Surface energetics,dispersion, and nanotribomechanical behavior of POSS/PP hybrid nanocomposites

Hybrid organic–inorganic polymer nanocomposites incorporating polyhedral oligomeric silsesquioxane (POSS) nanoparticles are of increasing interest for high performance materials applications. Octaisobutyl POSS/polypropylene nanocomposites were prepared at varying POSS concentrations via melt blending. The interplay of POSS molecular geometry, composition, and concentration in relation to the tribological, nanomechanical, surface energy, and bulk properties of the nanocomposites were investigated. Ultra‐low friction and enhanced hardness, modulus, and hydrophobicity were observed for the nanocomposite surfaces, with minimal changes in the bulk thermomechanical properties. Parallel AFM, SEM, TEM, and spectroscopic analyses demonstrated significant differences in POSS distribution and aggregation in the surface and the bulk, with preferential segregation of POSS to the surface. Additionally, contact angle studies reveal significant reduction in surface energy and increase in hysteresis with incorporation of POSS nanoparticles. The differences in bulk and surface properties are largely explained by the gradient concentration of POSS in the polymer matrix, driven by POSS/POSS and POSS/polymer interactions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2441–2455, 2007     

Polymerization and nanocomposites properties of multifunctional methylmethacrylate POSS

Thermally induced polymerization of multifunctional methylmethacrylate POSS (MMA‐POSS) was studied in this work for preparation of polymer/POSS nanocomposites. The polymerization of MMA‐POSS could be promoted with benzoyl peroxide (BPO). Self‐assembly of POSS into a layer‐by‐layer structure in the MMA‐POSS polymer (TP‐MMA‐POSS) is observed with a transmission electron microscopy. An ultra‐low‐k value of about 1.85 is measured with TP‐MMA‐POSS. In addition, polyimide‐POSS nanocomposites are also prepared. These nanocomposites demonstrate good homogeneity and enhanced mechanical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5157–5166, 2008     

Effect of nano‐size nodular structure induced by CNT‐promoted phase separation on the fabrication of superhydrophobic polyvinyl chloride films

The nonsolvent‐induced phase separation (NIPS) method was employed to fabricate the porous films based on polyvinyl chloride loaded with carbon nanotubes (CNTs). The combinational addition of CNTs and a proper nonsolvent (ethanol) resulted in a porous surface layer with the nano‐size nodular structure possessing an exact superhydrophobic behavior (water contact angle [WCA] = 157° and sliding angle [SA] <5°). The size of PVC nodules at the surface layer varies in the range of 200 to 800 nm depending on the nonsolvent concentrations, and polymer molecular weight. The effects of various nonsolvent concentrations as well as PVC molecular weight on the surface properties of the films were also investigated. Morphological and roughness analyses revealed the pronounced role of PVC molecular weight on the size of nodules, and the structural uniformity of the surface morphology based on the thermodynamic parameters such as relaxation time and dynamic of polymer chains. The concurrent use of CNTs and nonsolvent led to promote the NIPS process due to the nucleating role of CNTs, which were localized within the polymer‐rich phase leading to an ultra‐fine and packed nodular surface structure. Transmission electron microscopy results also proved the very well dispersion quality of CNTs. Glass transition temperature of PVC was also assessed, and the results were correlated to the associating ability of CNTs with polymer chains during the phase separation process. Overall, the promising potential of CNT/ethanol combination on the surface porosity and hydrophobicity of PVC nanocomposite films was revealed in this study, which could further extend its application window.     

Surface modification of gold nanoparticles with polyhedral oligomeric silsesquioxane and incorporation within polymer matrices

A new approach to achieve polymer‐mediated gold ferromagnetic nanocomposites in a polyhedral oligomeric silsesquioxane (POSS)‐containing random copolymer matrix has been developed. Stable and narrow distributed gold nanoparticles modified by 3‐mercaptopropylisobutyl POSS to form Au‐POSS nanoparticles are prepared by two‐phase liquid‐liquid method. These Au‐POSS nanoparticles form partial particle aggregation by blending with poly(n‐butyl methacrylate) (PnBMA) homopolymer because of poor miscibility between Au‐POSS and PnBMA polymer matrix. The incorporation the POSS moiety into the PnBMA main chain as a random copolymer matrix displays well‐dispersed gold nanoparticles because the POSS‐POSS interaction enhances miscibility between gold nanoparticles and the PnBMA‐POSS copolymer matrix. This gold‐containing nanocomposite exhibits ferromagnetic phenomenon at room temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 811–819, 2009     

Self‐Healable Organogel Nanocomposite with Angle‐Independent Structural Colors

Structural colors have profound implications in the fields of pigments, displays and sensors, but none of the current non‐iridescent photonic materials can restore their functions after mechanical damage. Herein, we report the first self‐healable organogel nanocomposites with angle‐independent structural colors. The organogel nanocomposites were prepared through the co‐assembly of oleophilic silica nanoparticles, silicone‐based supramolecular gels, and carbon black. The organogel system enables amorphous aggregation of silica nanoparticles and the angle‐independent structural colors in the nanocomposites. Moreover, the hydrogen bonding in the supramolecular gel provides self‐healing ability to the system, and the structural colored films obtained could heal themselves in tens of seconds to restore storage modulus, structural color, and surface slipperiness from mechanical cuts or shear failure repeatedly.     

Effect of silica nanofillers on isothermal crystallization of poly(vinyl alcohol): In-situ ATR-FTIR study

Isothermal crystallization behavior of poly(vinyl alcohol) (PVA) in the presence and absence of silica nanoparticles was systematically investigated using in-situ attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy. The content, size, and surface characteristics of silica nanoparticles were considered as main factors affecting the crystallization behavior, and the effect of annealing time and temperature was also examined. First, very low concentrations of silica nanoparticles (less than 0.5 wt%) could accelerate the crystallization process, whereas higher silica loadings reduced the degree of crystallization. In the PVA/silica (0.5 wt%) nanocomposites, 22-nm silica nanoparticles provided the most suitable interparticle space for nucleation and crystal growth. Compared with hydrophobic silica nanoparticles, hydrophilic silica nanoparticles are favorable to achieve higher crystallinity due to the increased chemical affinity in the nanocomposites. The degree of crystallization became higher with increasing annealing time and it was also enhanced in a high-temperature region. When 0.5 wt% of 22-nm silica nanoparticles was used as a nucleating agent for the crystallization of PVA, the crystallinity of nanocomposites was ca. 20% higher than that of pristine PVA.     

Preparation and Flame Retardancy of Polyurethane/POSS Nanocomposites

Polyurethane/polyhedral oligomeric sisesquioxane (PU/POSS) nanocomposites were syn-thesized via polymerization utilizing the compatibility between POSS nanoparticles and 4,4'-diphenyl methylene diisocyanate. Scanning electron microscope images and Fouriertransform infrared spectra revealed that POSS nanoparticles were dispersed in PU matrix.Thermal gravimetric analysis was employed to investigate the thermal decomposition be-havior of PU/POSS nanocomposites at elevated temperatures. Then fire performance wasevaluated by limiting oxygen index, underwriters laboratories 94 testing and char residue morphology. These results showed that the addition of POSS promoted the formation of char residues which were covered on the surface of polymer composites, leading to the im-provement of thermal stability and flame retardancy.     

POSS‐nylon 6 nanocomposites: Influence of POSS structure on surface and bulk properties

Hybrid organic/inorganic nanocomposites based on polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals and nylon 6 were prepared via melt mixing. Two structurally and chemically different POSS molecules, a closed cage, nonpolar octaisobutyl POSS (Oib‐POSS) and an open cage, polar trisilanolphenyl POSS (Tsp‐POSS) with differing predicted solubility parameters were evaluated in the nylon matrix. Surface analysis, including quasi‐static and dynamic nanoindentation and nanotribological techniques, revealed exceptional improvements in modulus and hardness along with significant reductions in friction. Additionally, surface wetting characteristics of the nylon were reversed, with POSS incorporation yielding low surface energy, highly hydrophobic surfaces. AFM, TEM/EDAX, spectroscopic techniques and thermomechanical analysis were used to evaluate nanoscale dispersion and bulk properties of the composites. Both POSS molecules exhibit preferential surface segregation behavior in the nylon matrix. Tsp‐POSS, with its higher predicted solubility in nylon, exhibited enhanced dispersion and tribomechanical properties at both nano and bulk scale. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1088–1102, 2009     

Effect of polyaniline as a surface modifier of TiO2 nanoparticles on the properties of polyvinyl chloride/TiO2 nanocomposites

Surface of TiO2 nanoparticles was modified with the in situ chemical oxidative polymerization of aniline. Polyaniline modified TiO2 nanoparticles (PANI-TiO2 ) were characterized with the FT-IR, XRD, SEM and TEM techniques. Results confirmed that PANI was grafted successfully on the surface of TiO2 nanoparticles, therefore agglomeration of nanoparticles decreased dramatically. Polyvinyl chloride nanocomposites filled with 1 wt% 5 wt% of PANI-TiO2 and TiO2 nanoparticles were prepared via the solution blending method. PVC nanocomposites were analyzed with FT-IR, XRD, SEM, TG/DTA, DSC and tensile test techniques. Effect of PANI as surface modifier of nanoparticles was discussed according to the final properties of PVC nanocomposites. Results demonstrated that deposition of PANI on the surface of TiO2 nanoparticles improved the interfacial adhesion between the constituents of nanocomposites, which resulted in better dispersion of nanoparticles in the PVC matrix. Also PVC/PANI-TiO2 nanocomposites showed higher thermal resistance, tensile strength and Young’s modulus compared to those of unfilled PVC and PVC/TiO2 nanocomposites.     

Synthesis and characterization of polyethylene/clay–silica nanocomposites: A montmorillonite/silica‐hybrid‐supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT‐Si) supported catalyst, was developed. MT‐Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT‐Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay–silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 941–949, 2004     

Effect of the Spherical Silica Surface on the Photoluminescence of the Loaded CdS Nanoparticles

CdS nanoparticles were formed on the surface of silica microspheres by the improved layer‐by‐layer self‐assembled technique. High‐resolution electron microscope (HRTEM) image and energy dispersive x‐ray analysis (EDX) confirmed formation of a quasi‐continuous CdS nanoparticles film on the silica microspheres. The results of UV‐vis and fluorescence spectra display that the spherical silica surface has a great effect on the photoluminescence of the loaded CdS nanoparticles. In contrast to the CdS nanoparticles powder, the composite can exhibit the emission ascribed to the band gap transition when the CdS nanoparticles film is relatively thick. This phenomenon is probably due to an enhancement of the crystallinity of CdS nanoparticles induced by the silica spheres.     

Thermal and Surface Properties of Phenolic Nanocomposites Containing Octaphenol Polyhedral Oligomeric Silsesquioxane

Summary: We have synthesized a new polyhedral oligomeric silsesquioxane (POSS) containing eight phenol functional groups and copolymerized it with phenol and formaldehyde to form novolac‐type phenolic/POSS nanocomposites exhibiting high thermal stabilities and low surface energies. Our DSC results indicate that the glass transition temperature of these nanocomposites increased initially upon increasing their POSS content, but then decreased at POSS content above 10 wt.‐%, presumably because of the formation of relatively low molecular weight species and POSS aggregation as evidenced from MALDI‐TOF mass analyses. Our TGA analyses indicated that the 5‐wt.‐%‐mass‐loss temperatures (T_d) increased significantly upon increasing the POSS content because the incorporation of the POSS led to the formation of an inorganic protection layer on the nanocomposite's surface. XPS and contact angle data provided positive evidence to back up this hypothesis. In addition, contact angle measurements indicated a significant enhancement in surface hydrophobicity after increasing the POSS content.

Syntheses procedures of phenolic/OP‐POSS nanocomposites.     

Simultaneous Preparation of PI/POSS Semi‐IPN Nanocomposites

Summary: This investigation presents a simultaneous and convenient approach to produce a high‐performance polyimide with a low dielectric constant by introducing the octa‐acrylated polyhedral oligomeric silsesquioxane (methacrylated‐POSS) into a polyimide matrix to form polyimide semi‐interpenetrating polymer network (semi‐IPN) nanocomposites. The differential scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) results indicate that the self‐curing of methacrylated‐POSS and the imidization of polyamic acid (PAA) occurs simultaneously. The morphology of a semi‐IPN structure of polyimide/POSS‐PI/POSS nanocomposites with POSS nanoparticles embedded inside the matrix is elucidated. The POSS particles are uniform and are aggregated to a size of approximately 50–60 nm inside the polyimide matrix. The interconnected POSS particles are observed at high POSS content. The structure is highly cross‐linked, so the PI/POSS nanocomposites have an enhanced glass transition temperature. The high porosity of the PI/POSS nanocomposites markedly reduces the dielectric constant of PI because of the nanometer‐scale porous structure of POSS.

FT‐IR spectra of the various compounds of A) methacrylate‐POSS before curing, B) methacrylate‐POSS after curing, C) PAA containing 15 wt.‐% POSS, and D) PI/POSS containing 15 wt.‐% POSS.     

Characterization of PBT/POSS nanocomposites prepared by in situ polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS

Novel poly(butylene terephthalate) (PBT)/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized by ring‐opening polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS with various feed ratios. The impact of POSS incorporation on melting and crystallization behaviors of PBT/POSS nanocomposites was investigated by means of X‐ray diffraction and differential scanning calorimetry. It was found that the novel organic–inorganic association result in the significant alterations in the melting and crystallization behavior of PBT. Thermal studies confirmed that the incorporation of POSS can enhance the thermal stability of the polymers, and the copolymer glass transition temperature increased with the increasing of POSS macromonomer content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1853–1859, 2010     

Facile Synthesis of Boronic Acid‐Functionalized Magnetic Mesoporous Silica Nanocomposites for Highly Specific Enrichment of Glycopeptides

In the work, aminophenylboronic acid (APB)‐functionalized magnetic mesoporous silica, which holds the attractive features of high magnetic responsivity and large surface area, was developed to enrich glycopeptides. At first, magnetic mesoporous silica nanocomposites were prepared. And then, the nanocomposites were functioned with glycidoxypropyltrimethoxysilane (GLYMO) for boronic acid immobilization. Due to that the boronic acid group on the surface of magnetic mesoporous silica nanocomposites can form tight yet reversible covalent bond with glycopeptides containing cis‐1,2‐diols groups, the magnetic mesoporous silica nanocomposites were successfully applied to selective enrichment of glycopeptides. APB functionalized magnetic mesoporous silica was also demonstrated to have high selectivity for the glycopeptides in the presence of a 10‐fold excess bovine serum albumin (BSA) over horseradish peroxidase (HRP) in the tryptic digest. We also find that magnetic mesoporous silica has better sensitivity in HRP digest compared with that of commercial aminophenylboronic acid‐functionalized magnetic nanoparticles beads. The limit of detection for glycopeptides from glycoprotein HRP is about 0.01 ng/µL.     

Investigation on Structures and Properties of Shape Memory Polyurethane/Silica Nanocomposites

In this study, high performance shape memory polyurethane (SMPU)/silica nanocomposites with different silica weight fraction including SMPU bulk, 3%, 4.5%, 6%, 7.5%, 10%, were prepared by sol‐gel process initiated by the solid acid catalyst of p‐toluenesulfonic acid (PTSA). Field emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) observation show that the silica nanoparticles are dispersed evenly in SMPU/silica nanocomposites. Tensile test and dynamic mechanical analysis (DMA) suggest that the mechanical properties and the glass transition temperature (T_g) of the nanocomposites were significantly influenced by silica weight fraction. Thermogravimetric analysis (TGA) was utilized to evaluate the thermal stability and determine the actual silica weight fraction. The TGA results indicate that the thermal stability can be enhanced with the hybridization of silica nanoparticles. Differential scanning calorimetry (DSC) was conducted to test the melting enthalpy (ΔH) and the results suggest that the ΔH was markedly improved for the SMPU/silica nanocomposites. Thermomechanical test was conducted to investigate the shape memory behavior and the results show that the shape fixity is improved by hybridization of silica and good shape recovery can be obtained with the increasing of cycle number for all the samples.     

A General Route to Hollow Mesoporous Rare‐Earth Silicate Nanospheres as a Catalyst Support

Hollow mesoporous structures have recently aroused intense research interest owing to their unique structural features. Herein, an effective and precisely controlled synthesis of hollow rare‐earth silicate spheres with mesoporous shells is reported for the first time, produced by a simple hydrothermal method, using silica spheres as the silica precursors. The as‐prepared hollow rare‐earth silicate spheres have large specific surface area, high pore volume, and controllable structure parameters. The results demonstrate that the selection of the chelating reagent plays critical roles in forming the hollow mesoporous structures. In addition, a simple and low‐energy‐consuming approach to synthesize highly stable and dispersive gold nanoparticle–yttrium silicate (AuNPs/YSiO) hollow nanocomposites has also been developed. The reduction of 4‐nitrophenol with AuNPs/YSiO hollow nanocomposites as the catalyst has clearly demonstrated that the hollow rare‐earth silicate spheres are good carriers for Au nanoparticles. This strategy can be extended as a general approach to prepare multifunctional yolk–shell structures with diverse compositions and morphologies simply by replacing silica spheres with silica‐coated nanocomposites.     

Antimicrobial,mechanical, optical and thermal properties of PVC/ZnO‐EDTA nanocomposite films

Covalent surface functionalization of synthesized ZnO nanoparticles (NP)s with ethylenediaminetetraacetic acid (EDTA) was successfully carried out. Modified ZnO‐EDTA NPs as a viable and inexpensive filler were incorporated into poly(vinyl chloride) PVC matrix after their chemical modification to investigate the agglomeration behavior. All prepared materials including modified NPs and PVC/ZnO‐EDTA nanocomposites (NC)s were analyzed by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, thermogravimetric analysis, X‐ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. Fabricated PVC/ZnO‐EDTA NCs were reported to have high transparency and improved mechanical properties compared with PVC. Modified ZnO and the fabricated NCs were shown to exhibit excellent antibacterial activity against two bacteria species: Escherichia coli and Staphylococcus aureus. The obtained NCs could be considered as self‐extinguishing materials on the basis of the LOI values. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanocomposites based on polyamidoimide and octahedral silsesquioxanes

New polymeric nanocomposites were prepared by covalent bonding of nanosized octahedral silsesquioxane particles containing reactive glycidyl group to polyamidoimides containing a carboxy group in the pendant chain. The influence of temperature, molecular weight of the polymer, and reaction time on the covalent bonding of polyhedral oligomeric silsesquioxane (POSS) nanoparticles was revealed. The effect of the POSS nanoparticle incorporation on the structure, dielectric and deformation-strength properties, and heat resistance of the new polymeric nanocomposites was examined.     

Molecularly imprinted polymer functionalized magnetic Fe3O4 for the highly selective extraction of triclosan

We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe₃O₄ nanoparticles with core‐shell structure via sol–gel condensation for recognition and enrichment of triclosan. The Fe₃O₄ nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self‐assembled with the functional monomer 3‐aminopropyltriethoxysilane on the silica‐coated Fe₃O₄ nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica‐coated Fe₃O₄ nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffractometry, vibrating sample magnetometry, and re‐binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 μg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p‐chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.