eXPRESS Polymer Letters Vol.6, No.

5 (2012) 410–416
Available online at www.expresspolymlett.com
DOI: 10.3144/expresspolymlett.2012.43

Macro-micro relationship in nanostructured functional

composites
A. Zanotto1, A. Spinella1, G. Nasillo1, E.Caponetti1,2, A. S. Luyt3*
1CentroGrandi Apparecchiature, UninetLab, Via Marini 14, 90128 Palermo Italy
2Dipartimento di Chimica “Stanislao Cannizzaro” Università degli studi di Palermo Viale delle Scienze 17, 90128
Palermo, Italy
3Department of Chemistry, University of the Free State, Private Bag X13, 9866 Phuthaditjhaba, South Africa

Received 11 October 2011; accepted in revised form 2 December 2011

Abstract. This paper examines the results of the characterization of two functional composites: Poly(methyl methacrylate)
(PMMA)-Ce:YAG (yttrium aluminium garnet doped with cerium) and PMMA-cobalt hexacyanoferrate (CoHCF). The
composites were prepared as possible emitters in the fields of lighting thermal sensors. The prepared composites were char-
acterized using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, thermogravi-
metric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) analyses to study
the correlation between micro and macro characteristics. We found that the molecular interactions of the two different
fillers with the matrix were localized in different sites of the polymer chains. Moreover, the composites showed an
increased thermal strength and stiffness, in particular the PMMA-Ce:YAG composite.

Keywords: nanocomposites, PMMA, yttrium aluminium garnet doped with cerium (Ce:YAG), cobalt hexacyanoferrate
(CoHCF), interfacial interaction

1. Introduction geneous distribution for the nanofiller to exhibit a

The production of nanostructures, nanoparticles and, big surface area for optical applications. During
generally, nanostructured materials has become part composite formation it is important that the dis-
of everyday scientific life, whether in the research persed material stays in suspension, allowing conti-
or industrial laboratories. The embedding of nano- nuity in the system.
fillers inside polymeric systems allows us to utilize The macroscopic characteristics of the composite
the nano-features of (nanostructured) materials in often reflect its own microstructure. The properties
addition to their functionality. Such combinations of composites depend on the unique filler properties
produce ductile materials possessing switchable and on the morphology and interface features of the
functionalities, not only for basic research, but for composite [2]. Such composites will exhibit inter-
the development of industrial applications. esting electric, optical and magnetic properties. The
The amount of filler used plays an important role in characteristics of these systems depend on the com-
modifying the mechanical properties of polymers, patibility of the constituents and the sizes of their
creating new materials [1]. In functional composites contact surfaces.
the polymers allow the dispersed materials to better One of the challenges of preparing nanocomposite
express their own qualities in three-dimensional materials is to mix compatible and homogeneous
space. The role of polymers is to guarantee a homo- nanofillers in a polymer matrix, guaranteeing or

*
Corresponding author, e-mail: [email protected]
© BME-PT

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improving the matrix performance. Poly(methyl because of its transparency, ductility, recyclability
methacrylate) (PMMA) is a commonly used ther- and low price.
moplastic matrix for fibres, sheet and particles.
There have been several studies on PMMA-fibre 2. Experimental
composites prepared by in situ polymerization [3], 2.1. Materials
solution mixing [4], or melt blending [5]. The last Potassium hexacyanoferrate(III) K3[Fe(CN)6]
one is already an industrial process for fabricating (Sigma-Aldrich ACS reagent, 244023, ! 99.0%,
carbon fibre-reinforced thermoplastic composites. Schnelldorf, Germany), cobalt(II) chloride hexahy-
A combination of solvent casting and melt mixing drate CoCl2"6H2O (Fluka Purum, crystallized,
allowed to build composites with enhanced mechan- ! 98.5%, Schnelldorf, Germany) and 2,2-diethoxy-
ical and electrical properties and exceptional fibre- acetophenone (Sigma-Aldrich, 227102, > 95%,
alignment [6]. Platelets and sheets also influence Schnelldorf, Germany), and methyl methacrylate
the composite's thermal and mechanical properties, (MMA) (Sigma-Aldrich, M55909, # 30 ppm MEHQ
in relation to the material's composition and disper- as inhibitor, 99%, Schnelldorf, Germany) were all
sion state within the matrix [7]. used as received. CoHCF nanoparticles were
Musbah et al. [8] have just discovered that nanopow- obtained by the reaction of potassium hexacyano-
ders of phosphors Y2O3(Eu3+) embedded in a ferrate and cobalt chloride hexahydrate. 16.5 mg of
PMMA matrix, prepared using a laboratory mixing K3[Fe(CN)6], dissolved into 5 mL of water (0.01 M)
molder, influence almost linearly the optical and were added to 5 mL of stirred water containing
dynamic mechanical properties of the nanocompos- 17.8 mg of CoCl2"6H2O (0.015 M) at room temper-
ites. The intensity of the luminescence emission ature. This instantly created a dark red suspension.
spectra and storage modulus, loss modulus and Y(NO3)3"6H2O (Sigma-Aldrich, 237957, 99.8%,
glass transition temperature (Tg) of the polymer Schnelldorf, Germany), Al(NO3)3"9H2O (Sigma-
composites increased with increasing content of the Aldrich ACS reagent, 237973, ! 98%, Schnelldorf,
nanophosphor powder. Germany), and Ce(NO3)3"6H2O (Sigma-Aldrich,
We prepared two nanostructured composites, cobalt 392219, 99.99%, Schnelldorf, Germany) were the
hexacyanoferrate (CoHCF) nanoparticles in PMMA, sources of Y(III), Al(III), and Ce(III) ions, respec-
and yttrium aluminium garnet doped with cerium tively. The other reagents were ammonia solution
(Ce:YAG) nanoparticles in PMMA. CoHCF nano- (E. Merck, 25 v/v%) and 2-methacrylic acid (MAA)
particles show thermochromic behaviour, exhibit- (Sigma-Aldrich, 155721, 250 ppm MEHQ as
ing a significant and non-reversible colour change inhibitor, 99%, Schnelldorf, Germany).
around 100°C. A new thermocromic optical sensor Ce:YAG nanopowder was prepared by dissolving
with memory could be developed from this new yttrium, aluminium, and cerium nitrates in deion-
composite [9]. Ce:YAG, combined with GaN blue ized water. The hydroxides were precipitated by
light emitting diodes (LED), is used for white light dropwise addition of 5 M ammonia to the nitrates
solid-state LED. In previous work it was described solution, under constant stirring, until a pH value of
how the presence of filler (Ce:YAG) in the PMMA 8. The gelatinous precipitate thus obtained was fil-
matrix can cause an organization of the structure tered and washed several times with water to
into a lamellar shape around the particles [10]. This remove the residual ammonia and nitrate ions. Then
organization could influence the macro features of the precipitate was dried at 50°C for 24 hours. The
the composites. mixed hydroxides were calcined at 900°C for two
The purpose of the present work was to study the hours.
possible relationships between macro- and micro- PMMA nanocomposite preparation: A 5 wt% sus-
features of PMMA/CoHCF and PMMA/Ce:YAG pension of filler nanopowder in MMA and MAA
nanocomposites by means of transmission electron monomers (molar ratio 4:1) was formed. 2,2-
microscopy (TEM) and nuclear magnetic resonance diethoxyacetophenone was added to start the pho-
(NMR) spectroscopy, as well as thermal and thermo- tocuring process [3]. The dispersion was main-
mechanical analyses. PMMA was chosen as matrix tained under ultrasound and continuously irradiated

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Figure 1. Picture of CoHCF-PMMA (a) and Ce:YAG-PMMA (b) composites

with a 256 nm lamp until polymerization occurred. of 1.5 µs, and a repetition delay of 2 s. The opti-
A transparent coloured solid product, composed of mization of the Hartmann-Hahn condition was
the PMMA polymeric matrix containing nanoparti- obtained using an adamantine standard. All samples
cles, was obtained. A portion was cut and lapped to were placed in a 4 mm zirconia rotor with KEL-F
obtain a disk having a diameter of 1 cm. For the sake caps using silica as a filler to avoid inhomogeneities
of comparison, pure PMMA was also prepared fol- inside the rotor.
lowing the same procedure. The disks are shown in The proton spin-lattice relaxation time in the rotat-
Figure 1. ing frame T1$(H) was indirectly determined, with a
variable spin-lock pulse sequence, by carbon nucleus
2.2. Methods observation using a 90-% spin-lock pulse sequence
2.2.1. Transmission electron microscopy (TEM) prior to cross-polarization. Data acquisition was
TEM micrographs were recorded on a high-resolu- performed by 1H decoupling with spin-lock pulse
tion transmission electron microscope (HR-TEM) durations ranging from 0.1 to 7.5 ms and a contact
JEOL JEM-2100 operating at 80 kV accelerating time of 1.5 ms.
voltage. Elemental analysis was carried out using
an Oxford Instruments energy dispersive X-ray detec- 2.2.3. Differential scanning calorimetry (DSC)
tor (EDS). The composite was cut into thin slices Differential scanning calorimetry (DSC) analyses
using a Leica EM-UC6 ultramicrotome. The 200 nm were carried out in a Perkin Elmer DSC7 differen-
slices were deposited on a 200-mesh copper grid, tial scanning calorimeter under flowing nitrogen
which was carbon-coated to better disperse the high atmosphere (20 mL·min–1). The instrument was cal-
energy electron beam. ibrated using the onset temperatures of melting of
indium and zinc standards, and the melting enthalpy
2.2.2. Nuclear magnetic resonance (NMR) of indium. Polymer samples (between 5 and 10 mg)
spectroscopy were initially heated from 30 to 200°C at 10°C·min–1,
13C cross-polarization magic-angle spinning nuclear
held at that temperature for 1 min to eliminate ther-
magnetic resonance (13C {1H} CP-MAS NMR) spec- mal history effects, and then cooled to 30°C at
tra were obtained at room temperature using a 10°C·min–1. They were kept there for 1 min, heated
Bruker Avance II 400 MHz (9.4 T) spectrometer again to 200°C at 10°C·min–1, and cooled to 30°C
operating at 100.63 MHz for the 13C nucleus with a at the same rate.
MAS rate of 13 kHz for 1024 scans, a contact time

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2.2.4. Thermogravimetric analysis (TGA) 170°C. The sample dimensions were round disks of
Thermogravimetric analyses (TGA) were carried 10 mm diameter and 2.5 mm thick.
out in a Perkin Elmer TGA7 thermogravimetric
analyser. Polymer samples (between 5 and 10 mg) 3. Results and discussion
were heated from 30 to 850°C at 20°C·min–1 under A 4:1 polymeric blend of methylmethacrylate
flowing nitrogen (20 mL·min–1). (MMA) and methacrylic acid (MAA) allowed the
homogeneous dispersion of CoHCF nanoparticles
2.2.5. Dynamic mechanical analysis (DMA) and gave a dark red transparent composite, while
DMA analyses were conducted in a Perkin Elmer Ce:YAG nanoparticles gave a yellow transparent
Diamond DMA using a dual cantilever in the tor- composite (Figure 1).
sion mode. The experiments were done at a fre- Morphological and elemental characterization of a
quency of 1 Hz and a temperature range of 25 to 200 nm thin slide of sample was carried out by

Figure 2. TEM micrographs at different enlargements of PMMA-CoHCF (a and b) and PMMA-Ce:YAG (c and d)
nanocomposites. In the insert is a proof of the crystallinity of Ce:YAG.

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TEM and EDS. The EDS investigations were nec- istic peaks of the PMMA matrix in agreement with
essary to confirm the composition of the samples. A literature [11]. When comparing the spectra, no new
representative example of a low enlargement micro- signals, changes in peak shapes or chemical shifts
graph is shown in Figure 2a, where a homogeneous are observed, so the presence of nanofiller did not
distribution of CoHCF aggregates is observed. The induce chemical modifications in the polymeric
CoHCF easily forms aggregates when the polar iso- matrix.
propanol-water solvent escapes during MMA poly- The NMR data show some specific interactions.
merization. The reason is that in a concentrated envi- The spin-lattice (T1$) relaxation times in the rotat-
ronment the nanoparticles strongly attract each other ing frame are sensitive to molecular motions that
and so the aggregates are more stable. The square occur in the kHz range [12]. These motions are typ-
structure of the CoHCF nanoparticles favours the ically associated with arrangements of the poly-
square shape of the agglomerates. Figure 2c shows meric chains that develop from collective motions
a homogeneous dispersion in the matrix of Ce:YAG of a large number of monomeric units [13]. Long
nanoparticles with different sizes in the range 5– range cooperative motions are those motions that
50 nm. In this case the nanoparticles are dry when define a polymer’s response to mechanical pertur-
dispersed in the monomer, and therefore remain dis- bations [14, 15]. Moreover, T1$ in the kHz fre-
persed during the polymerization process. Unfortu- quency range is inversely proportional to the spec-
nately the Ce:YAG powder, during cutting opera- tral density of the motion.
tion, creates lacerations in the 100 nm polymer The T1$ values of PMMA and the composites are
slice. reported in Table 1. The values in the table show an
A single aggregate of CoHCF nanoparticles in the increase in the rigidity of both nanocomposites,
composite is shown in Figure 2b. The CoHCF probably due to immobilization of the polymer
aggregates are constituted by 15–25 nanoparticles chains by means of filler-matrix interactions. The
randomly displaced with regular dimensions between interactions are also locally different. The highest
40 and 60 nm. The nanoparticles have a quasi variation in the PMMA-CoHCF relaxation times is
squared transversal section. Figure 2d shows a sin- located in the quaternary (3) and methylenic (2) car-
gle Ce:YAG nanoparticle with an average diameter bons on the backbone chain. An increase of T1$(H)
smaller than 20 nm. The insert in Figure 2d con- in PMMA-Ce:YAG occurs for peaks (4) and (5), the
firms a highly crystalline matter. methoxylic and carbonylic groups. The interaction
The interaction between the filler and the matrix between the nanofiller and PMMA is principally
was studied by 13C-NMR CP-MAS spectroscopy localized around these nuclei.
and by acquiring spin-lattice relaxation times in the The TGA curves of all three investigated samples
rotating reference system (T1$). The 13C-NMR spec- are shown in Figure 4. It is clear that the presence of
tra of pure PMMA and the composites are reported both CoHCF and Ce:YAG nanoparticles improves
in Figure 3. In all the spectra there are the character- the thermal stability of PMMA. In the case of CoHCF
the improvement is fairly insignificant, probably
because the kinds of interaction between CoHCF
and PMMA (as pointed out in the discussion of the
NMR results) are not as strong as in the case of
Ce:YAG, where there is an almost 50°C improve-
ment in thermal stability. As shown in the discus-

Table 1. T1$(H) values for all the peaks in the 13C spectra of
PMMA, PMMA-CoHCF and PMMA-Ce:YAG
T1!(H) [ms]
Peak ppm
PMMA CoHCF/PMMA Ce:YAG-PMMA
1 16.4 6.6±0.2 20.4±0.4 9.0±0.4
2 45.5 7.0±0.2 44.2±0.2 12.8±0.2
3 52.7 7.6±0.3 71.9±0.3 13.6±0.3
Figure 3. 13C, {1H} CP-MAS NMR spectra of PMMA and 4 55.1 7.2±0.2 15.0±0.4 15.0±0.4
its composites 5 178.1 6.4±0.4 24.8±0.7 24.8±0.7

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Figure 4. TGA curves of PMMA and its composites Figure 6. DMA loss modulus curves of PMMA and its
composites
sion above, there is a much better dispersion of Ce:
YAG nanoparticles in PMMA, and a much stronger increase of 35°C in the glass transition temperature
interaction between PMMA and Ce:YAG. This will compared to that of the pure polymer. This transi-
not only immobilize the polymer chains but also the tion is, however, not very well resolved. This shows
free radicals that take part in the degradation process. that the interaction between the Ce:YAG nanoparti-
This stronger interaction is probably also the result cles and the PMMA chains, and the resultant immobi-
of a local structured distribution of PMMA chains lization of the polymer chains, was much stronger.
around the Ce:YAG nanoparticles [10]. The DMA loss modulus curves in Figure 6 confirm
The second heating DSC curve of PMMA-CoHCF the DSC observations of the changes in the glass
(Figure 5) shows a shift in Tg to a higher tempera- transition in the presence of the nanofillers. In this
ture by about 6°C. These results are reported in the case, however, the Tg are significantly higher than
Table 2. The higher glass transition temperature indi- those observed in the DSC curves, but such behav-
cates the immobilization of the polymer chains iour was observed before [16, 17], and there could
because of their interaction with the nanoparticles. be a number of reasons for this. However, the
The DSC curve of PMMA-Ce:YAG shows an important thing is that the difference between the Tg
values for PMMA and PMMA-CoHCF is 6°C, as
Table 2. Glass transition temperatures for the different was also observed from the DSC curves. The differ-
investigated samples ence between these values for PMMA and PMMA-
Sample Tg [°C] Ce:YAG is, however, only 17°C from the DMA
PMMA 84.1
curves, but it is quite possible that the Tg value from
PMMA-CoHCF 89.8
PMMA-Ce:YAG 119.5 the DSC curve of PMMA-Ce:YAG is not com-
pletely correct because of the badly resolved glass
transition.

4. Conclusions
Both the investigated PMMA-Ce:YAG and PMMA-
CoHCF composites show a homogeneous distribu-
tion of nanoparticles inside the polymer. The CoHCF
is mostly agglomerated, while the Ce:YAG shows
more dispersed nanoparticles. The presence of these
nanofillers improved the thermal stability of PMMA
for both CoHCF and Ce:YAG, and in particular
PMMA-Ce:YAG shows a 50°C improvement in
thermal stability. The Tg of both composites were
Figure 5. Second heating DSC curves of PMMA and its higher than that of the matrix, with the largest
composites

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increase observed for PMMA-Ce:YAG. The inter- [8] Musbah S. S., Radojevi& V. J., Borna N. V., Stojanovi&
actions of CoHCF with PMMA are localized around D. B., Drami&anin M. D., Marinkovi& A. D., Aleksi&
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around the methoxylic and carbonylic groups. DOI: 10.2298/JSC100330094M
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Acknowledgements Giorgetti M., Zamponi S., Caponetti E.: Cobalt hexa-
The National Research Foundation of South Africa and the cyanoferrate–poly(methyl methacrylate) composite:
University of the Free State are acknowledged for financial Synthesis and characterization. Materials Chemistry
support of this project. and Physics, 120, 118–122 (2010).
DOI: 10.1016/j.matchemphys.2009.10.032
[10] Saladino M. L., Zanotto A., Martino D. C., Spinella A.,
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