Low dielectric constant nanoporous poly(methyl silsesquioxane) using poly(styrene-block-2-vinylpyridine) as a template

Low dielectric constant nanoporous poly(methyl silsesquioxane) (PMSSQ) was prepared through the templating of an amphiphilic block copolymer, poly(styrene-b-2-vinylpyridine) (PS-b-P2VP). The experimental and theoretical studies suggest that the intermolecular hydrogen bonding interaction is existed between the PMSSQ precursor and PS-b-P2VP. The result of modulated differential scanning calorimeter (MDSC) indicates the miscible hybrid of the PMSSQ precursor/PS-b-P2VP. The miscible hybrid and the narrow thermal decomposition of the PS-b-P2VP lead to nanopores in the prepared films from the results of transmission electronic microscopy (TEM), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). The effects of the loading ratio and the PS block volume ratio (f_PS: 0.74, 0.46 and 0.35) on the morphology and properties of the prepared nanoporous PMSSQ films were investigated. The AFM and TEM studies suggest that the uniform pore morphology should be prepared from a modest porogen loading level for the optimum intermolecular hydrogen bonding. The PS-b-P2VP with a smaller f_PS requires a higher loading level to obtain the uniform pores. The refractive index and dielectric constant of the prepared nanoporous films could be tuned by the loading ratio in the range of 1.361-1.139 and 2.359-1.509, respectively. However, both properties are independent of the f_PS. The prepared study demonstrates the control of the morphology and properties of the nanoporous films through the polymer structure.     

Shell-core-corona aggregates formed from poly(styrene)-poly(4-vinylpyridine) block copolymer induced by added homopolymer via interpolymer hydrogen-bonding

The solution behavior of poly(styrene)-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer with added poly(4,4′-oxydiphenylenepyromellitamic acid) (POAA) homopolymer in DMF is studied by dynamic light scattering (DLS), nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM). It is found that coaggregation takes place when mixing PS-b-P4VP block copolymer and POAA homopolymer in DMF due to the strong interpolymer hydrogen-bonding between POAA chains and P4VP blocks. The coaggregation is a diffusion-controlled process and the complexation-induced aggregates are very stable. NMR measurements demonstrate that the resultant aggregates are much more swollen compared with typical amphiphilic block copolymer core-shell micelles. DLS measurements with Eu³⁺ as a probe combined with TEM observation, are employed to study the structure of the aggregates. Results reveal that the formed aggregates are core-shell spheres with the P4VP/POAA complexes as core and the PS blocks as shell when the weight ratio of POAA to PS-b-P4VP is lower. However, a core-shell-corona structure forms with a thin layer of POAA chains adsorbed on the initial core-shell aggregates with increasing weight content of POAA to 60%. Finally, possible mechanisms of the structural transitions are proposed.     

Hexagonally ordered arrays of metallic nanodots from thin films of functional block copolymers

We demonstrate a new and simple route to fabricate highly dense arrays of hexagonally close packed inorganic nanodots using functional diblock copolymer (PS-b-P4VP) thin films. The deposition of pre-synthesized inorganic nanoparticles selectively into the P4VP domains of PS-b-P4VP thin films, followed by removal of the polymer, led to highly ordered metallic patterns identical to the order of the starting thin film. Examples of Au, Pt and Pd nanodot arrays are presented. The affinity of the different metal nanoparticles towards P4VP chains is also understood by extending this approach to PS-b-P4VP micellar thin films. The procedure used here is simple, eco-friendly, and compatible with the existing silicon-based technology. Also the method could be applied to various other block copolymer morphologies for generating 1-dimensional (1D) and 2-dimensional (2D) structures.     

Study of the time evolution of the surface morphology of thin asymmetric diblock copolymer films under solvent vapor

The time development of the surface morphology of asymmetric polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) thin films ‘annealing’ in methanol vapor, a selective solvent for minority P4VP block, was investigated by atomic force microscopy(AFM). For PS-b-P4VP with cylindrical structure in bulk, as annealing time progressed, the surface morphology underwent structural transitions from featureless topography to hybrid morphology of cylindrical and spherical pits, to cylinders, to nanoscale depressions, back to cylinders again. The different film thickness made the number of the transitions observed, at any given annealing time, different. The thicker the film is the more transitions at a given annealing time can be observed. If the film was not thick enough, depressions appeared. For PS-b-P4VP with spherical structure in bulk, it displayed nanoscale depressions with the annealing time increasing. A possible mechanism of the transition of morphologies during solvent annealing was proposed.     

A facile preparative method for gold-containing vesicles from poly(styrene-block-2-vinylpyridine) block copolymer/HAuCl4 complexes

It is found that the complexes of PS-b-P2VP and HAuCl₄ in THF can form a compound vesicle when the THF solution is treated at 40 °C. The compound vesicle is composed of an insoluble wall formed by P2VP/HAuCl₄ complexes and a soluble PS shell. The vesicular character of the aggregates was investigated by dynamic light scattering (DLS) and transmission electron microscope (TEM). The decrease of the solubility of P2VP blocks in THF drives the PS-b-P2VP/HAuCl₄ complexes to aggregate into vesicles, which are stable upon dilution or crosslinking. Based on this study, the vesicles decorated with gold nanoparticles can be produced, which hold potential for the facile organization of the vesicle-supported precious metal catalysts.     

Exfoliation of organoclay nanocomposites based on polystyrene-block-polyisoprene-block-poly(2-vinylpyridine) copolymer: Solution blending versus melt blending

Exfoliated nanocomposites based on polystyrene-block-polyisoprene-block-poly(2-vinylpyridine) (SI2VP triblock) copolymer were prepared by solution blending and melt blending. Their dispersion characteristics were investigated using transmission electron microscopy, X-ray diffraction, and small-angle X-ray scattering (SAXS). For the study, SI2VP triblock copolymers with varying amounts of poly(2-vinylpyridine) (P2VP) block (3, 5, and 13 wt%) and different molecular weights were synthesized by sequential anionic polymerization. In the preparation of nanocomposites, four different commercial organoclays, treated with a surfactant having quaternary ammonium salt, were employed. It was found from SAXS that the microdomain structure of an SI2VP triblock copolymer having 13 wt% P2VP block (SI2VP-13) transformed from core-shell cylinders into lamellae when it was mixed with an organoclay. It was found further that the solution-blended nanocomposites based on a homogeneous SI2VP triblock copolymer having 5 wt% P2VP block (SI2VP-5) gave rise to an exfoliated morphology, irrespective of the differences in chemical structure of the surfactant residing at the surface of the organoclays, which is attributable to the presence of ion-dipole interactions between the positively charged N⁺ ion in the surfactant residing at the surface of the organoclay and the pyridine rings in the P2VP block of SI2VP-5 and SI2VP-13, respectively. Both solution- and melt-blended nanocomposites based on microphase-separated SI2VP-13 having an order-disorder transition temperature (T_ODT) of approximately 210 °C also gave rise to exfoliated morphology. However, melt-blended nanocomposite based on a high-molecular-weight SI2VP triblock copolymer having a very high T_ODT (estimated to be about 360 °C), which was much higher than the melt blending temperature employed (200 °C), gave rise to very poor dispersion of the aggregates of organoclay. It is concluded that the T_ODT of a block copolymer plays a significant role in determining the dispersion characteristics of organoclay nanocomposites prepared by melt blending.     

Fabrication of fibril like aggregates by self-assembly of block copolymer mixtures via interpolymer hydrogen bonding

This paper describes the formation of fibril like aggregates from the self-assembly of block copolymer mixture (polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and polystyrene-b-poly(acrylic acid) (PS-b-PAA)) via interpolymer hydrogen bonding in nonselective solvent. The hydrogen bonding between P4VP and PAA in chloroform leads to the formation of complex. When all the pyridine units in P4VP were all hydrogen bonded to acrylic acid in PAA, the formed complex is insoluble, resulting in the formation of spherical micellar aggregates and nanorods. However, two kinds of supramolecules with insoluble or soluble complex are formed in the solution when PS-b-P4VP and PS-b-PAA are mixed with equal mole ratio. The fibril like aggregates can be formed from the self-assembly of supramolecule with soluble complex during spin-coating process. The effects of evaporation rate of solvent and solution concentrations on the formation of fibril like aggregates were investigated. The results prove that the kinetic factors play an important role in the formation of the fibril like aggregates.     

Structures and rheological properties of reactive solutions of block copolymers. Part I. Diblock copolymers in a liquid epoxy monomer

P(S-b-MMA) and P(B-b-MMA) diblock copolymers (BCP) have been solubilized in a liquid epoxy. The obtained solutions have been characterized by rheology and small angle X-ray scattering (SAXS). As in the solid state, BCP can self-organize in solution to form well-ordered micellar structures. The two blocks respective roles have been clearly identified: at room temperature the PS or the PB block microsegregates while the PMMA block for which epoxy constitutes a good solvent, acts as a stabilizer of the microphase separation. The geometries and thermal stabilities of the ordered structures depend strongly on the molar masses and the chemical nature of the BCP blocks. For instance, the total molar mass of the BCP has to be high enough to obtain a periodic structure. On the contrary, if this molar mass is too high, too long relaxation times prevent the system from reaching its equilibrium. For the P(S-b-MMA) copolymer solution, a transition temperature from an order to a disorder state (T_ODT) is observed. The origin of this transition has been attributed to a solubilization of the PS domains around T_ODT. Macroscopically, this transition can be defined as a solid-like to a liquid-like transition. In the case of the P(B-b-MMA) copolymer solution, no order-disorder transition has been observed: it can be explained by the fact that the PB blocks are not soluble in epoxy at any temperature, up to T=200 °C.     

Phase segregation of poly(3-dodecylthiophene)-block-poly(methyl methacrylate) copolymers

We investigated, via small angle X-ray scattering (SAXS), the ordered-to-disordered transition temperature (T_ODT) of symmetric poly(3-dodecylthiophene)-block-poly(methyl methacrylate) copolymers (P3DDT-b-PMMA) with different molecular weights synthesized by anionic coupling reaction. When the molecular weight of P3DDT-b-PMMA was properly chosen, the T_ODT was observed within experimentally accessible temperature range (higher than the glass transition and melting temperature for PMMA and P3DDT, respectively, but lower than the thermal degradation temperature). We also measured the temperature dependence of Flory–Huggins interaction parameter (χ) between P3DDT and PMMA as χ = 0.1109 + 76.63/T, in which T is the absolute temperature.     

Dynamic study of polystyrene-block-poly(4-vinylpyridine) copolymer in bulk and confined in cylindrical nanopores

AAO template is highly recommended to nanostructure polymers and to study polymer properties under confinement. The dynamic properties of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) under confinement using broadband dielectric spectroscopy are investigated in this work and the results compared to those of the bulk. Anodized aluminum oxide (AAO) membranes, having pore diameters from tens to hundreds of nanometers in size, were used to confine PS-b-P4VP. Moreover, the influence of gold nanoparticles (AuNPs) in the copolymer matrix was also studied. The morphology and structure of the bulk copolymer and the copolymer confined in the AAO templates were characterized by transmission electron microscopy, scanning electron microscopy and Small Angle X-Ray Scattering. For PS-b-P4VP in bulk, dielectric relaxation techniques allowed studying selectively the P4VP segmental dynamics within the diblock. At high temperature this copolymer presents a dominant peak (MWS relaxation), most likely originated by the relatively high conductivity combined with the presence of interfaces emerging in the nanostructured samples. Moreover, a pronounced β-relaxation is observed for the copolymer compared with that of pure P4VP. This is likely due to a non-negligible contribution from the α-relaxation of the PS component. The γ-relaxation is markedly different in the copolymer, which is evidenced by a distinct temperature dependence of the resulting relaxation times. When the copolymer is embedded in alumina nanopores with small pore diameters (25 and 35 nm) there are significant changes, where the tendency is going to a faster dynamics when the pore diameter decreases more likely related to the relevance of surface effects. The presence of the AuNPs in the system enhances this effect. These results are in agreement with segregated structures found in the block copolymer by TEM and SAXS.     

Complicated phase behavior and ionic conductivities of PVP-co-PMMA-based polymer electrolytes

We have used DSC, FTIR spectroscopy, and ac impedance techniques to investigate the interactions that occur within complexes of poly(vinylpyrrolidone-co-methyl methacrylate) (PVP-co-PMMA) and lithium perchlorate (LiClO₄) as well as these systems' phase behavior and ionic conductivities. The presence of MMA moieties in the PVP-co-PMMA random copolymer has an inert diluent effect that reduces the degree of self-association of the PVP molecules and causes a negative deviation in the glass transition temperature (T_g). In the binary LiClO₄/PVP blends, the presence of a small amount of LiClO₄ reduces the strong dipole-dipole interactions within PVP and leads to a lower T_g. Further addition of LiClO₄ increases T_g as a result of ion-dipole interactions between LiClO₄ and PVP. In LiClO₄/PVP-co-PMMA blend systems, for which the three individual systems—the PVP-co-PMMA copolymer and the LiClO₄/PVP and LiClO₄/PMMA blends—are miscible at all compositional ratios, a phase-separated loop exists at certain compositions due to a complicated series of interactions among the LiClO₄, PVP and PMMA units. The PMMA-rich component in the PVP-co-PMMA copolymer tends to be excluded, and this phenomenon results in phase separation. At a LiClO₄ content of 20 wt% salt, the maximum ionic conductivity occurred for a LiClO₄/VP57 blend (i.e., 57 mol% VP units in the PVP-co-PMMA copolymer).     

Selective distribution of interacting magnetic nanoparticles into block copolymer domains based on the facile inversion of micelles

We demonstrate a simple methodology to incorporate interacting magnetic nanoparticles (mNPs) into cylinder forming block copolymer templates. Poly(styrene-block-isoprene) (PS-b-PI) with PI cylinders and poly(styrene-block-4vinylpyridine) (PS-b-P4VP) with PS cylinders were used as the block copolymer templates and γ-Fe₂O₃ NPs coated with oleic acids were pre-synthesized for the interacting mNPs. Regardless of the template block copolymers, the selective location of mNPs and the size of mNP aggregates are clearly altered by changing casting solvents. When good solvents for both blocks were used as casting solvents, mNPs are readily aggregated during the solvent evaporation. In contrast, under selective casting solvents for the minor blocks, the mNPs were selectively trapped into the cylinder domains through the facile inversion of micelles during solvent evaporation. The interplay between mNPs and block copolymers was also tested with different molecular weights of block copolymers.     

Nanostructured polystyrene-block-poly(4-vinyl pyridine)(pentadecylphenol) thin films as templates for polypyrrole synthesis

Polypyrrole has been chemically synthesized on thin film nanostructures obtained from comb-shaped supramolecules of polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) hydrogen bonded with pentadecylphenol (PDP). PDP was washed from thin films of cylindrical and lamellar self-assembled comb-copolymer systems, which resulted in removal of the upper layers of microdomains, leaving single cylindrical and lamellar layers covering a substrate, with P4VP segregated at the bottom as well as at the free air interface. This P4VP was complexed with Cu²⁺ ions, after which chemical oxidation polymerization of pyrrole resulted in a thin polypyrrole layer covering the nanostructured block copolymer. The use of a catalytic amount of bipyrrole greatly improved the quality of the obtained product. The conductivity was measured to be ∼0.7 S cm⁻¹.     

Block copolymers containing pyridine moieties: Precise synthesis and applications

This review highlights the precise synthesis and application of various well-defined rod–coil and coil–coil block copolymers composed of poly(2-(or 4-)vinylpyridine) (P2VP or P4VP) block(s) with pyridine moieties. These polymers were synthesized by means of living anionic polymerization. Poly(hexyl isocyanate) (PHIC) was used as the rod-like segment, because hexyl isocyanate undergoes living anionic polymerization under carefully selected conditions. This review describes the syntheses of the block copolymers, polystyrene-b-P2VP, polystyrene-b-P4VP, polyisoprene-b-P2VP, P2VP-b-poly(methyl methacrylate), P2VP-b-poly(ethylene oxide), P2VP-b-poly(2-(N-carbazolyl)ethyl methacrylate), P2VP-b-PHIC, P2VP-b-PHIC-b-P2VP, and PHIC-b-P2VP-b-PHIC. The formation of self-organized nanostructured materials and molecular assemblies by such block copolymers and their possible applications are also described. These assemblies include monolayers, microphase-separated periodic-ordered nanostructures, micelles, polymer–metal complexes, nanoparticles, inorganic and metal layers, and nanoporous films with nanoparticles.     

Control over the surface plasmon band of block copolymer/Ag/Au nanoparticles composites by the addition of single walled carbon nanotubes

In this study, we demonstrate control over the localized surface plasmon band (SPB) of a micellar poly(styrene-block-4vinylpyridine) (PS-b-P4VP) copolymer thin film composite that includes Ag and Au nanoparticles (NPs) in the presence of single walled carbon nanotubes (SWCNTs). Ag and Au NPs are preferentially located in the P4VP core and the PS corona of ordered spherical PS-b-P4VP copolymer micelles, respectively. This structure gave rise to a single SPB due to the coupling of Ag and Au SPBs. The non-covalent addition of SWCNTs in the block copolymer micelles shifts the coupled SPB to a lower wavelength. The maximum shift in the coupled SPB of approximately 30 nm was achieved in the PS-b-P4VP/Ag/Au NPs composite. The carbon nanotube induced modulation of the coupled SPB stems from the charge accumulation effect of the SWCNTs placed between the two types of nanoparticles.     

Nanostructure and hydrogen bonding in interpolyelectrolyte complexes of poly(?-caprolactone)-block-poly(2-vinyl pyridine) and poly(acrylic acid)

Nanostructured poly(?-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP)/poly(acrylic acid) (PAA) interpolyelectrolyte complexes (IPECs) were prepared by casting from THF/ethanol solution. The morphological behaviour of this amphiphilic block copolymer/polyelectrolyte complexes with respect to the composition was investigated in a solvent mixture. The phase behaviour, specific interactions and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy (OM), dynamic light scattering (DLS) and atomic force microscopy (AFM). Micelle formation occurred due to the aggregation of hydrogen bonded P2VP block and polyelectrolyte (PAA) from non-interacted PCL blocks. It was observed that the hydrodynamic diameter (D_h) of the micelles in solution decreased with increasing PAA content up to 40 wt%. After 50 wt% PAA content, D_h again increased. The micelle formation in PCL-b-P2VP/PAA IPECs was due to the strong intermolecular hydrogen bonding between PAA homopolymer units and P2VP blocks of the block copolymer. The penetration of PAA homopolymers into the shell of the PCL-b-P2VP block copolymer micelles resulted in the folding of the P2VP chains, which in turn reduced the hydrodynamic size of the micelles. After the saturation of the shell with PAA homopolymers, the size of the micelles increased due to the absorption of added PAA onto the surface of the micelles.     

Ionic transport behavior in poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) and LiClO4 complex

The effect of LiClO₄ on the ionic transport behavior in poly(ethylene oxide)₂₀-poly(propylene oxide)₇₀-poly(ethylene oxide)₂₀ (P123) polymer electrolyte was studied. Its conductivity reaches maximum as molar ratio between ether O atoms and lithium ions [n(O)/n(Li)] equals 8. The results show that LiClO₄ could interact with P123 well and has impacts on polymer organization and chain dynamics. As LiClO₄ concentration decreases, the glass transition temperature (T_g) decreases and the free ion percentage increases. The tendency of conductivity with LiClO₄ concentration is the result of competing effects between polymer chain mobility and free charge carrier concentration.     

Surface morphology evolution of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H⁺) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression of cylindrical nanodomains was formed by the block of P4VP(H⁺) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H⁺) and PMCMA was varied through changing the molecule weight (M_w) of PMCMA, the volume fraction of the block of P4VP(H⁺), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.     

Deposition of silver nanoparticles on single wall carbon nanotubes via a self assembled block copolymer micelles

We demonstrate a facile route to decorate the surface of networked single walled carbon nanotubes (SWNTs) with silver nanoparticles (Ag NPs). The method is based on utilization of either spherical poly(styrene-b-4vinylpyridine) (PS-b-P4VP) or cylindrical poly(styrene-b-acrylic acid) (PS-b-PAA) copolymer micelles capable of stabilizing nanotubes in solution and subsequently forming a thin and uniform block copolymer/SWNTs composite film upon spin coating. The selective doping of silver acetate into either P4VP or PAA domains in a thin composite film, followed by thermal treatment, results in the formation of Ag NPs in the cores of micelles. Further heat treatment at 500 °C sufficiently high for degrading both block copolymers allows us to fabricate a thin SWNTs network in which Ag NPs are efficiently deposited on the surface of nanotubes. A sharp surface plasmon absorption band around 400 nm of the networked SWNTs with Ag NPs confirms the presence of Ag NPs with narrow distribution in their size.     

The fabrication of graphitic thin films with highly dispersed noble metal nanoparticles by direct carbonization of block copolymer inverse micelle templates

Ordered arrays of Au or Ag nanoparticles supported on two-dimensional graphitic carbon films were prepared by direct carbonization of stabilized asymmetric polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) inverse micellar films loaded with metal precursors. Crosslinked PS-b-P4VP thin film templates with metal precursors selectively distributed in P4VP domains were converted to carbonaceous thin films having well-defined, highly dispersed metal nanoparticle (NP) arrays by ultraviolet (UV) irradiation under vacuum and subsequent carbonization. Mesoporous carbon films were also obtained after extracting the metal NPs by sonication in selected solvents. PS-b-P4VP was employed not only as carbon source, but also as template for introducing metal NPs in a nanopatterned configuration. The characteristic features and properties of thus generated hybrid carbon nanostructures were investigated by microscopy, UV–visible spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction measurement, and Raman spectroscopy.