Self-cleaning and wear-resistant polymer nanocomposite surfaces

Superhydrophobic self-cleaning and wear-resistant nanocomposite surfaces were produced by mimicking the hierarchical structure of the lotus leaf using a combination of rapid self-assembly and a UV nano-imprint lithography (UVNIL) process with a silicone master. Two different acrylate formulations containing acrylated silica nanoparticles and an acrylated silicone surfactant were used. The presence of the silicone master did not suppress the spontaneous migration of the surfactant to the polymer surface, which increased its hydrophobic character. Adding acrylated silica particles considerably increased the viscosity of the acrylate suspensions and led to a shear-thinning behavior. However the particles did not prevent the fast migration process of the surfactant and further increased the hydrophobicity of the material, due to increased nanoscale roughness of the nanocomposite surface. The largest increase of hydrophobicity was achieved for the UVNIL printed lotus surfaces using the acrylate formulation with lowest viscosity. These surfaces became superhydrophobic for the highest investigated concentration of silica. These nanocomposite lotus surfaces were, in addition, very hard with a microhardness above 400 MPa and particularly wear-resistant, and were self-cleaning with respect to hydrophobic contamination.

Light trapping polymer-based coatings for cost effective flexible thin film photovoltaics

Marina Aymara González Lazo

Thin film silicon solar cells benefit from a lower fabrication cost than crystalline silicon cells, but they have a lower efficiency. The aim of this thesis was to explore the light-management capabilities of sub-micron polymer-based textures, both for the back reflector and for the front encapsulation of thin film silicon solar cells. The thin active layers of these devices require some form of photon path length enhancement to increase their efficiency. For this purpose, light trapping textures were replicated using transparent low shrinkage acrylate hyperbranched polymer nanocomposites. To enable low pressure replication of textures with enhanced mechanical performance, silica nanoparticles and silicon-based sol-gel precursors were combined to create novel low viscosity hybrid nanocomposite resins. Indeed, the viscosity of these hybrid suspensions was found to be one to two orders of magnitude lower than that of particulate suspensions with an equivalent silica loading. The hybrid resins were cured by combined UV polymerization and condensation, and the mechanical performance of the resulting nanocomposites was characterized in terms of their Vickers microhardness. The Vickers microhardness increased from 112 MPa for the unmodified polymer matrix to 190 MPa and 148 MPa for the hybrid nanocomposites and particulate nanocomposites, respectively, at 20 vol% silica, and reached as much as 287 MPa for the hybrid nanocomposites at 30 vol% silica. For the back reflector, light scattering (LS) textures in the form of random sub-micron pyramidal features were replicated in the nanocomposites using a nickel template and UV-nanoimprint lithography. The influence of nanoparticle content and pressure on the morphology and light scattering properties of the replicas was studied using scanning electron microscopy and optical analysis. The roughness and coherence length of the textures were similar to those of the template for all the compositions and process pressures investigated. After optimization of the dual-cure process, very high replication fidelity could be obtained in each case, leading to haze greater than 99 % over the whole of the visible light spectrum and very effective light scattering performance for a broad range of angles. A durable antireflective (AR) front encapsulation is also key to enhancing the photovoltaic performance of thin film silicon solar cells. The AR performance of hyperbranched polymer nanocomposite textures replicated from a moth eye pattern using UV-nanoimprint lithography was established both experimentally and through simulations. Optimum patterns were found on the basis of effective medium theory (EMT) to be arrays of paraboloids with a periodicity of 340 nm, which provided stable AR performance for aspect ratios in the range of 0.6 to 1.75. Good agreement was obtained between the simulated and measured optical behavior of such AR arrays, with a normal reflectance in the visible range of around 4 % when using a glass substrate. The simulations also predicted a reduction in the hemispherical reflectance from 15 % to 6 % for this texture. A hierarchical texture was replicated from a lotus leaf into the hyperbranched polymer modified with a perfluorinated acrylate, and the same material was also used to replicate the AR moth eye texture. In both cases, the replication fidelity was again found to be excellent and the textures exhibited improved hydrophobicity. [...]

EPFL2015

Low-Stress UV-Curable Hyperbranched Polymer Nanocomposites for High-Precision Devices

Valérie Geiser

The aim of this thesis was to investigate the process-structure-property relationships of UV-curable hyperbranched polymer (HBP)/silica nanocomposites. Special attention was paid to the interplay between photo-conversion, rheological behavior, shrinkage, and stress dynamics. This knowledge was used to maximize the shape fidelity and dimensional stability of imprinted nano-patterns made with these nanocomposites. Two different processing routes, resulting in different nanocomposite morphologies, were compared. The first and more conventional approach was ultrasonic, solvent-assisted mixing with solid silica nanoparticles followed by UV curing, which led to a discrete dispersion of silica particles in the matrix. The second and more novel approach was a dual-cure process combining UV and sol-gel processing with liquid tetraethyl orthosilicate. The sol-gel process, using a low-viscosity organometallic precursor, overcame the potential processing issue of the highly viscous particulate nanocomposites and led to a hybrid material with a homogeneous silica network at nanometer scale. Rheological analysis of silica nanoparticle suspensions up to the concentrated regime in the HBP showed an exponential increase of the viscosity with the particle fraction for well-dispersed discrete particle systems. A liquid-to-solid transition occurred in the 5 to 10 vol% range, which was correlated with an immobilized layer of polymer hydrogen-bonded to the silanol groups on the surface of the particles, as was confirmed by calorimetric analysis. Polymerization kinetics of HBP nanocomposites and hybrids were analyzed by means of photo differential scanning calorimetry using an autocatalytic model. A time-intensity-superposition principle with power-law dependence was established, which invalidated the classic radiation dose equivalence principle. Gelation and modulus build-up were monitored using photo-rheology. The calorimetric and rheological data were combined in the form of time-intensity-transformation diagrams. It was found that gelation was delayed with respect to conversion up to 36% when lower UV intensities were used, which favored reduce polymerization stresses. The dynamics of polymerization shrinkage and internal stress build-up were investigated using photo-hyphenated interferometry and beam-bending methods. The linear shrinkage of the HBP was as low as 4.5%, which was further reduced to 3.3% with the addition of 20 vol% nanoparticles. The residual stress of HBP/SiO2 nanocomposites was below 5.5 MPa. That is well below the level of standard non-reinforced resins, in spite of an increased stiffness. For the sol-gel hybrids with 20 vol% SiO2, stress reduction by 50% with simultaneous stiffness increase by 20% with respect to corresponding particulate composites was demonstrated. The coefficient of thermal expansion was also lowered by 30%. Finally, nanogratings with a period of 360 nm and a step height of 12 nm were fabricated using UV-nanoimprint lithography with a glass or nickel master in a low-pressure (max. 6 bar) and rapid (≈1 min) process. Stable gratings were imprinted in the composite material containing up to 25 vol% of silica nanoparticles, despite the high viscosity of such compositions. Thanks to the exudation of a HBP-rich surface layer, the shape fidelity in terms of period of the replicated patterns was within 98% of the master, with shape distortion increasing with internal stress. The obtained nanogratings were used as a substrate for grated high refractive index TiO2 waveguides and then applied as wavelength-interrogated optical sensors (WIOS). An immunoassay with the polymer WIOS showed the same ultrahigh detection sensitivity as the standard glass-based devices. Therefore, the novel polymer-based sensor should be useful to probe contaminants in liquids with concentrations as low as a few ppb.

EPFL2010

Impact properties of shear thickening fluid impregnated foams

Véronique Michaud, Mathieu Soutrenon

Concentrated colloidal suspensions of silica particles in polyethylene glycol exhibit a shear thickening behavior: above a critical shear rate in a confined environment, they show a steep increase of viscosity. This reversible transition from a low to a high viscosity state is associated with a large energy absorption that could be harnessed for impact protection. As these suspensions are liquid at rest, however, shear thickening fluids (STFs) are difficult to use in practical applications. Furthermore, their specific rheological properties exist within a narrow range of concentration, so they tend to disappear when the material is in contact with air and humidity. In this work, a soft foam scaffold was impregnated with STF to provide a three-dimensional shape to the assembly at rest, while a silicone was cast around it to serve as a physical barrier to the external environment. A method to quickly impregnate the foam was proposed. Impact tests were carried out on the STF/foam/silicone composite pads using a free fall impact tower. Compared to rubber or pure silicone, larger energy absorptions, up to 85%, were observed, which could be repeated for multiple impacts. The transmitted shock waves were also reduced, showing the potential of this system for impact protection of structures.