Conclusion and outlooks: LED-cured self-replenishing coatings

Conclusion and outlooks

LED-cured self-replenishing coatings

Conclusion and outlooks: LED-cured self-replenishing coatings

This thesis aimed at developing hydrophobic UV-cured coatings, able to self-repair

surface functionality after damage. Self-replenishing behavior was provided by a
sufficient mobility and a homogeneous distribution of fluorinated dangling chains
chemically bonded to the polymeric network, in order to create a reservoir and avoid
extreme surface segregation. This concept was previously reported by researchers
from the Laboratory of Materials and Interface Chemistry (TU/e), for a model system
based on a low Tg polycaprolactone network cured under a thermal process. There
was thus a need of a polymer network that could afford higher mechanical properties
for industrial applications without changing the self-replenishing mechanism. Among
the different polymeric materials, interpenetrating polymer networks (IPNs) that
combine the properties of their different components were found particularly attractive
for this project. Synthesized with eco-friendly and fast UV-curing process, they are
really appealing for coatings applications. To address the drawbacks of the model
polycaprolactone-based system, namely thermal curing and Tg far below room
temperature (-40 C), it was envisaged to develop UV-cured IPNs combining low Tg
and flexible acrylate networks together with high Tg and resistant epoxide resins. By
this way, the resulting material would show better mechanical properties and
resistance, a Tg above room temperature, and less energy and time consumption.
Then, to get rid of the harmful radiation of UV, it was decided to cure these coatings
under friendlier LED light at 395 nm. These features, namely LED-curing and
enhanced final properties compared to the model system previously developed, offer
the prospect of real applications in the coating industry. The development of such
networks was carefully developed jointly by the Laboratory of Materials and Interface
Chemistry in TU/e and the Laboratory of Macromolecular Photochemistry and
Engineering at University of Haute Alsace, in collaboration with industrial partners of
the coating industry (DSM, Akzo Nobel, Saint-Gobain Recherche and Altana).

The first step of the project aimed at selecting promising acrylate / epoxide
candidates for low and hard phases combined in IPNs. A wide screening determined
potential combinations able to associate flexibility and resistance, without being too
brittle. Furthermore, thermomechanical characterizations spotted two systems
showing opposite morphologies, namely phase separation or high interpenetration,
chosen for thorough characterizations.

Conclusion and outlooks: LED-cured self-replenishing coatings

The second part focused on an IPN consisting of a polybutadiene dimethacrylate

and a dicycloaliphatic epoxide. The inherent thermodynamic parameters, structures
and properties of the two monomers, as well as the kinetics of formation of the final
film led to co-continous networks with different extents of phase separation
depending on IPN composition. This research set up a methodology and brought
understanding on morphology predictions using solubility parameters, phase
diagrams and kinetics of radical and cationic photopolymerizations. Furthermore, an
important property relied in the morphology obtained for the films, which influences
the bonding and the self-replenishing ability of the fluorinated dangling chains.
Consequently, a special attention was paid to morphology characterizations.
Dynamic mechanical analysis and atomic force microscopy techniques were coupled
to give trustful and detailed results about the amount of interpenetration in these
IPNs. Particularly, the acoustic mode of the AFM was implemented to give insight in
the difference of elasticity of samples surface via the monitoring of changes of the
contact resonance frequency. Images obtained represent sample stiffness and,
combined with phase imaging, they led to even more reliable results.

third

research

axis

investigated

an

IPN

system,

composed

of

polyethyleneglycol diacrylate and a dicycloaliphatic epoxide. Structures and

properties of these two monomers, together with their similar solubility parameters
were expected to lead to a high amount of interpenetration in the IPN structures,
whatever the acrylate / epoxide ratio. This was confirmed by DMA and AFM
characterizations, through desummation process and image analysis. Concerning the
curing of these IPNs under LED irradiation, a detailed investigation of radical and
cationic photoinitiating systems suitable for 395 nm wavelength was carried out, for
homopolymers as well as for IPNs. It resulted in the selection of a system composed
of a photosensitizer (isopropyl thioxanthone), a hydrogen donor (benzyl alcohol) and
an onium salt (Irgacure 250), efficient for the concomitant free radical and free radical
promoted cationic photopolymerization of these two networks at this wavelength.
Formation, viscoelastic properties and morphologies of the polyethyleneglycol
diacrylate / dicycloaliphatic epoxide IPNs cured under LED light were examined.
They showed only slight differences compared to UV-cured ones, in term of
thermomechanical properties and shape of DMA thermograms. These modifications

Conclusion and outlooks: LED-cured self-replenishing coatings

were explained by the sequence of formation of the two networks, which varied
between UV and LED light.

Finally, hydrophobic fluorinated dangling chains were incorporated into the IPNs
and photocuring was ensured under LED irradiation. Characterizations performed for
IPNs with and without dangling chains showed that their addition into the network did
not influence neither conversion and Tg values, nor shape of the tan curves. The
last part consisted in characterizing the self-reorientation behavior of these LEDcured coatings. All the examined films exhibited a multiple self-replenishing ability
upon consecutive surface damage, with a surface enriched with fluorine. However,
the self-repairing capacity was found to be linked to the thermomechanical properties
of the materials. Indeed, the softer the network, the easier the self-replenishing, with
hydrophobicity recovery kinetic faster and in a higher extent. The Tg of the
polycaprolactone-based model system was around -40 C. UV-cured acrylate-based
networks firstly developed showed Tg ranging from -40 C to 20 C depending on the
length of the PEGDA chain. To address this main hindrance, prepared LED-cured
IPN coatings possessed Tg between -10 C and 80 C depending on the system
composition. Even if the self-replenishing was found to happen faster and in a higher
amount in low Tg IPN networks, autonomous self-repairing of the surface functionality
was proved for coatings with Tg at 80 C, far above room temperature. This
improvement in thermomechanical properties combined with the economical and
ecological LED-curing process pave the way for new sustainable functional coatings
which could be used in industrial applications.

Despite the progress made towards real applications of these coatings, such as
LED-curing and improvement in mechanical properties, some issues are still to be
taken into account. The major drawback of the developed surface relies in the use of
perfluoroalkyl compounds for the dangling chains. An alternative would be to
incorporate poly(hexafluoro propylene oxide) compounds (PHFPO), as they have
less restrictions regarding environmental and health issues, because of their easier
degradation into small fragments. Such PHFPO dangling chains could be used in the
current films developed, or in other acrylate / epoxide IPN combinations. Therefore,
the synthesis of a polycaprolactone network bearing PHFPO end groups is currently
under investigation at TU/e. Another strategy consists of employing more eco-friendly

Conclusion and outlooks: LED-cured self-replenishing coatings

poly(dimethylsiloxane) (PDMS) based dangling chains to provide the hydrophobicity.

OH-functionalized PDMS dangling chains with Mw of 500 g.mol-1, connected to a
polycaprolactone spacer of 16 units have been successfully synthesized at TU/e, and
were proved to bring a self-replenishing effect for thermally-cured polycaprolactonebased coatings. Modification of these more ecological hydrophobic molecules with a
vinyl group is under progress. Thereafter, it is envisaged to incorporate these
methacrylate-terminated PDMS dangling chains into UV-cured acrylate networks and
IPNs and investigate the self-replenishing behavior. However, miscibility issues
between PDMS dangling chains and currently used acrylate / epoxide systems have
to be considered. Possible solutions for improving the compatibility would consist in
using IPNs composed of acrylated functionalized silicone / epoxide with low and high
Tg, respectively, or developing organic / inorganic networks via the photo sol-gel
process. Such hybrid coatings would be interesting as they can combine the
advantages of inorganic materials with those of organic polymers (namely rigidity
together with flexibility), resulting in a new single material with unique properties.

A step towards industrial applications of new innovative autonomous selfreplenishing coatings has been achieved, and the desire of bringing such functional
materials to end-users in the automotive industry becomes closer.