Radiation Physics and Chemistry 142 (2018) 94–99

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Radiation Physics and Chemistry

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

Polyurethane acrylate networks including cellulose nanocrystals: a MARK

comparison between UV and EB- curing
K. Furtak-Wronaa, P. Kozik-Ostrówkaa, K. Jadwiszczaka, J.E. Maigretb, V. Aguié-Béghinb,
⁎
X. Coquereta,
a
CNRS UMR 7312, Université de Reims Champagne-Ardenne, Institut de Chimie Moléculaire de Reims, BP 1039, 51687 Reims, France
b
INRA, UMR FARE 614 Fractionnement des Agro-Ressources et Environnement INRA/URCA, BP 224, 51686 Reims, France

A R T I C L E I N F O A B S T R A C T

Keywords: A water-based polyurethane (PUR) acrylate water emulsion was selected as a radiation curable matrix for
Cellulose nanocrystals preparing nanocomposites including cellulose nanocrystals (CNC) prepared by controlled hydrolysis of Ramie
Nanocomposites fibers. Cross-linking polymerization of samples prepared in the form of films or of 1 mm-thick bars was either
Polyurethane networks initiated by exposure to the 395 nm light of a high intensity LED lamp or by treatment with low energy electron
UV curing, EB-curing
beam (EB). The conversion level of acrylate functions in samples submitted to increasing radiation doses was
Thermal and mechanical properties of PUR
networks
monitored by Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimetry (DSC) and
Dynamic Mechanical Analysis (DMA) were used to characterize changes in the glass transition temperature of
the PUR-CNC nanocomposites as a function of acrylate conversion and of CNC content. Micromechanical testing
indicates the positive effect of 1 wt% CNC on Young's modulus and on the tensile strength at break (σ) of cured
nanocomposites. The presence of CNC in the PUR acrylate matrix was shown to double the σ value of the
nanocomposite cured to an acrylate conversion level of 85% by treatment with a 25 kGy dose under EB, whereas
no increase of σ was observed in UV-cured samples exhibiting the same acrylate conversion level. The occurrence
of grafting reactions inducing covalent linkages between the polysaccharide nanofiller and the PUR acrylate
matrix during the EB treatment is advanced as an explanation to account for the improvement observed in
samples cured under ionizing radiation.

1. Introduction exploit the unique properties of cellulose nanocrystals (CNCs) (Veigel

Nanocomposites form a new class of materials with enhanced
physical, mechanical or use properties that continues to receive
increasing interest (Ansari et al., 2015; Barari et al., 2016; Dufresne,
2013; Lee et al., 2014; Samir et al., 2005; Siqueira et al., 2010).
Bionanocomposites can be defined as a subclass of nanocomposites
either comprising a bio-based matrix with inorganic or synthetic
nanofillers (e.g. plasticized starch blended with nanoclays (Prakobna
et al., 2015)) or a non bio-based matrix including nanoparticles
obtained from biomass (e. g. synthetic thermoplastic with dispersed
cellulose nanowhiskers) (Ozgur Seydibeyoglu and Oksman, 2008; Yao
et al., 2014)), or a mixture of both bio-based matrix and nanoparticle
components (e. g. poly (lactic acid) with dispersed cellulose microfibrils
and nanowhiskers) (Fujisawa et al., 2013; Miao and Hamad, 2016)).
As a part of our current research on radiation-cured materials with
improved physical and mechanical properties (Pichavant and Coqueret,
2008; Mougharbel et al., 2009), we have examined the possibility to
et al., 2014) as reinforcing additives in polyurethane acrylate materials.
The recent developments in water-based polyurethane acrylates
(Kozakiewicz, 2015, 2016; Xu et al., 2012) offer an interesting
opportunity to introduce CNC in the form of aqueous suspension into
the emulsion of matrix precursors. Using water as a common phase for
polymer and CNC mixing is expected to mitigate the risks for
uncontrolled CNC aggregation. Such a procedure avoids mixing
freeze-dried CNCs with molten or dissolved polymers that is known
to induce the formation of nanocrystal bundles in nanocomposites
(Khoshkava and Kamal, 2014; Santamaria-Echart et al., 2016).
Controlled acid hydrolysis of purified cellulose yields CNCs in the
form of rod-like nanoparticles with a section in the range of 3–25 nm
and lengths of a few hundred nanometers to 1–2 µm. Their size,
dimension, as well as their shape depend primarily on the origin of
cellulose source (Miriam de Souza Lima and Borsali, 2004), but also on
the conditions of hydrolytic preparation, such as the nature and
concentration of the acid, reaction time and temperature, purity of

⁎
Corresponding author.
E-mail address: xavier.coqueret@univ-reims.fr (X. Coqueret).

http://dx.doi.org/10.1016/j.radphyschem.2017.04.013
Received 10 November 2016; Accepted 21 April 2017
Available online 22 April 2017
0969-806X/ © 2017 Elsevier Ltd. All rights reserved.
K. Furtak-Wrona et al.
the starting material, and ultrasonic treatment. The relative degree of
crystallinity and the geometrical aspect ratio (length/cross-section) are
the main parameters that control the properties of CNC-based materials
(Lu and Hsieh, 2010; Siqueira et al., 2009).
A recent article (Poaty et al., 2014) reports on the use of CNCs
chemically modified for UV-curable wood coating formulations. In this
work, CNCs were acrylated for inducing the formation of covalent
bonds between the nanofiller and the host PUR acrylate matrix upon
UV-initiated polymerization. Gloss and haze measurements have shown
that the modified nanocellulose fibers ensure maintaining of esthetic
properties of coatings and impart enhanced abrasion resistance of the
coating at CNC contents as low as 2 wt% in the cured matrix.
Our work was aimed at comparing the influence of the irradiation
method on the properties of cured PUR acrylate networks comprising
small amounts (typically 1–5 wt%) of CNCs. The potential benefits of
electron beam radiation in comparison with UV–visible was a central
issue worth to be addressed. We have selected CNCs obtained from
Ramie as bio-based reinforcing nanofillers with an aspect ratio about to
30:1 (Aguié-Béghin et al., 2016) for enhancing the mechanical proper-
ties of radiation-cured materials.
Because of the formation of sulfate ester groups during the sulfuric
acid hydrolysis of cellulose, the obtained CNCs are negatively charged
(Li and Ragauskas, 2011). Consequently, the nanoparticles are expected
to exhibit improved stability in aqueous solution that facilitates their
blending with the water-based PUR acrylate emulsions.
2. Experimental
2.1. Materials
The polyurethane acrylate dispersion (Bayhydrol UV 2282, aqueous
emulsion with 39 wt% of dry matter) was received from Bayer
(Material Science), France. The photoinitiator (PI) used for UV-curing
experiments was 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur
1173) obtained from BASF.
2.2. CNC preparation
CNC were prepared from Ramie (Boehmeria nivea). The washed
fibers were cut into small pieces and treated with 2 wt% NaOH at 20 °C
for 48 h to remove hemicelluloses, traces of pectin and residual
proteins. The obtained suspension was hydrolyzed overnight with
65 wt% H2SO4 at 35 °C with mechanical stirring. After washing with
water until neutrality and dialysis with 6000 Da cut-off membranes, the
purified aqueous colloidal suspension contains 3% (w/w) dry matter of
CNC. The stock suspension was stored at 4 °C and slightly sonicated
with a Sonics vibra-cell (750 W, Fisher-Bioblock) before use
(Hambardzumyan et al., 2012).
2.3. Preparation of films and bars
CNC suspension (1 wt% with the respect to the dry content of the
PUR acrylate dispersion) was added to the PUR acrylate emulsion and
stirred for 16 h with magnetic stirrer. The photoinitiator (1 wt% with
the respect to the dry content of the PUR acrylate dispersion) was added
to the formulations to be cured under UV–visible light. Formulations
were cast in silicone molds and allowed to dry for 2 days at room
temperature, and for 2 more days at 25 °C. A final treatment at 50 °C
was applied for achieving the coalescence process yielding a uniform
and transparent samples (10–50 µm-thick films or of 1 mm-thick bars)
in the form of a free-standing material.
2.4. Radiation-induced curing
The resulting dry samples (10–50 µm-thick films) were irradiated by
high intensity UV–vis LED lamp (FireLine™, Phoseon Technology
95
Radiation Physics and Chemistry 142 (2018) 94–99
395 nm, 8 W cm−2) or with a 150 kV EB laboratory accelerator
operated at a typical dose rate of 8 kGy s−1 (Advanced Electron
Beam, Wilmington, USA). Radiation curing of thicker samples (1 mm-
thick bars) was performed at IONISOS (Chaumesnil, France) with a
10 MeV Linac electron accelerator at room temperature and under air
(25 kGy or 2×25 kGy doses, at an average dose rate of 15 kGy s−1).
2.4.1. Characterization of radiation-cured samples
Determination of acrylate conversion – Fourier Transform Infrared
(FTIR) analyses were performed with a Vertex 70 spectrometer (Bruker,
Germany). Polymerization monitoring was performed by Mid-InfraRed
spectroscopy (MIR) for thin films (10–50 µm) coated on a Si wafer or as
free-standing films, and by near-infrared (NIR) for free-standing
samples with the thickness up to 1 mm. Spectra were recorded using
32 scans at a resolution of 4 cm−1 from 400 to 4000 cm−1 and from
2000 to 7000 cm−1, respectively for MIR and NIR. The degree of
conversion (π) was calculated by the following formula:
⎛ Aacrylate × A 0 ⎞
π = ⎜⎜1− ⎟⎟ × 100%
ref
0
⎝ Aref × Aacrylate ⎠ (1)
where: Aacrylate is the absorbance for acrylate peak for irradiated sample
(at 810 cm−1 for MIR or at 6164 cm−1 for NIR), Aref 0
is the absorbance
for reference peak for irradiated sample, Aref corresponds to the
absorbance for reference peak for non-irradiated sample and Aacrylate 0
to the absorbance for acrylate band for non-irradiated sample (at
810 cm−1 for MIR analyses or at 6164 cm−1 in the case of NIR).
Thermo-physical properties – Differential Scanning Calorimetry
(DSC) analysis was carried out with a DSC Q100 differential calorimeter
(TA Instruments, USA) fitted with a liquid nitrogen cooling system.
Aluminum pans filled with the water-based formulations were heated at
55 °C on a heating plate during 8 h for allowing extensive water
evaporation. The samples were irradiated with dose 25 kGy or
2×25 kGy. The heating and cooling rates were 5 °C min−1 from
−50 °C to 150 °C to examine the effect of CNC content on the thermal
properties (particularly the glass transition temperature, Tg) of the
nanocomposite films.
Dynamic Mechanical Analysis (DMA) – Rheometric characterization
of nanocomposite films was carried out with a DMA Q800 equipment
(TA Instruments, USA) working in tensile mode. The measurements
were performed at a frequency of 1 Hz, with a strain amplitude of
0.05%, in the temperature range from −80 °C to 200 °C and a heating
rate of 5 °C min−1. The samples were prepared by cutting strips from
the composite films (5×25 mm2 samples of thickness 200–300 µm).
2.4.2. Measurements of the tensile properties of cured materials
The mechanical behavior for the unfilled matrix and the nanocom-
posites was analyzed with a micromechanical testing instrument
(Deben Ltd, UK). Experiments were performed with the elongation
speed of 0.4 mm min−1 on a total displacement of 20 mm at room
temperature. Samples (width 5 mm, length 25 mm) were prepared by
cutting strips from the nanocomposite films. The results were the
average of at least five measurements.
3. Results and discussion
The comparison between the two modes of radiation-initiated
polymerization that were selected for the present investigation requires
careful preparation of the nanocomposites from water-based suspen-
sions and of the unfilled PUR acrylate matrix. Particular attention was
devoted to the experimental preparation of dry films and dry bars by
evaporation and coalescence of the PUR acrylate emulsions including
the desired additives (CNC, photoinitiator for UV–visible curing
experiments), and to the control of the degree of curing in the samples
submitted to physical analyses.
K. Furtak-Wrona et al.
Scheme 1. Typical molecular structure of an emulsible PUR acrylate and schematic of the corresponding emulsified particle in water.
3.1. Preparation of CNCs and of radiation curable formulations
The base PUR acrylate material (Scheme 1) is available as milky
fluid with 39 wt% of dry matter having a slightly alkaline pH (about
7.5). The blends for elaborating nanocomposite materials are thus
easily prepared by adding the desired amount of CNC suspension. For a
final CNC content of 1 wt% in the PUR acrylate matrix, the volume of
CNC suspension to be added to a prepolymer emulsion of volume V0
represents about 13% of that volume, with limited impact on the drying
process and coalescence phenomena for obtaining free-standing mate-
rials ready for radiation curing. Obviously, when larger amounts of CNC
are desired in the nanocomposite, much greater volumes of water will
be added and have to be evaporated.
For UV–visible curing under the 395 nm LED light, the photoini-
tiator is added and mixed under stirring at concentration of 1 part for
100 parts of PUR acrylate. The low absorbance of PI at the working
wavelength allows for the penetration of the light in the depth of the
samples without significant gradient of photon absorption, even in
1 mm thick bars obtained after evaporation of the water.
The drying of the formulated proceeds in a sequence of steps
eventually leading to clear and homogeneous materials after extensive
coalescence of the soft PUR acrylate particles (Steward et al., 2000).
The initial stage consists in the evaporation of excess water leading to
the compaction of the particles that gradually adopt a hexagonal type of
packing. Interdiffusion of the polymer segments is facilitated by the low
minimum film forming (MFF) temperature of the selected emulsion
(TMFF=0 °C). This step is finished when a dry film is formed as a
transparent and free-standing material.
As CNC are present in the form of rigid nanorods in the water
suspension, with low ability to diffuse inside the prepolymer particles,
we can reasonably assume that they are located at the interfaces of
hexagons during concentration stage and that they can play a beneficial
role by reinforcing the interstitial domain between the initially isolated
prepolymer particles. A schematic representation of the coalesced
material including CNC is shown in Scheme 2.
After having tested different drying conditions, we have adopted the
protocol detailed in the experimental part which afforded materials
with uniform appearance. We also focused our attention to samples
containing limited amount of 1 wt% of CNC for two main reasons.
Scheme 2. Simplified representation of the location of CNCs at the boundary between
PUR acrylate latex particles undergoing coalescence.
96
Radiation Physics and Chemistry 142 (2018) 94–99
Firstly, higher level of nanofillers (e.g. 5–10 wt% with respect to the
PUR acrylate matrix) require introducing excessive amounts of water
that may not lead to well-defined and regular nanocomposites, the large
amount of fluid likely favoring the transport of some materials and
possibly inducing macroscale phase separation between the ingredients
present in the complex suspensions. Secondly, we considered that the
saturation by CNC of the interfaces between the prepolymer particles
undergoing coalescence may lead to a very complex microstructure that
would not allow for a good control of the system uniformity and for a
simple interpretation of the effects on nanocomposites mechanical
properties.
3.2. Control of the degree of curing in PUR acrylate materials by FTIR
The mechanical properties of the uniform materials obtained after
drying are essentially driven by their chemical composition and by the
degree of conversion of the acrylate functions. A detailed investigation
of the reactivity of different blends was conducted by FTIR spectroscopy
(Patacz et al., 2000). MIR analyses were performed for thin films
(50–100 µm-thick) and NIR measurements for thicker samples prepared
in the form of plates or bars (up to 1 mm thick). Typical spectra
recorded are reproduced in Fig. 1a) and 1 b). The progress of acrylate
conversion as a function of radiation dose can be measured accurately
by using invariant bands as internal standards.
The degree of conversion of acrylate in the unfilled and in the
nanocomposite materials was quantified on the basis of the changes of
IR absorbance according to Eq. (1), as detailed in the experimental part.
The corresponding kinetic profiles of unfilled and nanocomposite
samples irradiated with 395 nm LED array are shown on the plots of
Fig. 2 that reveal almost no difference in polymerization rates at the
different stage of the curing process. High levels of conversion are
obtained within less than 1 min of exposure to UV–visible light, in spite
of the low absorbance of the selected PI at 395 nm. The polymerization
rate levels off when acrylate reaches 70–80% of conversion, as the
network starts vitrifying.
Similar conclusions were drawn from MIR monitoring of the curing
process in thin films submitted to the beam of the 150 keV laboratory
accelerator, with kinetic profiles resembling those already reported
earlier for non water-based PUR acrylates (Patacz et al., 2000). The
presence of 1 wt% CNC in the nanocomposite material was shown not
to induce any significant differences with respect to the kinetic profiles
recorded with the unfilled PUR acrylate.
For comparing the physical and mechanical properties of the
unfilled and the nanocomposite samples, we defined target values of
85 and 90 mol-% for acrylate conversion. These values correspond to
the application of doses of 25 and 2×25 kGy, respectively, for 1 mm-
thick samples exposed to the 10 MeV Linac beam.
The conditions for curing 1 mm-thick bar samples under UV–visible
light were adjusted to reach the desired acrylate conversion level that
was controlled by NIR spectroscopy. The corresponding times of
exposure were typically between 40 and 180 s under the 395 nm LED
K. Furtak-Wrona et al.
Fig. 1. FTIR spectra for PUR acrylate including 1 wt% of CNC upon 395 nm LED irradiation (8 W cm−2) a) MIR spectra recorded from a 50 µm-thick film at t=0, 16, 50, 100, 170, 240,
310, 380, 450, 520, 610, 700 s); b) NIR spectra recorded from a 1 mm-thick bar at t=0, 5, 15, 30, 60, 105, 165, 225 s).
100
80
Conversion (%)
60
40
20
0 ducted with higher levels of CNCs (up to 5 wt%) incorporated in PUR
0 50 100 150 200
Irradiation time (s)
Fig. 2. Comparison of the kinetic profiles of acrylate conversion in thin films, unfilled (◻)
and in nanocomposite including 1 wt% of CNC (○) upon UV–visible curing with a 395 nm
LED (1 wt% of PI, 8 W cm−2).
array.
3.3. Thermal and mechanical behaviors of nanocomposites
The changes of thermo-physical properties of UV- and EB-cured PUR
acrylate materials, either unfilled or filled with 1 wt% of CNC, were
characterized by DSC and by DMA.
To evaluate the impact of the presence of CNC on thermal properties
of nanocomposites, the glass transition temperature was determined
from the inflexion point of the variation of heat capacity in the DSC
thermograms and from the maximum of the loss factor (tan δ)
associated with the α relaxation appearing in the thermomechanical
spectra (DMA).
The Tg measured for acrylate prepolymers was already shown to
depend strongly on the radiation dose via the induced change of
conversion which is the relevant descriptor of the curing process
(Krzeminski et al., 2010a, 2010b). In the case of EB irradiation of
1 mm-thick samples at a dose of 25 kGy, the measured values of Tg were
around 60–65 °C, for the unfilled and filled material prepared under
soft drying conditions. The Tg of the unfilled polymer material reached
slightly higher value when the sample was irradiated with the dose of
2×25 kGy. This is the expectable consequence of the increase of
conversion which progresses from 85% to 91%. However, the Tg of
samples containing 1 wt% of CNC submitted to 2×25 kGy dose was
maintained at the same level (Tg=64 °C) as the value measured for
samples cured with the dose of 25 kGy, in spite of a small increase of
conversion. The uncertainty on the degree of conversion as well the
possible of variable amounts of moisture from one sample to the other
incite us to be cautious on the potential effect on the influence of the
presence of CNCs on the glass transition of the nanocomposites.
DMA analysis did not reveal significant differences in the position of
Radiation Physics and Chemistry 142 (2018) 94–99
the maximum of the loss factor tan δ between unfilled and nanocom-
posite samples cured under the same conditions at a given level of
acrylate conversion. More visible changes were observed by comparing
the Tg of samples cured under different radiation sources, and/or at
different doses. The lowest Tg were obtained for samples irradiated with
LED lamp, with Tg values ranging from 70 °C to 72 °C. Higher Tg values
were observed for the EB-cured materials, in the range of 73–78 °C after
treatment at 25 kGy, and up to about 80 °C for a 2×25 kGy dose,
regardless of the presence of CNC in PUR acrylate material. We can
conclude to absence of noticeable effect of CNC's on the relaxation
behavior of the cured networks. Another series of experiments con-
250 emulsions dried in different conditions (in the presence of ethanol, film
formation at higher temperatures) and processed under EB to doses as
high as 200 kGy confirms the very small influence of the presence of
CNC in samples cured under the same conditions.
3.4. Mechanical properties of radiation-cured materials
Tensile measurements performed with a micromechanical testing
equipment allowed for the comparison of the cured materials in terms
of Young's modulus and tensile stress at break. Because of the know
sensitivity of ultimate tensile properties to small defects associated with
sample preparation or with the measurement itself, a large number of
specimens were tested so as to enable significant comparison between
samples of different composition or with different conditions of curing.
With respect to Young's modulus, the data presented in Fig. 3 reveal
a significant enhancement of the rigidity of radiation cured nanocom-
posite materials.
This behavior was present in all types nanocomposite samples,
irrespective of the irradiation source that was used. However, the
highest enhancement of such features was observed for samples
exposed to the moderate EB dose of 25 kGy. The enhancement of
Fig. 3. Young's modulus of unfilled cured PUR acrylate samples (hatched bars) or filled
with 1 wt% CNC materials (uniform gray bars) and submitted to EB irradiation, as
determined by mechanical microtesting.
97
K. Furtak-Wrona et al.
Table 1
Influence of the presence of CNC on the tensile strength of cured PUR acrylate samples
submitted to EB or to UV–vis LED −395 nm (PI content of 1 wt%) irradiation.
Radiation type Sample composition Radiation dose Acrylate
(in wt-parts) conversion
(%)
PUR PI CNC
EB 100 – – 25 kGy 85
100 – – 2×25 kGy 91
100 – 1 25 kGy 85
100 – 1 2×25 kGy 92
UV–vis LED 100 1 – 200 J cm−2 89
100 1 1 200 J cm−2 92
Young's modulus was in the range of about 500 MPa. The lowest
increase in modulus (about 300 MPa) was recorded for nanocomposite
samples cured with EB with the dose of 2×25 kGy.
It is worth to add here that more experiments were achieved for
examining the influence of the CNC content at levels up to 10 wt% of
the formulation. However, no significant increase in Young's Modulus
was observed upon increasing of the content of reinforcing cellulose
nanofibers. As already discussed, the conditions of elaboration of such
samples and the possible saturation of interstitial domains during
coalescence cast some doubts on the relevance of measurements
performed on samples with high CNC contents.
The ultimate tensile properties for UV- and EB-cured samples are
gathered in Table 1. Comparison of the data interestingly reveals
contrasting effects.
An efficient reinforcing effect associated with the presence of 1 wt%
of CNC is observed in EB-cured samples. The samples cured by
photopolymerization do not benefit from the presence of CNC. This
phenomenon can be explained by the limited radiolysis of the cellulose
in EB-cured samples. Additionally, a covalent coupling between the
nanofiller and the matrix could be caused by free radical grafting
reaction at the interface between the cellulosic particles and the PUR
acrylate matrix. During the irradiation with electron beam with the
dose of 25 kGy the degradation of cellulose by chain scission was
expected not to alter dramatically the polysaccharide structure.
Samples submitted to 2 passes of 25 kGy gained a smaller improvement
of mechanical properties when comparing with samples irradiated with
dose of 25 kGy. This is probably caused by some degradation of the
polysaccharide chains during the exposure on EB of 2×25 kGy. For
samples cured by photopolymerization, no significant enhancement of
mechanical properties is observed. Indeed, the selectivity of the
activation that only induces the photolysis of the initiator only triggers
acrylate polymerization without causing significant free radical grafting
onto the polysaccharide nanofiller.
4. Conclusions
CNCs available as dilute aqueous solutions can be easily introduced
into PUR acrylate emulsions. Appropriate conditions were defined for
curing samples in the form of thin films (50–100 µm) or 1 mm-thick
bars with well-controlled conversion levels that can be precisely
measured by MIR or NIR spectroscopy, depending on the thickness of
the samples. Treatment under 395 nm LED light or by EB processing
allowed for preparing by the two initiation methods samples with the
same curing level. At a given conversion degree for the acrylate
functions, the Tg of nanocomposite films was not significantly affected
by the presence of 1 wt% of CNC. The presence of CNC in the PUR
acrylate matrix was shown to double the σ value of the nanocomposite
cured to an acrylate conversion level of 85% by treatment with a
25 kGy dose under EB, whereas no increase of σ was observed in UV-
cured samples exhibiting the same acrylate conversion level. The
occurrence of grafting reactions inducing covalent linkages between
Radiation Physics and Chemistry 142 (2018) 94–99
the polysaccharide nanofiller and the PUR acrylate matrix during the
EB treatment is advanced as an explanation to account for the
improvement observed in samples cured under ionizing radiation.
Stress σ The benefits observed on the mechanical properties of samples contain-
(MPa) ing 1 wt% of CNC cured by exposure to a 25 kGy dose were not as high
when the material was submitted to 2 consecutive 25 kGy passes under
the electron beam. The loss of in the intrinsic mechanical properties of
20 ± 2 the polysaccharide nanofiller as a consequence of radiation-induced
28 ± 10 degradation is believed to reduce the reinforcing effect observed at
39 ± 8 25 kGy. Increasing of the content of CNC above 1 wt% did not show
35 ± 1 further increasing in the values of modulus. Further work is needed to
24 ± 7 gain a deeper understanding of this phenomenon related to the
23 ± 4 uniformity of CNC dispersion in the PUR acrylate matrix.
Acknowledgement
This work was conducted in the frame of the IAEA Coordinated
Research Project “Radiation processing of (nano)composites for enhan-
cing the features and utility in health care and industry”. Financial
support by Conseil Regional Grand Est, MENESR and EU-FEDER
Programme (CPER Project PlAneT) and IAEA is gratefully acknowl-
edged. The authors are grateful to Dr. C. Kowandy and to Dr. G. Tataru.
KFW and PKO (UMCS, Lublin, Poland) as well as KJ (UT Lodz, Poland)
acknowledge the support received from the European Union exchange
program Erasmus for their mobility to URCA, France.
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