Polymer grafted nanoparticles: Effect of chemical and physical heterogeneity in polymer grafts on particle assembly and dispersion

Macroscopic properties of polymer nanocomposites depend on the microscopic composite morphology of the constituent nanoparticles and polymer matrix. One way to control the spatial arrangement of the nanoparticles in the polymer matrix is by grafting the nanoparticle surfaces with polymers that can tune the effective interparticle interactions in the polymer matrix. A fundamental understanding of how graft and matrix polymer chemistries and molecular weight, grafting density, and nanoparticle size, and chemistry affect interparticle interactions is needed to design the appropriate polymer ligands to achieve the target morphology. Theory and simulations have proven to be useful tools in this regard due to their ability to link molecular level interactions to the morphology. In this feature article, we present our recent theory and simulation studies of polymer grafted nanoparticles with chemical and physical heterogeneity in grafts to calculate the effective interactions and morphology as a function of chemistry, molecular weights, grafting densities, and so forth. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Impact of solvent quality on nanoparticle dispersion in semidilute and concentrated polymer solutions

We investigated how solvent quality affects the stability of polymer-grafted nanoparticles in semidilute and concentrated polymer solutions, which extends our previous studies on these types of dispersions in good solvents [Langmuir 2008, 24, 5260-5269]. As discussed in the current article, dynamic light scattering (DLS) was used to quantify the diffusion of polydimethylsiloxane-grafted silica nanoparticles, or PDMS-g-silica, in bromocyclohexane as well as in PDMS/bromocyclohexane solutions. We established that bromocyclohexane is a theta solvent for PDMS by varying the temperature of the solutions with PDMS-g-silica nanoparticles and detecting their aggregation at a theta temperature of T(Θ) = 19.6 °C. Using this temperature as a benchmark for the transition between good and bad solvent conditions, further stability tests were carried out in semidilute and concentrated polymer solutions of PDMS in bromocyclohexane at T = 10-60 °C. Irrespective of temperature, i.e., solvent quality, we found that the nanoparticles dispersed uniformly when molecular weight of the graft polymer was greater than that of the free polymer. However, when the free polymer molecular weight was greater than that of the graft polymer, the nanoparticles aggregated. Visual studies were also used to confirm the correspondence between nanoparticle stability and graft and free polymer molecular weights in a wide range of marginally poor solvents with PDMS. Further, the correspondence between nanoparticle stability and instability with graft and free polymer molecular weight and solvent quality was also supported with self-consistent mean-field calculations. Thus, by relating experiment and theory, our results indicate that nanoparticle stability in semidilute and concentrated polymer solutions is governed by interactions between the graft and free polymers under conditions of variable solvency.     

Interacting nanoparticles with functional surface groups

Functionalized nanoparticles with ionizable groups have generated a large variety of structures with important potential applications in technology. The nature of their interactions is crucial to determining their solubility and to exploring assemblies with diverse symmetries. Here, we use a molecular theory to describe the interactions between two nanoparticles coated with short polymer chains that contain ionizable (functional) end‐groups immersed in aqueous salt solution. It is shown here that the fraction of ionized functional groups in the system depends on factors such as the ionic strength and pH of solution, grafting density of polymer chains, the chain length, as well as the separation distance between the nanoparticles. The interactions between two neighboring nanoparticles influence the charge regulation of the end‐groups, which consequently induces an asymmetric distribution of these charged end‐groups on the nanoparticles, and thus confers a preferred directionality in nanoparticle–nanoparticle interactions. We show that the charge regulating system is less repulsive than an equivalent system with a fixed charge distribution. This is due to a decrease in the charge density of the weak acid end‐groups, to avoid a local increase in counterion confinement (condensation) in the region between neighboring nanoparticles, when their separation decreases. The anisotropic degree of ionization found in our results can be used to design aggregates of nanoparticles with reduced symmetries. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

The effect of nanoparticle shape on polymer‐nanocomposite rheology and tensile strength

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007     

Synthesis of gold–poly(methyl methacrylate) core–shell nanoparticles by surface‐confined atom transfer radical polymerization at elevated temperature

Surface‐confined atom transfer radical polymerization was used to prepare gold nanoparticle–poly(methyl methacrylate) core–shell particles at elevated temperature. First, gold nanoparticles were prepared by the one‐pot borohydride reduction of tetrachloroaurate in the presence of 11‐mercapto‐1‐undecanol (MUD). MUD‐capped gold nanoparticles were then exchanged with 3‐mercaptopropyltrimethoxysilane (MPS) to prepare a self‐assembled monolayer (SAM) of MPS on the gold nanoparticle surfaces and subsequently hydrolyzed with hydrochloric acid. The extent of exchange of MUD with MPS was determined by NMR. The resulting crosslinked silica‐primer layer stabilized the SAM of MPS and was allowed to react with the initiator [(chloromethyl)phenylethyl] trimethoxysilane. Atom transfer radical polymerization was conducted on the Cl‐terminated gold nanoparticles with the CuCl/2,2′‐bipyridyl catalyst system at elevated temperature. The rates of polymerization with the initiator‐modified gold nanoparticles exhibited first‐order kinetics with respect to the monomer, and the number‐average molecular weight of the cleaved graft polymer increased linearly with the monomer conversion. The presence of the polymer on the gold nanoparticle surface was identified by Fourier transform infrared spectroscopy and transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3631–3642, 2005     

Synthesis,characterization and cleavage of linear polymers attached to silica nanoparticles formed using thiol‐acrylate conjugate addition reactions

This study investigates the formation of linear polymer grafts using thiol‐acrylate conjugate addition reactions on nanoparticle surfaces. Silica nanoparticles were first modified with an amine functionality, followed by the attachment of a photocleavable acrylate. Dithiol‐diacrylate films were attached to the particles through the surface acrylate groups at various stoichiometric ratios of thiol to acrylate by conducting amine‐catalyzed conjugate addition polymerizations. The particles were then exposed to UV light to release the grafted polymer by photocleavage. The cleaved, grafted polymers were analyzed using infrared spectroscopy and gel permeation chromatography and compared to polymers formed in the bulk, which remained unattached to the particles. The measured number and weight average molecular weights were similar for both polymer types within experimental error and increased from 2000 to 5000 g/mol and 4000 to 10,000 g/mol, respectively, as the ratio of limiting to excess functionality increased from 0.8 to 1. Both number and weight average molecular weights followed the trend of step growth polymers with the highest molecular weight achieved for stoichiometric monomeric mixtures. Surface coverage of the nanoparticles was estimated using the molecular weight and thermogravimetric data and was found to be uniform (～0.15 chains/nm²) irrespective of the stoichiometry of the reacting monomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6896–6906, 2008     

The preparation and characterization of carboxylic acid‐coated silica nanoparticles

The preparation of carboxylic acid‐coated silica nanoparticles was investigated. A monolayer of carboxylic acid residues with controllable graft density was anchored to the nanoparticle by a ring‐opening reaction with succinic anhydride. Poly(methacrylic acid) [poly(MAA)] grafted nanoparticles were prepared via a polymerization–deprotection strategy. Tert‐butyl methacrylate was polymerized from the surface of silica nanoparticles in a predictable manner and with excellent control over the molecular weight distribution. Subsequent removal of the tert‐butyl group resulted in poly (MAA) grafted nanoparticles. The polymer nanoparticles were also functionalized with dyes, which may be useful in tracking the particles in biological systems. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Tailored composite polymer–metal nanoparticles by miniemulsion polymerization and thiol‐ene functionalization

A simple and modular synthetic approach, based on miniemulsion polymerization, has been developed for the fabrication of composite polymer–metal nanoparticle materials. The procedure produces well‐defined composite structures consisting of gold, silver, or MnFe₂O₄ nanoparticles (～10 nm in diameter) encapsulated within larger spherical nanoparticles of poly(divinylbenzene) (～100 nm in diameter). This methodology readily permits the incorporation of multiple metal domains into a single polymeric particle, while still preserving the useful optical and magnetic properties of the metal nanoparticles. The morphology of the composite particles is retained upon increasing the inorganic content and also upon redispersion in organic solvents. Finally, the ability to tailor the surface chemistry of the composite nanoparticles and incorporate steric stabilizing groups using simple thiol‐ene chemistry is demonstrated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1594–1606, 2010     

Polymerized pickering HIPEs: Effects of synthesis parameters on porous structure

A polyHIPE is a highly porous polymer synthesized from monomers within the external phase of a high internal phase emulsion (HIPE). The large amount of difficult to remove surfactant needed for HIPE stabilization can affect the properties of the resulting polymer. A Pickering emulsion is a surfactant‐free emulsion stabilized by solid particles that preferentially migrate to the interface. In this article, the synthesis of crosslinked polyacrylate polyHIPEs based on Pickering HIPEs stabilized using silane‐modified silica nanoparticles is described and the effects of the synthesis parameters on the porous structure are discussed. The silane chemistry, silane content, and nanoparticle content had significant effects on the size of the polyhedral, relatively closed‐cell polyHIPE voids that resulted from aqueous‐phase initiation. Increasing the mixing intensity reduced the wall thickness and produced a more open‐cell structure. The locus of initiation had a significant effect on polyHIPE morphology. Organic‐phase initiation yielded larger, more spherical voids from the more extensive coalescence before the structure could be “locked‐in” at the gel point. Most significantly, the nanoparticles were located within the polymer walls rather than at the interface, as might be expected. The void walls were shown to be an assembly of nanoparticle agglomerate shells that become embedded within the polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1516–1525, 2010     

Functionalization of nanoparticles for dispersion in polymers and assembly in fluids

The fluorescent, magnetic, and conductive properties of nanoparticles can transform polymer-based materials into composites with higher levels of sophistication than found in polymers alone. The ligand chemistry of nanoparticles is critically important in the development of polymer–nanoparticle composites to prevent nanoparticle aggregation and direct their assembly within polymers. Nanoparticle ligands can also prevent aggregation in solution and direct the assembly of nanoparticles at fluid–fluid interfaces, where interfacial chemistries can be performed to provide new routes to ultrathin composite sheets and capsules. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5076–5086, 2006     

Janus hybrid hairy nanoparticles

Janus hairy nanoparticles (JHNPs) represent a new class of hybrid materials with a nanoparticle core and a layer of bicompartmentalized polymer brushes. This unique structure combines the complex properties of polymer brushes, the amphiphilic nature of surfactant, and the mechanical, optical, and electronic properties of nanoparticles. Over the past decade, tremendous efforts have been devoted to synthesizing JHNPs and understanding their structure and properties. In this review, we will summarize the recent progresses in the field, including fabrication approaches and the self- and directed assembly behavior of such JHNPs. We will specifically focus on the newly developed polymer single crystal directed nanoparticle assembly approach. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1620–1640     

Functional oligomers for the control and fixation of spatial organization in nanoparticle assemblies

Interactions in nanoparticle assemblies play an important role in modulating their interesting magnetic and optical properties. Controlling and fixing the distance between nanoparticles is therefore crucial to the development of next-generation nanodevices. Here, we show that the interparticle distance in two-dimensional assemblies can be quantitatively controlled by functionalizing the nanoparticles with short polymers containing one functional end group that binds to the nanoparticle. Carboxy-functional poly(dimethylsiloxane) (PDMS) ligands are attached to the nanoparticle surface by a simple ligand exchange process with the oleic acid synthesis ligands. The distance between nanoparticles is manipulated by adjusting either the number of PDMS ligands per molecule or their molecular weight. The use of PDMS ligands is unique in that they provide a means to permanently and robustly fix the spatial distribution of nanoparticles because PDMS is readily converted to silicon oxide by a simple UV/ozone treatment. The distance between nanoparticles can be designed a priori, as it is found to scale well with theoretical predictions for the thickness of the surface-bound polymer brush layer.     

Nanoprecipitation for ultrafiltration membranes

Polymer nanoparticles are readily obtainable by rapidly mixing a dilute polymer solution and a poor solvent. The nanoparticles of poly(vinylphenol), poly(vinylidene fluoride), and emeraldine base polyaniline prepared by nanoprecipitation become sticky when their diameters decrease down to a few tens of nanometers, and such polymer nanoparticles spontaneously assemble into rigid fractal networks of the nanoparticles. By filtering these fibrous nanoparticle networks on a microfiltration membrane, ultrafiltration membranes with a thin free‐standing filter cake layer made of nanoparticles are obtainable. The nanoparticle membranes are robust at least up to the applied pressure of 2 MPa and can separate 99% of 10 nm Au nanoparticles from the aqueous dispersion at the flux of more than 1835 L m^?2 h^?1 even at very low pressure difference of 0.08 MPa. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 615–620     

Synthesis and chemical modification of magnetic nanoparticles covalently bound to polystyrene-SiCl2-poly(2-vinylpyridine)

The present article offers a new approach to create a multifunctional material based on magnetic nanoparticles, which can be dispersed in aqueous and organic media. The preparation of this material was performed by binding covalently polymer chains based on a reactive diblock-copolymer of the polystyrene-SiCl₂-poly(2-vinylpyridine) type, with average molecular weight per number (M_n) equal to 14,700 g/mol and a polydispersity index (PDI) less than 1.1, onto the surface of γ-Fe₂O₃ magnetic nanoparticles. The dichlorosilane moiety of the diblock-copolymer reacted with the  OH groups of the magnetic nanoparticles immobilizing the polymer chain onto its surface. This reaction was monitored by FTIR and the polymer grafting density was determined by TGA and BET. Dynamic light scattering revealed that the hydrodynamic diameter of the nanoparticles increased after immobilizing the polymer. Contact angle measurements demonstrated the ability of the hybrid material to interact with organic and aqueous media allowing its dispersion in solvents with different polarities. This property was used to prepare a magnetically active emulsion. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1668–1675, 2010     

Polymer nanocomposites

Polymer nanocomposites are distinguished by the convergence of length scales corresponding to the radius of gyration of the polymer chains, a dimension of the nanoparticle and the mean distance between the nanoparticles. The consequences of this convergence on the physics of the polymer chains are considered, and some of the outstanding issues and their potential consequences on structure—property relations for polymer nanocomposites are highlighted. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3252–3256, 2007     

Chain confinement in polymer nanocomposites and its effect on polymer bulk properties

The issue of chain confinement in nanocomposites remains largely unanswered because experimental systems are plagued by additional complicating variables such as particle–polymer interactions and free volume increases brought upon by the addition of the particles. Using computer simulation of high length chain polymers, we show that simple excluded volume interactions between polymer and nanoparticles lead to a wealth of changes in the diffusion coefficient and entanglement density of the chains. This opens up the possibility of using nanoparticles for tuning polymer properties, such as toughness, melt viscosity, and transient rubberlike behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 687–692, 2010     

Building nanostructures using RAFT polymerization

Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied controlled/living radical polymerization methods that has been used to prepare well‐defined nanostructured polymeric materials. This review, with more 650 references illustrates the range of well‐defined functional nanomaterials that can be accessed using RAFT chemistry. The detailed syntheses of macromolecules with predetermined molecular weights, designed molecular weight distributions, controlled topology, composition and functionality are presented. RAFT polymerization has been exploited to prepare complex molecular architectures, such as stars, blocks and gradient copolymers. The self‐assembly of RAFT‐polymer architectures has yielded complex nanomaterials or in combination with other nanostructures has generated hybrid multifunctional nanomaterials, such as polymer‐functionalized nanotubes, graphenes, and inorganic nanoparticles. Finally nanostructured surfaces have been described using the self‐organization of polymer films or by the utilization of polymer brushes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Self‐assembly of polymer‐coated ferromagnetic nanoparticles into mesoscopic polymer chains

The self‐assembly of dispersed polymer‐coated ferromagnetic nanoparticles into micron‐sized one‐dimensional mesostructures at a liquid–liquid interface was reported. When polystyrene‐coated Co nanoparticles (19 nm) are driven to an oil/water interface under zero‐field conditions, long (≈ 5 μm) chain‐like assemblies spontaneously form because of dipolar associations between the ferromagnetic nanoparticles. Direct imaging of the magnetic assembly process was achieved using a recently developed platform consisting of a biphasic oil/water system in which the oil phase was flash‐cured within 1 s upon ultraviolet light exposure. The nanoparticle assemblies embedded in the crosslinked phase were then imaged using atomic force microscopy. The effects of time, temperature, and colloid concentration on the self‐assembly process of dipolar nanoparticles were then investigated. Variation of either assembly time t or temperature T was found to be an interchangeable effect in the 1D organization process. Because of the dependence of chain length on the assembly conditions, we observed striking similarities between 1D nanoparticle self‐assembly and polymerization of small molecule monomers. This is the first in‐depth study of the parameters affecting the self‐assembly of dispersed, dipolar nanoparticles into extended mesostructures in the absence of a magnetic field. © 2008 Wiley Periodicals, Inc.* J Polym Sci Part B: Polym Phys 46: 2267–2277, 2008     

Mean‐field theoretical analysis of brush‐coated nanoparticle dispersion in polymer matrices

The equilibrium dispersion of nanoparticles with grafted polymer chains into polymer matrices, of the same chemical structure as the brush, is studied through the device of mean‐field theory. Our results show that the disperion of brush‐coated nanoparticles into a matrix polymer is improved with (i) decreasing particle radius and (ii) increasing brush chain length. Both of these aspects can be understood based on the fact that, unlike the case of planar surfaces, homopolymer chains end‐grafted to spherical nanoparticle surfaces tangentially spread away from the surface thus alleviating the packing frustration that is created by the relatively high grafting densities. This permits significant brush/matrix overlap, even at high grafting densities, a regime that has only recently become experimentally available due to advances in polymer synthesis (i.e., the “grafting‐to” methods). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 351–358, 2008