The presented paper describes a novel procedure for the preparation of inorganic nanoparticles and their surface functionalization in situ dedicated to an application in technical polymers. Using an inverse emulsion technique and amphiphilic block or statistical copolymers as stabilizers, a broad variety of nanoparticles such as ZnO, CdS, MgCO3, Ni, or Cu can be prepared. The amphiphilic polymers serve not only as surface active compounds in the emulsion but also to hydrophobize the inorganic particles as they remain adsorbed on the surface after the precipitation. As a consequence of the high degree of surface coverage by polymer chains, organic solvents are able to redisperse these particles in the aggregate free manner. The utilization of the block copolymers instead of statistical copolymers resulted in the formation of the particles, which were larger in size and possessed a much broader size distribution. The chemical nature of the adsorbed polymer layer on the particle surface is crucial to the preparation of polymer nanocomposites. The primary goal of this contribution is to demonstrate the universality of such a one-pot synthetic procedure, which was found to be relevant for industrial use. 相似文献
The preparation of complex inorganic/organic core-shell particles and their in situ hydrophobization via an inverse emulsion
technique is described here. Typically, aqueous solutions of precursor salts are dispersed with the help of statistical copolymers
in an organic phase and subsequently polymer-stabilized nanoparticles precipitate at room temperature (e.g., barium- or strontium-based
perovskite nanoparticles). By this technique, core-multiple-shell ZnO–silica–polymer nanoparticles may also be obtained, whereby
the polymer matrix is protected against the photocatalytically active ZnO by the silica shell. The particles are characterized
by X-ray, transmission electron microscopy, and dynamic light scattering. In this approach, amphiphilic statistical copolymers
act not only as stabilizers for inverse emulsions, but they also hydrophobize the remaining complex inorganic particles shelled
on the surface after the precipitation. The preparation of hybrid nanoparticles is performed by a one-pot procedure, which
makes this process attractive for industrial applications. 相似文献
An inverse emulsion technique which allows the anisotropic growth of a broad variety of inorganic nanoparticles, together with an efficient hydrophobization, is described. This method is based upon the combined use of amphiphilic copolymers, which act as emulsifiers as well as compatibilizers, and structure-directing agents that control the crystallization of the inorganic nanoparticles. As a consequence, water-soluble, structure-directing agents can now be applied for the synthesis of hydrophobic, shape-anisotropic nanocrystals. More precisely, spherical, rod-like, and branched CdS as well as Au nanoparticles were prepared. Due to their excellent hydrophobization, these particles were homogeneously incorporated into a poly(2-ethylhexyl methacrylate) matrix. Their shape-dependent properties were transferred to nanocomposites as demonstrated for branched CdS nanocrystals. In comparison to more traditional materials composed of branched CdS nanoparticles, which are stabilized by low molecular weight amphiphiles, our composites show much less scattering. This is due to the homogenous distribution of the nanoparticles in the matrix. 相似文献
Amphiphilic block copolymers provide useful templates for fabrication of nanostructured materials that are appealing for a wide variety of applications. The preparation of polymer-particle hybrid materials requires a good understanding of the chemical nature and topology of the amphiphilic molecules as well as their interactions with the embedded nanoparticles. This article reports a density functional theory (DFT) for a coarse-grained model of block copolymer-nanoparticle mixtures that is able to account for the properties of particles and copolymers within a self-consistent framework. It predicts various well-organized structures that can be effectively controlled by adjusting the polymer chain length and polymer-particle interactions. Illustrative examples based on relatively short chains suggest that, in qualitative agreement with experiments, large particles tend to be excluded from a polymer brush near a solid substrate, whereas smaller particles may be dissolved. The DFT is able to capture the dispersion of large particles in the microdomain of block copolymer that is energetically favorable, but localization of smaller particles at the microdomain interfaces. 相似文献
Hybrid gold–polymer nanoparticles are obtained by self‐assembly of amphiphilic copolymers (Pluronics) in solutions containing preformed gold nanoparticles (diameter ca. 12 nm). Dynamic light scattering, TEM, cryo‐TEM, and small‐angle neutron scattering experiments with contrast variation are used to characterize the structure of the gold–polymer particles. Five Pluronics (F127, F68, F88, F108, P84) with different molecular weights and hydrophilic/hydrophobic balances are investigated. Gold nanoparticles are individually embedded within globules of polymer, even under conditions for which Pluronics micelles do not form in solution. The hybrid particles are several tens of nanometers in size (larger than micelles of the corresponding Pluronics), and the size can be tuned by changing the temperature. 相似文献
We report on a robust approach to the size-selective and template-free synthesis of asymmetrically functionalized ultrasmall (<4 nm) gold nanoparticles (AuNPs) stably anchored with a single amphiphilic triblock copolymer chain per NP. Directed NP self-assembly in aqueous solution can be facilely accomplished to afford organic/inorganic hybrid micelles, vesicles, rods, and large compound micelles by taking advantage of the rich microphase separation behavior of the as-synthesized AuNP hybrid amphiphilic triblock copolymers, PEO-AuNP-PS, which act as the polymer-metal-polymer analogue of conventional amphiphilic triblock copolymers. Factors affecting the size-selective fabrication and self-assembly characteristics and the time-dependent morphological evolution of NP assemblies were thoroughly explored. 相似文献
We have already shown that polylactide (PLA) nanoparticles covered with a hydrophilic polymeric layer can be prepared by simple emulsion/solvent evaporation by using amphiphilic copolymers as surfactants during the procedure. The external layer is then constituted by the hydrophilic part of the macromolecular surfactant. This kind of nanospheres is useful for the encapsulation of lipohilic molecules. The use of amphiphilic copolymers as surfactants in the preparation of PLA nanospheres with controlled surface properties, was then applied to the double emulsion/solvent evaporation procedure. The aim was to allow the encapsulation of water-soluble bioactive molecules in PLA particles with controlled surface properties. In this paper, we describe the results obtained with three different water-soluble monomethoxypolyethylene oxide (MPEO)-b-PLA diblock copolymers used as surfactants in the preparation of nanoparticles by double emulsion/solvent evaporation. After organic solvent evaporation, the obtained nanospheres were proved to be really covered by a MPEO layer whose characteristics were determined. It was firstly shown that the MPEO-covered particles did not flocculate at 25 degrees C, even in 4 M NaCl while suspensions of bare nanospheres were destabilized for a NaCl concentration as low as 0.04 M. On the other hand, the suspensions of MPEO-covered nanoparticles in 0.3 M Na2SO4 were found to be very sensitive to temperature as they flocculated at a temperature lying between 45 and 55 degrees C depending on the MPEO-b-PLA composition. This property was attributed to the fact that MPEO is a polymer with a low critical solution temperature. The concentration of MPEO at the nanoparticle surface was then calculated for the three kinds of particles, from the initial flocculation temperature, and was found to be comparable to the value determined directly. 相似文献
Summary: The paper considers various possibilities to produce inorganic – polymeric nanocomposites via aqueous heterophase polymerization. Special emphasis is placed on strategies to synthesize nanocomposite particles via joint nucleation or joint polymerization. The former strategy is used to make composite particles with CaCO3 as inorganic component. The strategy of joint polymerization takes advantage from the condition that aqueous heterophase polymerization is a convenient possibility to synthesize amphiphilic block copolymers. This method relies on the fact that polymeric radicals can survive in isolated latex particles that are stabilized by hydrophilic blocks. This strategy can be successfully applied to produce silica-containing block copolymer particles in a one-step procedure. 相似文献
Polymersomes assembled from amphiphilic block copolymers containing a glassy hydrophobic segment can be further re-engineered to perform a controlled shape transformation from a thermodynamically stable spherical morphology to a kinetically trapped stomatocyte structure. The stable bowl-shape stomatocyte morphology is ideal for the specific physical entrapment of nanoparticles for potential use in heterogeneous catalysis and drug delivery. Herein we report two approaches to obtain a selective and controlled entrapment of platinum nanoparticles (PtNP) of different sizes and shapes inside the stomatocyte structure. In the first approach, the stomach of the stomatocytes is used to template the growth of the PtNP by controlling and confining the nucleation points inside the cavity. In the second method, preformed nanoparticles are engulfed during the stomatocyte formation process. Synergistically, the reverse effect is observed, that is, differently shaped nanoparticles were shown to exhibit a templating effect on the stomach formation of the stomatocytes. 相似文献
Controllable self-assembly of nanoscale building blocks into larger specific structures provides an effective route for the fabrication of new materials with unique optical, electronic, and magnetic properties. The ability of nanoparticles (NPs) to self-assemble like molecules is opening new research frontiers in nanoscience and nanotechnology. We present a new class of amphiphilic "colloidal molecules" (ACMs) composed of inorganic NPs tethered with amphiphilic linear block copolymers (BCPs). Driven by the conformational changes of tethered BCP chains, such ACMs can self-assemble into well-defined vesicular and tubular nanostructures comprising a monolayer shell of hexagonally packed NPs in selective solvents. The morphologies and geometries of these assemblies can be controlled by the size of NPs and molecular weight of BCPs. Our approach also allows us to control the interparticle distance, thus fine-tuning the plasmonic properties of the assemblies of metal NPs. This strategy provides a general means to design new building blocks for assembling novel functional materials and devices. 相似文献
High‐performance catalysts and photovoltaics are required for building an environmentally sustainable society. Because catalytic and photovoltaic reactions occur at the interfaces between reactants and surfaces, the chemical, physical, and structural properties of interfaces have been the focus of much research. To improve the performance of these materials further, inorganic porous materials with hierarchic porous architectures have been fabricated. The breath figure technique allows preparing porous films by using water droplets as templates. In this study, a valuable preparation method for hierarchic porous inorganic materials is shown. Hierarchic porous materials are prepared from surface‐coated inorganic nanoparticles with amphiphilic copolymers having catechol moieties followed by sintering. Micron‐scale pores are prepared by using water droplets as templates, and nanoscale pores are formed between the nanoparticles. The fabrication method allows the preparation of hierarchic porous films from inorganic nanoparticles of various shapes and materials.
Nanostructured materials have drawn a great deal of attention in recent yearsbecause of their promising potentials in future applications.The fabrication of nano-materials has become a highly active research area involving scientists in many differentfields,e.g.,physics,chemistry,biology and materials science and engineering. Theinorganic synthesis including biomineralization by using intermolecular bonds to act in acooperative manner in order to construct organized supramolecular systems by s… 相似文献
We report on a method of fabricating stimuli-responsive core-shell nanoparticles using block copolymers covalently bound to a silica nanoparticle surface. We used the "grafting to" approach to graft amphiphilic block copolymer brushes of poly(styrene-b-2-vinylpyridine-b-ethylene oxide) and poly(styrene-b-4-vinylpyridine) onto silica nanoparticles with two different diameters: colloidal silica 200 nm in diameter and fumed silica 15 nm in diameter. We used the pH-responsive properties of the grafted brush to regulate the interactions between the particles, and between the particles and their environment. We show that this behavior can be applied for a reversible formation of particle aggregates, and can be used to tune and stabilize the secondary aggregates of particles of the appropriate size and morphology in an aqueous environment. The suspensions of the particles form a textured hydrophilic coating on various substrates upon casting and the evaporation of water. Heating above the polymer's glass transition temperature or treatment in acidic water result in back and forth switching between superhydrophobic and hydrophilic surfaces, respectively. 相似文献
The production of silver and copper particles by laser ablation in an organic solvent and their in situ functionalization with amphiphilic copolymers bearing fluorinated side chains is presented. Aside the stabilization of the particles, the fluorinated side chains render the modified particles compatible with a perfluorinated matrix, which results in a homogeneous distribution of the particles in the matrix. The incorporation of silver particles in perfluorinated matrices is of special interest for the preparation of antibacterial composites, e.g. PTFE, which might be applied in antibacterial implants, e.g. antibacterial vascular prostheses. Laser ablation in liquids as a general method to produce charged nanoparticles of any metal is hence combined with sophisticated surface active compounds. 相似文献
Wet foams are used in many important technologies either as end or intermediate products. However, the thermodynamic instability of wet foams leads to undesired bubble coarsening over time. Foam stability can be drastically improved by using particles instead of surfactants as foam stabilizers, since particles tend to adsorb irreversibly at the air-water interface. Recently, we presented a novel method for the preparation of high-volume particle-stabilized foams which show neither bubble growth nor drainage over more than 4 days. The method is based on the in-situ hydrophobization of initially hydrophilic particles to enable their adsorption on the surface of air bubbles. In-situ hydrophobization is accomplished through the adsorption of short-chain amphiphiles on the particle surface. In this work, we illustrate how this novel method can be applied to particles with various surface chemistries. For that purpose, the functional group of the amphiphilic molecule was tailored according to the surface chemistry of the particles to be used as foam stabilizers. Short-chain carboxylic acids, alkyl gallates, and alkylamines were shown to be appropriate amphiphiles to in-situ hydrophobize the surface of different inorganic particles. Ultrastable wet foams of various chemical compositions were prepared using these amphiphiles. The simplicity and versatility of this approach is expected to aid the formulation of stable wet foams for a variety of applications in materials manufacturing, food, cosmetics, and oil recovery, among others. 相似文献