In situ synthesis of transparent TiO2 nanoparticle/polymer hybrid

Transparent TiO₂ nanoparticle/polymer hybrids were synthesized from titanium isopropoxy methacrylate via hydrolysis and polymerization in 2-methoxymethanol. Crystalline TiO₂ nanoparticles were uniformly dispersed in the polymer matrix. A highly transparent free-standing TiO₂ nanoparticle/polymer hybrid film was synthesized. The refractive index (RI) of the hybrid films on Si substrates could be controlled by varying the concentration of TiO₂ nanoparticles: the RI increased with increase in Ti content. A further increase in the RI was achieved upon irradiation with ultraviolet light. A TiO₂ nanoparticle/PMMA hybrid without the silica component exhibited an RI of 1.717 and an Abbe number of 21.6.     

Hierarchically structured polymer blends based on silsesquioxane hybrid nanocomposites with quaternary ammonium units for antimicrobial coatings

The paper reports the first study on hierarchical assemblies (nanofibrillar micelles confined within semi-cylindrical shells) with silsesquioxane and quaternary ammonium units obtained through polymer blending intended for antimicrobial/antifungal stone coatings. The formation of hierarchical structures on solid surfaces is due to the multiple intermolecular ionic interactions, intermolecular Van der Waals and hydrophobic interactions acting among the component molecules. Their antimicrobial/antifungal properties toward the Gram-negative bacteria, Escherichia coli, Gram-positive bacteria, Staphylococcus aureus, and Candida albicans fungus were determined in aqueous solution and were found to be strongly dependent of the topographical features of the coating.     

Microchip dialysis of proteins using in situ photopatterned nanoporous polymer membranes

Chip-level integration of microdialysis membranes is described using a novel method for in situ photopatterning of porous polymer features. Rapid and inexpensive fabrication of nanoporous microdialysis membranes in microchips is achieved using a phase separation polymerization technique with a shaped UV laser beam. By controlling the phase separation process, the molecular weight cutoffs of the membranes can be engineered for different applications. Counterflow dialysis is used to demonstrate extraction of low molecular weight analytes from a sample stream, using two different molecular weight cutoff (MWCO) membranes; the first one with MWCO below 5700 for desalting protein samples, and the second one with a higher MWCO for size-based fractionation of proteins. Modeling based on a simple control volume analysis on the microdialysis system is consistent with measured concentration profiles, indicating both that membrane properties are uniform, well-defined, and reproducible and that diffusion of subcutoff analytes through the membrane is rapid.     

Hierarchically structured superhydrophobic coatings fabricated by successive Langmuir-Blodgett deposition of micro-/nano-sized particles and surface silanization

The present study demonstrates the creation of a stable, superhydrophobic surface by coupling of successive Langmuir-Blodgett (LB) depositions of micro-?and nano-sized (1.5?μm/50?nm, 1.0?μm/50?nm, and 0.5?μm/50?nm) silica particles on a glass substrate with the formation of a self-assembled monolayer of dodecyltrichlorosilane on the surface of the particulate film. Particulate films, in which one layer of 50?nm particles was deposited over one to five sublayers of larger micro-sized particles, with hierarchical surface roughness and superhydrophobicity, were successfully fabricated. Furthermore, the present 'two-scale' (micro-?and nano-sized particles) approach is superior to the previous 'one-scale' (micro-sized particles) approach in that both higher advancing contact angle and lower contact angle hysteresis can be realized. Experimental results revealed that the superhydrophobicity exhibited by as-fabricated particulate films with different sublayer particle diameters increases in the order of 0.5?μm>1.0?μm>1.5?μm. However, no clear trend between sublayer number and surface superhydrophobicity could be discerned. An explanation of superhydrophobicity based on the surface roughness introduced by two-scale particles is also proposed.     

Growth of aligned ZnO nanorods on transparent electrodes by hybrid methods

The fabrication of ZnO (80 nm) thin film was achieved by hybrid atomic layer deposition (ALD) to prevent the reaction between the reactants and conductive layer of the substrates. ZnO nanorods (ZnO-NRs) growth over the substrates was performed by wet chemical procedure in which Zn(NO₃)₂ and hexamethylenetetramine were used as the precursors. HR-TEM, SAED, FE-SEM, X-ray diffraction (XRD), and UV–Vis spectroscopy were employed to characterize the ZnO-NRs samples on the substrates. XRD and HR-TEM analyses confirmed that the ZnO nanorod structure is hexagonal wurtzite type with growth in the [0001] direction. Length and thickness of the ZnO-NRs ranged between 45  and 90 nm and 480  and 600 nm, respectively. It was observed that the growth rate of NRs in [0001] direction is 10 times higher than in [1000] direction. The growth mechanism and resulted dimensions of nanorods are function of the synthesis parameters (in hybrid ALD process) such as reaction time, temperature, precursor molar ratio, and thickness of ZnO film.     

In situ growth of silver nanoparticles in porous membranes for surface-enhanced raman scattering

We demonstrate the in situ growth of silver nanoparticles in porous alumina membranes (PAMs) for use as a surface-enhanced Raman scattering (SERS) detection substrate. This fabrication method is simple, cost-effective, and fast, while providing control over the size of silver nanoparticles through the entire length of the cylindrical nanopores with uniform particle density inside the pores unachievable by the traditional infiltration technique. The in situ growth of silver nanoparticles was conducted from electroless-deposited nanoscale seeds on the interior of the PAM and resulted in the formation of numerous hot spots, which facilitated significantly higher SERS enhancement for these substrates compared with previously reported porous substrates.     

In situ synthesis of manganese zinc ferrite nanoparticle/polymer hybrid nanocomposite from metal organics

A manganese zinc ferrite nanoparticle/polymer hybrid nanocomposite was synthesized in situ from metal acetylacetonates at 80 °C. A mixture of manganese(II) acetylacetonate (MA), zinc(II) acetylacetonate (ZA), and iron(III) 3-allylacetylacetonate (IAA) was hydrolyzed and polymerized, yielding a spinel oxide nanoparticle/organic hybrid. The crystallite size of the spinel particles was dependent upon the hydrolysis conditions of MA–ZA–IAA. Crystalline manganese zinc ferrite nanoparticles less than 5 nm in size were uniformly dispersed in the organic matrix. The magnetization of the hybrid increased as the amount of water for hydrolysis increased. The magnetization versus field curve for the manganese zinc ferrite nanoparticle/organic hybrid showed neither remanence nor coercivity above 11 K. The magnetization versus H/T curves from 50 to 200 K were superimposed on the same curve described by the Langevin equation. The remanent magnetization and coercive field of the hybrid were 2.1 emu/g and 20 Oe, respectively, at 4.2 K. The absorption edge of the hybrid film was blue-shifted as compared to that of bulk ferrite.     

Intercalation/Exfoliation mechanism of hybrid formation in polypropylene/lamellar mesostructured silica nanocomposites

Understanding the optimal processing conditions for the fabrication of polymer nanocomposites is of fundamental importance in designing materials with balance of properties. To understand these conditions in the case of maleic anhydride grafted polypropylene (PP-g-MA)/layered mesostructured silica (LMS) nanocomposites, the effect of temperature, shear rate, and residence time during processing on the structure of the nanocomposites were studied. The results showed that the combination of temperature, residence time, and mechanical shears have strong effect on the structure of the nanocomposites, rather than just interfacial interactions between the polymer matrix and silicate layers. However, interfacial interactions between the polymer matrix and silicate layers primarily play an important role to the intercalation of polymer chains into the silicate galleries. On the basis of our experimental results, a first explanation of the formulation mechanism of PP-g-MA/LMS nanocomposites is proposed. Finally, a general concept of processing conditions for manufacturing of polymer nanocomposites by melt-compounding process in a batch-mixer is described.     

Performance of polymer/ZnO hybrid photovoltaic devices determined by reaction time for oriented ZnO nanorod growth

The performance of hybrid polymer/metal oxide photovoltaic devices based on poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) and oriented ZnO nanorods is studied. The ZnO nanorods on indium tin oxide-coated glass were prepared by hydrothermal method, where the length and the defect concentration of ZnO nanorods were controlled by the reaction time (T_r) for nanorod growth. Increasing T_r results in longer ZnO nanorods and higher defect concentration. Results show that both photocurrent and electron lifetime have strong dependence on the nanorod length (i.e., growth time) due to the exponential attenuation of incident light intensity in the device, offering a peak conversion efficiency of 0.337% under 1.5 AM illumination for T_r = 120 min. Combinational analyses of the data in this experiment and the previous data for the electrodeposited ZnO nanorods provide the insights into the dependence of the device performance on the intrinsic property of the ZnO nanorods.     

Low-temperature fabrication of porous and transparent ZnO films with hybrid structure by self-hydrolysis method

Porous, transparent and controllable ZnO nanoparticulate films were fabricated by self-hydrolysis of zinc salts in its crystalline water without any additions at 65 °C by an evaporating acetone solvent. The crystallite size of ZnO nanoparticles was about 30 nm, and the thickness of the nanoparticle film was controllable by simply changing the coating times. ZnO nanoparticulate films in thickness of 500 nm showed a high transmittance (>90%) in the visible range and widen bandgap (3.35 eV). The c-axis oriented ZnO nanoarray film was fabricated by a subsequent heterogeneous nucleation and growth in an aqueous solution. As-grown ZnO hybrid films showed a good transmittance (>85%) in the visible range.     

Synthesis of silver/silica nanocomposites anchored by polymer via in situ reduction

Silver/silica nanocomposites were synthesized by in situ reduction of silver salt and anchorage of the formed silver nanoparticles to silica nanospheres using a polymer anchor. Synthesis conditions including reductants, anchor polymers, and surfactants were determined. The successful formation of the nanocomposites was governed by the reduction of silver nitrate in citrate aqueous solution by sodium borohydride and adsorption onto polyvinylpyrrolidone coated silica nanospheres. The size and structure of the nanocomposites were observed by light scattering measurement and scanning electron microscopy, respectively. Optical properties of the nanocomposites were determined by UV-visible absorption spectra.     

Removal of organic impurities from sewage by evaporation through polymer membranes

Pervaporational nonporous membranes are obtained on the basis of synthetic rubber. The possibility of using the method of evaporation through the obtained membrane is considered for treatment of sewage resulting from styrene, polysterene, polycarbonate, and polysulfone production. “Kiev Polytechnic Institute” National Technical University of Ukraine. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 69, No. 6, pp. 986–988, November–December, 1996.     

Lamination of alumina membranes to polymer surfaces: thick, hard, transparent, crack-free alumina films on polymers with excellent adhesion

Hard and transparent alumina (Al(2)O(3)) films with thicknesses in the range of 500 nm to 5 μm were successfully formed on polymethylmethacrylate (PMMA) and polystyrene (PS) surfaces. Our process is based on a lamination of anodized aluminum membranes (AAMs) to the polymer surfaces, followed by chemical etching. Because of capillary force, molten PS and liquid PMMA precursor were successfully pulled into the nanopores (10 nm diameter) within the Al(2)O(3) layers and solidified by cooling or polymerization, respectively. Our resulting AAM-laminated surfaces exhibited excellent adhesion and surface mechanical properties similar to those of fused silica, remaining crack-free and transparent even with Al(2)O(3) thicknesses exceeding 1 μm.     

Synthesis of optical transparent and electrical conductive polymer/nanocarbon composite films by infiltration method

Optical transparent and electrical conductive (PMMA)/nanocarbon composite films can be prepared through the infiltration of the polymer between the carbon aggregates of a preformed percolation cluster. This cluster is prepared by Langmuir-Blodgett technique as a thick film (2-20 μm in thickness). The performed direct current electrical measurements have shown that PMMA/Multiwall Nanotubes present a lower electrical surface resistivity and a higher optical transmittance than PMMA/carbon nanoparticles composite films. Much simpler and cheaper than other methods, the infiltration method allowed us to prepare composite films with a 75% in transparency and 1 MΩ/square in surface electrical resistivity. The composite films prepared by infiltration method have a good adhesion to the glass substrates but in some specific conditions can be integrally removed as free-standing films.     

Real-time characterization of film growth on transparent substrates by rotating-compensator multichannel ellipsometry

A multichannel spectroscopic ellipsometer in the fixed-polarizer-sample-rotating-compensator-fixed-analyzer (PSC(R)A) configuration has been developed and applied for real-time characterization of the nucleation and growth of thin films on transparent substrates. This rotating-compensator design overcomes the major disadvantages of the multichannel ellipsometer in the rotating-polarizer-sample-fixed-analyzer (P(R)SA) configuration while retaining its high speed and precision for the characterization of thin-film processes in real time. The advantages of the PSC(R)A configuration include (i) its high accuracy and precision for the detection of low-ellipticity polarization states that are generated upon reflection of linearly polarized light from transparent film-substrate systems, and (ii) the ability to characterize depolarization of the reflected light, an effect that leads to errors in ellipticity when measured with the P(R)SA configuration. A comparison of the index of refraction spectra for a glass substrate obtained in the real-time PSC(R)A mode in 2.5 s and in the ex situ fixed-polarizer-fixed-compensator-sample-rotating-analyzer (PCSA(R)) mode in ~10 min show excellent agreement, with a standard deviation between the two data sets of 8 x 10(-4), computed over the photon energy range from 1.5 to 3.5 eV. First, we describe the PSC(R)A ellipsometer calibration procedures developed specifically for transparent substrates. In addition, we describe the application of the multichannel PSC(R)A instrument for a study of thin-film diamond nucleation and growth on glass in a low-temperature microwave plasma-enhanced chemical vapor deposition process.     

Fabrication of PU/PEGMA crosslinked hybrid scaffolds by in situ UV photopolymerization favoring human endothelial cells growth for vascular tissue engineering

Poly(ethylene glycol) methacrylate (PEGMA) was introduced into a polyurethane (PU) solution in order to prepare electrospun scaffold with improving the biocompatibility by electrospinning technology for potential application as small diameter vascular scaffolds. Crosslinked electrospun PU/PEGMA hybrid nanofibers were fabricated by a reactive electrospinning process with N,N'-methylenebisacrylamide as crosslinker and benzophenone as photoinitiator. The photoinduced polymerization and crosslinking reaction took place simultaneously during the electrospinning process. The electrospinning solutions with various weight ratios of PU/PEGMA were successfully electrospun. No significant difference in the scaffold morphology was found by SEM when PEGMA content was <20 wt%. The crosslinked fibrous scaffolds of PU/PEGMA exhibited higher mechanical strength than the pure PU scaffold. The hydrophilicity of scaffolds was controlled by varying the PU/PEGMA weight ratio. The tissue compatibility of electrospun nanofibrous scaffolds were tested using human umbilical vein endothelial cells (HUVECs). Cell morphology and cell proliferation were measured by SEM, fluorescence microscopy and thiazolyl blue assay (MTT) after 1, 3, 7 days of culture. The results indicated that the cell morphology and proliferation on the crosslinked PU/PEGMA scaffolds were better than that on the pure PU scaffold. Furthermore, the appropriate hydrophilic surface with water contact angle in the range of 55-75° was favorable of improvement the HUVECs adhesion and proliferation. Cells seeded on the crosslinked PU/PEGMA (80/20) scaffolds infiltrated into the scaffolds after 7 days of growth. These results indicated the crosslinked electrospun PU/PEGMA nanofibrous scaffolds were potential substitutes for artificial vascular scaffolds.     

Graphene/PANI hybrid film with enhanced thermal conductivity by in situ polymerization

Heat dissipation in time is essential for long-term reliability of electrical devices. Graphene, with superior thermal conductivity and excellent flexibility, exhibits a potential to substitute currently used graphite film for thermal management. In this work, a free-standing film with enhanced thermal conductivity and better flexibility was achieved by a facile and environmentally friendly in situ polymerization. The ‘molecular welding’ strategy was introduced for preparation of graphitized graphene oxide/polyaniline (gGO/PANI) hybrid film, and the uniformly distributed PANI, serving as a solder, connected adjacent graphene sheets and filled in air voids of GO films. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and Raman spectroscopy were used to determine the structure of PANI and the interaction between GO and PANI. The in-plane thermal conductivity of gGO/PANI film is enhanced by 38% to 1019.7 ± 0.1 W m^?1 K^?1 with addition of 12 wt% PANI, compared with that of pristine gGO film. Besides, the gGO/PANI film shows better flexibility than gGO film after 180° bending for 500 times.     

In situ synthesis of catalytic metal nanoparticle-PDMS membranes by thermal decomposition process

Nanoparticles of various transition elements such as palladium, iron, and nickel were synthesized in situ in the polydimethylsiloxane (PDMS) matrix by thermal decomposition of their corresponding acetylacetonate salts. Various complementary techniques such as XRD, TEM and XPS were used to characterize the nanoparticles formed in the polymer matrix. This synthesis route results in relatively monodisperse nanoparticles with a narrow particle size distribution. In addition, the composite films are pore-free and mechanically stable, making them attractive for a range of applications. Palladium-PDMS membranes can be used as catalytic membrane reactors and show enhanced catalytic activity in ethylene hydrogenation.