Nanofibrous polysulfone/TiO2 nanocomposites: Surface properties and their relation with E. coli adhesion

Solution blow spinning, SBS, was used to prepare fibrous films of thermoplastic nanocomposites with potential antibacterial properties based on polysulfone, PSF, filled with well dispersed TiO₂ nanoparticles. The PSF/TiO₂ nanocomposites were produced with different nanoparticles content up to 10% by weight. A wide characterization was carried out focusing on the morphology at the nanoscale, roughness, contact angles, and surface free energy. Cell adhesion was studied by inspection by scanning electron microscopy (SEM). A uniform dispersion of the nanofiller was achieved, with the nanoparticles evenly embedded in the polymer along the fibers when they were created during the blow spinning process. TiO₂ content influenced the topography of the films, most likely due to a direct effect on the solvent evaporation rate. The results obtained pointed out that an increase of the surface hydrophobicity as a result of the increased roughness induced by the presence of TiO₂ nanoparticles was the main contribution to the reduction of DH5α Escherichia coli cells adhesion. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1575–1584     

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.     

Thermo-responsive and antifouling PVDF nanocomposited membranes based on PNIPAAm modified TiO2 nanoparticles

A novel hydrophilic nanocomposite additive(TiO2-g-PNIPAAm) was synthesized by the surface modification of titanium dioxide(TiO2) with N-isopropylacrylamide(NIPAAm) via "graft-from" technique. And the nanocomposite membrane of poly(vinylidene fluoride)(PVDF)/TiO2-g-PNIPAAm was fabricated by wet phase inversion. The graft degree was obtained by thermo-gravimetric analysis(TGA). Fourier transform infrared attenuated reflection spectroscopy(FTIR-ATR) and X-ray photoelectronic spectroscopy(XPS) characterization results suggested that TiO2-g-PNIPAAm nanoparticles segregated on membrane surface during the phase separation process. Scanning electron microscopy(SEM) was conducted to investigate the surface and cross-section of the modified membranes. The water contact angle measurements confirmed that TiO2-g-PNIPAAm nanoparticles endowed PVDF membranes better hydrophlilicity and thermo-responsive properties compared with those of the pristine PVDF membrane. The water contact angle decreased from 92.8° of the PVDF membrane to 61.2° of the nanocompostie membrane. Bovine serum albumin(BSA) static and dynamic adsorption experiments suggested that excellent antifouling properties of membranes was acquired after adding TiO2-gPNIPAAm. The maximum BSA adsorption at 40 °C was about 3 times than that at 23 °C. The permeation experiments indicated the water flux recover ratio and BSA rejection ratio were improved at different temperatures.     

Influence of surface modified TiO2 nanoparticles by gallates on the properties of PMMA/TiO2 nanocomposites

Nanocomposites based on poly(methyl methacrylate) (PMMA) and TiO₂ nanoparticles were synthesized by in situ radical polymerization of MMA in solution. The surface of TiO₂ nanoparticles was modified with four gallic acid esters (octyl, decyl, lauryl and cetyl gallate). The content of gallates present on the surface of TiO₂ was calculated from the TGA results. The influence of length of hydrophobic tail of amphiphilic alkyl gallates on dispersability of surface modified TiO₂ nanoparticles in PMMA matrix, the molecular weight and glass transition temperature of PMMA, as well as the thermal stability of the prepared PMMA/TiO₂ nanocomposites in nitrogen and air was investigated. The influence of content of TiO₂ nanoparticles on the properties of these nanocomposites was also examined. The formation of a charge transfer complex between the surface Ti atoms and the gallates was confirmed by FTIR and UV spectroscopy. TEM micrographs of the PMMA/TiO₂ nanocomposites revealed that degree of TiO₂ aggregation can be significantly lowered by increasing the length of aliphatic part of the used gallates. The molecular weight of PMMA slightly decreases with the increase of TiO₂ content, indicating that used TiO₂ nanoparticles act as radical scavengers during the polymerization of MMA. The presence of surface modified TiO₂ nanoparticles do not have an influence on the mobility of PMMA chain segments leading to the same values of glass transition temperature for all investigated samples. Thermal and thermo-oxidative stability of the PMMA matrix are improved by introducing TiO₂ nanoparticles modified with gallates.     

Poly (ethylene-co-vinyl acetate) films prepared by solution blow spinning: Surface characterization and its relation with E. coli adhesion

Solution blow spinning, SBS, a quite novel processing method, was used to obtain poly (ethylene-co-vinyl acetate), EVA, films with controlled surface properties. The influence of the surface characteristics of EVA films on the adhesion of DH5α Escherichia coli was studied. In particular, the initial concentration of the EVA solution to be blow spun was varied in order to get different surface topographies. Considering the potential use of EVA based materials in applications such as food packaging or scaffolds for tissue engineering all factors affecting proliferation of microorganisms on their surfaces should be studied and understood. Structural, morphological and surface characterizations based on the use of infrared spectroscopy, FTIR, scanning electron microscopy, SEM, and contact angle measurements were performed to ascertain the main factor influencing the E. coli adhesion on the EVA films. Roughness data were determined at different scales from 3D surfaces obtained using a stereoscopic reconstruction of SEM images. It was concluded that, depending on the conditions of the SBS process, only variations of topography were found on the EVA films, being therefore the unique cause of different adhesion capacity of E. coli cells. A correlation between roughness and the number of attached E. coli cells showed that the higher the roughness at microscale level the higher the biofilm development, demonstrating that, apart from specific interactions at nanoscale surface, heterogeneity at microscale can greatly modify the antibacterial action.     

Electrodeposition and characterization of Cu-TiO2 nanocomposite coatings

Cu-TiO₂ nanocomposites were prepared by electrodeposition method onto copper substrate using an acid copper plating bath containing dispersed nanosized TiO₂. The composition of codeposited TiO₂ nanoparticles in the composite coatings was controlled by the addition of different concentrations of TiO₂ nanoparticles in the bath solution. The average crystallite size was calculated by using X-ray diffraction analysis and it was ~32 nm for electrodeposited copper and ~33 nm for Cu-TiO₂ composite coatings. The crystallite structure was fcc for electrodeposited copper and Cu-TiO₂ nanocomposite coatings. The surface morphology and composition of the nanocomposites were examined by scanning electron microscopy and energy dispersive X-ray spectroscopy analysis. The effect of TiO₂ content on the corrosion and wear resistance properties of the nanocomposite coatings was also presented. The codeposited TiO₂ nanoparticles in the deposit increased the corrosion and wear resistance, which were closely related with TiO₂ content in the nanocomposites. The wear resistance and microhardness of the Cu-TiO₂ nanocomposite coatings were higher than electrodeposited copper. The corrosion resistance property of the electrodeposited copper and Cu-TiO₂ nanocomposite coatings was evaluated by electrochemical impedance and Tafel polarization studies. Cu-TiO₂ composite coatings were more corrosion resistant than electrodeposited copper.     

Sustainable fabrication of silver-titania nanocomposites using goji berry (Lycium barbarum L.) fruit extract and their photocatalytic and antibacterial applications

Silver-titania nanocomposites (Ag-TiO₂ NCs) have unique functional attributes due to their photocatalytic and antibacterial properties. In this study, titania nanoparticles (TiO₂-NPs) were successfully in-situ decorated with silver nanoparticles (Ag-NPs) using the aqueous extract of goji berries (Lycium barbarum L.) as a bioreducing and stabilizing agent. Different Ag-TiO₂ NCs were synthesized by treating different concentrations of silver nitrate with a specific concentration of TiO₂-NPs in the presence of fruit extract. The green-synthesized NCs were characterized using several techniques viz., ultraviolet–visible spectrophotometry, X-ray diffractometry (XRD), scanning electron microscopy, field-emission transmission electron microscopy (FE-TEM), Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. XRD analysis revealed the formation of face-centered cubic (fcc) crystals, and FE-TEM analysis revealed the embedment of Ag-NPs throughout the surface of TiO₂-NPs. The average size of Ag-NPs on TiO₂-NPs increased from 11.2 ± 3.05 nm to 16.4 ± 4.5 nm with an increase in the concentration of silver ions, and the morphology of Ag-NPs was predominantly quasi-spherical and hexagonal. These NCs exhibited an excellent photocatalytic degradation of an azo dye, methylene blue (MB). The synthesized Ag-TiO₂ NCs (3:1) showed higher photocatalytic degradation efficiency of ∼ 93.4% for MB in 130 min under visible light irradiation. Ag-TiO₂ NC_S also exhibited good antibacterial activities towards Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). Therefore, the formation of Ag-NPs on the surface of TiO₂-NPs to form Ag-TiO₂ NCs exhibits eco-friendly photocatalytic degradation of azo dye contaminants as well as antibacterial activity.     

NMR study of styrene-butadiene rubber (SBR) and TiO2 nanocomposites

The chemical behavior of styrene-butadiene rubber (SBR) and of the SBR/TiO₂ and photodegraded SBR/TiO₂ nanocomposites was investigated through nuclear magnetic resonance spectroscopy (NMR) in the solid state with magic angle spinning (MAS). The ¹³C cross polarization/magic angle spinning (CP/MAS) routine spectrum allowed us to obtain information on the polymer microstructure and also to evaluate the domain mobilities. The variation contact time and the proton spin-lattice relaxation time in the rotating frame (T₁ρH) were determinant factors to evaluate the dynamic molecular motion. The NMR spectrum of the nanocomposites was dislocated 5 ppm to higher chemical shift, indicating the presence of a strong interaction between the polymer chains and the TiO₂ nanoparticles. The VTC experiment showed a rigid domain in the SBR/TiO₂ photodegraded nanocomposite due to cross-linking reactions.     

纳米复合材料中界面动态特性的扫描静电显微技术研究

纳米复合材料中的微观界面结构和界面作用对材料的宏观介电性能, 如介电常数、介电损耗、击穿强度等有十分重要的影响. 本文发展了一种基于扫描静电显微探针技术的测量方法, 可以直接表征二氧化钛/环氧树脂纳米复合材料的微观界面结构及相应的动态介电响应行为. 实验中利用扫描探针的纳米尺度分辨能力, 探测到不同温度下环氧树脂纳米复合材料的局域动态介电响应变化过程, 从而获得纳米颗粒与高分子界面相互作用及极化相关的温度特性. 进一步通过对二氧化钛纳米颗粒进行表面修饰, 得到了两种不同特性的二氧化钛/环氧树脂界面, 验证了不同界面作用引起的复合材料界面区域与非界面区域高分子链介电损耗图像的反差.     

Mechanical and thermal properties of nanosized titanium dioxide filled rigid poly(vinyl chloride)

Nano-sized rod-like titanium dioxide (TiO2) filled rigid poly(vinyl chloride) (PVC) nanocomposites were prepared by using injection-molding method. Vicat, Charpy impact and tensile tests as well as thermogravimetric and dynamic mechanical analyses were used to characterize the structure and properties of the nanocomposites. The results showed that nano-TiO2 could improve Vicat softening temperature and also improve thermal stability of PVC during the stages of dehydrochlorination and formation of carbonaceous conjugated polyene sequences, which can be ascribed to restriction of the nanoparticles on the segmental relaxation as being evidenced by raises in glass transition and β-relaxation temperatures of PVC upon filling TiO2. Addition of TiO2 nanoparticles less than 40 phr (parts per hundreds of resin) could significantly improve impact strength of the composites while the TiO2 agglomeration at high contents leads to a reduction in impact toughness.     

Synthesis of 3D hierarchical porous TiO2/InVO4 nanocomposites with enhanced visible-light photocatalytic properties

Three-dimensional (3D) hierarchical porous TiO₂/InVO₄ nanocomposites were fabricated by loading TiO₂ nanoparticles on the surface of porous InVO₄ microspheres. X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis spectroscopy and photoluminescence spectroscopy (PL) were adopted to analyze the structure–property relationship of samples. The results show that the surface of as-prepared TiO₂/InVO₄ nanocomposites are composed of uniformly interconnected bi-phase nanocrystals, forming a close interface between these two components, which is favorable for the highly efficient interparticle electron transfer to achieve enhanced photocatalytic properties. However, the adsorption ability is decreased due to the loading of TiO₂ nanoparticles on the surface of InVO₄. Therefore, under the joint action of these factors, the TiO₂/InVO₄ nanocomposites achieve the best photocatalytic activity when the mole ratio of In:Ti reaches 4:1, and the visible-light photocatalytic activity is about as 3.3 times high as that of pure InVO₄ without modification.     

In situ radical polymerization of methyl methacrylate in a solution of surface modified TiO2 and nanoparticles

Surface modified TiO₂ nanoparticles dissolved in toluene were encapsulated in PMMA by in situ radical polymerization of methyl methacrylate initiated by 2,2′-azobisisobutyronitrile. The surface modification of the TiO₂ nanoparticles (average diameter of 4.5 nm) was achieved by the formation of a charge transfer complex between TiO₂ nanoparticles and 6-palmitate ascorbic acid. The surface modified TiO₂/nanoparticles were characterized using UV−Vis and FTIR spectroscopy, while the obtained polymer nanocomposites were characterized using reflection and ¹H NMR spectroscopy, as well as gel permeation chromatography. The influence of the TiO₂ nanoparticles on the thermal properties of the PMMA matrix was investigated using thermo-gravimetric analysis and differential scanning calorimetry. The glass transition temperature of the polymer was not influenced by the presence of the nanoparticles while the thermal stability was significantly improved.     

Thermodynamic aspects of fibroblastic spreading on diamond-like carbon films containing titanium dioxide nanoparticles

The combination of low friction, wear resistance, high hardness, biocompatibility, and chemical inertness makes diamond-like carbon (DLC) films suitable in numerous applications in biomedical engineering. The cytotoxicity of DLC films containing TiO₂ nanoparticles was practical and theoretically evaluated. The films were grown on 316L stainless steel substrates from a dispersion of TiO₂ nanopowder in hexane. Raman spectroscopy shows that the presence of TiO₂ increased the graphite-like bonds in the films. The incorporation of TiO₂ nanoparticles into DLC films increases surface roughness, decreases water contact angle (increased hydrophilic character), and increases the total free surface energy due to the higher polar component. As the concentration of TiO₂ increased, the films increased the cell viability (MTT assay), becoming more thermodynamically favorable to cell spreading (??F _Adh values became more negative). This was evidenced through the increasing number of projections (philopodia and lamellipodia), indicating a higher adhesion between the L929 cells and the films. The practical and theoretical findings of this study show that the incorporation of TiO₂ into DLC films is effective in enhancing cell viability. These results show the potential use of DLC and TiO₂-DLC films in biomedical applications.     

Effect of the method of production of TiO<Subscript>2</Subscript>/CdS nanohetero film structures on the effectiveness of photoinduced charge separation

The properties of TiO₂/CdS nanohetero structures produced by the chemical and photocatalytic deposition of CdS nanoparticles on the surface of nanocrystalline films of TiO₂ under the conditions of laser pulse photolysis were studied. It was shown that in the case of photocatalytically formed TiO₂/CdS nanocomposites the spatial separation of the photogenerated charges between the components of the hetero structure, leading to the formation of intermediates of the photochemical transformations (Ti^III centers in the TiO₂ nanoparticles and S^– radical-anions in the CdS nanoparticles), is an order of magnitude more effective.     

Wet-Chemical Synthesis of TiO2/PVDF Membrane for Energy Applications

To satisfy the ever-increasing energy demands, it is of the utmost importance to develop electrochemical materials capable of producing and storing energy in a highly efficient manner. Titanium dioxide (TiO₂) has recently emerged as a promising choice in this field due to its non-toxicity, low cost, and eco-friendliness, in addition to its porosity, large surface area, good mechanical strength, and remarkable transport properties. Here, we present titanium dioxide nanoplates/polyvinylidene fluoride (TiO₂/PVDF) membranes prepared by a straightforward hydrothermal strategy and vacuum filtration process. The as-synthesized TiO₂/PVDF membrane was applied for energy storage applications. The fabricated TiO₂/PVDF membrane served as the negative electrode for supercapacitors (SCs). The electrochemical properties of a TiO₂/PVDF membrane were explored in an aqueous 6 M KOH electrolyte that exhibited good energy storage performance. Precisely, the TiO₂/PVDF membrane delivered a high specific capacitance of 283.74 F/g at 1 A/g and maintained capacitance retention of 91% after 8000 cycles. Thanks to the synergistic effect of TiO₂ and PVDF, the TiO₂/PVDF membrane provided superior electrochemical performance as an electrode for a supercapacitor. These superior properties will likely be used in next-generation energy storage technologies.     

The release of TiO2 and SiO2 nanoparticles from nanocomposites

There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO₂ or amorphous SiO₂ nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO₂ and TiO₂ nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles.     

Improving piezoelectric performance of lead-free polymer composites with high aspect ratio BaTiO3 nanowires

Flexible and lead-free piezoelectric nanocomposites were synthesized with BaTiO₃ nanowires (filler) and poly(vinylidene fluoride) (PVDF) (matrix), and the piezoelectric performances of the composites were systematically studied by varying the aspect ratio (AR) and volume fraction of the nanowire and poling time. BaTiO₃ nanowires with AR of 18 were synthesized and incorporated into PVDF to improve the piezoelectric performance of the composites. It was found that high AR significantly increased the dielectric constant up to 64, which is over 800% improvement compared to those from the composites containing spheroid shape BaTiO₃ nanoparticles. In addition, the dielectric constant and piezoelectric coefficient were also enhanced by increasing the concentration of BaTiO₃ nanowires. The piezoelectric coefficient with 50-vol% BaTiO₃ nanowires embedded in PVDF displayed 61 pC/N, which is much higher than nanocomposites with spheroid shape BaTiO₃ nanoparticles as well as comparable to, if not better, other nanoparticle-filled polymer composites. Our results suggest that it is possible to fabricate nanocomposites with proper mechanical and piezoelectric properties by utilizing proper AR fillers.     

Preparation and characterization of poly(vinyl alcohol)/organo-modified cloisite Na+ with chiral L-leucine amino acid/TiO2 nanocomposites

Poly(vinyl alcohol)/organo-clay/TiO₂ nanocamposites films were prepared with 10 wt % of organo-nanoclay and various amount of TiO₂ nanoparticles. Cloisite Na⁺ has been modified via cation exchange reaction using ammonium salt of natural L-leucine amino acid as a cationic surfactant. After that poly(vinyl alcohol)/organo-nanoclay/TiO₂ nanocomposites were synthesized by dispersion of TiO₂ on the surfaces of organo-nanoclay in poly(vinyl alcohol) matrix by using ultrasonic energy. Three nanocomposites with different loading of TiO₂ were prepared and characterized by X-ray diffraction, fourier transform infrared spectroscopy, field emission type scanning electron microscope, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis and ultraviolet-visible transmission spectra. The results showed that the organo-nanoclay and TiO₂ were dispersed homogeneously in poly(vinyl alcohol) matrix and also showed improvement in their thermal properties compared with the pure poly(vinyl alcohol).     

Investigation of structural and thermal characteristics of PVDF/ZnO nanocomposites

The structural and thermal behavior of PVDF/ZnO nanocomposites have been investigated by employing scanning electron microscopy (SEM),TEM, DSC, powder X-ray diffraction (XRD), thermally stimulated discharge current (TSDC), and transient current techniques. SEM/TEM observation indicated the homogeneous dispersion of functionalized ZnO nanoparticles throughout PVDF matrix. DSC shows that the crystallinity is influenced by the presence of ZnO nanoparticles in the PVDF matrix because the filler acts as efficient nucleating agent to facilitate PVDF crystallization. DSC results indicated the enhancement of the glass transition temperature (T _g), melting temperature (T _m) and crystallization temperature (T _c) of nanocomposites compared to pristine PVDF. XRD shows that the full-width at half maximum decreases with increasing ZnO content, which is attributed to the improvement in crystallinity. The incorporation of ZnO nanoparticles influences the modification of polarization process in PVDF as observed by means of TSDC and transient current study.     

Formation of appropriate sites on nanofiltration membrane surface for binding TiO2 photo-catalyst: Performance, characterization and fouling-resistant capability

Titanium dioxide (TiO₂) nanoparticles were assembled on the surface of nanofiltration blend membrane. For settling TiO₂ on the membrane surface, two membrane categories were used: (i) unmodified polyethersulfone (PES)/polyimide (PI) blend membrane, and (ii) –OH functionalized PES/PI blend membrane with different concentrations of diethanolamine (DEA). These membranes were radiated by UV light after TiO₂ depositing with different concentrations. 15 min immersion in colloidal suspension and 15 min UV irradiation with 160 W lamps were used for modification. The modification resulted in the formation of a photo-catalytic property with enhanced membrane hydrophilicity. The self-assembly of TiO₂ nanoparticles was established through coordinance bonds with –OH functional groups on the membrane surface. A comparison between the UV irradiated TiO₂ deposited blend membrane and deposited-functionalized blend membranes showed that –OH groups originate excellent adhesion of TiO₂ nanoparticles on the membrane surface, increase reversible deposition, and diminish irreversible fouling. The membranes were characterized using SEM, FTIR, EDX, contact angle, cross flow filtration, and antifouling measurements. SEM images show that the presence of –OH groups on the DEA-modified membrane surface is the main parameter for extra uniformly settlement of TiO₂ nanoparticles on the membrane surface. This procedure is a superior technique for modification of PES/PI nanofiltration membranes to enhance water flux and minimization membrane fouling.