Hybrid Nanocomposites with Tunable Alignment of the Magnetic Nanorod Filler

For many important applications, the performance of polymer-anisotropic particle nanocomposite materials strongly depends on the orientation of the nanoparticles. Using the very peculiar magnetic properties of goethite ({\alpha}-FeOOH) nanorods, we produced goethite-poly(hydroxyethyl methacrylate) nanocomposites in which the alignment direction and the level of orientation of the nanorods could easily be tuned by simply adjusting the intensity of a magnetic field applied during polymerization. Because the particle volume fraction was kept low (1-5.5 vol \%), we used the orientational order induced by the field in the isotropic phase rather than the spontaneous orientational order of the nematic phase. At the strongest field values (up to 1.5 T), the particles exhibit almost perfect antinematic alignment, as measured by optical birefringence and small-angle X-ray scattering. The results of these two techniques are in remarkably good agreement, validating the use of birefringence measurements for quantifying the degree of orientational order. We also demonstrate that the ordering induced by the field in the isotropic suspension is preserved in the final material after field removal. This work illustrates the interest, for such problems, of considering the field-induced alignment of anisotropic nanoparticles in the isotropic phase, an approach that is effective at low filler content, that avoids the need of controlling the nematic texture, and that allows tuning of the orientation level of the particles at will simply by adjusting the field intensity

Replacing Metals with Oxides in Metal-Assisted Chemical Etching Enables Direct Fabrication of Silicon Nanowires by Solution Processing

Metal-assisted chemical etching (MACE) has emerged as an effective method to fabricate high aspect ratio nanostructures. This method requires a catalytic mask that is generally composed of a metal. Here, we challenge the general view that the catalyst needs to be a metal by introducing oxide-assisted chemical etching (OACE). We perform etching with metal oxides such as RuO2 and IrO2 by transposing materials used in electrocatalysis to nanofabrication. These oxides can be solution-processed as polymers exhibiting similar capabilities of metals for MACE. Nanopatterned oxides can be obtained by direct nanoimprint lithography or block-copolymer lithography from chemical solution on a large scale. High aspect ratio silicon nanostructures were obtained at the sub-20 nm scale exclusively by cost-effective solution processing by halving the number of fabrication steps compared to MACE. In general, OACE is expected to stimulate new fundamental research on chemical etching assisted by other materials, providing new possibilities for device fabrication

Block-Copolymers Enable Direct Reduction and Structuration of Noble Metal-Based Films

Noble metal nanostructured films are of great interest for various applications including electronics, photonics, catalysis, and photocatalysis. Yet, structuring and patterning noble metals, especially those of the platinum group, is challenging by conventional nanofabrication. Herein, an approach based on solution processing to obtain metal-based films (rhodium, ruthenium (Ru) or iridium in the presence of residual organic species) with nanostructuration at the 20 nm-scale is introduced. Compared to existing approaches, the dual functionality of block-copolymers acting both as structuring and as reducing agent under inert atmosphere is exploited. A set of in situ techniques has allowed for the capturing of the carbothermal reduction mechanism occurring at the hybrid organic/inorganic interface. Differently from previous literature, a two-step reduction mechanism is unveiled with the formation of a carbonyl intermediate. From a technological point of view, the materials can be solution-processed on a large scale by dip-coating as polymers and simultaneously structured and reduced into metals without requiring expensive equipment or treatments in reducing atmosphere. Importantly, the metal-based films can be patterned directly by block-copolymer lithography or by soft-nanoimprint lithography on various substrates. As proof-of-concept of application, the authors demonstrate that nanostructured Ru films can be used as efficient catalysts for H-2 generation into microfluidic reactors

Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization

Herein we discuss band gap modification of MIL-125, a TiO2/1,4-benzenedicarboxylate (bdc) metal-organic framework (MOF). Through a combination of synthesis and computation, we elucidated the electronic structure of MIL-125 with aminated linkers. The band gap decrease observed when the monoaminated bdc-NH2 linker was used arises from donation of the N 2p electrons to the aromatic linking unit, resulting in a red-shifted band above the valence-band edge of MIL-125. We further explored in silico MIL-125 with the diaminated linker bdc(NH2)(2) and other functional groups (-OH, -CH3, -Cl) as alternative substitutions to control the optical response. The bdc-(NH2)2 linking unit was predicted to lower the band gap of MIL-125 to 1.28 eV, and this was confirmed through the targeted synthesis of the bdc-(NH2)(2)-based MIL,-125. This study illustrates the possibility of tuning the optical response of MOFs through rational functionalization of the linking unit, and the strength of combined synthetic/computational approaches for targeting functionalized hybrid materials

Hybrid materials science: a promised land for the integrative design of multifunctional materials

International audienceFor more than 5000 years, organic-inorganic composite materials created by men via skill and serendipity have been part of human culture and customs. The concept of ``hybrid organic-inorganic'' nanocomposites exploded in the second half of the 20th century with the expansion of the so-called ``chimie douce'' which led to many collaborations between a large set of chemists, physicists and biologists. Consequently, the scientific melting pot of these very different scientific communities created a new pluridisciplinary school of thought. Today, the tremendous effort of basic research performed in the last twenty years allows tailor-made multifunctional hybrid materials with perfect control over composition, structure and shape. Some of these hybrid materials have already entered the industrial market. Many tailor-made multiscale hybrids are increasingly impacting numerous fields of applications: optics, catalysis, energy, environment, nanomedicine, etc. In the present feature article, we emphasize several fundamental and applied aspects of the hybrid materials field: bioreplication, mesostructured thin films, Lego-like chemistry designed hybrid nanocomposites, and advanced hybrid materials for energy. Finally, a few commercial applications of hybrid materials will be presented

Novel hybrid poly(l-lactic acid) from titanium oxo-cluster via reactive extrusion polymerization

This paper reports the synthesis of novel hybrid poly(lactic acid) by use of a titanium oxo-cluster, acting both as a catalyst and crosslinking agent of the polymer matrix. The already reported oxo-cluster Ti16O16(OEt)32 ([Ti]16) was synthesized and screened at the lab-scale as catalyst for the bulk polymerization of L-lactide (L-LA). [Ti]16 was found to be highly active for this reaction as up to 90% conversion in 30 min was obtained, affording PLLAs with Mn up to 65 000 g·mol−1 and relatively narrow dispersities (1.2–1.6). These polymerization reactions were further transposed to reactive extrusion process in which [Ti]16 oxo-cluster kept its high activity, affording hybrid-PLLA materials with Mn close to 58 000 g·mol−1 (some PLLAs could not be dissolved). Electronic microprobe analysis of the resulting hybrid materials confirmed that the titanium oxo-cluster was well dispersed all over the PLLA matrix. Finally, it was shown that the hybrid PLLA containing [Ti]16 display superior dimensional stability under heat than commercial PLLA of same molar mass

Hybrid piezochromic coatings for impact detection on composite substrates for aeronautic

Structural Health Monitoring (SHM) is a major issue in the aeronautic field, especially for impact detection on composite materials which can be time consuming. Impact-sensitive coatings are an interesting way to save costs and time associated with these monitoring operations. This paper describes the successful preparation of a reversible piezochromic coating for impacts detection on composite substrates. It results from the incorporation of piezochromic pigments into a hybrid organic-inorganic matrix. It has been optimized by studying and quantifying their piezochromic behavior by UV-visible spectroscopy. It revealed that the piezochromic properties of the sensitive coating and the pigments alone are quite different and ruled by the hardness of the film. The obtained sensitivity and threshold pressure are determined to be 28% GPa−1 and 0.2 GPa respectively.Revêtements Piézochromes Réversibles pour la Détection d'Impacts sur Supports Composite

Hybrid piezochromic coatings for impact detection on composite substrates for aeronautic

International audienceStructural Health Monitoring (SHM) is a major issue in the aeronautic field, especially for impact detection on composite materials which can be time consuming. Impact-sensitive coatings are an interesting way to save costs and time associated with these monitoring operations. This paper describes the successful preparation of a reversible piezochromic coating for impacts detection on composite substrates. It results from the incorporation of piezochromic pigments into a hybrid organic-inorganic matrix. It has been optimized by studying and quantifying their piezochromic behavior by UV-visible spectroscopy. It revealed that the piezochromic properties of the sensitive coating and the pigments alone are quite different and ruled by the hardness of the film. The obtained sensitivity and threshold pressure are determined to be 28% GPa−1 and 0.2 GPa respectively

A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate

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