Functionalized nanoporous thin films from metallo-supramolecular diblock copolymers

A polystyrene-[Ni(2+)]-poly(ethylene oxide) metallo-supramolecular block copolymer (PS-[Ni(2+)]-PEO), where -[ is a terpyridine, is used to create nanoporous thin films with free terpyridine ligands homogenously distributed on the pore walls. The PS-[Ni(2+)]-PEO block copolymer is synthesized by a two step assembly process, and is then self-assembled into a thin film in order to obtain PEO cylinders oriented perpendicularly to the film surface. The supramolecular junction is opened by exposing the film to an excess of a competing ligand, and the free PEO block is then rinsed away by a selective solvent. The presence of the terpyridines on the pore walls is evidenced by fluorescence spectroscopy after formation of a fluorescent complex with an europium salt.     

Monte Carlo simulations of cylinder-forming ABC triblock terpolymer thin films

We systematically study the cylinder-forming ABC triblock terpolymer thin films using canonical ensemble Monte Carlo simulations. The simulated annealing procedure is applied to the self-assembling process. By judicious choice of the system dimensions, we elaborately investigate the effect of film thickness on the orientation of the cylinders. This confined triblock terpolymer system exhibits different phase behavior under the weak and strong surface fields. In addition, we also investigate the ensemble-averaged chain orientations and relative density profiles.     

Vesicles with asymmetric membranes from amphiphilic ABC triblock copolymers

A new amphiphilic ABC triblock copolymer (poly(ethylene oxide)-poly(dimethyl siloxane)-poly(methyl oxazoline)) has been synthesized and demonstrated to form vesicular structures with asymmetric membranes in aqueous media.     

Self-assembly of star ABC triblock copolymer thin films: self-consistent field theory

Microphase separation and morphology of star ABC triblock copolymers confined between two identical parallel walls (symmetric wetting or dewetting) are investigated with self-consistent field theory (SCFT) combined with the "masking" technique to describe the geometric confinement of the films. In particular, we examine the morphology of confined near-symmetric star triblock copolymers under symmetric and asymmetric interactions as a function of the film thickness and the surface field. Under the interplay between the degree of spatial confinement, characterized by the ratio of the film thickness to bulk period, and surface field, the confined star ABC triblock copolymers are found to exhibit a rich phase behavior. In the parameter space we have explored, the thin film morphologies are described by four primary classes including cylinders, perforated lamellae, lamellae, and other complex hybrid structures. Some of them involve novel structures, such as spheres in a continuous matrix and cylinders with alternating helices structure, which are observed to be stable with suitable film thickness and surface field. In particular, complex hybrid network structures in thin films of bulk cylinder-forming star triblock copolymers are found when the natural domain period is not commensurate with the film thickness. Furthermore, a strong surface field is found to be more significant than the spatial confinement on changing the morphology of star triblock copolymers in bulk. These findings provide a guide to designing novel microstructures involving star triblock copolymers via geometric confinement and surface fields.     

Synthesis of atypical nanoparticles by the nanostructure in thin films of triblock copolymers

We report the synthesis of atypical nanoparticles in donut shape with or without additional spherical nanoparticles attached on them by using the donut-like nanostructure formed in a thin film of triblock copolymers. In a high-humidity condition, a spin-coated film of triblock copolymer had donut-like holes consisting of the periphery and the center. By selective coordination of precursors of nanoparticles to the periphery of the holes, donut-like oxide nanoparticles were synthesized by oxygen plasma treatment on the film. Moreover, we were able to attach spherical nanoparticles on the donut-like nanoparticles by incorporating the other type of precursors to the center of the holes. Thus, beyond the synthesis of typical spherical nanoparticles, the results here extend potentials of the block copolymer approach to control the shape and complexity of nanoparticles.     

Morphological changes in ABC triblock copolymers by chemical modification

Various SBT triblock copolymers with S being polystyrene, B being polybutadiene, and T being poly(tert-butyl methacrylate) and their saponified analogues, SBA with A being poly(methacrylic acid) are characterized in terms of their morphology. The chemical modification of the third block leads to a change of the overall morphology observed in solution cast films, which is interpreted as a consequence of the change of the incompatibility between the different components and the solvent.     

Self-assembling of ABC linear triblock copolymers in nanocylindrical tubes

By employing Monte Carlo simulations for various tube diameters and preferences of the tube surface for the A, B, and C segments, the morphologies of A(5)B(5)C(5), A(5)B(10)C(5), and A(5)B(5)C(10) triblock copolymer melts confined in nanocylindrical tubes were examined. The interaction parameters between different segments were considered constant epsilon(AB)=epsilon(AC)=epsilon(BC)=0.3k(B)T, the tube diameter was changed from d=9xlattice parameter to d=33xlattice parameter, and the preferences of the tube surface for the segments A, B, and C (-epsilon(AS),-epsilon(BS), and -epsilon(CS)) were varied between 0.05k(B)T and k(B)T. ABCCBA alternately stacked disks were generated in most tubes when the preference of the tube surface for any of the segments was weak, and the morphologies tended to transform into curved lamellae in tubes with large diameters when the preference for one of the segments was high. Numerous novel morphologies, such as ABC double helixes, AB single helix+C double helixes, AB double helixes+C quadruple helixes, plate morphologies with fins, dendrites, etc., which were located in the phase diagram between the stacked disks and the curved lamellar structures, were identified. Additionally, the orientation parameters indicating the alignments of the polymer chains were calculated and correlated with the morphologies.     

Stability of hierarchical lamellar morphologies formed in ABC star triblock copolymers

The stability of hierarchical lamellar morphologies formed in ABC star triblock copolymers, is studied using the self‐consistent mean‐field theory. The hierarchical lamellae consist of repeating period of the largest block A‐formed layer and B/C coformed layer where B and C domains are arranged alternatively. An angle, which is used to characterize the shifting magnitude between two neighbor B/C coformed layers, varies from 0 to 180 degrees. By comparing the free energy among the lamellar morphologies with various shift angle, their relative stability is analyzed. Our results show that the morphology with larger shift has lower entropic energy and higher internal energy. In general, the morphology with the largest shift of 180‐degree is stable compared with those with smaller shift as the entropic energy dominates the internal energy. However, the relative stability can be tuned by the interactions among the three components as well as their relative compositions. PACS numbers: 61.25.Hq, 64.60.Cn, 64.75.+g. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1001–1109, 2010     

Nanoporous thin films from ionically connected diblock copolymers

An ionically connected polystyrene-block-poly(ethylene oxide) diblock copolymer (PS^?+PEO) has been prepared by blending a PEO block functionalized by a dimethylamino group at one extremity with a sulfonic acid terminated PS block. Proton transfer occurs from the sulfonic acid to the dimethylamino group, resulting in the formation of an ion pair acting as a junction between the two polymer blocks. This copolymer was further used to prepare thin films with a cylindrical morphology consisting of PEO cylinders embedded in a PS matrix and oriented perpendicularly to the film surface. Nanoporous thin films with sulfonate groups on the pore walls have been finally obtained after solvent extraction of the PEO microphases. The presence of those sulfonate groups was evidenced by grafting a positively charged fluorescent dye on the pore walls.     

Organogels from ABA triblock copolymers

ABA triblock copolymers with two polystyrene endblocks connected by a poly(ethylene/butylene) midblock form highly elastic gels in a solvent which is incompatible for the endblocks but a good solvent for the midblock, for example, paraffin oil. In this situation the polystyrene endblocks aggregate into micelles. The midblocks can either form loops or build up bridges between different micelles; thus, domains and networks of interconnected micelles are produced. We have studied organogels of this kind consisting of a polymer with a molar mass of 90,000 and a styrene content of 31% per weight (Kraton G 1650) in paraffin oil. Rheological, calorimetric (differential scanning calorimetry) and small-angle X-ray scattering experiments were performed on these systems. An interesting result of our work which was not described previously is that the size (r˜ 6.8 nm) and the separation (d˜ 36 nm) of the micellar aggregates does not seem to be influenced by the block copolymer content in the concentration range investigated. Received: 12 March 2001 Accepted: 5 April 2001     

Pore morphologies in disordered nanoporous thin films

Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology.     

Nanostructures and phase diagrams of ABC star triblock copolymers in pore geometries

The nanostructures and phase diagrams of ABC star triblock copolymers in pore geometries are investigated using the real-space self-consistent field theory in two-dimensional space. Two types of pores with neutral surfaces, namely, pores with small and large diameters, are considered. A rich variety of nanostructures are exhibited by the ABC star triblock copolymers in these two types of pores, which differ from those observed in bulk and in other confinements. These structures include perpendicular undulating lamellae, concentric core-shell cylinders, polygonal tiling with cylindrical arrangements, and other complex structures. Triangular phase diagrams for the ABC star triblock copolymers are constructed. The small pores clearly affect the corner and central space of the phase diagrams by distorting the bulk structures into concentric arrangements. Meanwhile, the large pores induce the transformation of bulk structures into concentric structures in most of the phase space, but slightly affect the structures at the center of the phase diagrams. Furthermore, the order-order and order-disorder phase transitions, as well as the stable and metastable phases, in the triangular phase diagrams are examined by analyzing their free energies. These observations on the ABC star triblock copolymers in the pore geometries provide a deeper insight into the behavior of macromolecules in a confined system.     

Self-assembled architectures from biohybrid triblock copolymers

The synthesis and self-assembly behavior of biohybrid ABC triblock copolymers consisting of a synthetic diblock, polystyrene-b-polyethylene glycol (PSm-b-PEG113), where m is varied, and a hemeprotein, myoglobin (Mb) or horse radish peroxidase (HRP), is described. The synthetic diblock copolymer is first functionalized with the heme cofactor and subsequently reconstituted with the apoprotein or the apoenzyme to yield the protein-containing ABC triblock copolymer. The obtained amphiphilic block copolymers self-assemble in aqueous solution into a large variety of aggregate structures. Depending on the protein and the polystyrene block length, micellar rods, vesicles, toroids, figure eight structures, octopus structures, and spheres with a lamellar surface are formed.     

Fabrication of nanoporous templates from diblock copolymer thin films on alkylchlorosilane-neutralized surfaces

The fabrication of nanoporous templates from poly(styrene)-b-poly(methyl methacrylate) diblock copolymer thin films (PS-b-PMMA, volume ratio 70:30) on silicon requires precise control of interfacial energies to achieve a perpendicular orientation of the PMMA cylindrical microdomains relative to the substrate. To provide a simple, rapid, yet tunable approach for surface neutralization, we investigated the self-assembled ordering of PS-b-PMMA diblock copolymer thin films on silicon substrates modified with a partial monolayer of octadecyldimethyl chlorosilane (ODMS), i.e., a layer of ODMS with a grafting density less than the maximum possible monolayer surface coverage. We demonstrate herein the fabrication of nanoporous PS templates from annealed PS-b-PMMA diblock copolymer thin films on these partial ODMS SAMs.     

Self-assembly of ABC star triblock copolymer thin films confined with a preferential surface: a self-consistent mean field theory

The microphase separation and morphology of a nearly symmetric A(0.3)B(0.3)C(0.4) star triblock copolymer thin film confined between two parallel, homogeneous hard walls have been investigated by self-consistent mean field theory (SCMFT) with a pseudospectral method. Our simulation experiments reveal that under surface confinement, in addition to the typically parallel, perpendicular, and tilted cylinders, other phases such as lamellae, perforated lamellae, and complex hybrid phases have been found to be stable, which is attributed to block-substrate interactions, especially for those hybrid phases in which A and B blocks disperse as spheres and alternately arrange as cubic CsCl structures, with a network preferred structure of C block. The results show that these hybrid phases are also stable within a broad hybrid region (H region) under a suitable film thickness and a broad field strength of substrates because their free energies are too similar to being distinguished. Phase diagrams have been evaluated by purposefully and systematically varying the film thickness and field strength for three different cases of Flory-Huggins interaction parameters between species in the star polymer. We also compare the phase diagrams for weak and strong preferential substrates, each with a couple of opposite quality, and discuss the influence of confinement, substrate preference, and the nature of the star polymer on the stability of relatively thinner and thick film phases in this work.     

Polyimide polydimethylsiloxane triblock copolymers for thin film composite gas separation membranes

This article demonstrates the successful fabrication of thin‐film‐composite (TFC) membranes containing well‐defined soft‐hard‐soft triblock copolymers. Based on “hard” polyimide (PI) and “soft” polydimethylsiloxane (PDMS), these triblock copolymers (PDMS‐b‐PI‐b‐PDMS), were prepared via condensation polymerization, and end‐group allylic functionalization to prepare the polyimide component and subsequent “click” coupling with the soft azido functionalized PDMS component. The selective layer consisted of pure PDMS‐b‐PI‐b‐PDMS copolymers which were cast onto a precast crosslinked‐PDMS gutter layer which in turn was cast onto a porous polyacrylonitrile coated substrate. The TFC membranes' gas transport properties, primarily for the separation of carbon dioxide (CO₂) from nitrogen (N₂), were determined at 35 °C and at a feed pressure of 2 atm. The TFC membranes showed improvements in gas permselectivity with increasing PDMS weight fraction. These results demonstrate the ability for glassy, hard polymer components to be coated onto otherwise incompatible surfaces of highly permeable soft TFC substrates through covalent coupling. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3372–3382     

Oxyethylene-oxypropylene-oxyethylene triblock copolymers crystallised from dilute solution

Following a method of self-seeding described by Leute and Smith, the oxyethylene-oxypropylene-oxyethylene triblock copolymers Pluronic F127 and Pluriol SC9361 have been crystallised from dilute solution under conditions which lead to a high proportion of monolayer single crystals. Electron microscopy has been used to follow the crystallisation process and to monitor changes in the crystallisation conditions. Changes in molecular weight and composition, accompanying crystallisation from dilute solution, have been detected. Comparison is made between the properties of single crystal mats and crystallised melts.     

ABC and BAC triblock copolymers - morphological engineering by variation of the block sequence

Different morphologies and phase transitions of ternary triblock copolymers with different block sequences (ABC and BAC) are discussed qualitatively. The interplay between interfacial energies and elastic energies of the different blocks leads to various morphologies and enhances or prevents mixing of different blocks, depending on composition and topology.