c t

Article history: Gels of exfoliated a-zirconium phosphate in 3,4-epoxycyclohexylmethyl-30 ,40 -epoxycyclo-

Received 18 March 2009 hexane carboxylate (hereafter BCDE) were polymerised by a UV-induced process and the
Received in revised form 19 June 2009 resulting nanocomposites were characterised by TEM, X-ray diffraction, thermogravimetric
Accepted 28 June 2009
analysis and dynamic-mechanical thermal analysis. Real-time FT-IR spectroscopy was used
Available online 2 July 2009
to investigate the photopolymerisation kinetics. The polymerisation rate of the gels is fas-
ter than that of neat BCDE, especially when the filler is functionalised with aminoalcohols
Keywords:
(HO(CH2)nNH2, with n = 3, 4, 5). The composites exhibit lower Tg values in comparison with
Photochemical processing
Dynamic mechanical analysis
neat polymerised BCDE. Because of the barrier effect towards oxygen diffusion due to the
Thermogravimetric analysis high aspect ratio of the filler particles, all composites also exhibit enhanced thermal
Epoxy nanocomposite stability.
Zirconium phosphate Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction fully employed to perform this kind of nanocomposite

preparation [4]. After dispersion of the clay in the liquid
In recent years, polymer nanocomposites have attracted monomer and upon irradiation in the presence of a suit-
great interest because of their excellent performances able photoinitiator, polymeric thermoset matrices can be
compared to conventional composites. They usually consist built through a process which is fast, does not use solvents
of nanosized mineral particles dispersed into a polymeric and does not require any heating. In the literature some
matrix: among them polymer–clay nanocomposites are examples of UV-cured nanocomposites based on modified
within the most explored, since the early works on polyam- montmorillonites and different polymeric matrices
ide 6–montmorillonite hybrids by the Toyota researchers (mainly acrylates) are described [5]. Two main types of
[1]. The polymer–clay nanocomposites consist of clay nano- structures are obtained when the layered clays are present
layers dispersed in a polymeric matrix. For their preparation within the crosslinked polymers: the intercalated struc-
several strategies have been developed: the filler can be di- ture, in which the polymer chains are intercalated between
rectly dispersed in the polymer melt or in a polymer solu- the silicate layers and form an ordered multilayer mor-
tion, alternatively it is swollen within the liquid monomer phology with alternating polymeric and inorganic layers;
and the polymer formation can occur in between the inter- the exfoliated structure, in which the silicate layers are
calated or exfoliated sheets [2,3]. The latter method is called completely and uniformly dispersed as single platelets in
in situ intercalative polymerisation. a continuous polymer matrix.
The UV-curing technique, which is widely used to pre- In the last years, in the field of nanocomposites, increas-
pare thermoset coatings, adhesives, inks, can be success- ing attention has been directed towards the use of syn-
thetic fillers, at least for research purpose if not as an
* Corresponding author. Fax: +39 075 585 5566.
alternative to clays. Among the many layered fillers, a-zir-
E-mail address: [email protected] (M. Casciola). conium phosphate (Zr(HPO4)2, hereafter ZrP) is particu-

0014-3057/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2009.06.022
 2488 R. Bongiovanni et al. / European Polymer Journal 45 (2009) 2487–2493

larly interesting. It was first synthesized by Clearfield [6] 2. Experimental

and since then extensive research has shown that tailor-
made ZrP can be prepared: not only size and shape can 2.1. Chemicals
be controlled by altering the reaction conditions, but also
its surface can be easily modified to make it compatible The bis-cycloaliphatic diepoxy monomer, 3,4-epox-
to different polymers. Up to now Nafion, sulfonated polye- ycyclohexylmethyl-30 ,40 -epoxycyclohexane carboxylate
therketones, polyethyleneoxide, polyacrylamide and poly- (BCDE) was supplied from Cytec Inc. (USA). A sulfonium
vinylidene fluoride has been used as polymer matrices salt was used as photoinitiator: Cyracure UVI-6974, which
(see [7–14] and references therein). Also epoxy nanocom- is a mixture of triarylsulfonium hexafluoro antimonate
posites were recently prepared [15–20], using a conven- salts in 50% solution of propylene carbonate, was kindly gi-
tional process: both the ZrP and the polymer precursor ven by Dow Chemicals. It was used as the photoinitiator at
(i.e., the epoxy monomer) were first dispersed in a solvent, 2 wt%. All other reagents were supplied by Aldrich and
then after its removal the curing agent was added and the were used as received without further purification. The
mixture was cured in a oven for few hours. structures of BCDE and of the photoinitiator are shown in
In the present work the preparation of epoxy-nanocom- Fig. 1.
posites containing ZrP is made using the UV-curing process,
which is much faster than thermal curing; in addition the 2.2. Preparation of ZrP, its modification by propylamine and
novelty of this process is based on the few reports that aminoalcohols, dispersion in the epoxy monomer
investigate the in situ polymerisation of epoxides by UV
light in the presence of either natural lamellar silicates or Crystalline ZrP was prepared by the direct precipitation
organophilic montmorillonites [21–24], none of them con- method in the presence of hydrofluoric acid [28].
MACROMOLECULAR NANOTECHNOLOGY

cerning UV-cured materials containing synthetic ZrP. A colloidal dispersion of a-ZrP intercalated with propyl-
In order to prepare UV-cured epoxy composites, ZrP amine (ZrPPrN, where PrN = C3H7NH2) in water was pre-
was properly modified with different aminoalcohols hav- pared according to Ref. [29] by titrating a suspension of
ing different molecular weight. Besides assuring a better 0.5 g ZrP in 33 mL water with 16.6 mL of 0.1 M propylamine.
compatibility with the epoxy matrix, the presence of hy- The dispersion was treated with 6 mL of 1 M HCl (final
droxy terminated modifier is interesting. In fact upon irra- pH < 2) so as to regenerate the hydrogen form of zirconium
diation, in the presence of a suitable photoinitiator, phosphate. The solid was separated from the solution and
epoxides polymerise following a cationic mechanism: in washed with water under vigorous stirring. A gelatinous
the presence of hydroxyl groups a chain transfer reaction precipitate settled by centrifugation at 3000 rpm. Washing
takes place, which changes the reaction kinetics [25–27]. was repeated up to elimination of chloride ions. The gel thus
The paper therefore considers at first the effect of ZrP, in obtained contained 1.5–2.5 wt% anhydrous ZrP.
particular its organic modifier, on the kinetics of the poly- Functionalization of ZrP with aminoalcohols (NH2(CH2)n
merisation process of a bis-cycloaliphatic diepoxy resin, OH, with n = 3, 4, 5) was carried out by slowly adding a suit-
(3,4-epoxycyclohexylmethyl-30 ,40 -epoxycyclohexane car- able volume of 0.1 M aqueous solutions of aminoalcohol to
boxylate), then reports the characterisation of the resulting the ZrP/H2O gel so that the NH2(CH2)nOH/Zr molar ratio was
composites by means of X-ray diffraction, transmission 0.6. Aminoalcohol functionalised ZrP will be hereafter indi-
electron microscopy (TEM), thermogravimetric analysis cated as ZrPAn, where n is the number of carbon atoms of
and dynamic-mechanical thermal analysis. the aminoalcohol.

Fig. 1. Structure of BCDE and of the photoinitiator.

 R. Bongiovanni et al. / European Polymer Journal 45 (2009) 2487–2493 2489

To obtain gels of ZrP or ZrPAn in tetrahydrofuran (THF), copper grid. The glass transition temperature (Tg) of the
an amount of the corresponding gel in water, containing x samples was determined by dynamic-mechanical thermal
mL water, was washed three times with 4x mL of THF. analysis (DMTA) on a MK III Rheometrics Scientific Instru-
After each washing, the gel was separated from the solu- ment at 1.0 Hz frequency in the tensile configuration and
tion by centrifuging at 3000 rpm. Gels of ZrP or ZrPAn in heating rate of 5.0 °C min1. The size of the specimen
BCDE were prepared by mixing suitable volumes of THF was about 40  5  2 mm. The storage modulus, E0 , and
gels and BCDE and subsequent THF evaporation at 40 °C the loss factor, tan d, were measured as a function of tem-
in a rotavapor. The volumes of THF gels and BCDE were perature in the range 20–250 °C.
chosen so that the filler content was 3 wt% after THF
evaporation. 3. Results and discussion

2.3. Film preparation 3.1. Preparation of nanocomposites and kinetics

measurements
The BCDE gels were added of 2% of photoinitiator; then
they were coated onto a PET substrate using a 2 mm wire- Gels of exfoliated ZrP in water can be prepared through
wound applicator and exposed to UV irradiation. The cur- intercalation–deintercalation of propylamine in aqueous
ing reaction was performed under air with a medium pres- solution; water can then be replaced by a large variety of
sure Hg lamp (Italquartz, Milano, Italy), having a light organic solvents without significant alteration of the de-
intensity I = 25 mW/cm2 at the sample level. The mixtures gree of exfoliation of ZrP [7]. This allows to obtain easily
were exposed for 2 min to UV light. ZrP gels in organic solvents which are miscible with water.
If one wants to prepare ZrP gels in solvents that are immis-
cible with water, it is necessary to prepare an intermediate

MACROMOLECULAR NANOTECHNOLOGY
2.4. Kinetic investigations
gel in a solvent which is miscible with both water and the
The kinetics of the photopolymerisation was deter- final solvent. The gel solvent can also be a liquid monomer.
mined by real-time FT-IR spectroscopy, employing a Ther- In this case the gel can be polymerised and form nanocom-
mo - Nicolet 5700 apparatus (USA). The formulations were posites containing ZrP, if the original degree of exfoliation
coated onto a silicon wafer in a very thin layer (around is retained upon polymerisation.
10 lm). The samples were exposed simultaneously to the We followed this strategy in the present work. First ZrP
UV beam, which induces the polymerisation and to the IR gels in water were prepared as described in the experi-
beam, which analyses in situ the extent of the reaction. Be- mental section; functionalised ZrP was also prepared, by
cause the IR absorbance is proportional to the monomer addition of aminoalcohols NH2(CH2)nOH, with n = 3, 4, 5
concentration, conversion versus irradiation time profiles (ZrPAn). Gels of 3 wt% ZrP or ZrPAn in BCDE (which is
can be obtained. Epoxy group conversion was followed, immiscible with water) were then prepared by replacing
by monitoring the decrease in the absorbance due to epoxy water with THF in the starting gel and THF with BCDE in
groups in the region 760–780 cm1 and normalized it to the intermediate gel. The gels thus obtained could be cured
the ester band at 1670 cm1. A medium pressure mercury in the presence of a photoinitiator by UV irradiation.
lamp equipped with an optical waveguide was used to in- BCDE is a reactive monomer that can homopolymerise
duce the photopolymerisation (light intensity on the sur- via a cationic mechanism. This mechanism is widely dis-
face of the sample of about 10 mW/cm2). All the cussed in the literature [30]: the initiation depends on
polymerisation reactions were performed at room temper- Brönsted acids whose generation from a photoinitiator
ature at constant humidity (RH = 25–30%). (as the one used in this study) involves complex reactions;
the propagation is the addition of the epoxy monomer onto
2.5. Techniques the initial protonated species. Chain transfer reactions oc-
cur when hydroxyl groups are present in the form of alco-
The samples, after irradiation, were stored for one night hols, polyols, water or humidity [25,26]. In a chain transfer
at 50 °C before characterising them. The gel content of the reaction the hydroxyl attacks a carbon atom bonded to a
cured products was determined by measuring the weight positively charged epoxy function, binds to the polymeric
loss after 24 h of extraction at room temperature with chain thus blocking its growth and releases a proton which
chloroform according to the standard test method ASTM can catalyze the growth of a new chain (Fig. 2). As a conse-
D2765-84. quence, shorter polymer chains are formed, the resulting
X-ray powder patterns were collected with a Philips X- network is more flexible and the photopolymerisation
Pert PW3710 powder diffractometer using a Cu Ka radia- kinetics faster.
tion source. Thermogravimetric determinations were car- The photopolymerisation of BCDE and its gels contain-
ried out in an air flow by a NETZSCH STA 449 Jupiter ing ZrP or ZrPAn was followed by infrared spectroscopy,
thermal analyser connected to a NETZSCH TASC 414/3 A monitoring in real time, during the irradiation, the de-
controller at a heating rate of 10 °C min1. crease of the epoxy group concentration. The experimental
TEM analysis was carried out by an HRTEM JEOL, JEM- curves of the conversion as a function of irradiation time
2010 high resolution transmission electron microscope are plotted in Fig. 3. The curve concerning the neat BCDE
with an operating voltage of 200 kV. Ultrathin sections of shows that the rate of photopolymerisation is very high
about 100 nm were cut by a Power TOME X microtome at the beginning of the process, then it diminishes and
equipped with a diamond knife and placed on a 200-mesh the conversion reaches a nearly constant value of 40% in
 2490 R. Bongiovanni et al. / European Polymer Journal 45 (2009) 2487–2493

Fig. 2. Mechanism of the chain transfer reaction for a generic RC2H3O epoxide; R0 is the growing polymer chain.

2 min. Notwithstanding the limited conversion, the poly- lonite [23,35] and silica [36], we can suggest that also in
mer obtained is not tacky and is highly crosslinked as its this case the filler takes part of chain transfer reactions
insoluble fraction is quite high, around 88%. These results through its alcoholic or acidic OH groups.
are in agreement with the literature: differential scanning From Fig. 3 one can also observe that the initial photo-
calorimetry (DSC) and real time infrared spectroscopy data polymerisation rate of the BCDE/ZrPAn gels changes
MACROMOLECULAR NANOTECHNOLOGY

show that the conversion of BCDE is uncomplete and gen- according to the sequence: A5 > A4 > A3. Interestingly, the
erally is less than 50% [31]. As a cycloaliphatic epoxide, same sequence, but with higher conversions, was found
BCDE is more reactive in cationic polymerisation than for mixtures of BCDE and n-alkanols (CnH2n+1OH, with n
open-chain based epoxides, which in turn are more reac- from 3 to 5) where the alkanol amount, in moles, was
tive than glycidyl ethers and glycidyl esters [32,33]. The the same as the aminoalcohol amount in the correspond-
stop of the conversion was explained by Scott, in his work ing BCDE/ZrPAn gel (Fig. 4). The similar kinetic behaviour
on cationic polymerisation of vinyl esters [34]: he stated exhibited by the BCDE/ZrPAn gels and by the BCDE–n-alk-
that the photocuring process proceeds until vitrification, anol mixtures indicate that also in the gels the alcoholic
when the material reaches a glass transition temperature OH groups contribute significantly to the chain transfer
close to the photocuring temperature. reactions. As to the slower photopolymerisation rate of
Examining the conversion curves of BCDE when either the gels compared to the alcohol–BCDE mixtures, an obvi-
neat or functionalised ZrP are present (Fig. 3), it is evident ous explanation lays in the different viscosity of the sys-
that the photopolymerisation of BCDE is faster and the tems and different mobility of the reactive species.
conversion of the gels is about 10–20% higher compared Besides that, it can be pointed out that aminoalcohols are
to the conversion of neat BCDE. The photopolymerisation basic enough to deprotonate the monohydrogen phosphate
kinetics is therefore affected by the filler and by the type group of ZrP [37]: the surface of the filler particles bears
of organic modifier. The reasons can be many. First of all basic „PO groups whose negative charge is balanced by
the acidic groups of the filler surface can enhance the ring the protonated aminoalcohols. Therefore, in the presence
opening of the epoxide. Moreover, on the basis of past of the aminoalcohol functionalised ZrP, protons which cat-
results on the photopolymerisation of epoxides in the pres- alyze the polymerisation reaction may bind to the „PO
ence of other inorganic fillers such as sodium montmoril- groups of the filler surface, thus breaking the ionic bond
between „PO and ANH3+. On the basis of these consider-
ations, the aminoalcohol functionalised ZrP appears to
have a twofold role: if on one hand it contributes to the for-
mation of shorter polymer chains through the chain trans-
fer mechanism, on the other hand the protonation of the
surface sites decreases the catalyst concentration thus
making the reaction kinetics of the modified gels slower
in comparison with the mixtures of BCDE and free alcohols.

3.2. Nanocomposite characterisation

In order to characterise the composites obtained upon

irradiation, 100 lm thick samples were prepared. After a
2 min irradiation, they were subjected to a 24 h treatment
at 50 °C: at the end of this annealing the insoluble fraction
was found equal to 99–100%. This treatment was necessary
as the BCDE photopolymerisation is essentially non-termi-
Fig. 3. Photopolymerisation kinetic curves for neat BCDE and for BCDE/ nating and the active centers formed are long living, there-
ZrP and BCDE/ ZrPAn gels. fore there is a significant post-curing: Scranton also
 R. Bongiovanni et al. / European Polymer Journal 45 (2009) 2487–2493 2491

Fig. 4. Photopolymerisation kinetic curves for mixtures of BCDE and the

indicated n-alkanols.

showed that these long-living species can cause ‘shadow

MACROMOLECULAR NANOTECHNOLOGY
curing’, i.e., they can lead to the polymerisation of BCDE
monomers that were never exposed to light [38]. Both
post-curing and shadow curing can be enhanced by
increasing the temperature, but it is proved that these pro-
cesses take place also at 30–40 °C [38,39] or at tempera-
tures close to the photocuring temperature.
The composite samples obtained were homogeneous
and transparent. Fig. 5 shows TEM pictures of a ZrP based
composite. The ZrP particles are randomly dispersed in the
photopolymerised BCDE matrix and have thickness of few
nanometres with an extremely high aspect ratio. As the
thickness of a single ZrP layer does not exceed 1 nm, the
ZrP particles consist of stacks of few layers. Therefore the
nanocomposite can be defined as partially exfoliated. Fur-
ther information on the filler exfoliation is obtained by Fig. 5. TEM pictures for a sample of cured BCDE containing 3 wt%
comparing the X-ray powder patterns of a sample (A) pre- exfoliated ZrP.
pared from a BCDE/ZrP gel with the pattern of a sample (B)
obtained from a physical mixture of BCDE and the same
amount of ground microcrystalline ZrP (3 wt%). In Fig. 6
the pattern of sample B shows sharp characteristic reflec-
tions of ZrP at 2h = 11.6° and 25.3° [40,41] besides the
broad signal centred around 2h = 17.5°, which is due to
the polymeric matrix. In particular, the reflection at
2h = 11.6° arises from the stacking of the a-layers with
an interlayer distance, d, of 0.76 nm. This reflection is miss-
ing in the pattern of sample A, obtained from the gel: here
a weak peak appears at 2h = 8.9° (d = 0.98 nm) which may
be ascribed to BCDE intercalated ZrP. On the basis of the
width at half peak height, the thickness of the ZrP particles
is estimated by using the Debye–Scherrer formula to be
around 9 nm, in qualitative agreement with the TEM
picture. On the other hand, the X-ray powder pattern
of the ZrPA5 composite (Fig. 6) do not show any filler
Fig. 6. X-ray powder patterns of composites prepared from gels of BCDE/
reflection thus indicating that the aminoalcohol favours
ZrP (A), BCDE/ZrPA5 (C) and from a physical mixture of BCDE and 3 wt%
the filler dispersion in the organic solvents used for the ZrP (B).
gel preparation.
The thermal behaviour the cured BCDE oligomer and its
ZrP based composites was investigated by DMTA analysis of the maximum of the tan d vs. temperature curves. The
and thermogravimetric determinations. DMTA experi- spectra describing the cured BCDE and its homologue con-
ments allowed to determine Tg values from the position taining ZrPA3 are reported in Fig. 7, while all the Tg values
 2492 R. Bongiovanni et al. / European Polymer Journal 45 (2009) 2487–2493

are collected in Table 1. The presence of the filler decreases

the Tg from 212 °C for neat BCDE to 187 °C for BCDE/ZrP,
while the composites containing functionalised ZrP have
Tg values in the range 170–181 °C. These values are close
to those of samples prepared from the BCDE–n-alkanol
mixtures: the flexibilisation effect due to the functional-
ised filler is thus comparable with that arising from alka-
nols. This is a further confirmation that the filler interacts
with the growing cationic species through the alcoholic

Fig. 9. Temperature shift (T) of the weight loss curves of cured BCDE/
ZrPand BCDE/ZrPAn gels referred to the curve of cured BCDE as a
function of the number of carbon atoms of the aminoalcohols. DT is the
shift corresponding to 20% weight loss.

function and acts as a chain transfer agent, reducing the

chain length and enhancing the epoxy conversion.
MACROMOLECULAR NANOTECHNOLOGY

The presence of the nanosized filler resulted in all cases

in the shift towards higher temperatures of the thermal
decomposition of the polymer. As an example Fig. 8 shows
the weight loss in air of composites containing ZrP and
ZrPA5. The shift to high temperature of the thermogravi-
metric curves of the composites referred to the curve of
Fig. 7. Log E0 and tan d as a function of temperature for cured BCDE and
for the cured BCDE/ZrPA3 gel.
cured BCDE is maximum, in all cases, for a weight loss
around 20%. Fig. 9 shows that the temperature shift corre-
sponding to 20% weight loss increases with the number of
Table 1 carbon atoms of the aminoalcohol chain and reaches a
Glass transition temperatures for photopolymerised BCDE, for its compos- maximum of about 40 °C for NH2(CH2)5OH.
ites with ZrP and its mixtures with n-alkanols. It can be pointed out that no shift was observed for the
Sample Tg [°C] samples obtained from BCDE and alcohol mixtures where
BCDE 212
the amount of alcohol is equal to the amount of aminoalco-
BCDE/ZrP 187 hol used in the composites to functionalise ZrP. Thus the
BCDE/ZrPA3 170 enhanced thermal stability of the composites must be as-
BCDE/ZrPA4 171 cribed to the barrier effect towards oxygen diffusion deter-
BCDE/ZrPA5 184
mined by the presence of high aspect ratio filler particles.
BCDE + C3H7OH 178
BCDE + C4H9OH 192 Moreover, the dependence of the temperature shift on
BCDE + C5H10OH 182 the number of carbon atoms of the aminoalcohols appears
to be a consequence of the fact that the increasing length of
the alkyl chain favours the filler dispersion in the organic
solvents used for gel preparation and its retainment upon
polymerisation.

4. Conclusion

UV-curing of gels of exfoliated ZrP in BCDE allowed the

preparation of polymerised-BCDE/ZrP nanocomposites. In
comparison with the neat polymer, the presence of the
exfoliated filler makes the photopolymerisation kinetics
faster, enhances the thermal stability and lowers the glass
transition temperature of the composites. These changes
are even greater when ZrP is functionalised with aminoal-
cohols. The filler influence on the photopolymerisation
kinetics and on the physical properties of polymerised
BCDE is consistent with the flexibilisation of the polymer
Fig. 8. Weight loss curves for cured BCDE and for cured BCDE/ZrP and network induced by the occurrence of chain transfer
BCDE/ZrPA5 gels. reactions.
 R. Bongiovanni et al. / European Polymer Journal 45 (2009) 2487–2493 2493

Acknowledgements [17] Boo WJ, Sun LY, Liu J, Clearfield A, Sue HJ, Mullins MJ, et al.
Morphology and mechanical behavior of exfoliated epoxy/alpha-
zirconium phosphate nanocomposites. Compos Sci Technol
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ibridi inorgano – organici nanostrutturati”. The authors
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