Flexible /PET/batio3/ layer–layer composite film with enhanced dielectric properties fabricated by highly loaded /batio3/ coating with acrylic resin as binder

Flexible layer–layer poly(ethylene phthalate) (PET)/BaTiO₃ composite films with enhanced dielectric permittivity were fabricated by spin coating method, consisting of PET substrate film layer and modified BaTiO₃/acrylic resin hybrid coating layer. The thickness of coating layer was less than 3 μm (about 2% of PET film thickness), and therefore, the PET/barium titanate (BT) composite films remained flexible even at high volume fraction of BaTiO₃ fillers. The volume contents of BaTiO₃ were varied from 0 to 80%, and the solid contents of BaTiO₃/acrylic resin were in the range of 51.8–72.9%. Scanning electron microscopy showed strong interaction of finely dispersed BaTiO₃ particles with acrylic resin. Morphological profile also displayed uniform coating layer of modified BaTiO₃/acrylic resin and its strong adhesion with PET film. The dielectric constant of the PET/BaTiO₃ composite films increased by about 26% at 60 vol % BaTiO₃ loading when compared with the pristine PET film, whereas the dielectric loss decreased slightly. In addition, PET‐grafted poly(hydroxylethyl methacrylate) brushes were used as substrate to introduce covalent bonding with the coating layer. Further enhancement of dielectric constant and reduction of dielectric loss were realized when compared with the composite films with bare PET substrate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42508.     

Photoreduction of CO<Subscript>2</Subscript> into CH<Subscript>4</Subscript> using Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> double-layered dense films

Nano-sized bismuth sulfide (Bi₂S₃) and titanium dioxide (TiO₂) with the orthorhombic and anatase tetragonal structures, respectively, were synthesized for application as catalysts for the reduction of carbon dioxide (CO₂) to methane (CH₄). Four double-layered dense films were fabricated with different coating sequences—TiO₂ (bottom layer)/Bi₂S₃ (top layer), Bi₂S₃/TiO₂, TiO₂/Bi₂S₃: TiO₂ (1 : 1) mix, and Bi₂S₃: TiO₂ (1 : 1) mix/Bi₂S₃: TiO₂ (1 : 1) mix—and applied to the photoreduction of CO₂ to CH₄; the catalytic activity of the fabricated films was compared to that of the pure TiO₂/TiO₂ and Bi₂S₃/Bi₂S₃ doubled-layered films. The TiO₂/Bi₂S₃ double-layered film exhibited superior photocatalytic behavior, and higher CH₄ production was obtained with the TiO₂/Bi₂S₃ double-layered film than with the other films. A model of the mechanism underlying the enhanced photoactivity of the TiO₂/Bi₂S₃ double-layered film was proposed, and it was attributed in effective charge separation.     

Ultrasonic-vibration-assisted laser annealing of fluorine-doped tin oxide thin films for improving optical and electrical properties: Overlapping rate optimization

An ultrasonic-vibration-assisted laser annealing method was developed to enhance the performance of fluorine-doped tin oxide (FTO) thin films. The influences of ultrasonic vibration, laser scan line overlapping rate (L_OR) and laser spot overlapping rate (S_OR) on surface morphology, FTO layer thickness, RMS roughness, crystal structure and photoelectric properties of the FTO films were investigated. The results indicated that the presence of ultrasonic vibration during laser annealing could significantly enhance the film compactness, and using moderate L_OR and S_OR values resulted in significantly decreased FTO layer thicknesses and RMS roughnesses as well as slightly increased crystallite sizes, thus yielding significantly improved optical transmittance values and slightly enhanced electrical conductivity values. It was found that the optimal L_OR and S_OR values for ultrasonic-vibration-assisted laser annealing of the FTO films were 80% and 90%, respectively. The as-obtained film possessed the best overall photoelectric property with an average transmittance (400–800?nm) of 85.9%, a sheet resistance of 8.7?Ω/sq and a figure of merit of 2.51?×?10^–2 Ω^–1. This work may be of great significance in terms of performance optimization of transparent conducting oxide (TCO) thin films.     

Electrical and optical properties of Al-doped ZnO and ZnAl2O4 films prepared by atomic layer deposition

ZnO/Al₂O₃ multilayers were prepared by alternating atomic layer deposition (ALD) at 150°C using diethylzinc, trimethylaluminum, and water. The growth process, crystallinity, and electrical and optical properties of the multilayers were studied with a variety of the cycle ratios of ZnO and Al₂O₃ sublayers. Transparent conductive Al-doped ZnO films were prepared with the minimum resistivity of 2.4 × 10⁻³ Ω·cm at a low Al doping concentration of 2.26%. Photoluminescence spectroscopy in conjunction with X-ray diffraction analysis revealed that the thickness of ZnO sublayers plays an important role on the priority for selective crystallization of ZnAl₂O₄ and ZnO phases during high-temperature annealing ZnO/Al₂O₃ multilayers. It was found that pure ZnAl₂O₄ film was synthesized by annealing the specific composite film containing alternative monocycle of ZnO and Al₂O₃ sublayers, which could only be deposited precisely by utilizing ALD technology.     

Fabrication of Sb2S3 thin films by sputtering and post-annealing for solar cells

The semiconductor antimony sulfide (Sb₂S₃) is a potential absorber materials for the top sub-cell of Si-based tandem solar cells because of its appropriate band-gap, simple binary composition, nontoxic elements, and long-term stability. In this study, polycrystalline Sb₂S₃ films were fabricated by post-annealing of radio frequency (RF) magnetron sputtered precursors using an Sb2S3 target. The effects of the post-annealing temperature and atmosphere on Sb₂S₃ film properties and device performances were investigated. A high-performance device having a 2.41% power conversion efficiency was obtained by making use of a uniform Sb2S3 absorber layer. This preliminary experimental study shows that Sb2S3 thin films could be used as top sub-cell absorber materials for third-generation high efficiency, stable, and environmentally friendly Sb₂S₃/Si tandem solar cells.     

A modified composite film electrode of polyoxometalate/carbon nanotubes and its electrocatalytic reduction

Keggin-type polyoxometalate (H₄SiMo₁₂O₄₀) and carbon nanotubes (CNTs) coated by poly(allylamine hydrochloride) (PAH) were alternately deposited on glassy carbon (GC) electrodes by an electrochemical growth method in acidic aqueous solution. The preparation of the film electrode was simple and convenient. Thus-prepared multilayer films and the electrochemical behavior of the composite film modified electrode were characterized by UV–vis spectroscopy and cyclic voltammetry. It was shown that the multilayer films are uniform and stable. The resulting multilayer film modified electrode behaves as an electrochemical sensor because of its low overpotential for the catalytic reduction of S₂O₈ ²⁻ and NO₂ ⁻ in acidic aqueous solution.     

Study of nisin adsorption on plasma-treated polymer surfaces for setting up materials with antibacterial properties

Setting up antibacterial materials by nisin adsorption on surfaces depends mainly on the surface properties and the surface treatments allowing the modification of such properties. In order to investigate the factors affecting such adsorption, the native low density polyethylene (LDPE) was modified using Argon/Oxygen (Ar/O₂) plasma, nitrogen (N₂) plasma and plasma-induced grafting of acrylic acid (AA). The films were studied by various characterization techniques. The chemical surface modification was confirmed by X-ray photoelectron spectroscopy (XPS), the wettability of the surfaces was evaluated by contact angle measurements, the surface charge was determined by the zeta potential measurements, and the changes in surface topography and roughness were revealed by atomic force microscopy (AFM). Nisin was adsorbed on the native and the modified surfaces. The antibacterial activity, the nisin adsorbed amount, and the peptide distribution were compared for the four nisin-functionalized films. The highest antibacterial activity was recorded on the Ar/O₂ followed by AA then by N₂ treated films and the lowest activity was on the native film. The observed antibacterial activity was correlated to the type of the surface, hydrophobic and hydrophilic interactions, surface charge, surface topography, nisin adsorbed amount, and nisin distribution on the surfaces.     

Growth of nanolaminate structure of tetragonal zirconia by pulsed laser deposition

Alumina/zirconia (Al₂O₃/ZrO₂) multilayer thin films were deposited on Si (100) substrates at an optimized oxygen partial pressure of 3 Pa at room temperature by pulsed laser deposition. The Al₂O₃/ZrO₂ multilayers of 10:10, 5:10, 5:5, and 4:4 nm with 40 bilayers were deposited alternately in order to stabilize a high-temperature phase of zirconia at room temperature. All these films were characterized by X-ray diffraction (XRD), cross-sectional transmission electron microscopy (XTEM), and atomic force microscopy. The XRD studies of all the multilayer films showed only a tetragonal structure of zirconia and amorphous alumina. The high-temperature XRD studies of a typical 5:5-nm film indicated the formation of tetragonal zirconia at room temperature and high thermal stability. It was found that the critical layer thickness of zirconia is ≤10 nm, below which tetragonal zirconia is formed at room temperature. The XTEM studies on the as-deposited (Al₂O₃/ZrO₂) 5:10-nm multilayer film showed distinct formation of multilayers with sharp interface and consists of mainly tetragonal phase and amorphous alumina, whereas the annealed film (5:10 nm) showed the inter-diffusion of layers at the interface.     

Preparation and characterization of antimicrobial films based on nanocrystalline cellulose

Nanocrystalline cellulose (NCC) has great potential in applications in medical and food packaging due to its abundance, high specific surface area, biodegradability, biocompatibility, and reproducibility. N-Halamine is one of the most effective antibacterial agents, with broad-spectrum efficacy against microorganisms, good stability, and reproducibility. Due to the nanosize effect and high specific surface area of NCC, N-halamine-modified NCC is potentially an excellent biocidal compound. In this paper, an N-halamine precursor 1-hydroxymethyl-5,5-dimethylhydantoin (HDH) was used to modify NCC with cyanuric chloride (cych) as the bonding agent. After chlorination, the produced NCC-cych-HDH-Cl became antibacterial. The synthesized NCC-cych-HDH-Cl was added to a chitosan (CS) and polyvinyl alcohol (PVA) solution to prepare antibacterial films. The optimum mixing ratio of PVA and CS in the PVA/CS films and concentration of NCC-cych-HDH-Cl were investigated. The surface morphologies and mechanical properties of the antibacterial films were characterized with scanning electron microscopy, transmission electron microscopy, and mechanical strength tests. The results indicated that the film with 90/10 PVA/CS and 7.0% loading of NCC-cych-HDH-Cl exhibited excellent tensile strength. The antibacterial film with 5.91 × 10¹⁷ atoms/cm² of active chlorine displayed an excellent antibacterial property against Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47101.     

Effect of TiO2 nanoparticles on the antibacterial and physical properties of polyethylene-based film

TiO₂ nanoparticles and their application in packaging systems have attracted a lot of attention because of its antimicrobial activity. In this work, effect of TiO₂ nanoparticles on the antibacterial and physical properties of polyethylene (PE)-based film was investigated. Results indicated that the antibacterial activity of TiO₂-incorporated PE films should be due to the killing effect property of TiO₂ nanoparticles against microorganisms. The TiO₂-incorporated PE film exhibited more effective antibacterial activity for Staphylococcus aureus. The antibacterial activity to inactivate Escherichia coli or S. aureus was improved by UV irradiation. The inhibition ratio of TiO₂-incorporated PE films sample irradiated for 60 min by UV light was improved significantly, which were 89.3% for E. coli and 95.2% for S. aureus, respectively, compared to that of TiO₂-PE film without UV irradiation. The analysis of physical properties revealed that TiO₂ nanoparticles increased the tensile strength and elongation at break of PE-based film. The climate resistance of nano-TiO₂ films is greatly enhanced, compared to that of the blank PE film. Water vapor transmission increased from 18.1 to 24.6 g/m²·24 h with the incorporation of TiO₂ nanoparticles. Results revealed that PE based film incorporating with TiO₂ nanoparticles have a good potential to be used as active food packaging system.     

Morphologies of nanostructured TiO2 doped with F on Ti–6Al–4V alloy

The formation of nanotubes in sulphuric/hydrofluoric acid electrolyte at controlled voltage is investigated on Ti–6Al–4V alloy used for load-bearing prosthetic applications. The effects of anodizing time and voltage on film morphology, composition and microstructure are studied by scanning and transmission electron microscopy, Rutherford backscattering spectroscopy (RBS), and Raman spectroscopy. Fluorine content in the films was of a particular interest for enhancement of antibacterial properties of the surface. The efficiencies of film formation are determined as about 40% and 80% for anodizing at 20 V and 60 V respectively for shorter anodizing time and as about 1 and 5% for longer anodizing time. For 5 min of anodizing, higher voltage conditions results in a thicker barrier layer. At extended anodizing time a further disruption of the nanotubular morphology and formation of approximately 1.5 μm-thick nanoporous film is promoted. The films grown at 20 V contain from 4 at.% to 6 at.% of fluorine. RBS detects about 13 at.% of fluorine incorporated in the film formed at 60 V for 60 min, possibly associated with a greater film thickness. The oxide film material consists of amorphous titania matrix doped with V₂O₅ and Al₂O₃.     

Effect of PbTiO3 seed layer on the orientation behavior and electrical properties of Bi(Mg1/2Ti1/2)O3–PbTiO3 ferroelectric thin films

High Curie-temperature 0.63Bi(Mg_1/2Ti_1/2)O₃–0.37PbTiO₃ (BMT–PT) films were fabricated on Pt(111)/Ti/SiO₂/Si substrates by the sol–gel spin-coating method. The oriented growth behavior of thin films was controlled by introducing a PT seed layer onto the platinum electrode surface. The effect of the annealing method of the PT seed layer on the orientation behavior and electrical properties of BMT–PT films was investigated. It was found that BMT–PT thin film exhibits higher (100) orientation degree when the PT seed layer was treated by rapid thermal annealing. The dielectric permittivity increases while the remanent polarization and coercive field decrease with increasing the (100) orientation degree. These results were explained according to the relationship between the preferential orientation and the spontaneous polarization directions of the films.     

Effect of GO/CS/PbS nanocomposite films on tetraethyoxysilane sensing

In this work, a new method for generating highly fluorescent graphene oxide (GO)/chitosan (CS)/PbS nanocomposite films in a mild environment was developed via electrostatic interactions and in situ growth methods. The growth of PbS nanoparticles was initiated by ion complexation with –NH₂ in the CS chain, followed by the thioacetamide treatment of S^2? obtained from decomposed samples. Moreover, the distinct features of the nanocomposite films were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, UV–vis, and scanning electron microscopy. Polymer molecules could control nucleation and PbS growth on the surface of GO/CS films to stabilize nanoparticles. The fluorescence spectral measurements clearly showed that the fluorescence of the nanocomposite film was gradually enhanced with tetraethyoxysilane addition. This enhancement was ascribed to the gradual decrease in solvent polarity. Moreover, the CS conformation changed in an extension state, which increased the distance between PbS and GO and reduced their quenching effect. The fluorescence results revealed that the GO/CS/PbS nanocomposite films were sensitive to tetraethoxysilane and could easily be recovered and reused for sensing. Therefore, the nanocomposite films may be specific sensor materials for tetraethoxysilane. Such a simple and efficient strategy would provide an opportunity for the large-scale production of various heterostructures with wide potential applications in the sensing field.     

A design of Ti-6Al-4V/ZrB2 multilayers with good thermal stability to enhance mechanical properties of titanium alloy

The inserting a ZrB₂ modulation layer into TC4 (Ti-6Al-4V) film to form TC4/ZrB₂ multilayers was developed to improve the performance of TC4 film. The enhanced crystallinity of ZrB₂ not only enhanced mechanical properties of multilayers with the modulation ratio decreases, but also restricted the propagation of shear bands and promoted the nucleation of new shear bands, which was of help for the plasticity enhancement of TC4 layer. Moreover, the highest hardness (22.54 GPa) and elastic modulus (262.25 GPa) values were reached at l_TC4:l_ZrB2 of 1:5, and the law of variation was like that simulated by the rule of mixture. The highest critical fracture load (L_max= 57.6 mN). With the stability of the mixed interface, the multilayers also exhibited excellent thermal stability. High temperature annealing experiments proved that the multilayers maintain good microstructure and the hardness increased about 3 GPa after annealed.     

Preparation,characterization, antibacterial properties,and hemostatic evaluation of ibuprofen‐loaded chitosan/gelatin composite films

Ibuprofen‐loaded chitosan/gelatin (CS/GE) composite films were fabricated in this work. The morphology of the composite film was investigated using scanning electron microscopy. The functional groups of the composite film before and after crosslinking were characterized using Fourier transform infrared spectroscopy. Meanwhile, the mechanical properties, antibacterial performance, cytocompatibility, and hemostatic activity of the composite films were investigated. The results show that the amount of CS affected the mechanical properties and liquid uptake capacities of the composite films. The composite film showed better bactericidal activity against Staphylococcus aureus than Escherichia coli. In vitro drug‐release evaluations showed that crosslinking could control the drug‐release rate and period in wound healing. Both types of CS/GE and drug‐loaded CS/GE composite films also showed excellent cytocompatibility in cytotoxicity assays. The hemostatic evaluation indicated that the composite film crosslinked by glutaraldehyde in rabbit livers had a dramatic hemostatic efficacy. Therefore, ibuprofen‐loaded CS/GE composite films are potentially applicable as a wound dressing material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45441.     

Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Improvement in the properties of PAN‐based carbon films by modification with cobaltous chloride

Carbon films were developed from polyacrylonitrile (PAN) modified with cobalt chloride. The modification was carried out by immersing PAN in a 5% cobaltous chloride (CoCl₂) solution at 90°C for 5 min, oven‐dried, and then manufactured into films. The original and modified PAN films were oxidized at 220°C for 2 and 6 h in air, respectively, and finally carbonized at 1300°C. The density, microstructure, elemental analyzer, electrical conductivity, and morphology were all studied. According to the results, it was found that films modified with cobalt chloride have a greater stacking height of carbon‐layer planes (L_c), density, electrical conductivity, and nitrogen content after carbonization. Moreover, during the carbonization stage, the cobalt ions promote a catalytic action. The carbon films developed from the modified film not only improved electrical conductivity by 12–38%, but also increased tensile strength by 29–36% and the tensile modulus by 69–110%. Therefore, carbon films having better mechanical properties can be obtained after such modification. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1745–1751, 1999     

Synthesis and investigation of desalinating,antibacterial, and mechanical properties of tetraethylorthosilicate crosslinked chitosan/polyethylene glycol (PEG-300) membranes for reverse osmosis

Solution casting method was used to synthesize chitosan (CS)-based membranes for reverse osmosis (RO) using PEG-300 and tetraethylorthosilicate as a crosslinker. Their salt rejection (%) and permeate flux (mL/h.m²) was measured by using lab scale RO plant. FTIR spectroscopy reveals interactions between CS and PEG by shifting of  OH peak from 3237 cm⁻¹ to lower wavenumber in modified membranes. SEM results showed pores in modified membranes while pure CS membranes had uniform nonporous and dense microstructure. DMA results demonstrated that the addition of PEG lowers the T_g value up to 6.5%. Water content of membranes increases up to 82.63% as the amount of PEG increases owing to its hydrophilic nature. The bacterial killing ability showed that the modified membranes possess good antibacterial activity against Escherichia coli in comparison to the control film. The permeation results revealed that salt rejection and flux of the modified membranes increased up 60% and 86.36 mL/h.m², respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48870.     

Polarization characteristics of poly(vinyl alcohol) films containing metal iodide

The polarization properties of iodine complex layer deposited by oxidation of poly(vinyl alcohol) (PVA) containing metal iodide were investigated. Heat-resistant polarizing films with high polarization efficiency were produced by oxidizing and stretching the PVA containing metal iodide. The results indicate that i) the polarization efficiency of a polarizing film prepared by oxidation of a PVA film containing 1 mmol or more of potassium iodide (KI)/g PVA at 0°C for 120 s in a 10 wt.-% aqueous solution of H₂O₂ and a degree of stretching of 400% is high, ii) the heat resistance of the polarizing film in this experiment is higher than that of a filter prepared from a commercial PVA film.     

In situ plasma diagnostics of the chemistry behind sulfur doping of CVD diamond films

Microwave plasma enhanced chemical vapour deposition (CVD) has been used to grow sulfur doped diamond films using a 1% CH₄/H₂ gas mixture with various levels of H₂S addition (100–5000 ppm), upon undoped Si substrates. X-Ray photoelectron spectroscopy has shown that S is incorporated into the diamond at number densities (≤0.2%) that are directly proportional to the H₂S concentration in the gas phase. Four-point probe measurements showed the resistivity of these S-doped films to be a factor of three lower than undoped diamond grown under similar conditions. Sulfur containing diamond film was also obtained using a 0.5% CS₂/H₂ gas mixture, although the high resistivity of the sample indicated that the sulfur had been incorporated into the diamond lattice in a different manner compared with the H₂S grown samples. Molecular beam mass spectrometry has been used to measure simultaneously the concentrations of the dominant gas phase species present during growth, for a wide range of H₂S doping levels (1000–10 000 ppm in the gas phase). CS and CS₂ have been detected in significant concentrations in the plasma region as a result of gas phase reactions. Additional measurements from a 1% CS₂/H₂ plasma gave similar species mole fractions except that no CS was detected. These results suggest that CS may be the first step toward CS bond formation in the film and thereby a pathway allowing S incorporation into diamond. Optical emission spectroscopy has shown the presence of S₂ in both gas mixtures, consistent with the observed deposition of sulfur on the cool chamber walls.