Prokopios Georgopanos

Robust Block Copolymer Mask for Nanopatterning Polymer Films

The formation of well-oriented cylinders with perpendicular morphology for polystyrene-b-polydimethylsiloxane (PS-PDMS) thin films was achieved by spin coating. The self-assembled PS-PDMS nanostructured thin films were used as templates for nanopatterning; the PDMS blocks can be oxidized as silicon oxy carbide microdomains, whereas the PS blocks were degenerated by a simple oxygen plasma treatment for one-step oxidization. As a result, freestanding silicon oxy carbide thin films with hexagonally packed nanochannels were directly fabricated and used as masks for pattern transfer to underlying polymeric materials by oxygen reaction ion etching (RIE) to generate topographic nanopatterns. By taking advantage of robust property and high etching selectivity of the SiOC thin films under oxygen RIE, this nanoporous thin film can be used as an etch-resistant and reusable mask for pattern transfer to various polymeric materials. This approach demonstrates a simple, convenient, and cost-effective nanofabrication technique to create the topographic nanopatterns of polymeric materials.

Influence of Poly(ethylene glycol) Segment Length on CO2 Permeation and Stability of PolyActive Membranes and Their Nanocomposites with PEG POSS.

Three grades of PolyActive block copolymers are investigated for CO2 separation from light gases. The polymers are composed of 23 wt % poly(butylene terephthalate) (PBT) and 77 wt % poly(ethylene glycol terephthalate) (PEGT) having the poly(ethylene glycol) segments of 1500, 3000, and 4000 g/mol, respectively. A commercial PEG POSS (poly(ethylene glycol) functionalized polyoctahedral oligomeric silsesquioxanes) is used as a nanofiller for these polymers to prepare nanocomposites via a solvent casting method. Single gas permeabilities of N2, H2, CH4, and CO2 are measured via the time-lag method in the temperature range from 30 to 70 °C. The thermal transitions of the prepared membranes are studied by differential scanning calorimetry (DSC). It is found that the length of PEG segment has a pronounced influence on the thermal transition of the polymers that regulates the gas separation performance of the membranes. The stability of the nanocomposites is also correlated with the thermal transition of the polyether blocks of the polymer matrices.

Silicon oxy carbide nanorings from polystyrene-b-polydimethylsiloxane diblock copolymer thin films

A silicon-containing diblock copolymer, poly(styrene)-b-poly(dimethylsiloxane) (PS-PDMS), with PDMS cylinders in a PS matrix has been synthesized through sequential anionic polymerization. PS-PDMS thin film was prepared by spin coating on silicon wafer. Perpendicular PDMS cylinders in the PS-PDMS thin film can be obtained by solvent annealing. The PS-PDMS thin film was employed as template for the formation of core-shell cylinder thin films through surface reconstruction. By taking advantage of the silicon-containing character, silicon oxy carbide nanopattern can be fabricated due to the crosslinking of PDMS blocks and the degradation of PS blocks through one-step oxygen plasma treatment. As a result, the formation of silicon oxy carbide nanoring arrays can be achieved. This method provides a convenient way to create silicon oxy carbide nanoring arrays from diblock copolymers.

Effect of the reactive amino and glycidyl ether terminated polyethylene oxide additives on the gas transport properties of Pebax® bulk and thin film composite membranes

This paper considers Pebax® MH 1657 as a material for the CO2/N2 separating layer in thin film composite (TFC) membranes. The CO2 permeability of Pebax® can be improved via blending with various poly(ethylene oxide) (PEO) based materials without loss of CO2/N2 selectivity. Analogous blends containing PEOs with reactive end groups have been investigated for the possibility of a network formation within the Pebax® matrix. The formation of network is possible through the reaction between two types of additives containing two reactive end groups. The thick film samples and TFC membranes were prepared from mixtures of Pebax® MH 1657, PEG DG526 and JEFFAMINE® with different molecular weights. The samples were characterized by single gas permeation measurements, DSC, and NMR. The samples with incorporated networks show improved and stable gas transport properties compared to the original polymer for both thick films and TFC membranes.

Synthesis, molecular characterization and self-assembly of (PS-b-PDMS)n type linear (n = 1, 2) and star (n = 3, 4) block copolymers

Well-defined linear (n = 1, 2) and star (n = 3, 4) architecture [polystyrene-b-poly(dimethylsiloxane)]n or (PS-b-PDMS)n block copolymers were synthesized by anionic polymerization and using various chlorosilanes as linking agents. The self-assembly of the novel synthesized copolymers revealed that microphase separation for the star-block copolymers is significantly influenced by entropy constraints due to the increased number of junction points.

Morphology and elasticity of polystyrene-block-polyisoprene diblock copolymers in the melt

The influence of morphology on the viscoelastic properties of melts of microphase-separated polystyrene-block-polyisoprene (PS-b-PI) diblock copolymers was investigated in oscillatory shear and creep recovery experiments. By means of anionic polymerization, three PS-b-PI diblock copolymers with a narrow molecular weight distribution and different types of morphology (spherical, cylindrical and lamellar microstructure) were prepared. Linear viscoelastic shear oscillations and creep recovery experiments in shear were performed in order to determine the elastic and viscous properties of the diblock copolymers in the melt at small and large time scales. Our analysis reveals that melts of diblock copolymers are characterized by a pronounced elastic behavior leading to a relatively large recoverable deformation in creep recovery experiments. The elasticity of the diblock copolymers is also revealed by the appearance of the creep-ringing effect. Morphological investigations were carried out to establish relations between microstructure and melt elasticity. Since ordering phenomena take place in melts of diblock copolymers until an equilibrium morphology is achieved, the storage modulus G′ of diblock copolymer melts increases with time up to a steady-state value.

Analysis of glass transition and relaxation processes of low molecular weight polystyrene-b-polyisoprene diblock copolymers

The objective of this study is to analyze the glass transition temperature and relaxation processes of low molecular weight polystyrene-block-polyisoprene diblock copolymers with different compositions, synthesized via anionic polymerization. Thermal properties were investigated by differential scanning calorimetry and dynamic-mechanical thermal analysis, while the morphologies at room temperature were investigated by transmission electron microscopy and small-angle X-ray scattering. The χN values indicate that the diblock copolymers lie near the weak segregation regime. Three different experimental techniques were applied to determine the dynamic properties, i.e., linear viscoelastic shear oscillations, creep recovery experiments, and dielectric spectroscopy. The rheological experiments were performed above the order–disorder transition temperature where the diblock copolymers behave like a Maxwell fluid. Our results indicate that the presence of the polyisoprene segments strongly influences the monomeric friction coefficient and the tendency to form entanglements above the order–disorder temperature. Consequently, the zero-shear rate viscosity of a diblock copolymer is much lower than the zero-shear rate viscosity of the neat polystyrene block (the polystyrene precursor of the polymerization procedure). Dielectric spectroscopy enables the analysis of relaxation processes below the glass transition of the polystyrene microphase. Frequency sweeps indicate the dynamic glass transition of the polyisoprene blocks, which are partly mixed with the polystyrene blocks, which are always the majority component in the block copolymers of this study.

Development and Characterization of Defect-Free Matrimid® Mixed-Matrix Membranes Containing Activated Carbon Particles for Gas Separation

In this work, mixed-matrix membranes (MMMs) for gas separation in the form of thick films were prepared via the combination of the polymer Matrimid® 5218 and activated carbons (AC). The AC particles had a mean particle size of 1.5 μm and a mean pore diameter of 1.9 nm. The films were prepared by slow solvent evaporation from casting solutions in chloroform, which had a varying polymer–AC ratio. It was possible to produce stable films with up to a content of 50 vol % of AC. Thorough characterization experiments were accomplished via differential scanning calorimetry and thermogravimetric analysis, while the morphology of the MMMs was also investigated via scanning electron microscopy. The gas transport properties were revealed by employing time-lag measurements for different pure gases as well as sorption balance experiments for the filler particles. It was found that defect free Matrimid® MMMs with AC were prepared and the increase of the filler content led to a higher effective permeability for different gases. The single gas selectivity αij of different gas pairs maintained stable values with the increase of AC content, regardless of the steep increase in the effective permeability of the pure gases. Estimation of the solubilities and the diffusivities of the Matrimid®, AC, and MMMs allowed for the explanation of the increasing permeabilities of the MMMs, with the increase of AC content by modelling.

Directed Self-Assembly of Star-Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism

Exploring the ordering mechanism and dynamics of self-assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self-assembling mechanism and kinetics of silicon-containing 3-arm star-block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self-assembly using topographically patterned substrates. The ordering process of the star-block copolymer within fabricated topographic patterns with PS-functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well-ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self-assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top-down and bottom-up approaches.

Exceptionally strong, stiff and hard hybrid material based on an elastomer and isotropically shaped ceramic nanoparticles

In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12–20 GPa and hardness of 15–18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.