Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites

Owing to the improvement of properties including conductivity, toughness and permeability, polymer nanocomposites are slated for applications ranging from membranes to fuel cells. The enhancement of polymer properties by the addition of inorganic nanoparticles is a complex function of interfacial interactions, interfacial area and the distribution of inter-nanofiller distances. The latter two factors depend on nanofiller dispersion, making it difficult to develop a fundamental understanding of their effects on nanocomposite properties. Here, we design model poly(methyl methacrylate)-silica and poly(2-vinyl pyridine)-silica nanocomposites consisting of polymer films confined between silica slides. We compare the dependence of the glass-transition temperature (Tg) and physical ageing on the interlayer distance in model nanocomposites with the dependence of silica nanoparticle content in real nanocomposites. We show that model nanocomposites provide a simple way to gain insight into the effect of interparticle spacing on Tg and to predict the approximate ageing response of real nanocomposites.     

Structural and photoluminescence investigation of ZnSe nanocrystals dispersed in organic and inorganic matrices

In this work, we report on the investigation of the effect of dispersion of zinc selenide (ZnSe) nanocrystallites into polystyrene (PS) and silica (SiO₂) thin films on their structural, morphological and photoluminescence properties. The ZnSe/PS nanocomposites thin films were synthesized by a direct dispersion of ZnSe crystallites into polymers solution, whereas the ZnSe–SiO₂ films were prepared on glass substrates by the sol–gel dip-coating technique. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-rays (EDX), UV–visible spectrophotometry and photoluminescence spectroscopy (PL) techniques have been used to study the structural, morphological and optical properties of the prepared nanocomposite thin films. XRD patterns have demonstrated the incorporation of cubic ZnSe in both organic and inorganic matrices. SEM micrographs have indicated that ZnSe dispersion in the films is homogeneous. UV–visible absorption spectra of the nanocomposite thin films have put into evidence that the dispersion of ZnSe nanocrystals in the thin film matrices improved their optical absorption. Room temperature PL spectra have shown that the addition of ZnSe enhanced the UV emission of PS and all the emission of SiO₂ thin films.     

Investigation of the optical properties of polyfluorene/ZnO nanocomposites

Polyfluorene (PF) and its derivatives are very promising candidates for organic light emitting diodes (OLEDs) in lighting applications because of their high photoluminescence and electroluminescence efficiencies. Recent investigations of potential materials for OLEDs have shown that introducing n-type inorganic nanoparticles into conjugated polymers is efficient to produce stable and high performance devices. In this study, composite thin films made by incorporation of zinc oxide (ZnO) nanoparticles into a PF derivative have been prepared and their optical properties have been investigated.The prepared thin films were stored in different media (in air, in vacuum, in the dark or exposed to light) in order to study environmental influences on the material stability. Analysis of spectral data obtained from infrared (IR), Raman, UV-vis, and photoluminescence (PL) measurements shows a large enhancement in luminescence for polymer nanocomposites while using high nanoparticle concentrations (within a limit of 10% ZnO). Time-resolved PL performed on those nanocomposite films corroborated the above result: it indicated that the light-emission enhancement can be explained by efficient energy transfer from nanoparticles to the polymer chains and increase of the chain separation distance. In addition, the nanocomposites were found to be more stable than pristine polymer films whatever the storage conditions were used. It was confirmed by IR analysis that incorporation of nanoparticles into polymers prohibited the formation of fluorenonyl groups in PF chains, which was identified as the main cause of the degradation of the polymer under photo-oxidation.     

CdTe quantum dots and polymer nanocomposites for x-ray scintillation and imaging

Investigations are reported on the x-ray scintillation and imaging application of CdTe quantum dots (QDs) and their polymer nanocomposites. Aqueous CdTe QDs with emissions ranging between 510 and 680 nm were prepared and incorporated into polyvinyl alcohol or polymethyl methacrylate polymer matrices. The x-ray luminescent properties were evaluated and a resolution of 5 lines∕mm was obtained from the nanocomposite films. Additionally, the fast decay time, nonafterglow, and superior spectral match to conventional charge coupled devices, show that CdTe QD nanocomposites have high promise for x-ray imaging applications.     

Polymer/organosilica nanocomposites based on polyimide with benzimidazole linkages and reactive organoclay containing isoleucine amino acid: Synthesis,characterization and morphology properties

Polyimide–silica nanocomposites are attractive hybrid architectures that possess excellent mechanical, thermal and chemical properties. But, the dispersion of inorganic domains in the polymer matrix and the compatibility between the organic and inorganic phases are critical factors in these hybrid systems. In this investigation, a reactive organoclay was prepared via ion exchange reaction between protonated form of difunctional l-isoleucine amino acid as a swelling agent and Cloisite Na⁺ montmorillonite. Amine functional groups of this swelling agent formed an ionic bond with the negatively charged silicates, whereas the remaining acid functional groups were available for further interaction with polymer chains. Then organo-soluble polyimide (PI) have been successfully synthesized from the reaction of 2-(3,5-diaminophenyl)-benzimidazole and pyromellitic dianhydride in N,N-dimethylacetamide. Finally, PI/organoclay nanocomposite films enclosing 1%, 3%, 5%, 7% and 10% of synthesized organoclay were successfully prepared by an in situ polymerization reaction through thermal imidization. The synthesized hybrid materials were subsequently characterized by Fourier transform infrared spectroscopy, X-ray diffraction, electron microscopy, and thermogravimetric analysis techniques. The PI/organoclay nanocomposite films have good optical transparencies and the mechanical properties were substantially improved by the incorporation of the reactive organoclay.     

Preparation of hydrophobic organic-silicanano composites

In this paper, we use silica nanoparticles modified by methacryloxy propyl trimethoxylsilane (KH570) as the core material, and employ polymers including hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and acrylic ester as the shell materials to prepare the hydrophobic inorganic–organic hybrid nanocomposites with a seed emulsion polymerization strategy. The size, morphologyandproperties of the core-shell structured nanoparticles are investigated by TEM and SEM. The results showthat the polymer nanocomposite has three concentric layers with silica nanoparticles in the center, acrylic polymer as the internal shell and fluorosilicone polymer as the outmost shell. By controlling the ratio of the silica nanoparticles and monomers, we can achieve each composite particle has the core-shell structure with silica nanoparticles as the core and the thin layer of fluorosilicone polymer as the shell. Compared with the traditional polymer film, the nanocomposite film shows a hydrophobic property with a contact angle of up to 100 degree. Therefore, it is feasible to prepare hydrophobic organic–inorganic nanocomposites using the method proposed here.     

Evaporation-induced self-assembly of organic–inorganic ordered nanocomposite thin films that mimic nacre

The present study attempts to incorporate acrylate-based polymers into ordered lamellar organic–inorganic nanocomposite thin films composed of alternating Poly(TPGDA)/ITO layers. The films were prepared by dip-coating from a homogeneous solution containing the soluble inorganic metal salts (InCl₃·4H2O and SnCl₂·2H₂O), surfactant, cross-linkers, organic monomers, and initiators, thus leading to composite lamellar nanocomposite materials through evaporation-induced self-assembly method. The final polymer/ITO nanocomposite thin film was obtained by a separate free-radical polymerization step, initiated by UV exposure. Structures and composition of the films were characterized using FTIR, XRD, UV–Vis spectrophotometer and TEM. The results indicated that the films were composed of organic and inorganic layers with orderly interlaced arrangement.     

Design of iron oxide/silica/alginate hybrid magnetic carriers (HYMAC)

A large number of natural and synthetic polymers have already been evaluated for the design of nanomaterials incorporating magnetic nanoparticles for biomedical applications. The possibility to use hybrid (bio)-organic/inorganic nano-carriers have been much less studied. Here we describe the design of Hybrid MAgnetic Carriers (HYMAC) consisting of alginate/silica nanocomposites incorporating magnetite nanoparticles, based on a spray-drying approach. Transmission electron microscopy and X-ray energy dispersive spectrometry confirm the successful incorporation of magnetic colloids within homogeneous hybrid capsules. X-ray diffraction data suggest that surface iron ions are partially desorbed by the spray-drying process, leading to the formation of lepidocrocite and of an iron silicate phase. Magnetic measurements show that the resulting nanocomposites exhibit a superparamagnetic behaviour with a blocking temperature close to 225 K. Comparison with un-silicified capsules indicate that the mineral phase enhances the thermal stability of the polymer network and do not modify of the amount of incorporated iron oxide nanoparticles. Moreover, evaluation of nanocomposite up-take by fibroblasts indicates their possible internalization. A selective intracellular alginate degradation is observed, suggesting that these HYMAC nanomaterials may exhibit interesting properties for the design of drug delivery devices.     

Multicomponent semiconducting polymer systems with low crystallization-induced percolation threshold

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline-crystalline/semiconducting-insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself.     

Integrated Circuits Based on Bilayer MoS(2) Transistors

Two-dimensional (2D) materials, such as molybdenum disulfide (MoS(2)), have been shown to exhibit excellent electrical and optical properties. The semiconducting nature of MoS(2) allows it to overcome the shortcomings of zero-bandgap graphene, while still sharing many of graphene's advantages for electronic and optoelectronic applications. Discrete electronic and optoelectronic components, such as field-effect transistors, sensors, and photodetectors made from few-layer MoS(2) show promising performance as potential substitute of Si in conventional electronics and of organic and amorphous Si semiconductors in ubiquitous systems and display applications. An important next step is the fabrication of fully integrated multistage circuits and logic building blocks on MoS(2) to demonstrate its capability for complex digital logic and high-frequency ac applications. This paper demonstrates an inverter, a NAND gate, a static random access memory, and a five-stage ring oscillator based on a direct-coupled transistor logic technology. The circuits comprise between 2 to 12 transistors seamlessly integrated side-by-side on a single sheet of bilayer MoS(2). Both enhancement-mode and depletion-mode transistors were fabricated thanks to the use of gate metals with different work functions.     

LLDPE/EVA/ZnO纳米复合材料的制备与BP-Markov性能预测研究

制备了LLDPE/EVA/ZnO纳米复合材料,并测试了其力学性能.结合BP 神经网络和Markov链建立了BP-Markov模型,并利用此模型对LLDPE/EVA/ZnO纳米复合材料的多指标性能进行了预测.结果表明BP-Markov模型应用于聚合物/无机物纳米复合材料的多指标性能预测具有较高的精度和可靠性,Markov链解决了神经网络在做多指标性能预测时误差的随机性和波动性问题,充分的发挥了神经网络与Markov链预测模型的优点,为在数据有限且具有随机因素的情况下实验数据的分析提供了一种新的思路.     

Synthesis and characterization of FeNi/polymer nanocomposites

Alloyed spherical FeNi-polymer nanocomposites were prepared via wet chemical method using hydrazine as a reducing agent and polymers (PVP and PEG) as reducing and stabilizing agent. Structural studies performed using XRD and TEM shows uniform dispersion of fine FeNi nanocrystallites in nanocomposite particles. The size and thermal stability of FeNi-polymer nanocomposite particles prepared under same reaction condition was found to be dependent on the type and the molecular weight of the polymer used. However, the magnetic properties of nanocomposite particles were not influenced by the polymers. The study highlights subtle differences in using polymers during the synthesis of alloyed nanocomposite particles.     

Poly(3-hexylthiophene)/hexamine modified ZnO hybrid nanocomposite: structural,optical, thermal and electrical transport studies

This paper reports the synthesis of poly(3-hexylthiophene) (P3HT)/HA@ZnO nanocomposite by in situ polymerization and demonstrates their thermal, morphological and optoelectronic properties. Zinc oxide (ZnO) nanoparticles were prepared by the simple approach of co- precipitation method using zinc acetate dihydrate as precursor modified by hexamine (HA) acting as a capping agent. Structural and photo physical studies shows that conjugated polymer chains intimately contact with the inorganic semiconductor. ZnO has wurtzite structure with average crystallite size of 40 nm. The emission spectra indicate that modified ZnO nanoparticles results in more efficient photo induced charge transfer than that of the simple nanocomposite of P3HT/ZnO. The morphological studies revealed that the transformation of granular morphology of P3HT to the clusters in P3HT/HA@ZnO hybrid nanocomposites. Cyclic voltammeter elucidates the electrochemical behavior and the HOMO–LUMO energy levels of the nanocomposites. The results indicate that the P3HT/HA@ZnO nanocomposite has energy gap of 0.72 eV, indicating this composite has potential for the fabricating hybrid organic–inorganic solid state solar cells. A solar to electric energy conversion efficiency of 0.1238 % was attained with the system.     

Dual‐Phase CsPbBr3–CsPb2Br5 Perovskite Thin Films via Vapor Deposition for High‐Performance Rigid and Flexible Photodetectors

Inorganic perovskites with special semiconducting properties and structures have attracted great attention and are regarded as next generation candidates for optoelectronic devices. Herein, using a physical vapor deposition process with a controlled excess of PbBr₂, dual‐phase all‐inorganic perovskite composite CsPbBr₃–CsPb₂Br₅ thin films are prepared as light‐harvesting layers and incorporated in a photodetector (PD). The PD has a high responsivity and detectivity of 0.375 A W^?1 and 10¹¹ Jones, respectively, and a fast response time (from 10% to 90% of the maximum photocurrent) of ≈280 µs/640 µs. The device also shows an excellent stability in air for more than 65 d without encapsulation. Tetragonal CsPb₂Br₅ provides satisfactory passivation to reduce the recombination of the charge carriers, and with its lower free energy, it enhances the stability of the inorganic perovskite devices. Remarkably, the same inorganic perovskite photodetector is also highly flexible and exhibits an exceptional bending performance (>1000 cycles). These results highlight the great potential of dual‐phase inorganic perovskite films in the development of optoelectronic devices, especially for flexible device applications.     

Ultrasound-induced capping of polystyrene on TiO2 nanoparticles by precipitation with compressed CO2 as antisolvent

In this work, a route for the synthesis of inorganic/polymer core/shell composite nanoparticles was proposed, which can be called the antisolvent-ultrasound method. Compressed CO2 was used as antisolvent to precipitate the polymer from its solution dispersed with inorganic nanoparticles, during which ultrasonic irradiation was used to induce the coating of precipitated polymers on the surfaces of the inorganic nanoparticles. TiO2/polystyrene (PS) core/shell nanocomposites have been successfully prepared using this method. The transmission electronic micrographs (TEM) of the obtained nanocomposites show that the TiO2 nanoparticles are coated by the PS shells, of which the thickness can be tuned by the pressure of CO2. The phase structure, absorption properties, and thermal stability of the composite were characterized by X-ray diffraction (XRD), UV-vis spectra, and thermogravimetry, respectively. The results of X-ray photoelectron spectra (XPS) indicate the formation of a strong interaction between PS and TiO2 nanoparticles in the resultant products. This method has some potential advantages for applications and may be easily applied to the preparation of a range of inorganic/polymer core/shell composite nanoparticles.     

Heavy metallic oxide nanoparticles for enhanced sensitivity in semiconducting polymer x-ray detectors

Semiconducting polymers have previously been used as the transduction material in x-ray dosimeters, but these devices have a rather low detection sensitivity because of the low x-ray attenuation efficiency of the organic active layer. Here, we demonstrate a way to overcome this limitation through the introduction of high density nanoparticles having a high atomic number (Z) to increase the x-ray attenuation. Specifically, bismuth oxide (Bi(2)O(3)) nanoparticles (Z?=?83 for Bi) are added to a poly(triarylamine) (PTAA) semiconducting polymer in the active layer of an x-ray detector. Scanning electron microscopy (SEM) reveals that the Bi(2)O(3) nanoparticles are reasonably distributed in the PTAA active layer. The reverse bias dc current-voltage characteristics for PTAA-Bi(2)O(3) diodes (with indium tin oxide (ITO) and Al contacts) have similar leakage currents to ITO/PTAA/Al diodes. Upon irradiation with 17.5?keV x-ray beams, a PTAA device containing 60?wt% Bi(2)O(3) nanoparticles demonstrates a sensitivity increase of approximately 2.5 times compared to the plain PTAA sensor. These results indicate that the addition of high-Z nanoparticles improves the performance of the dosimeters by increasing the x-ray stopping power of the active volume of the diode. Because the Bi(2)O(3) has a high density, it can be used very efficiently, achieving a high weight fraction with a low volume fraction of nanoparticles. The mechanical flexibility of the polymer is not sacrificed when the inorganic nanoparticles are incorporated.     

Characterization of conjugated polymer/anodic aluminum oxide nanocomposites fabricated via template wetting

Solution-based template wetting is demonstrated as an effective means of producing semiconductor–insulator nanocomposites. The properties of such nanocomposites formed by incorporating two commonly investigated semiconducting polymers, poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene (MEH-PPV) and poly(3-hexylthiophene-2,5-diyl) (P3HT), along with their blend, into nanoporous aluminum oxide (AAO) are investigated electronically and spectroscopically. Significant improvement in hole mobility of amorphous MEH-PPV in a nanocomposite with AAO while such improvement is absent when the crystalline P3HT is utilized to fabricate the AAO nanocomposites. Spectral evidence indicates that increased molecular order is responsible for this observation. Carrier mobility intermediate to the homopolymer nanocomposites was observed in composites fabricated from an MEH-PPV:P3HT blend and an AAO membrane. Spectral evidence indicates that these two polymers phase segregate in the composite.     

Hybrid Intercalative Nanocomposites

This review focuses on organic-inorganic hybrid nanocomposites, a research area that has made rapid progress in recent years. Inorganic components (hosts) include both natural materials (clays, silicates, smectites, layered phosphates, and others) and compounds prepared by different synthetic techniques. Into their interlayer spaces, various organic guests—solvents, monomers, and polymers—can be intercalated. Among the hybrid nanocomposites analyzed in detail are those based on polyconjugated electrically conducting polymers, such as poly(aniline) and poly(pyrrole), and various mineral matrices. Particular attention is paid to polymer-metal chalcogenide nanocomposites and their applications as semiconducting materials. One of the most common and practically important intracrystalline processes in the fabrication of hybrid nanocomposites is the incorporation of monomer molecules into pores of the host, followed by controlled internal transformations into polymer, oligomer, or hybrid-sandwich products (in situ postintercalative transformations). This approach is often called “ship-in-the-bottle” polymerization. Another widely used approach is the incorporation of macromolecules into layered host lattices from solutions or melts. This process offers the possibility of producing graphite intercalation compounds and inorganic-organic multilayer composites, including self-assembled nanocomposites in the form of (P/M) _n multilayers, where M and P are oppositely charged inorganic and polymer nanolayers.     

Light-driven novel properties of TiO2-modified polypropylene-based nanocomposite films

Nanocomposite films obtained by TiO2 incorporation into a polypropylene (PP) polymer matrix were prepared via a straightforward melting process. The structural characteristics of the nanocomposite materials were examined by a multitechnique approach showing the outstanding morphological uniformity of the films. TiO2 incorporation into the polymer matrix renders self-sterilized and self-degradable materials which showed an impressive performance against gram-positive, gram-negative, coccus and yeast micro-organisms. Optimization of the novel properties of TiO2-PP nanocomposite films is reached with a 2 wt% of oxide content loading. The physico-chemical bases of this optimum are discussed.     

Morphology/behaviour relationship of nanocomposites based on natural rubber/epoxidized natural rubber blends

In order to analyze the effect of an epoxidized natural rubber (ENR) and filler treatment on the morphology and behavior of natural rubber (NR) nanocomposites, blends of these polymers have been prepared. The nature and extent of the clay dispersions in the filled samples were evaluated by X-ray diffraction. In the presence of ENR, an exfoliated structure was obtained which suggests that enough rubbery polymer was incorporated into the interlayer spacing. The effect of clay in rubber compounds was analyzed through rheological, mechanical and swelling characterization. A sensible improvement in the nanocomposite properties was observed by the addition of organoclay. It has been deduced that the properties of the compounds strongly depend on the extent of the silicate nanolayers dispersion into the rubber matrices as well as on the organoclay type and elastomer compatibility.