Odent poster smpc

1. IONIC STRENGTH REVISITED IN MULTI-RESPONSIVE NANOCOMPOSITES
J. Odent1,2, C. Samuel3, S. Barrau4, A. Enotiadis2, T. J. Wallin2, W. Pan2, K. Kruemplestaedter5, R. F. Shepherd5, E. P. Giannelis2, J.-M. Raquez1, Ph. Dubois1
1Laboratory of Polymeric and Composite Materials (LPCM) - Center of Innovation and Research in Materials & Polymers (CIRMAP), University of Mons (UMONS), 23 Place du Parc, B-7000 Mons, Belgium ; 2Department
of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA ; 3Department of Polymers and Composites Technology and Mechanical Engineering (TPCIM), Mines Douai, Rue Charles Bourseul 941,
CS 10838, 59508 Douai, France ; 4Unité Matériaux et Transformations (UMET)−CNRS UMR 8207, Université Lille 1, 59655 Villeneuve d’Ascq, France ; 5Sibley School of Mechanical and Aerospace Engineering, Cornell
University, Ithaca, NY 14853, USA
Despite extensive progress to engineer new polymer nanocomposites for a broad range of technologies and provide value-added performance to the system without the associated
property trade-offs, true demonstrations are few and far between. This feature has made dynamic polymer systems, where specific bonds or interactions can selectively undergo
reversible breaking and restoration under certain conditions, the focus of several scientific and engineering studies. Herein, we report for the first time the design and synthesis of a
novel family of materials, i.e. multi-responsive nanocomposites built on ionic interactions between charged imidazolium-functionalized polymeric canopy and surface-modified
sulfonated silica nanoparticles. This design offers the possibility to endow materials with multi-responsive properties from stimuli-responsiveness to shape-memory and self-healing.
Introduction
Approach and Results
LPCM thanks the Belgian Federal Government Office of Science Policy (SSTC- PAI 6/27) for general support and is much indebted to both “Région Wallonne” and the European
Commission “FSE and FEDER” for financial support in the frame of Phasing-out Hainaut. The authors also acknowledge support from the International Campus on Safety and
Intermodality in Transportation, the Nord-Pas-de-Calais Region, the Qatar National Research Fund (Grant # 5 -1437-1-243) and the use of facilities at the “Cornell Center for Materials
Research” supported by the National Science Foundation (Award No. DMR-1120296) and the King Abdullah University of Science and Technology (Award No. KUS-C1-018-02). J. Odent
gratefully thanks Wallonie-Bruxelles International (WBI, mobility grant) and the Belgian American Educational Foundation (BAEF) for its financial support. J-M. Raquez is a research
associate at F.R.S.-FNRS (Belgium).
Acknowledgments
Shape-memory behavior of polylactide/silica ionic hybrids
Fig. 1. Conventional, non-responsive polylactide (PLA) can be endowed with shape-memory behavior by
blending commercial PLA with imidazolium-terminated glassy PLA (im-PLA) and rubbery poly[ε-caprolactone-
co-D,L-lactide] (im-P[CL-co-LA]) oligomers and adding surface-modified silica nanoparticles (SiO2-SO3). The
new materials design leads to better nanoparticle dispersion with distinct morphologies in the hybrids.
PLA
+SiO2-SO3+im-PLA+im-P[CL-co-LA]
Fig. 3. A constant creep compliance, an extremely long
rubbery plateau and longer relaxation times are
consistent with the significant shape-memory behavior
observed for the ionic hybrids. This suggest that the
ionic interactions facilitate shape-memory by serving
as a permanent network and by preventing permanent
slippage.
Highly Elastic, Transparent, and Conductive 3D-Printed Ionic Composite Hydrogels
Fig. 4. The new nanocomposites leverage the electrostatic interactions of imidazolium-functionalized
polyurethanes (im-PU) and surface-modified sulfonate silica nanoparticles (SiO2-SO3H). This design
offers the possibility to endow materials with multi-responsive properties from stimuli-responsiveness to
shape-memory and self-healing.
Ultra-Stretchable Ionic Nanocomposites:
From Dynamic Bonding to Multi-Responsive Behavior
Fig. 5. Rheologically the materials transition from
liquid-like to solid-like behavior as the concentration
of SiO2-SO3H increases, confirming the
establishment of an extensive 3D particles network
within the system.
Fig. 6. All in all the nanocomposites not only
combine simultaneous improvements in stiffness,
toughness and extensibility but they also exhibit
unique strain-dependent behavior (i.e. the
deformation increases with increasing strain rate).
Fig. 2. A second, low-frequency relaxation was observed in the hybrids with SiO2 nanoparticles that we
attribute to strongly bound polymer chains on silica due to electrostatic interactions.
Fig. 7. A new family of ionic composite hydrogels were rapidly 3D-printed at high resolution using commercial stereolithography
technology. The key to our formulation is the addition of anionically charged sulfonated silica nanoparticles to the cationic
ammonium-containing pre-polymer acrylate solution, which endows the system with dynamic, reversible ionic interactions.
FAST
3D-PRINTING
Fig. 8. When fabricated, the composites are highly stretchable (up to 425 %), tough (up to 53.5 kJ·m-3), and resilient (up to 97 %).
Fig. 9. Our printed object act as truly 3-dimensional compliant ionic conductors(up to
2.9 S·m-1 at f = 1 MHz).
Fig. 10. Designing high surface to volume ratio structures from this chemistry permits
fast diffusive swelling for practical implantation of large osmotically-driven actuators.
Macromolecules, 2017, 50, 2896
J. Mater. Chem. A, 2017, 5, 133571
Adv. Funct. Mater., 2017, 1701807