Reactive block copolymer modified thermosets : highly ordered nanostructures and improved properties

A highly ordered poly(dimethyl siloxane)-poly(glycidyl methacrylate) (PDMS-PGMA) reactive diblock copolymer was synthesized and used to modify bisphenol A-type epoxy resin (ER). The PDMS-PGMA block copolymer consisted of epoxy-miscible PGMA blocks and an epoxy-immiscible PDMS block. The PGMA reactive block of the block copolymer formed covalent bonds with cured epoxy and was involved in the network formation, and the PDMS block phase separated to give different ordered and disordered nanostructures at different blend compositions. The solvent cast PDMS-PGMA diblock copolymer showed ordered hexagonal cylindrical morphology. A highly ordered morphology consisting of hexagonal cylinders inside the lamellar morphology was observed in the cured PDMS-PGMA block copolymer. In the cured ER/PDMS-PGMA blends, a variety of morphologies including lamellar, cubic and worm-like and spherical nanostructures were detected depending on the blend composition. Moreover, the addition of this reactive diblock copolymer significantly increases the hydrophobicity and the glass transition temperature. It also improves the tensile strength and tensile ductility of the nanostructured thermosets at low diblock copolymer contents.

Late Guadalupian (Middle Permian) Fusuline fauna from the Xiala formation in Xainza county, central Tibet : implication of the rifting time of the Lhasa Block

A fusuline fauna consisting of 9 species of 4 genera from the Xiala Formation of the Mujiucuo section, Xainza County, Tibet, China is described. The fusuline fauna is dominated by Nankinella and Chusenella and indicates a Midian (Late Guadalupian) age. The earliest record of fusuline fauna during the Midian in the Lhasa Block suggests that the block rifted later than the Qiangtang Block to the north and the Baoshan and Tengchong blocks to the east, all of which yield much earlier fusuline faunas of Yakhtashian (Artinskian) age, but had drifted away from Gondwana to a relatively warm temperate zone in the Late Guadalupian (Middle Permian).

The Lopingian series in the Lhasa Block, Tibet and its palaeogeographical implications

Latest investigation indicates that the Lopingian Series including both terrestrial and marine deposit s are developed in the Lhasa Block. The marine Lopinigian Series in the Lhasa Block contains the compound coral Waagenophyllum, fusulinid Reichelina, and foraminifer Colaniella faunas , and the terrestrial Lopingian Series is characterized by both Cathaysian floras and mixed floras consisting of Gondwanan element s such as Glossopteris , Noeggerathiopsis, Phyllotheca and Cathaysian elements such as Pecopteris ,Sphenopteris. An anlaysis of the Lopingian sequences in the Lhasa Block reveals that it experienced a regression stage f rom Guadalupian to Lopingian. By contrast , the Himalayan Tethys Zone south to the Lhasa Block is characterized by typical Gondwanan Glossopteris flora , coldwater brachiopod and solitary coral faunas. In addition, the Lopingian sequence in the Himalayan Tethys Zone reflect s a transgressive process from the terrestrial Qubu Formation to the shallow marine Qubuerga Formation. Therefore, the Lhasa Block shows significant differences in both biota and depositional features from the Himalayan Tethys Zone during the Lopingian, which implies that the Lhasa Block had rifted from the northern periGondwanan margin before the Lopingian.

Hydrogen bonded block copolymer systems : from microphase separation in solid state to self-assembly in aqueous solutions

Block copolymer systems with hydrogen bonding interactions have received relatively little attention. Recently, we have investigated the self-assembly and phase separation in such block copolymer systems with an attempt to elucidate the role of hydrogen bonding interactions both theoretically and experimentally [1-4]. In A-b-B/C diblock copolymer/homopolymer systems, the phase behavior was theoretically analyzed according to the random phase approximation and correlated with hydrogen bonding interactions in terms of the difference in inter-association constants (K). To examine how the hydrogen bonding determines the self-assembly and morphological transitions in these systems, we have introduced the K values as a new variable into the phase diagram which we established for the first time (Fig. 1). Multiple vesicular morphologies were formed in aqueous solution of A-b-B/A-b-C diblock copolymer complexes of PS-b-PAA and PS-b-PEO. Interconnected compound vesicles (ICCVs) were observed for the first time as a new morphology (Fig. 2), along with other aggregated nanostructures including vesicles, multilamellar vesicles, thick-walled vesicles and irregular aggregates. Complexation of two amphiphilic diblock copolymers provides a viable approach to vesicles in aqueous media.

Microphase separation in double crystalline poly (ethylene oxide)-block-poly (caprolactone)/poly (4-vinyl phenol) blends

We report microphase separation induced by competitive hydrogen bonding interactions in double crystalline diblock copolymer/homopolymer blends of poly(ethylene oxide)-block-poly(ɛ-caprolactone) (PEO-b-PCL) and poly(4-vinyl phenol) (PVPh). The diblock copolymer PEO-b-PCL consists of two immiscible crystallizable blocks wherein both PEO and PCL blocks can form hydrogen bonds with PVPh. In these A-b-B/C diblock copolymer/homopolymer blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically PVPh and PEO block interact strongly whereas PVPh and PCL block interact weakly. The TEM and SAXS results show that the cubic PEO-b-PCL diblock copolymer changes into ordered hexagonal cylindrical morphology upon addition of 20 wt % PVPh followed by disordered bicontinuous phase in the blend with 40 wt % PVPh and then to homogenous phase at 60 wt% PVPh and above. Up to 40 wt % PVPh there is only weak interaction between PVPh and PCL due to the selective hydrogen bonding between PVPh and PEO. However, with higher PVPh concentration, the blends become homogeneous since a sufficient amount of PVPh is available to form hydrogen bonds with both PEO and PCL. A structural model was proposed to explain the self-assembly and morphology of these blends based on the experimental results obtained. The formation of nanostructures and changes in morphologies depend on the relative strength of hydrogen bonding interaction between each block of the block copolymer and the homopolymer (1-3).

A new route to nanostructured thermosets with block ionomer complexes

We report a novel approach to prepare nanostructured thermosets using block ionomer complexes. Neither block copolymer polystyrene-block-poly(ethylene-ran- butylene)-block-polystyrene (SEBS) nor block ionomer sulfonated SEBS (SSEBS) is miscible with diglycidyl ether of bisphenol A (DGEBA) type epoxy resin. It is thus surprising that the block ionomer complex of SSEBS with a tertiary amine-terminated poly(3-caprolactone) (PCL), denoted as SSEBS-c-PCL, can be used to prepare nanostructured epoxy thermosets. The block ionomer complex SSEBS-c-PCL is synthesized via neutralization of SSEBS with 3-dimethylamino- propylamine-terminated PCL. Sulfonation of SEBS yields the block ionomer SSEBS which is immiscible with epoxy. But the block ionomer complex SSEBS-c-PCL can be easily mixed with DGEBA. When the curing agent 4,4'-methylenedianiline (MDA) is added and the epoxy cures, the system retains the nanostructure. In cured epoxy thermosets containing up to 30 wt% SSEBS-c-PCL, the exclusion of the poly(ethylene-ran-butylene) (EB) phase forms spherical micro-domains surrounded by separated sulfonated polystyrene phase while the PCL side-chains of SSEBS-c-PCL are dissolved in the cured epoxy matrix. The spherical micro-domains are highly aggregated in the epoxy thermosets containing 40 and 50 wt% SSEBS-c-PCL. The existence of epoxy-miscible PCL side-chains in the block ionomer complex SSEBS-c-PCL avoids macro-phase separation. Hence, the block ionomer complex can act as an efficient modifier to achieve nanostructured epoxy thermosets.

Development of an intelligent system for the solder paste printing process

A neurogenetic-based hybrid framework is developed where the main components within the framework are artificial neural networks (ANNs) and genetic algorithms (GAs). The investigation covers a mode of combination or hybridisation between the two components that is called task hybridisation. The combination between ANNs and GAs using task hybridisation leads to the development of a hybrid multilayer feedforward network, trained using supervised learning. This paper discusses the GA method used to optimize the process parameters, using the ANN developed as the process mode, in a solder paste printing process, which is part of the process in the surface mount technology (SMT) method. The results obtained showed that the GA-based optimization method works well under various optimization criteria

Nanostructured block copolymer blends and complexes via hydrogen bonding interactions

This thesis investigates the influence of hydrogen bonding interactions on the self-assembly, phase behaviour and nanostructures of the block copolymer/homopolymer systems. The different combinations of block copolymer blends and complexes of AB/C, AB/CD, and ABC/D mixtures open a convenient way to tailor various morphologies with controlled size and shape.

Overcoming interfacial affinity issues in natural fiber reinforced polylactide biocomposites by surface adsorption of amphiphilic block copolymers

This work demonstrates that the interfacial properties in a natural fiber reinforced polylactide biocomposite can be tailored through surface adsorption of amphiphilic and biodegradable poly (ethylene glycol)-b-poly-(L-lactide) (PEG-PLLA) block copolymers. The deposition from solvent solution of PEG-PLLA copolymers onto the fibrous substrate induced distinct mechanisms of molecular organization at the cellulosic interface, which are correlated to the hydrophobic/hydrophilic ratios and the type of solvent used. The findings of the study evidenced that the performance of the corresponding biocomposites with polylactide were effectively enhanced by using these copolymers as interfacial coupling agents. During the fabrication stage, diffusion of the polylactide in the melt induced a change in the environment surrounding block copolymers which became hydrophobic. It is proposed that molecular reorganization of the block copolymers at the interface occurred, which favored the interactions with both the hydrophilic fibers and hydrophobic polylactide matrix. The strong interactions such as intra- and intermolecular hydrogen bonds formed across the fiber−matrix interface can be accounted for the enhancement in properties displayed by the biocomposites. Although the results reported here are confined, this concept is unique as it shows that by tuning the amphiphilicity and the type of building blocks, it is possible to control the surface properties of the substrate by self-assembly and disassembly of the amphiphiles for functional materials.