Crystallization,mechanical, and fracture behaviors of spherical alumina‐filled polypropylene nanocomposites

The objectives of this paper are to study the crystallization behavior and fracture characteristics of spherical alumina (Al₂O₃) nanoparticle‐filled polypropylene (PP) composites. Nanocomposites containing 1.5–5.0 wt % of the Al₂O₃ nanoparticles (pretreated with silane coupling agent) were prepared for this investigation. Wide angle X‐ray diffraction (WAXD) results show that a small amount of β‐crystal of PP forms after adding the Al₂O₃ nanoparticles. According to differential scanning calorimetric (DSC) and optical microscopy (OM) measurements, the Al₂O₃ nanoparticles make PP spherulite size reduced and crystallization temperature of PP enhanced, by acting as effective nucleating agents. However, there are no obvious differences in the crystallinity for the virgin PP and the Al₂O₃/PP nanocomposites. Tensile test shows that both the Young's modulus and the yield strength of the Al₂O₃/PP nanocomposites increase with the particle content increasing, suggesting that the interfacial interaction between the nanoparticles and PP matrix is relatively strong. Under quasi‐static loading rate, the fracture toughness (K_IC) of the Al₂O₃/PP nanocomposites was found to be insensitive to nanoparticle content. Under impact loading rate, the Izod impact strength and the impact fracture toughness (G_c) indicate that the impact fracture toughness increases initially with the addition of 1.5 wt % of the Al₂O₃ nanofillers into the PP matrix. However, with the further addition of up to 3.0 and 5.0 wt % nanoparticles, both the Izod impact strength and impact G_c change very little. By observing the single‐edge‐double‐notch (SEDN) specimens with optical microscopy after four point bending (4PB) tests, it was found that numerous crazes and microcracks form around the subcritical crack tip, indicating that crazing and microcracking are the dominant fracture mechanisms. Scanning electron microscopy (SEM) observation confirms this result. In addition, when the strain rate of 4PB tests was increased, some wave‐like branches were formed along the fractured edge for the Al₂O₃/PP nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3652–3664, 2005     

Effect of MMT,SiO2, CaCO3, and PTFE nanoparticles on the morphology and crystallization of poly(vinylidene fluoride)

The crystallization and melting behaviors of poly (vinylidene fluoride) (PVDF) with small amount of nanoparticles (1 wt %), such as montmorillonite (MMT), SiO₂, CaCO₃, or polytetrafluoroethylene (PTFE), directly prepared by melt‐mixing method were investigated by scanning electron microscopy (SEM), polarizing optical microscopy, Fourier transform infrared spectroscopy, wide angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC). The nanoparticle structure and the interactions between PVDF molecule and nanoparticle surface predominated the crystallization behavior and morphology of the PVDF. Small amount addition of these four types of nanoparticles would not affect the original crystalline phase obtained in the neat PVDF sample (α phase), but accelerated the crystallization rate because of the nucleation effect. In these four blend systems, MMT or PTFE nanoparticles could be well applied for PVDF nanocomposite preparation because of stronger interactions between particle surface and PVDF molecules. The nucleation enhancement and the growth rate of the spherulites were decreased in the order SiO₂ > CaCO₃ > PTFE > MMT. The melting and recrystallization of PVDF was found in MMT addition sample, because of the special ways of ordering of the PVDF chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Core‐shell structured poly(glycidyl methacrylate)/BaTiO3 nanocomposites prepared by surface‐initiated atom transfer radical polymerization: A novel material for high energy density dielectric storage

Core‐shell structured barium titanate‐poly(glycidyl methacrylate) (BaTiO₃‐PGMA) nanocomposites were prepared by surface‐initiated atom transfer radical polymerization of GMA from the surface of BaTiO₃ nanoparticles. Fourier transform infrared spectroscopy confirmed the grafting of the PGMA shell on the surface of the BaTiO₃ nanoparticles cores. Transmission Electron Microscopy results revealed that BaTiO₃ nanoparticles are covered by thin brushes (～20 nm) of PGMA forming a core‐shell structure and thermogravimetric analysis results showed that the grafted BaTiO₃‐PGMA nanoparticles consist of ～13.7% PGMA by weight. Upon incorporating these grafted nanoparticles into 20 μm‐thick films, the resultant BaTiO₃‐PGMA nanocomposites have shown an improved dielectric constant (ε = 54), a high breakdown field strength (～3 MV/cm) and high‐energy storage density ～21.51 J/cm³. AC conductivity measurements were in good agreement with Jonscher's universal power law and low leakage current behavior was observed before the electrical breakdown field of the films. Improved dielectric and electrical properties of core‐shell structured BaTiO₃‐PGMA nanocomposite were attributed to good nanoparticle dispersion and enhanced interfacial polarization. Furthermore, only the surface grafted BaTiO₃ yielded homogenous films that were mechanically stable. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 719–728     

Isothermal crystallization kinetics and melting behavior of poly(ethylene terephthalate)/barite nanocomposites

Poly(ethylene terephthalate) (PET)/Barite nanocomposites were prepared by direct melt compounding. The effects of PET‐Barite interfacial interaction on the dynamic mechanical properties and crystallization were investigated by DMA and DSC. The results showed that Barite can act as a nucleating agent and the nucleation activity can be increased when the Barite was surface‐modified (SABarite). SABarite nanoparticles induced preferential lamellae orientation because of the strong interfacial interaction between PET chains and SABarite nanoparticles, which was not the case in Barite filled PET as determined by WAXD. For PET/Barite nanocomposites, the Avrami exponent n increased with increasing crystallization temperature. Although at the same crystallization temperature, the n value will decrease with increasing SABarite content, indicating of the enhancement of the nucleation activity. Avrami analyses suggest that the nucleation mechanism is different. The activation energy determined from Arrhenius equation reduced dramatically for PET/SABarite nanocomposite, confirming the strong interfacial interaction between PET chains and SABarite nanoparticles can reduce the crystallization free energy barrier for nucleus formation. In the DSC scan after isothermal crystallization process, double melting behavior was found. And the double endotherms could be attributed to the melting of recrystallized less perfect crystallites or the secondary lamellae produced during different crystallization processes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 655–668, 2009     

Enhanced dielectric performance and energy storage of PVDF‐HFP‐based composites induced by surface charged Al2O3

In order to enhance dielectric properties and energy storage density of poly(vinylidene fluoride‐hexafluoro propylene) (PVDF‐HFP), surface charged gas‐phase Al₂O₃ nanoparticles (GP‐Al₂O₃, with positive surface charges, ε’ ≈ 10) are selected as fillers to fabricate PVDF‐HFP‐based composites via simple physical blending and hot‐molding techniques. The results show that GP‐Al₂O₃ are dispersed homogeneously in the PVDF‐HFP matrix and the existence of nanoscale interface layer (matrix‐filler) is investigated by SAXS. The dielectric constant of the composites filled with 10 wt % GP‐Al₂O₃ is 100.5 at 1 Hz, which is 5.6 times higher than that of pure PVDF‐HFP. The maximum energy storage density of the composite is 4.06 J cm^?3 at an electrical field of 900 kV mm^?1 with GP‐Al₂O₃ content of 1 wt %. Experimental results show that GP‐Al₂O₃ could induce uniform fillers’ distribution and increase the concentration of electroactive β‐phase as well as enhance interfacial polarization in the matrix, which resulted in enhancements of dielectric constant and energy storage density of the PVDF‐HFP composites. This work demonstrates that surface charged inorganic‐oxide nanoparticles exhibit promising potential in fabricating ferroelectric polymer composites with relatively high dielectric constant and energy storage. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 574–583     

Glass‐transition temperature behavior of alumina/PMMA nanocomposites

Alumina/poly(methyl methacrylate) (PMMA) nanocomposites were synthesized by an in situ free‐radical polymerization process with 38 and 17 nm diameter γ‐alumina nanoparticles. At extremely low filler weight fractions (<1.0 wt % of 38 nm fillers or < 0.5 wt % of 17 nm fillers) the glass‐transition temperature (T_g) of the nanocomposites drops by 25 °C when compared to the neat polymer. Further additions of filler (up to 10 wt %) do not lead to additional T_g reductions. The thermal behavior is shown to vary with particle size, but this dependence can be normalized with respect to a specific surface area. The nanocomposite T_g phenomenon is hypothesized to be because of nonadhering nanoparticles that serve as templates for a porous system with many internal interfaces that break up the percolating structure of dynamically heterogeneous domains recently suggested by Long, D.; and Lequeux, F. Eur Phys J E 2001, 4, 371 to be responsible for the T_g reductions in polymer ultrathin films. The results also point to a far field effect of the nanoparticle surface on the bulk matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4371–4383, 2004     

Preparation and characterization of poly(l-lactic acid)/TiO2 nanoparticle nanocomposite films with high transparency and efficient photodegradability

Poly(l-lactic acid)-TiO₂ nanoparticle nanocomposite films were prepared by incorporating surface modified TiO₂ nanoparticles into polymer matrices. In the process of preparing the nanocomposite films, severe aggregation of TiO₂ nanoparticles could be reduced by surface modification by using carboxylic acid and long-chain alkyl amine. As a result, the nanocomposite films with high transparency, similar to pure PLA films, were obtained without depending on the amount of added TiO₂ nanoparticles. A TEM micrograph of the nanocomposite films suggests that the TiO₂ nanoparticles of 3-6 nm in diameter were uniformly dispersed in polymer matrices. Photodegradation of PLA-TiO₂ nanoparticle nanocomposite films was also investigated. The results showed that nanocomposite films could be efficiently photodegraded by UV irradiation in comparison with pure PLA.     

Synthesis,characterization and properties of multifunctional poly(arylene ether nitriles) (PEN)/CNTs/Fe3O4 nanocomposites

In this study, a novel multifunctional poly(arylene ether nitriles)(PEN)/carbon nanotubes/Fe₃O₄ nanocomposite with high tensile strength, magnetic, and electrical properties was investigated. First, we synthesized the monodisperse Fe₃O₄ nanoparticles on the surface of the multiwalled carbon nanotubes and then the hybrid material was compounded with PEN through the solution‐casting method. The SEM and TEM images indicated that the monodisperse Fe₃O₄ nanoparticles, with the diameters of 70∼80 nm, were self‐assembled along CNTs via the covalent bond method, which was confirmed by FTIR and XRD. The results of tensile properties showed that the tensile strength and modulus reached their highest values at the CNTs/Fe₃O₄ loading content of 1 wt % and both were greatly enhanced after heat treatment. Electrical conductivity of the polymer was dramatically enhanced at the low loading level of CNTs/Fe₃O₄; the electrical percolation of was in the range of 5∼8 wt % of CNTs/Fe₃O₄. The magnetic study showed that the saturation magnetization (M_s) of PEN/CNTs/Fe₃O₄ nanocomposites increased with the increase of CNTs/Fe₃O₄ loading content, and the coercive force (H_c) of the nanocomposite was independent of the CNTs/Fe₃O₄ content. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Thermally conductive and electrically insulative nanocomposites based on hyperbranched epoxy and nano‐Al2O3 particles modified epoxy resin

Novel epoxy nanocomposites based on a diglycidyl ether of bisphenol A (DGEBA) epoxy, an epoxy functionalized hyperbranched polymer (HTTE) and nano‐Al₂O₃ were synthesized with the aim of determining the effect of the nano‐Al₂O₃ particles and HTTE on the structure and properties of epoxy nanocomposites. The mechanical properties, thermal conductivity, bulk resistivity, and thermal stability of the nano‐Al₂O₃/HTTE/DGEBA ternary composites were evaluated and compared with the corresponding matrix. The improvement in impact properties of these nanocomposites was explained in terms of fracture surface analysis by SEM. The results indicate that the incorporation of nanoparticles and hyperbranched epoxy effectively improved the toughness of epoxy composites without sacrificing thermal conductivity and bulk resistivity compared to the neat epoxy and Al₂O₃/DGEBA, obtaining a well dispersion of nanoparticles in epoxy matrix and solving the drawbacks for single fillers filled epoxy nanocomposite. Copyright © 2010 John Wiley & Sons, Ltd.     

Impact of Al nanoparticles upon the microstructure and wear properties of Ni-Cr-Al nanocomposite coatings

Ni–7Cr and Ni–7Cr–2Al (wt.%) nanocomposite coatings were fabricated by co-electrodeposition of Ni with Cr (40 nm) or and Al (75 nm) nanoparticles from a nickel sulfate bath, their microstructure, friction and wear performance were comparably evaluated in order to elucidate the effect of Al nanoparticles on the properties of nanocomposite coatings. The results indicated that the co-deposition of minor Al nanoparticles significantly increases the microhardness and wear resistance because Al nanoparticles with surface amorphous oxides layers exert the dispersion-strengthening effect like Al₂O₃ nanoparticles.     

Magnetic polyvinylamine nanoparticles by in situ precipitation reaction

Magnetic nanoparticles represent emerging tools in biomedical and pharmaceutical research. Because in most cases, the surfaces of these nanoparticles are hydrophobic, surface modifiers are usually applied to stabilize the colloidal suspension in an aqueous media. This investigation reports a simple technique for the preparation of MnFe₂O₄ synthesized within polyvinylamine (PVAm) nanoparticle reactors. Magnetite nanoparticles were previously synthesized using a similar scheme; however, substituting MnFe₂O₄ for Fe₃O₄ improved nanoparticle magnetization properties and further established the synthetic approach. PVAm nanoparticles exhibited more than 18% manganese ferrite loading by weight, a saturation magnetization of ～ 40 emu/g of MnFe₂O₄, excellent colloidal stability, and reactive primary amines for possible drug conjugation or surface modification. Transmission electron micrographs revealed that the dispersions contained ～ 50 nm PVAm nanoparticles incorporating manganese ferrite particles with a size less than ～ 7 nm. This reaction scheme further justifies a unique synthetic methodology for magnetic nanoparticles offering potential use in contrast‐enhanced magnetic resonance imaging or drug delivery. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 991–996, 2010     

Methods for the surface functionalization of γ‐Fe2O3 nanoparticles with initiators for atom transfer radical polymerization and the formation of core–shell inorganic–polymer structures

Carboxylic acid capped γ‐Fe₂O₃ nanoparticles were prepared by the standard decomposition of Fe(CO)₅ in di‐n‐octyl ether and oleic acid. Two methods were employed to introduce surface functionality to the nanoparticles. First, a thermally stable, tert‐butyldiphenylsilyl‐protected hydroxyl group was incorporated into the carboxylic acid surfactant used during the synthesis. Subsequent deprotection and transformation installed a 2‐bromopropionyl ester group on the particle surface (the functional‐group‐interchange method). The resulting nanoparticles were 4.53 nm in average diameter and were characterized with IR spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction, and elemental analysis. Second, a 2‐bromopropionyl ester group was installed on the particle surface after synthesis via the exchange of the surface oleic acid with a carboxylic acid containing the desired 2‐bromopropionyl ester unit (the ligand‐exchange method). The resulting nanoparticles were 4.30 nm in average diameter and were characterized with IR spectroscopy, TEM, and elemental analysis. Monitoring the percentage of bromine incorporated into the nanoparticle sample versus the ligand‐exchange reaction time indicated that the number of initiator‐containing carboxylic acids that could be exchanged onto the surface was limited, presumably by the steric size of the 2‐bromopropionyl ester group. Styrene was then polymerized directly off γ‐Fe₂O₃ nanoparticles, and this yielded hybrid core–shell structures. The measurements of the magnetic properties of the samples demonstrated that the magnetism of the core γ‐Fe₂O₃ nanoparticle did not change during the performance of the chemical transformations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3675–3688, 2005     

Self-organized polymer nanocomposite inverse opal films with combined optical properties

Inverse opal films with unique optical properties have potential as photonic crystal materials and have stimulated wide interest in recent years. Herein, iridescent hybrid polystyrene/nanoparticle macroporous films have been prepared by using the breath‐figure method. The honeycomb‐patterned thin films were prepared by casting gold nanoparticle‐doped polystyrene solutions in chloroform at high relative humidity. Highly ordered hexagonal arrays of monodisperse pores with an average diameter of 880 nm are obtained. To account for the observed features, a microscopic phase separation of gold nanoparticles is proposed to occur in the breath‐figure formation. That is, individual gold nanoparticles adsorb at the solution/water interface and effectively stabilize condensed water droplets on the solution surface in a hexagonal array. Alternatively, at high nanoparticle concentrations the combination of breath‐figure formation and nanoparticle phase separation leads to hierarchical structures with spherical aggregates under a honeycomb monolayer. The films show large features in both the visible and NIR regions that are attributed to a combination of nanoparticle and ordered‐array absorptions. Organic ligand‐stabilized CdSe/CdS quantum dots or Fe₃O₄ nanoparticles may be loaded into the honeycomb structure to further modify the films. These results demonstrate new methods for the fabrication and functionalization of inverse opal films with potential applications in photonic and microelectronic materials.     

Self‐emulsion polymerization of amphiphilic monomers—a green route to synthesis of polymeric nanoscaffolds

Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe₃O₄ magnetic nanoparticle (Fe₃O₄ MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe₃O₄ MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM^?1 s^?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

The synthesis and characterization of polyorganosiloxane nanoparticles from 3-mercaptopropyltrimethoxysilane for preparation of nanocomposite films via photoinitiated thiol-ene polymerization

This article describes the synthesis of modified silica nanoparticles (SiO₂-MPTMS) via the condensation reaction carried out between silanol moieties of silica nanoparticles and the trialkoxy silyl groups of (3-mercaptopropyl) trimethoxysilane (MPTMS). Then, SiO₂-MPTMS nanoparticles in certain amounts (0.5 wt %, 1 wt %, 2.5 wt % and 5 wt %) were incorporated into thiol-ene resins consisting of bisphenol A glycerolate dimethacrylate and trimethylolpropane tris(3-mercaptopropionate) to prepare nanocomposite films via the photoinitiated thiol-ene polymerization in presence of 2,2-Dimethoxy-2-phenylacetophenone 99% as a photoinitiator. Fourier transform infrared spectroscopy, dynamic light scattering, scanning transmission electron microscopy, thermal gravimetric analyzer, and X-ray photoelectron spectrometer were employed to characterize SiO₂-MPTMS nanoparticles. It was revealed that the nanosilica surface was successfully grafted by MPTMS with the grafting ratio of 22.9%. Properties of the nanocomposite films such as decomposition temperature, thermal glass transition temperature, tensile strength, hardness, and particle distribution were investigated and the results were compared with each other and neat film. The addition of MPTMS-modified silica particles did not improve the thermal stability of the films. In scanning electron microscopy study, it was seen that 2.5 wt % of these nanoparticles used as additives were about 200 nm in size and dispersed homogeneously in the polymer matrix. The increase in tensile strength of nanocomposite films compared to the neat film was measured as 77.3% maximum.     

TiO2 nanoparticles/poly(butylene adipate‐co‐terephthalate) bionanocomposite films for packaging applications

In this present study, biodegradable PBAT nanocomposites containing different weight percentages (1, 3, 5, 7, and 10% w/w) of TiO₂ nanoparticles were prepared by using solvent casting technique, chloroform as a solvent. The microstructure and morphology of the as‐synthesized poly(butylene adipate‐co‐terephthalate) (PBAT)/TiO₂ nanocomposite films were characterized by Fourier‐transform infrared, X‐ray diffraction, scanning electron microscopy, and transmission electron microscope. The thermal degradation of PBAT composites was studied by using thermogravimetric analysis. The mechanical strength of the films was improved by increasing TiO₂ concentration. Tensile strength increased from 32.60 to 63.26 MPa, respectively. Barrier properties of the PBAT/TiO₂ nanocomposites were investigated by using an oxygen permeability tester. The oxygen permeability (oxygen transmission rate) decreased with increasing the TiO₂ nanoparticle concentrations. The PBAT/TiO₂ nanocomposite films showed profound antimicrobial activity against both Gram‐positive and Gram‐negative foodborne pathogenic bacteria, namely, Escherichia coli and Staphylococcus aureus, to understand to the zone of inhibition. These results indicated that filler–polymer interaction is important and the role of the TiO₂ as a reinforcement in the nanocomposites was evident. Copyright © 2017 John Wiley & Sons, Ltd.     

Crystallization of poly(ethylene terephthalate–co–isophthalate)

Melt crystallization behaviors of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐isophthalate) (PETI) containing 2 and 12 mol % of noncrystallizable isophthalate components were investigated. Differential scanning calorimetry (DSC) isothermal results revealed that the introduction of 2 mol % isophthalate into PET caused a change of the crystal growth process from a two‐dimensional to a three‐dimensional spherulitic growth. The addition of more isophthalate up to 12 mol % into the PET structure induced a change in the crystal growth from a three‐dimensional to a two‐dimensional crystal growth. DSC heating scans after completion of isothermal crystallization at various T_c's showed three melting endotherms for PET and four melting endotherms for PETI‐2 and PETI‐12. The presence of an additional melting endotherm is attributed to the melting of copolyester crystallite composed of ethylene glycol, tere‐phthalate, and isophthalate (IPA) or the melting of molecular chains near IPA formed by melting the secondary crystallite T_m (I) and then recrystallizing during heating. Analyses of both Avrami and Lauritzen‐Hoffman equations revealed that PETI containing 2 mol % of isophthalate had the highest Avrami exponent n, growth rate constant G_o, and product of lateral and end surface free energies σσ_e. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2515–2524, 2000     

Influence of Al2O3 Nanoparticles on the Thermal Stability of Ultra-Fine Grained Copper Prepared by High Pressure Torsion

Summary.  Ultra-fine grained (UFG) Cu (grain size 80 nm) containing 0.5 wt.% Al₂O₃ nanoparticles (size 20 nm) was prepared by high pressure torsion (HPT). Positron lifetime spectroscopy was employed to characterize the microstructure of this material, especially with respect to types and concentration of lattice defects. The evolution of microstructure with increasing temperature was studied by positron lifetime spectroscopy and X-ray diffraction measurements. The thermal stability of the Cu + 0.5 wt.% Al₂O₃ nanocomposite was compared with that of pure UFG Cu prepared by the same technique. The processes taking place during thermal recovery of the initial nanoscale structure in both studied materials are described. Received October 5, 2001. Accepted (revised) December 20, 2001     

Synthesis of magnetic,reactive, and thermoresponsive Fe3O4 nanoparticles via surface‐initiated RAFT copolymerization of N‐isopropylacrylamide and acrolein

A reversible addition‐fragmentation chain transfer (RAFT) agent was directly anchored onto Fe₃O₄ nanoparticles in a simple procedure using a ligand exchange reaction of S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate with oleic acid initially present on the surface of pristine Fe₃O₄ nanoparticles. The RAFT agent‐functionalized Fe₃O₄ nanoparticles were then used for the surface‐initiated RAFT copolymerization of N‐isopropylacrylamide and acrolein to fabricate structurally well‐defined hybrid nanoparticles with reactive and thermoresponsive poly(N‐isopropylacrylamide‐co‐acrolein) shell and magnetic Fe₃O₄ core. Evidence of a well‐controlled surface‐initiated RAFT copolymerization was gained from a linear increase of number‐average molecular weight with overall monomer conversions and relatively narrow molecular weight distributions of the copolymers grown from the nanoparticles. The resulting novel magnetic, reactive, and thermoresponsive core‐shell nanoparticles exhibited temperature‐trigged magnetic separation behavior and high ability to immobilize model protein BSA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 542–550, 2010     

Novel antimicrobial polyethylene composites prepared by metallocenic in situ polymerization with TiO2‐based nanoparticles

Polyethylene (PE) composites with titanium oxide (TiO₂) nanoparticles were produced via in situ polymerization representing a novel route to obtain antimicrobial polymeric materials. The TiO₂ nanoparticles synthesized by the sol–gel method were used either as‐synthesized or modified organically with hexadecyltrimethoxysilane (Mod‐TiO₂). These particles were added, together with the catalytic system (formed by a metallocenic catalyst and methylaluminoxane as cocatalyst), directly to the reactor, yielding in situ PE composites with 2 and 8 wt % content of nanofiller. The catalytic polymerization activity presented a slight decrease with the incorporation of the TiO₂ and Mod‐TiO₂ nanoparticles compared to polymerization without filler. Regarding the properties of the composites, crystallinity increased slightly when the different nanofillers were added, and the elastic modulus increased around 15% compared to neat PE. PE/TiO₂ nanocomposites containing 8 wt % of TiO₂ exposed to UVA irradiations presented antimicrobial activity against Escherichia coli. The PE/Mod‐TiO₂ nanocomposite with 8 wt % filler killed 99.99% of E. coli, regardless of light and time irradiation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012