236 research outputs found
Photoinduced 3D orientational order in side chain liquid crystalline azopolymers
We apply experimental technique based on the combination of methods dealing
with principal refractive indices and absorption coefficients to study the
photoinduced 3D orientational order in the films of liquid crystalline (LC)
azopolymers. The technique is used to identify 3D orientational configurations
of trans azobenzene chromophores and to characterize the degree of ordering in
terms of order parameters. We study two types of LC azopolymers which form
structures with preferred in-plane and out-of-plane alignment of
azochromophores, correspondingly. Using irradiation with the polarized light of
two different wavelengths we find that the kinetics of photoinduced anisotropy
can be dominated by either photo-reorientation or photoselection mechanisms
depending on the wavelength. We formulate the phenomenological model describing
the kinetics of photoinduced anisotropy in terms of the isomer concentrations
and the order parameter tensor. We present the numerical results for absorption
coefficients that are found to be in good agreement with the experimental data.
The model is also used to interpret the effect of changing the mechanism with
the wavelength of the pumping light.Comment: uses revtex4 28 pages, 10 figure
Poly(dimethylsiloxane)-Stabilized Polymer Particles from Radical Dispersion Polymerization in Nonpolar Solvent: Influence of Stabilizer Properties and Monomer Type
Particles used in electrophoretic display applications (EPD) must possess a number of specific properties ranging from stability in a nonaqueous solvent, high reflectivity, low polydispersity, and high charge density to name but a few. The manufacture of such particles is best carried out in the solvent of choice for the EPD. This opens up new interests in the study of nonaqueous dispersion polymerization methods, which deliver polymer particles suspended in low dielectric constant solvents. We explore in this article the use of a poly(dimethylsiloxane) macromonomer for the stabilization of poly(methyl methacrylate) polymer particles in dodecane, a typical solvent of choice for EPDs. The use of this stabilizer is significant for this method as it is directly soluble in the reaction medium as opposed to traditionally used poly(12-hydroxystearic acid)-based stabilizers. Additionally, the present study serves as a baseline for subsequent work, where nonaqueous dispersion polymerization will be used to create polymer particles encapsulating liquid droplets and solid pigment particles. In this article, the influence of the macromonomer molecular weight and concentration on the properties of the synthesized particles is studied. In addition, we investigate the possibility of synthesizing polymer particles from other monomers both as a comonomer for methyl methacrylate and as the only monomer in the process. The influence of macromonomer concentration is also studied throughout all experiments
Organic nanofibers embedding stimuli-responsive threaded molecular components
While most of the studies on molecular machines have been performed in
solution, interfacing these supramolecular systems with solid-state
nanostructures and materials is very important in view of their utilization in
sensing components working by chemical and photonic actuation. Host polymeric
materials, and particularly polymer nanofibers, enable the manipulation of the
functional molecules constituting molecular machines, and provide a way to
induce and control the supramolecular organization. Here, we present
electrospun nanocomposites embedding a self-assembling rotaxane-type system
that is responsive to both optical (UV-visible light) and chemical (acid/base)
stimuli. The system includes a molecular axle comprised of a dibenzylammonium
recognition site and two azobenzene end groups, and a dibenzo[24]crown-8
molecular ring. The dethreading and rethreading of the molecular components in
nanofibers induced by exposure to base and acid vapors, as well as the
photoisomerization of the azobenzene end groups, occur in a similar manner to
what observed in solution. Importantly, however, the nanoscale mechanical
function following external chemical stimuli induces a measurable variation of
the macroscopic mechanical properties of nanofibers aligned in arrays, whose
Young's modulus is significantly enhanced upon dethreading of the axles from
the rings. These composite nanosystems show therefore great potential for
application in chemical sensors, photonic actuators and environmentally
responsive materials.Comment: 39 pages, 16 figure
Stimuli Thresholds for Isomerization-Induced Molecular Motions in Azobenzene-Containing Materials.
We use large-scale molecular dynamics simulations of the isomerizations of azobenzene molecules diluted inside a simple molecular material to investigate the effect of a modification of the cis isomer shape on the induced diffusion mechanism. To this end we simulate incomplete isomerizations, modifying the amplitude of the trans-to-cis isomerization. We find thresholds in the evolution of the host molecules mobility with the isomerization amplitude, a result predicted by the cage-breaking mechanism hypothesis (Teboul, V.; Saiddine, M.; Nunzi, J. M.; Accary, J. B. J. Chem. Phys. 2011, 134, 114517) and by the gradient pressure mechanism theory (Barrett, C. J.; Rochon, P. L.; Natansohn, A. L. J. Chem. Phys. 1998, 109, 1505–1516.). Above the threshold the diffusion then increases linearly with the variation of the chromophore size induced by the isomerization
Spin Diffusion and Spin-Lattice Relaxation in Multiphase Polymers
A model which treats spin diffusion and spin-lattice relaxation in multiphase polymers on the same footing is proposed. This new approach allows for more accurate determination of domain sizes and interfacial thickness in the probed polymers. In a poly(styrene-b-isoprene) copolymer example a significant improvement in the agreement between the NMR measurements and the simulated results can be obtained with the incorporation of a spin-lattice relaxation term into the spin diffusion process. The obtained microphase structural parameters are similar to the small angle X-ray scattering results. In addition, the spin-lattice relaxation times (T1) in different domains can be predicted reasonably well based on T1s of the component homopolymers and on the microphase structure in the present model. © 1997 American Institute of Physics
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