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Design, Synthesis, and Use of Y-Shaped ATRP/NMP Surface Tethered Initiator.
2015
Heterogeneous polymer brushes on surfaces can be easily formed from a binary initiator on a silicon oxide substrate where two different types of polymers can be grown side-by-side. Herein, we designed a new Y-shaped binary initiator using straightforward chemistry for “grafting from” polymer brushes. This initiator synthesis takes advantage of the Passerini reaction, a multicomponent reaction combining two initiator sites and one surface linking site. This Y-shaped binary initiator can be synthesized in three steps with a higher yield than other similar initiators reported in the literature, and can be performed on a multigram scale. We were able to attach the initiator to a silicon oxide s…
Polysiloxane-backbone block copolymers in a one-pot synthesis: a silicone platform for facile functionalization.
2012
Block copolymers consisting exclusively of a silicon-oxygen backbone are synthesized by sequential anionic ring-opening polymerization of different cyclic siloxane monomers. After formation of a poly(dimethylsiloxane) (PDMS) block by butyllithium-initiated polymerization of D3, a functional second block is generated by subsequent addition of tetramethyl tetravinyl cyclotetrasiloxane (D4(V) ), resulting in diblock copolymers comprised a simple PDMS block and a functional poly(methylvinylsiloxane) (PMVS) block. Polymers of varying block length ratios were obtained and characterized. The vinyl groups of the second block can be easily modified with a variety of side chains using hydrosilylation…
Strategy for good dispersion of well-defined tetrapods in semiconducting polymer matrices.
2014
The morphology or dispersion control in inorganic/organic hybrid systems is studied, which consist of monodisperse CdSe tetrapods (TPs) with grafted semiconducting block copolymers with excess polymers of the same type. Tetrapod arm-length and amount of polymer loading are varied in order to find the ideal morphology for hybrid solar cells. Additionally, polymers without anchor groups are mixed with the TPs to study the effect of such anchor groups on the hybrid morphology. A numerical model is developed and Monte Carlo simulations to study the basis of compatibility or dispersibility of TPs in polymer matrices are performed. The simulations show that bare TPs tend to form clusters in the m…
Designing Medical Devices Based on Silicon Polymeric Material with Controlled Release of Local Anesthetics
2012
The drug delivery systems that are the object of this article take the form of a polymer matrix made of silicone containing a drug. These devices can be used as patches for local dermal applications releasing the drug in a controlled manner. The model active agent, lidocaine hydrochloride was chosen from the range of local anesthetics. When the drug is restricted to the surface, it is released more rapidly than when it is allowed to spread evenly throughout the silicon structure. When hydrophilic polymers such as PVA and HEC are mixed in with the lidocaine hydrochloride and deposited on the surface of the polymer matrix, we observed that the burst effect was eliminated without modifying the…
Processing and adjusting the hydrophilicity of poly(oxymethylene) (co)polymers: nanoparticle preparation and film formation
2016
Handling the insoluble POM: the preparation of nanoparticles based on hyperbranched-linear-hyperbranched ABA triblock copolymers with variable hydrophilicity and composed of short hyperbranched polyglycerol (hbPG) as the A-blocks and linear poly(oxymethylene) (POM) as a B-block is described. The POM-hbPG-nanoparticles with diameters in the range of 190 to 250 nm were generated in a convenient process, combining the solvent evaporation process with the miniemulsion technique, a water borne handling for POM-copolymers. Furthermore, the film formation properties of the nanoparticles were investigated by deposition on silicon and subsequent sintering, which leads to films with a thickness in th…
SPM and TOF-SIMS investigation of the physical and chemical modification induced by tip writing of self-assembled monolayers
2003
Abstract The nanoelectrochemical modification of alkyl self-assembled monolayers (SAMs) obtained on hydrogenated silicon surfaces via radical-initiated reactions of 1-octadecene has been investigated. Scanning Probe Microscopy (SPM) showed that the modification of the organic layer occurs by applying either positive or negative biases to the tip at a threshold of about ±5 V. When the bias absolute value was ≤6 V, the height of the monolayer was only faintly modified, whereas a consistent increase in tip/sample friction force was observed, in agreement with the formation of hydrophilic moieties at the organic surface. In addition to the increase of friction, bias absolute values larger than …
Nanowear on Polymer Films of Different Architecture
2007
In this paper, we describe atomic force microscope (AFM) friction experiments on different polymers. The aim was to analyze the influence of the physical architecture of the polymer on the degree and mode of wear and on the wear mode. Experiments were carried out with (1) linear polystyrene (PS) and cycloolefinic copolymers of ethylene and norbornene, which are stabilized by entanglements, (2) mechanically stretched PS, (3) polyisoprene-b-polystyrene diblock copolymers, with varying composition, (4) brush polymers consisting of a poly(methyl methacrylate) (PMMA) backbone and PS side chains, (5) PMMA and PS brushes grafted from a silicon wafer, (6) plasma-polymerized PS, and (7) chemically c…
Fully Vacuum-Processed Wide Band Gap Mixed-Halide Perovskite Solar Cells
2017
Methylammonium lead mixed-halide perovskites MAPb(BrxI1–x)3 are promising materials for the preparation of tandem devices. When exposed to light, MAPb(BrxI1–x)3 segregates in iodide- and bromide-rich phases, limiting the achievable photovoltage and hence the attainable device efficiency. To date only solution-processed mixed-halide perovskites have been demonstrated. We present fully vacuum-deposited mixed-halide perovskite thin films with band gap of 1.72 and 1.87 eV, prepared by controlling the deposition rates of the different halide precursors. When used in thin-film devices, these materials lead to power conversion efficiencies of 15.9 and 10.5%, respectively, which are among the highe…
Visible polarized light transmission spectroscopy of the electro-optic switching behaviour of surface stabilized ferroelectric liquid crystal cells
1991
Abstract We present in this paper an experimental and theoretical modelling study of the switching characteristics and electro-optic behaviour of chevron surface stabilized ferroelectric liquid crystal cells with planar (low pre-tilt) and non-planar (high pre-tilt) surface conditions. The visible polarized light transmission spectra were taken of the cells with glass plates coated with films of either rubbed polymer or obliquely evaporated silicon monoxide (SiO) at various applied voltages and in various stages of switching and compared with the theoretical values calculated numerically based on our director-polarization structure model for the aforementioned cells. The results provide evid…
ChemInform Abstract: Liquid-Crystalline Ordering as a Concept in Materials Science: From Semiconductors to Stimuli-Responsive Devices
2013
While the unique optical properties of liquid crystals (LCs) are already well exploited for flat-panel displays, their intrinsic ability to self-organize into ordered mesophases, which are intermediate states between crystal and liquid, gives rise to a broad variety of additional applications. The high degree of molecular order, the possibility for large scale orientation, and the structural motif of the aromatic subunits recommend liquid-crystalline materials as organic semiconductors, which are solvent-processable and can easily be deposited on a substrate. The anisotropy of liquid crystals can further cause a stimuli-responsive macroscopic shape change of cross-linked polymer networks, w…