Polymeric (Nano)composites Based on Poly(-caprolactone) and Mesoporous Silica SBA-15

for Controlled Release Applications

Nadine Antunes
nadine.antunes@tecnico.ulisboa.pt

Instituto Superior Técnico, Lisboa, Portugal

July 2021

Abstract
In this research different nanocomposites based on commercial poly(ε-caprolactone) (PCL) and mesoporous silica SBA-15
have been attained by melt extrusion as an attempt to understand the possible effect of this filler in enhancing the mechanical be-
haviour of PCL. The resulting materials were characterised through several experimental techniques such as: transmission electron
microscopy (TEM); high resolution field emission scanning electron microscopy (FESEM); thermogravimetric analysis (TGA); dif-
ferential scanning calorimetry (DSC); X-ray diffraction (XRD); strain-stress experiments and dynamic mechanical analysis (DMA).
The results indicate that the methodology used in preparing the composites didn’t alter the well-defined hexagonal arrangement
characteristic of the SBA-15 particles and allowed for a homogeneous dispersion of the nanofillers within the PCL matrix. It has
been found that, at temperature close to room temperature, the incorporation of small amount of SBA-15 resulted in stiffer materi-
als than the pristine PCL, and that it was higher for higher amounts of silica. Additionally, the results indicate there was no much
change to the PCL crystallinity nor to the thermal degradation processes it undergoes, as well as to the location of Tg and Tm and
to the position of the relaxation processes observed experimentally.

Keywords: polymer nanocomposites, PCL, SBA-15, reinforcement

1. Introduction porous SBA- 15 particles by melt extrusion, a cost-effective

Poly(ε-caprolactone) (PCL) finds many applications in sev-
eral fields such as in adhesives, compatibilizing agents and
films and in medicine. PCL also received great attention for its
use in biomedic applications in delivery systems and in tissue
engineering (TE).
Some key property requirements in these fields are good
mechanical behaviour and thermal characteristics. To achieve
these properties, PCL/silica composites have been studied
and reported in literature. The improved PCL materials ex-
hibited enhanced properties compared to the pristine compo-
nent in stiffness [1, 2, 3, 4], strength [1, 4], thermal stability
[3], biodegradation rate [5], bioactivity [6, 7], controlled drug
release capability [8, 9] and wetting/water absorption [10].
Mesoporous silica was first discovered in 1990 by Japanese
researchers and later, 1992, synthesised in Mobil Corpora-
tion Laboratories. This discovery promoted new research and
another mesoporous families started to appear, as the Santa
Barbara Amorphous family (SBA). SBA-15 is the most known
member from this family. It displays cylindrical pores arranged
in a highly ordered hexagonal structure, with pore sizes rang-
ing from 5-26 nm and length from 200nm to several microns
[11, 12, 13]. Among numerous applications, mesoporous sili-
cas show potential for enhancing polymer overall performance
if polymer macrochains can go inside those ordered hexago-
nal channels [14].
Thus, it becomes necessary to correctly assess the final
structure of the formed composites and the existence of con-
fined polymer chains in silica pores. Differential Scanning
Calorimetry (DSC) has been recently used to describe the
presence of semycristalline macrochains within SBA-15 chan-
nels for nanocomposites attained by melt extrusion [14] and in
situ polymerisation [15].
The present work aims the obtainment of nanocomposites
based on poly(ε-caprolactone) and different contents in meso-
and environmentally-friendly method with large industrial im-
plementation. Thermogravimetric analysis (TGA) will be per-
formed for assessing the accurate content in silica and its ef-
fect on PCL thermal degradation. Then, differential scanning
calorimetry (DSC) will be carried out for analysing the differ-
ent phases and their transitions, as well as, the existence of
trapped PCL chains within the silica pores. Moreover, X-ray
diffraction (XRD) experiments will be performed at wide an-
gle (WAXD) to analyse the PCL crystalline lattice as well as
to estimate crystallinity degree and at small angle (SAXS) to
determine PCL long spacing and to attain information of the
characteristic SBA-15 diffractions. Lastly, stress-strain experi-
ments and dynamic mechanical measurements will be carried
out to analyse the mechanical behaviour and viscoelastic re-
sponse of the nanocomposites.
2. Experimental Part
2.1. Materials and chemicals
A commercially available poly(ε-caprolactone) (PCL) from
Sigma-Aldrich (number-average molecular weight (Mn ) of
80,000 g/mol; density of 1.1450 g/cm3 ) was used in this study.
The SBA-15 particles were purchased from Sigma-Aldrich
(specific surface area, S(BET ) = 517 m2 /g; total pore volume,
Vt = 0.83 cm3 /g; average mesopore diameter, Dp = 6.25 nm
[16]) and used as received.
2.2. Nanocomposite and film preparation
Composites with different contents in SBA-15 particles (3,
6 and 9% in weight, labelled as PCL-SBA3, PCL-SBA6 and
PCL-SBA9, respectively) were processed by melt extrusion in
a co-rotating twin-screw microextruder (Rondol) at a rate of
60 rpm. Previous to extrusion, both the polymer and SBA-
15 were dried. The former was placed in an oven at 50 ° C
for 20 min followed by a drying under vacuum also at 50 ° C
for 20 h. The SBA-15 particles were dried under vacuum at

1
Table 1: TGA results under nitrogen and air atmospheres for neat PCL and
its composites prepared by melt extrusion: temperature of a loss weight of 10%
(T10% ) and temperature at the maximum (Tmax ) together with the SBA-15 wt.%
at 600 ºC in both environments and its average.
Inert atmosphere Oxidative atmosphere
Sample
Average
T10% (ºC) Tmax (ºC)
SBA-15
T10% (ºC) Tmax (ºC)
SBA-15 wt.% wt.%
PCL 0 359.0 360.0 wt.% 344.5
PCL-SBA3 3.3 357.5 359.5 3.8 350.5
PCL-SBA6 6.0 358.0 359.5 6.0 353.0
PCL-SBA9 9.0 358.5 361.0 9.3 347.0
100 ° C for 24 h. In the extruder, a screw temperature profile
of 100, 105, 110, 120 and 110 ° C was used from the hopper
to the die, being the length-to-diameter ratio 20:1. Films were
obtained by compression moulding in a hot-plate Collin press.
First stage was the maintenance of the material at a temper-
ature of 120 ° C and at a pressure of 30 bar for 6 minutes.
Then, a cooling process was applied to the different compos-
ites from their molten state to room temperature for 4 min at
the relatively fast rate of around 80 ° C/min and at a pressure
of 30 bar.
2.3. Transmission electron microscopy (TEM)
Measurements were performed at room temperature in a
200 kV JEM-2100 JEOL microscope. The particles were dis-
persed in acetone in an ultrasonic bath for 5 min and then
deposited in a holder prior to observation.
2.4. Scanning electron microscopy (SEM)
Images were attained in a S-8000 Hitachi equipment at
room temperature in different cryo-fractured sections of com-
posites at distinct mesoporous content. Those thin sections
of around 40 nm were cut by cryo-ultramicrotomy (Leica EM
UC6) at -120 ° C and deposited in a holder.
2.5. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed in a
Q500 equipment of TA Instruments under nitrogen or air at-
mosphere at a heating rate of 10 ° C/min. Degradation tem-
peratures of the distinct materials were determined, as well
as the exact SBA-15 amount incorporated into the compos-
ites prepared by extrusion, which has been estimated as an
average of values obtained from the two environments. The
resulting values of the SBA-15 content are listed in table 1.
2.6. Differential scanning calorimetry (DSC)
Calorimetric analyses were carried out in a TA Instruments
Q100 calorimeter connected to a cooling system and cali-
brated with different standards. The sample weights were
around 3 mg. A temperature interval from -30 to 180 ° C was
studied at a heating rate of 20 ° C/min. For crystallinity deter-
minations, a value of 135 J/g was considered for the melting
enthalpy of the 100% crystalline PCL [17, 18].
2.7. X-ray experiments with synchrotron radiation
Real-time variable-temperature simultaneous SAXS/WAXD
experiments were carried out with synchrotron radiation
in beamline BL11-NCD at ALBA (Cerdanyola del Valles,
Barcelona, Spain) at a fixed wavelength of 0.1 nm. A Pilatus
detector has been used for SAXS (off beam, at a distance of
296 cm from sample) and a Rayonix one for WAXD (at about
14.6 cm from sample, and a tilt angle of around 29 degrees).
A Linkam Unit, connected to a cooling system of liquid nitro-
gen, was employed for the temperature control. The calibra-
tion of spacings was obtained by means of silver behenate
and Cr2 O3 standards. The initial 2D X-ray images were con-
verted into 1D diffractograms, as function of the inverse scat-
SBA-15 tering vector, s = 1/d = 2 sin θ/λ, by means of pyFAI python
wt.%
356.0 0
code (ESRF), modified by ALBA beamline staff. Film samples
354.5 2.8 of around 5×5×0.1 mm were used in the synchrotron analy-
357.5 6.0
355.5 8.6 sis.
2.8. Dynamic mechanical thermal analysis
Viscoelastic relaxations were measured with a TA Q800 Dy-
namic Mechanical Thermal Analyser (DMTA), working in a
tensile mode. The storage modulus, E’, loss modulus, E”,
and the loss tangent, tan δ, of the different composites were
determined as function of temperature over the range from
–140 to 60 ° C at a fixed frequency of 3 Hz, and at a heating
rate of 1.5 ° C/min. For this analysis, strips of 2.2 mm wide
and 15 mm length were cut from the moulded films.
2.9. Mechanical behaviour by means of stress-Strain tests
Nominal stress-strain tests were performed at a tempera-
ture of 25 ° C and a stretching rate of 10 mm/min in MTS
Q-Test Elite dynamometer with a load-cell of 100 N. Speci-
mens for these experiments were punched out from the poly-
mer films. The dimensions of these strips were 15 mm long,
1.9 mm wide and around 0.20 mm thick. At least, six different
strips were stretched until fracture at a given specimen.
3. Results
3.1. Morphological Characteristics
TEM micrographs of the SBA-15 silica used for this inves-
tigation (figure 1a) show the distinctive vermicular elongated
shape of these particles with an approximate average size of
350 nm wide and 0.9 µm long, being in conformity with lit-
erature findings for mesoporous these particles synthesized
in the laboratory[15]. Its magnification, shown in figure 1b,
displays the particle morphology: a uniform, well-defined and
ordered channel structure (region within cyan squares) with a
hexagonal arrangement (region within the magenta ellipse).
(a)
(b)
Figure 1: TEM images of SBA-15 particles at a scale bar of (a) 1 µ m and (b)
200 nm.
A quite uniform distribution of SBA-15 particles is evident
in the FESEM micrographs for the different composites (fig-
ure 2), and an increase in the number of SBA-15 particles
found is observed as their content is raised in the final com-
posite (see precise compositions in table 1). Existence of
detectable bulky inorganic domains across the materials at
the different mesoporous silica contents was not observed,
although the formation of particles aggregates is favoured as
SBA-15 amount rises in the material (being more evident in
the PCL-SAB9 composite - figure 2c).
2
 The well-defined channel structure and its corresponding
regular hexagonal arrangement characteristic in these meso-
porous SBA-15 particles are maintained when they are em-
bedded in the PCL matrix for the different composites (see
Table 2: Average SBA-15 wt.% estimated from TGA measurements and DSC
results: glass transition (Tg ) -calculated from the first heating run-, melting (Tm )
and crystallisation (Tc ) temperatures, and overall crystallinity (normalised to the
m1
actual PCL content in the material) for the first melting (fc,N ORM ), crystallisa-
C 2 m
tion (fc,N ORM ) and second melting (fc,N ORM ) processes.

figures 2d and 2e). This fact points out that regularity at the
SBA-15 m1 C m2
mesoscale is not altered by the shear forces imposed during Sample
wt.%
Tg (ºC) Tm1 (ºC) fc,N ORM Tc (ºC) fc,N ORM Tm2 (ºC) fc,N ORM

PCL 0 -64.5 59.0 0.51 27.5 0.42 55.5 0.42

extrusion. PCL-SBA3 3.3 -64.5 58.5 0.50 30.5 0.41 55.0 0.41
PCL-SBA6 6.0 -64.0 59.0 0.50 29.5 0.41 55.5 0.41
3.2. Thermal stability PCL-SBA9 9.0 -64.0 59.0 0.51 29.0 0.40 55.5 0.40

Incorporation of nanoparticles within polymeric matrices in

a homogeneous manner has been proved to induce, occa-
sionally, thermal degradation of the resultant materials[6, 19].
Regarding the use of mesoporous silicas, it has to be said
that these particles have been also used, sometimes, as cat-
alysts for thermal decomposition of polymers. This effect was
found by Gomis et al. [20] while studying the degradation by
TGA of PE under N2 in the presence and absence of meso-
porous MCM-41. Other authors [21] showed the efficiency
of mesoporous alumino-silicate MCM-41 as promoter towards
degradation of polyolefins into liquid fuels.
3.3. Existing phases and respective transitions
DSC is used in the present study to find the different ther-
mal transitions occurring in the pristine PCL and its compos-
ites with SBA-15, and to evaluate the enthalpy changes that
can take place during melting and crystallisation processes.
Melting temperature is given by the maximum of the curve and
melting enthalpy is calculated from the area under the curve.
The degree of crystallinity of the sample can be determined
by the following expression:

Thermogravimetric analysis was used in the current inves- (∆Hm )experimental

tigation to determine exactly the content of mesoporous par-
ticles embedded in the PCL matrix of these composites (see
table 1), as well as to analyse their influence in thermal degra-
dation of the final materials.
Figure 3 shows the temperature dependence of the PCL
weight loss under inert conditions in these composites. The
TGA curve displays one main degradation process in the pris-
tine polymer with an inflection point at around 360° C, which
involves the most of the weight loss, around 95 %. Neverthe-
less, a careful examination of the DTGA trace (see inset in
figure 3b) highlights another minor consecutive mechanism at
higher temperature. Previous studies [22, 23] allowed propos-
ing a two-stage degradation mechanism. The first process
involves a statistical rupture of the polyester chains via ester
pyrolysis reaction, which originates H2 O, CO2 , and 5-hexenoic
acid, all in gaseous state. The second step leads to the for-
mation of ε-caprolactone (cyclic monomer) as result of an un-
zipping depolymerisation process.
Thermal PCL degradability is not considerably affected by
incorporation of SBA-15 particles when experiments are per-
formed in this atmosphere. Presence of mesoporous silica
does not change location of the main weight loss although
the process related to the PCL unzipping depolymerisation
becomes a shoulder and it is broadened in the composites
compared with that observed in the pristine PCL.
Weight loss under air follows a more complex process than
that seen in inert atmosphere (figure 4). It takes place in sev-
eral stages, since the PCL degradation occurs now via both
thermolysis and oxidation. The process involving the highest
weight loss is not considerably affected by the presence of
mesoporous SBA-15, as deduced from the Tmax listed in ta-
ble 1. Its effect is more evident in the value of T10% . This is
slightly shifted to higher temperatures in the composites, in-
dicating that SBA-15 postpones a little the beginning of PCL
weight loss.
The results achieved indicate that the presence of SBA-15
particles do not have a catalytic effect on composites with a
PCL matrix.
fc = (1)
(∆Hm )100%
where fc is the crystallinity of the sample, (∆Hm )100%
the melting enthalpy of 100% crystalline PCL and
(∆Hm )experimental the apparent melting enthalpy of
the sample. The value of 135 J/g is considered as the melting
enthalpy of 100% crystalline PCL [17, 18]. Errors in the
determination of temperatures, the calculation of the enthalpy
and the crystallinity were estimated at ±0.5° C, ±4 J/g and
±0.04 units, respectively.
Figure 5 depicts the calorimetric curves obtained for the
PCL and PCL-SBA9. Both materials are semicrystalline, ex-
hibiting amorphous and crystalline phases. Thus, several
transitions take place in the PCL within this interval analysed.
In the first and second heating runs, the PCL glass transition
temperature is observed at low temperatures at about -60° C,
which is related to a change from a rigid and glassy to a soft
and rubbery state within its amorphous regions. At higher
temperatures, an endothermic process related to the melting
of PCL crystals existing in its crystalline regions takes place in
both the pristine PCL polymer and its PCL-SBA9 composite.
A clear crystallisation process is seen along the cooling run
independently of absence or presence of mesoporous SBA-
15 particles. This feature means that PCL does maintain its
capability of ordering into crystallites even in the composite.
All the values deduced for the glass transition (Tg ), melting
(Tm ) and crystallisation (Tc ) temperatures, together with those
for crystallinity normalised to the actual PCL amount in the
different materials, are listed in table 2.
Figure 6a depicts the endotherms obtained in the range of
glass transition. It is clearly noticeable that intensity of the
PCL glass transition event is much smaller than that observed
for the melting process, indicating that PCL crystallises in a
considerable amount within the pristine PCL homopolymer
and in its composites with mesoporous SBA-15 silica.
Additionally, it is deduced from the curves represented in
the inset, where normalisation to the PCL content has been
performed, that intensity of this transition is dependent on sil-
ica content. This fact could either indicate that the quantity of

3
 (a) (b) (c)

(d) (e)

Figure 2: FESEM micrographs for the different composites: at a scale bar of 5 µm (a) PCL-SBA3; (b) PCL-SBA6; and, (c) PCL-SBA9 at a scale bar of; at a scale
bar of 300 nm (d) PCL-SBA3 (e) PCL-SBA6.

Figure 5: DSC curves, involving first melting, crystallisation and second melting
Figure 3: TGA curves under inert atmosphere (a) and their derivatives (b) for processes, for the neat PCL and its PCL-SBA9 composite prepared by melt
the neat PCL and its composites with SBA-15 at different contents prepared by extrusion. Curves have been shifted for the sake of clarity.
melt extrusion.

PCL amorphous regions has lowered by incorporation of sil-

ica particles or yet result from a hindrance of mobility because
of the mesoporous silica along the transition from the glass
to rubbery state within the amorphous regions. Nevertheless,
its location remains almost constant and only is observed a
slight displacement to high temperatures for the highest SBA-
15 content, as listed in table 2.

Figure 6b shows the DSC curves during first heating run

Figure 4: TGA curves under oxidant atmosphere (a) and their derivatives (b) for
the neat PCL and its composites with SBA-15 at different contents prepared by
melt extrusion.
for the temperature interval related to the melting of the PCL
crystallites for all the composites. A very complex melting pro-
cess is exhibited by the PCL in the pristine polymer and in all
the composite, and distinct endothermic events linked to the
various melting-recrystallisation stages are observed. These
multiples stages can be associated with the fast cooling from
the melt to room temperature imposed to the materials, which
originates thin and imperfect crystals able to evolve toward
thicker and more perfect ones during their maintenance at
room temperature. The main melting peak is rather similar

4
 (a)
(c)
Figure 6: DSC curves for the neat PCL and its composites prepared by melt extrusion in the range of glass transition (a), first heating run (b), cooling run (c)
and second heating run (d). Inset in (a) represents the heat flow (HF) normalised to the actual PCL amount at a given material. Inset in (b) represents a smaller
temperature range. In (a), (b) and (c) curves have been shifted for the sake of clarity.
in all these samples. This feature points out the size of PCL
crystallites is not affected by the incorporation of SBA-15 par-
ticles.
The results obtained during the first melting process after
normalisation of enthalpies by the actual PCL amount at each
composite are reported in table 2. Incorporation of meso-
porous silica does not change the PCL crystallinity in these
films processed by applying a fast cooling from the melt and
annealed at room temperature for two days.
Figure 6c depicts the curves attained for the subsequent
cooling process An exothermic event is noticeable since these
materials based on PCL are semicrystalline. Mesoporous
SBA-15 particles exert an evident nucleating effect in the PCL
crystallisation and its location is shifted to higher temperature
in the composites. This is more significant in the composite
with the lowest silica content, showing then the highest Tc . An
increase of the SBA-15 composition leads to a progressive
decrease of Tc , whose value is always superior to that found
in the pristine PCL.
Another crystallisation process is observed in the compos-
ites from 0 to 10° C, as seen in the inset of figure 6c. It be-
comes more evident for the PCL-SBA9 material and it is not
almost noticeable in the PCL-SBA3 one. The pure PCL does
not show any event in this temperature range (this will be dis-
cussed afterward).
Table 2 presents the estimation of PCL crystallinity after
normalisation of enthalpies by the actual PCL amount at each
composite . A reduction of crystallinity is observed com-
pared with that obtained for the samples taken from the as-
5
(b)
(d)
processed films. This decrease is obvious in spite of cooling
rate applied in the DSC experiments are slower than in the film
preparation, 20° C/min instead of approximately 80° C/min.
This difference is associated with the fact that the samples
from as-processed films were maintained at room temperature
for 2 days before their DSC testing and during that time crys-
tallites were able to undergo several melting-recrystallisation
processes that led to an increase of crystallinity. Incorporation
of mesoporous silica seems to not affect PCL crystallinity.
Figure 6d depicts the DSC curves of the second melting
after PCL crystallisation. A unique endothermic process is
observed, differently to the complex melting behaviour found
during the first heating scan. As this heating process is initi-
ated just after cooling is finished, the crystalline entities do not
have enough time to evolve toward more perfect crystallites.
Accordingly, melting-recrystallisation processes do not take
place in this second heating run and the Tm values are slightly
shifted to lower temperatures. Its location is rather indepen-
dent of the incorporation of SBA-15 particles. Absence of
those melting-recrystallisation processes makes crystallinity
to be lower than in the first melting processes.
The only effect of presence of SBA-15 is again seen in
the interval ranging between 25 and 45 ° C. The same event
was evident during first heating scan at identical temperature
range and during cooling in the interval ranging between -5
and 15° C.
These small endothermic events during heating runs, more
intense in the first than in the second melting process, are
assigned to the melting of the PCL crystals confined in-
Figure 7: Wide angle profiles at room temperature, obtained with synchrotron
radiation, for PCL homopolymer, SBA-15 and the composites prepared by ex- Figure 8: Determination of PCL crystallinity in the PCL-SBA9 composite. Total
trusion. composite and SBA-15 profiles, normalised at same area (left picture); total
composite profile and normalised SBA-15 pattern at its actual content in the
PCL-SBA9 composite (middle representation); and, subtracted profile, which
corresponds only to PCL (total composite profile - normalised SBA-15 pattern
side the SBA-15 pores, which are thinner than those out of at its actual content), and its deconvolution into the amorphous halo and the
different crystalline diffractions (right plot).
mesoporous particles. Therefore, the melting temperature of
the confined crystals are much lower than those outside the
Table 3: Characteristics of the PCL crystalline phase for the pristine polymer and
mesoporous particles. That can be explained considering the P CL
the different composites: fc,W AXD (crystallinity degree determined by WAXD
more general Gibbs-Thomson equation[24, 25]. These thinner at room temperature); s values (scattering vector); LP CL
SAXS (long spacing, s
−1
,
crystals hold very low values in their lateral size, as a result of estimated by SAXS at room temperature), and lc (most probable crystal size
P CL P CL
calculated assuming a two-phase model: lc = LSAXS x fc,W AXD . Standard
the pore diameter, which in turn leads to considerably cor- N ORM SAXS
errors: fc,W AXS ± 4%; L and lc ± 0.3nm.
responding low melting temperatures. On cooling, the small
exothermic process that takes place between -5 to 15° C cor- SBA-15
responds to the crystallisation of these thin crystallites within Sample P CL
fc,W AXD s (nm−1 ) LP CL
SAXS (nm) lc (nm)
wt.%
the SBA-15 channels. Temperature has been moved down PCL 0 0.57 0.059 17.1 9.7
because of their smaller size than those crystals developed PCL-SBA3 3.3 0.56 0.057 17.6 9.8
PCL-SBA6 6.0 0.55 0.056 17.8 9.8
out of the mesoporous particles.
PCL-SBA9 9.0 0.55 0.055 18.1 10.0
Small endotherms have been previously observed for in
situ polymerised nanocomposites based on distinct types of
polyethylene and mesoporous silicas [15, 26, 27, 28] and in to the total scattered intensity [34]. In the present study, the
iPP nanocomposites with either SBA-15 or MCM-41 silicas estimation of crystallinity does not exactly follow the conven-
obtained by extrusion [29, 30, 31, 32]. The location of these tional procedure, since the SBA-15 material exhibits its amor-
endotherms is dependent on the polymer under study and the phous halo at the same interval that the X-ray diffraction pat-
type of mesoporous silica incorporated. Because they require tern of neat PCL, as seen in figure 7. Then, the SBA-15
a small amount of enthalpy (since reptation is not favoured amorphous component must be subtracted prior to any fur-
in the molten state, within nanometric channels), polymeric ther determination. Figure 8 shows a summary of the protocol
chains are able to crystallise inside the confined spaces of that has been followed, displaying patterns for the PCL-SBA9
SBA-15 channels. composite, as an example.

Presence of PCL within constrained nanometric spaces of
SBA-15 means these systems can be named as nanocom-
posites.
3.4. Crystalline characteristics
In this investigation, XRD experiments have been per-
formed at wide angle (WAXD) to analyse the PCL crystalline
lattice as well as to estimate crystallinity degree and at small
angle (SAXS) to determine PCL long spacing and to attain
information of the characteristic SBA-15 diffractions.
Figure 7 shows the WAXD profiles at room temperature for
the pristine PCL, its composites and the neat SBA-15 silica.
The PCL is semicrystalline and crystallises into an orthorhom-
bic lattice [33]. There are not noticeable changes in the lo-
cation of its characteristic diffraction (100), (110) and (200)
peaks by the presence of mesoporous silica. This is amor-
phous at short-range showing a wide halo, which is centred at
an s value of 2.54 nm−1 .
The crystalline degree can be determined from X-ray
diffraction at the wide-angle scale if a two-phase model is con-
sidered, by comparison of the area under the crystalline peaks
PCL crystallinity values do not vary much in the compos-
ites when compared with the one found in the pristine PCL. A
decreasing trend is observed although results are within ex-
perimental error.
Figure 9 shows for the SAXS profiles found at room temper-
ature for the neat PCL, its composites and the mesoporous
SBA-15 silica. The ordering of the mesoporous particles has
been maintained throughout extrusion for the distinct compos-
ites. Thus, the characteristic reflections (100), (110), (200),
(210) and (300) (these two latest seen in the inset repre-
sented in logarithmic scale only for SBA-15 and the PLC-
SBA9 composite) of its hexagonal p6mm symmetry [35, 36]
are observed in the SAXS profiles. Additionally, a broad peak
can be observed for low values of s, which is linked to the dif-
ferent electron densities within the PCL matrix originated by
its semicrystalline nature and lamellar crystallites, i.e, imputed
to its most probable long spacing. The values for the different
samples are reported in table 3. Presence of SBA-15 particles
increases PCL long spacing, as much as mesoporous content
is raised in the composite. The most probable crystal size also
is enlarged in the composites, increasing with SBA-15 con-
tent. These thicker crystallites seem not to affect the Tm of

6

Figure 9: SAXS profiles at room temperature for the PCL, its composites the
mesoporous SBA-15 silica.
Figure 10: Stress-strain behaviour of pristine PCL and its composites with SBA-
15 particles prepared by extrusion.
the first melting, remaining almost constant (see table 2). This
fact is due to the existence of multiple melting-recrystallisation
processes along the heating run.
3.5. Viscoelastic Response
The effect of presence of mesoporous SBA-15 particles on
the viscoelastic response has been derived from stress-strain
tests and dynamic mechanical experiments.
Figure 10 shows the stress-strain curves for the pure PCL
and the different composites. The behaviour deduced from
the nominal stress-strain curves for all these specimens are
characteristic of ductile polymeric materials. The engineering
stress-strain curves display three distinct regions: initially, the
stress rises on strain in a linear dependence that allows de-
termining Young’s modulus, E. Afterward this initial stage, an
evident yield point is observed (see inset in figure 10) followed
by a narrow region where stress is kept rather constant. And,
finally, a third region where there is again an increase of the
stress, so that a considerable strain-hardening is observed,
related with stress-induced orientation of the polymeric PCL
chains. Therefore, the stress-strain curves of these speci-
mens depict the formation of a neck in the course of the defor-
mation process, which was also confirmed from the direct ob-
servation along the stretching process. On the other hand, the
narrow necking propagation stage also points out that these
materials are relatively soft.
7
Table 4: Mechanical parameters derived from stress-strain tests at 25° C for
the different samples: average Young’s modulus (E); yield stress (σY ). SBA-15
wt.% content, crystallinity by WAXD (fcP CLW AXD ) and crystallite size (lc )
have been also listed.
SBA-15
Sample fcP CLW AXD lc (nm) E (MPa) σY (MPa)
wt.%
PCL 0 0.57 9.7 285 13.6
PCL-SBA3 3.3 0.56 9.8 310 13.7
PCL-SBA6 6.0 0.55 9.8 350 14.5
PCL-SBA9 9.0 0.55 10.0 400 18.0
The main parameters achieved from the curves represented
in figure 10, Young’s modulus (E) and yield stress (σY ), are
listed in table 4 and represented in figure 11. The Young’s
modulus (E), which is defined as the ratio between the ap-
plied stress and the resulting deformation, can be estimated
by equation 2 [37]:
σ
E= (2)

Regarding the E values, incorporation of silica particles
leads to stiffer materials and dependence on content is al-
most linear. Accordingly, E values are higher than that for
the pristine PCL at any filler content. Two are the reasons
that can explain this behaviour. On one hand, silica is stiffer
than polymeric PCL. Thus, their inclusion, independently of
the amount, is expected to increase elastic modulus as much
as content is raised. SBA-15 particles play a reinforcement
role.On the other hand, although crystallinity does not change
much in the different specimens, and neither does crystallite
size, a raising trend can still be observed in lc with the meso-
porous amount. Consequently, it is conceivable that even the
PCL matrix within the nanocomposites is stiffer than the neat
PCL.
In relation to the yielding point, trend of yielding stress upon
SBA-15 content is somehow different to that seen for E values.
This could be associated with the fact that physical defects
existing in the dumbbell specimens when punched from initial
film become more evident once elastic region is exceeded.
Furthermore, different contributions other than those exclu-
sively related to rigidity (presence of loadings, polymer crys-
tallinity and crystal size, etc) exert an effect here when plastic
domain is initiated.
Figure 11 clearly shows that no important variations in the
absolutes σY values are observed between PCL and PCL-
SBA3 in spite of some change has been noticed in its stiffness.
This could be ascribed to the fact that all of these materials
behave as ductile, and the amount of filler is not very high. The
PCL-SBA6 and PCL-SBA9 composites exhibit larger values.
Figure 12 displays dependence of storage modulus (E’) and
the loss agent (tanδ) on temperature for the neat PCL and the
different SBA-15 composites. As observed from E deduced by
stress-strain tests, incorporation of mesoporous silica leads
to more rigid materials in the entire temperature interval anal-
ysed and, accordingly, to higher E’. Some values have been
taken from different temperatures and represented in figure
13.
The obtainment of stiffer materials based on PCL at temper-
ature close to room temperature and higher by incorporation
of small amount of SBA-15 could be very important from a
practical standpoint since PCL bioapplications are limited by

Figure 11: (a) Values of modulus, E; and, (b) yield stress, σY , deduced both
from stress-strain tests for the PCL homopolymer and composites with different
SBA-15 contents.
Figure 12: (a) Dependence of storage modulus on temperature (at 3 Hz); and,
(b) of tan δ for the pristine PCL and its composites prepared by melt extrusion.
Figure 13: Values of storage modulus at different temperatures for the different
specimens analysed.
8
its very poor mechanical performance. At 25° C under the dy-
namic conditions used, PCL presents an E’ value of 285 MPa,
which is increased by a factor of 1.8 for the PCL-SBA3, of
2.1 for PCL-SBA6 and 3.0 for PCL-SBA9. This increase in
more significant at 50° C: 2.0 for the PCL-SBA3, 2.3 for PCL-
SBA6 and 3.6 for PCL-SBA9. The PCL mechanical response
is significantly improved by presence of mesoporous SBA-15
particles.
Figure 12b shows the different relaxations that occur in the
neat PCL and its composites. Two clear processes are seen
in this temperature range: the β P CL and the αP CL processes.
The former is related to local mobility associated with mo-
tions involving three or more CH2 units [38, 39] similar to the
γ relaxation in polyethylene. Location of this process is not
affected by incorporation of SBA-15 although its intensity is
slightly increased.
The αP CL process is ascribed to movements involving long
segments of polymeric chains within the amorphous regions
of PCL; this relaxation occurs on the interval of PCL’s glass
transition [40, 41]. The significant decline perceived in the
E’ values (figure 12a) in the temperature interval of those mo-
tions is ascribed to the cooperative character of this relaxation.
Moreover, there is a slight decrease of the maximum value of
the tanδ intensity with the increase of SBA-15 content, indi-
cating that there are some restrictions in the mobility of the
amorphous PCL regions in the composites.
4. Conclusions
Composites based on PCL and different amounts of meso-
porous SBA-15 silica have been prepared by melt extrusion.
FESEM pictures and SAXS results show that the well-
defined hexagonal arrangement exhibited by the pristine SBA-
15 is maintained in the particles embedded within the PCL
matrix in the resultant composites. On the other hand, a rather
homogeneous dispersion of SBA-15 particles within the PCL
matrix is clearly noticed.
Presence of an endothermic event in the DSC first melting
curves, which takes place in the temperature interval ranging
from 30 to 45 ° C, indicates the development of crystals of
small size that are accommodated in the interior space of the
nanometric SBA-15 channels. That means that there are con-
fined PCL chains in the SBA-15 pores. This endotherm is min-
imised in the second melting process, because the PCL crys-
tallisation greatly evolves for its maintenance at room temper-
ature by successive melting-recrystallisation processes and
because the PCL crystallisation in those nanometric spaces is
hindered and takes a time longer than the DSC experiments.
Incorporation of SBA-15 particles does not affect much the
PCL thermal degradation processes under either inert or air
atmospheres, the location of Tg and main Tm , the crystallinity
values deduced from either DSC or WAXD experiments, and
the position of the relaxation processes observed from DMA
experiments. Nevertheless, PCL crystallites become thicker.
This latest feature together with the higher stiffness of the
SBA-15 particles is responsible for the reinforcement effect
observed in the composites. Accordingly, Young’s and stor-
age moduli rise as the SBA-15 content is increased.
SBA-15 incorporation seems to be an appropriate strategy
for the improvement of the PCL mechanical performance and
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