Oxidation effect on templating of metal oxide nanoparticles within block copolymers

Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.     

Polymer mediated formation of corona-embedded gold nanoparticles in block polyelectrolyte micelles

Micelles having a hydrophobic core of poly(tert-butylstyrene) and a hydrophilic corona of poly(sodium sulfamate/carboxylate-isoprene) anionic polyelectrolyte, were formed through self-assembly of the diblock copolymer poly[tert-butylstyrene-b-sodium (sulfamate/carboxylate-isoprene)] (BS-SCI) in water. HAuCl₄, as the metal precursor, was preferentially dissolved and coordinated into the corona of the micelles. Au nanoparticles were formed within the corona block by subsequent reduction of Au³⁺ to Au⁰ without introducing any reducing agent, since the amine group of the corona block acts as both the reducing and stabilizing agent. The kinetics of the Au reduction reaction was followed by UV-vis spectroscopy by direct observation of the exact position and the intensity of the surface plasmon resonance band of created Au nanoparticles. The colloidal stability and structural response of the BS-SCI/Au nanohybrid was studied as a function of pH, ionic strength and temperature by dynamic light scattering (DLS). Additional information on the structure of the hybrid systems and the metal nanoparticle characteristics were gathered by UV-vis spectroscopy, atomic force microscopy (AFM) and transmission electron microscopy (TEM). Taking into account the polyelectrolyte nature and biocompatibility of the SCI corona of the BS-SCI/Au nanoassembly, the interactions with a model globular protein (lysozyme) were investigated, aiming at exploring the potential application of such hybrid colloids in protein assay protocols.     

Homogeneous dispersion of SiO2 nanoparticles in an hydrosoluble polymeric network

The main difficulty still encountered in the elaboration of polymer/silica nanocomposites is the control of the nanoparticles dispersion homogeneity and the stability of the nanoparticle dispersion in the surrounding substance. The innovative point of this work is the elaboration of hybrid networks in aqueous solution performed with ASE (alkali swellable emulsion) thickeners grafted with silica nanoparticles. The thickening ability of the polymer should favour silica nanoparticles dispersion in fluid matrices. Two ASE copolymers were realised by copolymerisation in emulsion of MA (methacrylic acid) and EA (ethyl acrylate) and/or TFEM (trifluoroethyl methacrylate). The substitution of a part of EA by TFEM gave fluorinated ASE copolymers. Their free acid functions were then coupled with different ratio of amine functionalized silica nanoparticles to afford nanocomposites. The amounts of silica nanoparticles in the copolymers were determined by thermogravimetric experiments. Depending on the silica nanoparticles/copolymer ratio in basic aqueous solutions we achieved stable translucent gel like aqueous suspensions of silica nanoparticles containing 1 wt.% of the polymer/SiO₂ nanocomposite.     

Polyaldehydes: homopolymers,block copolymers and promising applications

This minireview gives a brief overview on the polymerization of higher aldehydes, discusses current applications of certain polyaldehydes, and points toward potential future applications of these interesting materials. Although it was discovered long ago that several aldehydes can be polymerized, the application potential of these polymers was largely overlooked. This is somewhat surprising as many polyaldehydes show interesting properties such as fast and complete depolymerization triggered by chemical or thermal stimuli. Such stimuli‐responsive polymers can be useful materials in many applications in for example nanotechnology or drug delivery. By incorporating polyaldehydes into functional block copolymers even more versatile materials can be created. The increasing number of recent research examples demonstrates the growing interest in polyaldehydes as smart materials and their potential for novel applications. Copyright © 2012 Society of Chemical Industry     

Viscoelastic properties of heterophase blends of homopolymers and block copolymers

Stress relaxation and dynamic mechanical measurements were carried out for two types of heterophase polyblends. One is obtained by blending homopolymers of butadiene and styrene (high impact polystyrene or HIPS); the other by blending homopolymer of butadiene with a triblock copolymer of styrene-butadiene-styrene (SBS/B). It was found that for HIPS, time temperature superposition is difficult, and the shift factors cannot be adequately interpreted by a reasonable model. For SBS/B it is impossible to carry out superposition. Modulus-temperature and loss tangent curves determined by dynamic mechanical experiments indicate the presence of new transition near ?40°C. Possible mechanisms giving rise to this new transition are discussed.     

Dispersion of Surface Modified Nanostructure Zinc Oxide in Optically Active Poly(Amide-Imide) Containing Pyromellitoyl-bis-L-isoleucine Segments: Nanocomposite Preparation and Morphological Investigation

Optically active zinc oxide/poly(amide-imide) (PAI) nanocomposites (NC)s were synthesized by using ultrasonic assisted technique. The polymers and zinc oxide (ZnO) nanoparticles were physically and/or chemically connected with each other through different kinds of interactions such as physical van der Waals forces, hydrogen bonding and/or covalent interactions. ZnO/PAI NCs were characterized by Fourier transform infrared spectra, X-ray diffraction patterns, and field emission scanning electron microscopy. The thermal stability studies indicated an enhancement of thermal stability of new NC materials compared with the pure polymer.     

Micro- and nano-structure in polypropylene/clay nanocomposites

Polypropylene (PP)/clay nanocomposites prepared by melt blending using different clays and coupling agents based on maleic anhydride-grafted PP (MA-PP) were studied. Clay dispersion using field emission gun scanning electron microscope (FEG-SEM) and transmission electron microscopy (TEM), and PP matrix morphology were characterized. Clay dispersion was improved in the presence of MA-PP, as shown by the higher particles surface density (number of particles/mm²) at all micro-, sub-micro- and nano-levels. The PP spherulite diameter was affected by both the presence of MA-PP and clay dispersion. Clay intercalation, characterized by both complementary X-ray diffraction (XRD) and TEM, was greatly influenced by the characteristics of MA-PP. The use of low molecular weight (M_w) MA-PP led to a good and uniform intercalation but with no further possibility to exfoliation. The use of higher M_w MA-PP led to a heterogeneous intercalation with signs of exfoliation. The crystallization behavior of nanocomposites was studied by differential scanning calorimetry (DSC). When fine clay dispersion was achieved with MA-PP, clay-nucleating effect was limited and lower crystallization temperature and rates were observed. It was also shown by wide angle X-ray diffraction (WAXD) that clay induced some orientation of α-phase PP crystallites.     

Processing-microstructure-property relationship in conductive polymer nanocomposites

The processing-microstructure-property relationship in conductive polymer nanocomposites was investigated. Nanocomposites of vapor grown carbon nanofiber (VGCNF)/high density polyethylene (HDPE) with different levels of nanofiber dispersion were formulated by changing the nanocomposites’ compounding temperature. Direct (SEM and optical microscopy) and indirect methods (linear viscoelastic properties) were used to characterize the dispersion of nanofiller. VGCNF aspect ratio before and after mixing was measured. Increasing processing temperature was found to increase the nanofiller agglomeration and reduce the breakage of nanofiller because of the decrease in the mixing shear stress and energy. The electrical and electromagnetic interference (EMI) shielding properties of the VGCNF/HDPE nanocomposites decreased with increase in processing temperature from 180 °C to 220 °C because the increase in the agglomeration of VGCNF was more significant than the preservation of the VGCNF aspect ratio. This finding does not mean that the increase in processing temperature will always lead to decrease in the electrical conductivity and EMI shielding properties for all polymer composites. For some composites, it is possible to preserve the filler aspect ratio enough so that the increase in agglomeration is less of a factor.     

Influence of carbon chain length on the synthesis and yield of fatty amine-coated iron-platinum nanoparticles

Iron oxide nanoparticles are among the most widely used and characterized magnetic nanoparticles. However, metal alloys such as superparamagnetic iron-platinum particles (SIPPs), which have better magnetic properties, are receiving increased attention. Scalable techniques to routinely synthesize SIPPs in bulk need further study. Here, we focus on the role played by the fatty amine ligand in the formation of the bimetallic FePt nanocrystal. More specifically, we compare the effect of varying lengths of fatty amine ligands on the shape, structure, uniformity, composition, and magnetic properties of the SIPPs. We synthesized SIPPs by employing a ‘green’ thermal decomposition reaction using fatty amine ligands containing 12 to 18 carbons in length. Greater fatty amine chain length increased the polydispersity, particle concentration, iron concentration, and the stability of the SIPPs. Additionally, longer reflux times increased the diameter of the particles, but decreased the iron concentration, suggesting that shorter reaction times are preferable. Fourier transform infrared spectroscopy of the SIPPs indicates that the ligands are successfully bound to the FePt cores through the amine group. Superconducting quantum interference device magnetometry measurements suggest that all of the SIPPs were superparamagnetic at room temperature and that SIPPs synthesized using tetradecylamine had the highest saturation magnetization. Our findings indicate that the octadecylamine ligand, which is currently used for the routine synthesis of SIPPs, may not be optimal. Overall, we found that using tetradecylamine and a 30-min reflux reaction resulted in optimal particles with the highest degree of monodispersity, iron content, stability, and saturation magnetization.

PACS

81.07.-b; 75.75.Fk; 61.46.Df     

The effect of TiO2 nanoparticles on the properties of sulfonated block copolymers

Block copolymers composed of styrene and different elastomeric blocks were sulfonated to high ion exchange capacities (IECs). Titanium dioxide (TiO₂) nanoparticles were added to these polymers to improve their mechanical and thermal stabilities, while influencing their transport properties for direct methanol fuel cell (DMFC) applications. Materials properties as proton exchange membranes (PEMs) were analyzed using: FT‐IR, water absorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), IEC, methanol permeability, and proton conductivity studies. Although there was no effect of TiO₂ nanoparticles on the thermal stability of the membranes, significant changes were observed in the mechanical properties of both sulfonated block copolymers studied. Water absorption increased at low TiO₂ content, but was then reduced with the incorporation of more nanoparticles. To enhance the interaction between the inorganic fillers and the polymers, sulfonic and amino groups were attached to the surface of the titania nanoparticles. The effect of sulfonated nanoparticles on the properties of the materials was more significant than the effect of the amino functionalized nanoparticles on all the properties evaluated, suggesting enhanced chemical interactions with the ionic domains of the polymer membranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42651.     

Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

Controlled synthesis of vinyl-functionalized homopolymers and block copolymers by RAFT polymerization of vinyl methacrylate

Reversible addition-fragmentation chain transfer (RAFT) polymerization of an asymmetrical divinyl monomer, vinyl methacrylate (VMA), was investigated under various conditions. RAFT polymerization of VMA using a dithioester-type chain transfer agent (CTA) under suitable conditions afforded soluble polymers with a high content of pendant vinyl ester side chains in sufficient yields (>70%). The monomer concentration, the nature of the CTA, and the CTA/initiator ratio were found to affect the polymerization reaction and the structure of the resulting polymers; this behavior is attributed to the relative propensities for intermolecular propagating/cross-linking reactions and intramolecular cyclization. A kinetic study of the RAFT polymerization of VMA with the dithioester-type CTA 1 suggested that the propagation reaction of the methacryloyl group proceeded predominantly with a certain level of intramolecular cyclization during the early stage of the polymerization and intermolecular cross-linking during the final stage of the polymerization. Block copolymers with one segment featuring pendant vinyl functionality were synthesized by RAFT polymerization of VMA using poly(methyl methacrylate) as a macro-chain transfer agent (macro-CTA).     

Nanofabrication of hybrid nanomaterials: Macroscopically aligned nanoparticles pattern via directed self-assembly of block copolymers

Periodic hybrid nanostructured materials based on aligned inorganic nanoparticles within self-assembled copolymer matrixes aimed to harness the collective properties of generated functional nanomaterials. The nanoparticles are desirable for their useful magnetic, optical, catalytic, and electronic properties owed to the quantum confinement effect. For instance, gold, palladium and platinum as nanoparticles, have shown significant change in the physiochemical properties in comparison to their bulk materials. If the nanoparticles are aligned into well-defined macroscopic periodic nanostructures in diverse of morphologies, the unique collective properties are significantly enhanced. These unique properties can be transformed to improve the performance of storage media, multi-contact tracks solar panels and optoelectronic devices. Within this review, the nanofabrication tools will be presented as an alternative route to conventional top-down methods for the fabrication of periodic nanostructured hybrid materials. A simple approach is reviewed to fabricate periodic nanostructured hybrid systems based on the directed assembly of inorganic nanoparticles into well-defined periodic three-dimensional nanostructures provided by the self-assembling ability of block copolymers. The fabrications of varieties morphologies and the formation mechanism at different dimensions will be discussed as well as the characterization techniques. Finally, several applications of the proposed hybrid nanostructures are highlighted for the next generation of miniaturized devices.     

Synthesis of poly(trioctylammonium p-styrenesulfonate) homopolymers and block copolymers by RAFT polymerization

A method to prepare sulfonated polystyrene-containing block copolymers has been investigated by neutralizing styrene sulfonic acid with trioctylamine to produce the hydrophobic monomer trioctylammonium p-styrenesulfonate (SS-TOA). This monomer was polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization to produce PSS-TOA homopolymers. A PSS-TOA homopolymer was then used as a macro-RAFT agent for the polymerization of styrene to prepare poly(trioctylammonium p-styrenesulfonate)-block-poly(styrene) (PSS-TOA-b-PS). These block copolymers could be ion-exchanged to produce either the hydrophilic sodium salt form of PSS or a hydrophobic quaternary ammonium salt. This approach will be useful for preparing PSS-containing block copolymers with a range of hydrophobic blocks for applications such as ion-exchange membranes.     

聚合物中纳米粒子气泡膨胀分散方法

提出了一种聚合物中纳米粒子气泡膨胀分散方法,并应用该方法制备了环氧树脂/SiO₂纳米复合材料。该方法将纳米粒子团聚体和压缩气体一同注射到聚合物熔体（溶液）中,形成内含纳米粒子的微气泡,并利用气泡急速膨胀时引起的高速拉伸作用实现纳米粒子在聚合物中的均匀分散。在对分散机理进行分析的基础上,通过数值仿真计算对其分散能力进行了分析。对气泡膨胀分散法制备的环氧树脂/SiO₂纳米复合材料进行了透射电镜（TEM）分析和DSC分析,结果表明,样品中SiO₂粒子粒径在15～30 nm之间,其玻璃化温度比高速搅拌法制备的对比样品高18℃。     

Dispersing hairy nanoparticles in polymer melts

The dispersion of hairy nanoparticles in polymer melts of chemically identical chains was investigated as a function of both molecular weight and volume fraction. Here we provide conclusive evidence that the shape of the phase diagram is determined primarily by the ratio of the chain length of the polymer melt to the chain length of the polymeric shell structure (or hair) of the core/shell nanoparticles, and that the phase behavior of different hairy particles in various polymer melts can be superimposed into one universal graph. Other factors, including the hair density and the particle diameter, are not nearly as significant as the above-noted ratio in this phase separation. In addition, we show that there is a strong connection between the rheological dynamics of the particle-filled system and the thermodynamics of the phase separation behavior. The shear-induced nonlinearity in the particle-filled system appears to display features of a singularity near the phase transition point.     

Encapsulation of inorganic nanoparticles into block copolymer micellar aggregates: Strategies and precise localization of nanoparticles

Precise assembly and localization of preformed inorganic nanoparticles (NPs) in block copolymer (BCP) assemblies are of great importance in realizing the formation of nano-hybrids with high performance. Properties of the nanocomposites depend not only on those of individual building blocks but also on their spatial organization at different length scales, demonstrating unique optical, electrical, and magnetic properties. With the aid of the BCPs, NPs can form a broader range of structures in the nanoscopically confined geometry. Thus, many studies have focused on the selective localization of NPs in BCP aggregates. In this paper, we will outline recent advances in the preparation strategies for precise localization of inorganic NPs into BCP micelles, including co-precipitation, supramolecular assembly, interfacial instabilities of emulsion droplets, heating–cooling, electrostatic interaction, and others. Manipulating the balance between enthalpic and entropic contributions provides one of the opportunities to precisely control the spatial distribution of NPs in BCPs assemblies. We will focus on the principles of precise control of dispersion and localization of the NPs in BCP micelles. Potential applications of the hybrid micelles will finally be discussed, followed by the summary and outlook of this emerging area.     

Synthesis, characterization and aggregation behavior of block copolymers containing a polyisocyanopeptide segment

Following up on previous preliminary communications the synthesis of a series of block copolymers by applying amine end-capped polymers as initiators for the nickel(II) catalyzed polymerization of isocyanides is reported. Using a polystyrene derivative as the initiator, superamphiphiles containing a hydrophobic polystyrene tail and a charged helical polyisocyanide headgroup were prepared. Under proper conditions these superamphiphiles self-assembled in water to give a variety of aggregate morphologies, among which are superhelical architectures. Initiators derived from carbosilane dendritic wedges gave block copolymers with a unique combination of structural elements, i.e. a flexible dendritic block and a rigid polyisocyanide block. Block copolymers derived from the 3rd generation dendrimers form well-defined micellar aggregates in the presence of Ag⁺ ions. These aggregates have been used to construct nanoarrays of metallic silver.     

Optical properties of block copolymers containing pendant carbazole groups and in situ synthesized CdS nanoclusters

Ultraviolet–visible absorption spectra and photoluminescence spectra were used to demonstrate efficient charge‐carrier migration in a novel bulk heterogeneous block copolymer system. One moiety of the block copolymer was functionalized with charge‐transporting carbazole groups, whereas the other block formed domains suitable for the in situ synthesis of CdS nanoclusters. The excitation of the cluster‐free copolymers with 350‐nm‐wavelength radiation led to a strong emission peak at 450 nm that was associated with the carbazole groups. When CdS clusters were present in nearby but spatially distinct domains, the carbazole emission was completely quenched and replaced by a very broad emission in the visible range (near 560 nm). The implications of these observations are discussed in the context of the energy‐transfer mechanism and possible device applications. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 177–182, 2003     

纳米粒子在聚合物中的分散研究进展

介绍了解决无机纳米粒子团聚的途径,以及目前解决无机纳米粒子在聚合物基体中均匀分散的最新研究情况。