Martin Etchells Vigild

Effect of shear on cubic phases in gels of a diblock copolymer

The effect of shear on the orientation of cubic micellar phases formed by a poly(oxyethylene)–poly(oxybutylene) diblock copolymer in aqueous solution has been investigated using small-angle x-ray scattering (SAXS) and small-angle neutron scattering (SANS). SAXS was performed on samples oriented in a Couette cell using steady shear, and SANS was performed on samples subject to oscillatory shear in situ in a rheometer with a shear sandwich configuration. A body-centered-cubic (bcc) phase observed for gels with concentrations greater than 30 wt % copolymer was found to orient into a polydomain structure, with the close-packed {110} planes both parallel and perpendicular to the shear plane. For gels with 30 wt % copolymer or less, a face-centered-cubic (fcc) phase was observed, and this was also observed on heating the more concentrated gels that formed a bcc phase at room temperature. The fcc phase could be oriented to form a highly twinned structure, with a significant deviation from the ABCABC… stacking se...

Surface Modification of Nanoporous 1,2-Polybutadiene by Atom Transfer Radical Polymerization or Click Chemistry

Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based on nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls through two different methodologies: (1) three-step chemical conversion of double bonds of PB into bromoisobutyrate, and (2) photochemical functionalization of PB with bromoisobutyrate groups. Azide functional groups were attached onto the pore walls before click reaction with alkynated MPEG. Following ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while the morphology was investigated by small-angle X-ray scattering and transmission electron microscopy.

UV patterned nanoporous solid-liquid core waveguides

Nanoporous Solid-Liquid core waveguides were prepared by UV induced surface modification of hydrophobic nanoporous polymers. With this method, the index contrast (deltan = 0.20) is a result of selective water infiltration. The waveguide core is defined by UV light, rendering the exposed part of a nanoporous polymer block hydrophilic. A propagation loss of 0.62 dB/mm and a bend loss of 0.81 dB/90 degrees for bend radius as low as 1.75 mm was obtained in these multimode waveguides.

Analysing the nanoporous structure of aramid fibres

After consideration of the applicability of classical methods, a novel analysis method for the characterization of fibre void structures is presented, capable of fitting the entire anisotropic two-dimensional scattering pattern to a model of perfectly aligned, polydisperse ellipsoids. It is tested for validity against the computed scattering pattern for a simulated nanostructure, after which it is used to fit the scattering from the void structure of commercially available heat-treated poly(p-phenylene terephtalamide) fibre and its as-spun precursor fibre. The application shows a reasonable fit and results in size distributions for both the lengths and the widths of the ellipsoidal voids. Improvements to the analysis methods are compared, consisting of the introduction of an orientation distribution for the nano-ellipsoids, and the addition of large scatterers to account for the effect of fibrillar scattering on the scattering pattern. The fit to the scattering pattern of as-spun aramid fibre is improved by the introduction of the large scatterers, while the fit to the scattering pattern obtained from the heat-treated fibre improves when an orientation distribution is taken into account. It is concluded that, as a result of the heat treatment, the average width and length of the scatterers increase.

Design of an Injectable in Situ Gelation Biomaterials for Vitreous Substitute

To adapt the physical properties of living materials to their biological function, nature developed various types of polymers with outstanding physical behavior. One example is the vitreous body, which is important intraocular elements not only because of its optical and mechanical performances, but also due to its important role in the pathogenesis and treatment of conditions affecting adjacent tissues and eventually the whole eye. Here, we report a novel biocompatible material for injectable vitreous substitute, composed of thermosensitive amphiphilic polymer, which is capable of forming a transparent gel in the vitreous cavity. It is nontoxic, provides adequate support for the retina, and allows light to reach the sensory elements at the back of the eye. The amphiphilic polymer exhibits mechanical stability by assembling to form highly interconnected hydrophobic domains, which leads to the constitution of a network structure.

Unexpected phase behavior of an asymmetric diblock copolymer

We report on measurements of the transmitted depolarized light intensity and on small-angle neutron scattering (SANS) measurements on a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) diblock copolymer studied in the bulk. SANS measurements were made both on isotropic and on shear oriented samples. Apart from the disordered phase, three different ordered morphologies were identified as a function of temperature: the body-centered cubic structure at the lowest temperature, a noncubic, slightly birefringent intermediate phase, and a cubic high-temperature structure which may be body-centered cubic. The available data cannot, however, finally prove this. These findings are in contrast to both available theories and to expectations based on analogous experiments on related diblock copolymer systems.

Physisorption of SDS in a Hydrocarbon Nanoporous Polymer

Surface modification of nanoporous 1,2-polybutadiene of pore diameter approximately 15 nm was accomplished by physisorption of sodium dodecyl sulfate (SDS) in water. Loading of the aqueous solution and the accompanying physisorption of SDS into the hydrophobic nanoporous films were investigated in a wide range of concentrations. The loading showed varying dependence on the SDS concentration. No loading was observed for SDS concentrations below 4.0 mM. At concentrations above 5.0 mM, the initial part of loading showed a linear dependence on the square root of time, which can be interpreted as diffusion-controlled dynamics. Both the specific equilibrium loading and the final SDS adsorption reached plateau values at concentrations above 6.8 mM. The infiltration of SDS into the nanoporous film was mainly followed by gravimetry and for a few samples confirmed by X-ray photoelectron spectroscopy (XPS). The SDS adsorption isotherm can be well described by the Langmuir model, consistent with a monolayer adsorption onto the pore walls. The surface modified by the surfactant clearly showed water wettability, in contrast to the original hydrophobic nanoporous 1,2-PB. We also looked at the release process of SDS out of the nanopores in the presence of excess of water or methanol. A discussion of the very different time scales of release in the two media is presented at the end of the paper.

Structural evolution of human recombinant αB-crystallin under UV irradiation

External stresses cause certain proteins to lose their regular structure and aggregate. In order to clarify this abnormal aggregation process, a structural evolution of human recombinant alphaB-crystallin under UV irradiation was observed with in situ small-angle neutron scattering. The abnormal aggregation process was identified to fall in three time zones: incubation, aggregation, and saturation. During the incubation time, the size of aggregates was almost unchanged but a deformation in the local structure was developing. After the incubation time, abnormal aggregation proceed. When the volume of the aggregates reached around twice the size as that of the initial aggregates, the aggregation rate slowed down, which marked the onset of saturation.

Gyroid nanoporous scaffold for conductive polymers

Conductive nanoporous polymers with interconnected large surface area have been prepared by depositing polypyrrole onto nanocavity walls of nanoporous 1,2-polybutadiene films with gyroid morphology. Vapor phase polymerization of pyrrole was used to generate ultrathin films and prevent pore blocking. The resulting nanoporous polymers exhibited a promising electroactivity.

Load–release of small and macromolecules from elastomers with reversible gyroid mesoporosity

A collapsed elastomeric matrix of lightly cross-linked 1,2-polybutadiene (1,2-PB) was prepared from a self-assembled 1,2-polybutadiene-b-polydimethylsiloxane (1,2-PB-b-PDMS) of gyroid morphology after the removal of the PDMS block. No mesoporosity could be observed in the material in the dry state. However, in the gel state in the presence of a good solvent the swollen matrix did show a nanoporous structure originated from the gyroid block copolymer precursor. Nanopores can be opened or closed depending on the presence or absence of a solvent. Macromolecules like PEG of different molecular weights or small molecules like the surfactant SDS were loaded into the opened nanoporous matrix in the presence of a solvent and remained trapped. The loaded molecules could be released again in the presence of a solvent. The load and release of the molecules in deuterated form were monitored by in situ time-resolved small angle neutron scattering, SANS. The bicontinuous gyroid pore structure is accessible to macromolecules without the need for sample pre-alignment. The materials presented here are model systems for a novel type of load-delivery systems that could show great potential in e.g. diagnostics or drug delivery applications.