Synthesis and characterization of polyester bionanocomposite membrane with ultrasonic irradiation process for gas permeation and antibacterial activity

Optically active bionanocomposite membranes composed of polyester (PE) and cellulose/silica bionanocomposite (BNCs) prepared with simple, green and inexpensive ultrasonic irradiation process. It is a novel method to enhance the gas separation performance. The novel optically active diol containing functional trifluoromethyl groups was prepared in four steps reaction and it was fully characterized by different techniques. Commercially available silica nanoparticles were modified with biodegradable nanocellulose through ultrasonic irradiation technique. Transmission electron microscopy (TEM) analyses showed that the cellulose/silica composites were well dispersed in the polymer matrix on a nanometer scale. The mechanical properties nanocomposite films were improved by the addition of cellulose/silica. Thermo gravimetric analysis (TGA) data indicated an increase thermal stability of the PE/BNCs in compared to the pure polymer. The results obtained from gas permeation experiments showed that adding cellulose/silica to the PE membrane structure increased the permeability of the membranes. The increase in the permeability of the gases was as follows: P_CH4 (38%) <P_N2 (58%) <P_CO2 (88%) <P_O2 (98%) Adding silica nanoparticles into the PE matrix, improved the separation performance of carbon dioxide/methane and carbon dioxide/nitrogen gases. Increasing the cellulose/silica mass fraction in the membrane increased the diffusion coefficients of gases considered in the current study. Further, antimicrobial test against pathogenic bacteria was carried out.     

Comparing the Effect of Sodium-Based and Calcium-Based Crosslinkers on the Swelling,Mechanical and Rheological Properties of Chitosan/Gelatin/Starch Films

Abstract

In this research chitosan/gelatin/starch films with a 47.5/47.5/5.0 (vol.%) composition were prepared by a solution casting method. To improve the mechanical and rheological properties of the chitosan-based films, two types of chemical crosslinkers, sodium triphosphate (STP) and calcium triphosphate (CTP), were used and the effects of these crosslinkers on the mechanical properties, swelling, water vapor transmission rate (WVTR) and the rheological-mechanical spectroscopy (RMS) of the films were investigated. For each crosslinker, two concentrations (0.05 and 0.1?wt% solutions) were used. The tensile test results showed that the samples with 0.05?wt% of STP or 0.1?wt% of CTP, had the best performance in enhancing the tensile strength and modulus of the films. The swelling tests indicated that 0.05?wt% of STP had the lowest swelling, and the performance with 0.1?wt% of CTP was also good. The results of the WVTR tests revealed that 0.05?wt% of STP and 0.1?wt% of CTP had the least and the most WVTR, respectively. Also, antibacterial tests were evaluated for the films based on an inhibition zone technique, and the results showed that the films containing the STP crosslinker has the best antibacterial activity. The RMS results indicated that the rheological properties of the films were enhanced by incorporating the crosslinkers, especially 0.1% concentration of CTP, into the film formulations.     

The modification of pomegranate polyphenol with ultrasound improves mechanical,antioxidant, and antibacterial properties of tuna skin collagen-chitosan film

To produce an edible film with high mechanical and physicochemical properties, Tuna skin collagen-chitosan (TSC-CTS) composite films were prepared by incorporating ultrasound (UT) and pomegranate polyphenols including gallic acid (GA), tannic acid (TA), and ellagic acid (EA), respectively. The tensile strength and the DPPH scavenging activity of the GA-UT-TSC-CTS film (ultrasound frequency of 28 ± 0.5 kHz, power of 100 W/L, sweep frequency cycle of 100 ms, duty ratio of 77% and time of 10 min; GA concentration of 1.0 g/L and reaction time of 10 min) were increased by 47.03% and 24.16 folds, respectively compared to the control (TSC-CTS film). Meanwhile, light transmittance and water vapor permeability of the GA-UT-TSC-CTS film were decreased by 29.26% and 15.70%, respectively. These positive modification results were attributed to the altered structure during the film formation process, which were verified by Fourier transform infrared spectroscopy (FTIR), circular dichroism (CD), X-ray diffraction (XRD), and thermogravimetry results. Moreover, the GA-UT-TSC-CTS film possessed moderate thermal stability and color indexes and improved antibacterial activity. The antibacterial effect of the film against Bacillus subtilis was the highest, followed by Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus. Overall, the combination modification of gallic acid and ultrasound was an efficient modification method to improve the mechanical, antioxidant, and antibacterial properties of edible TSC-CTS films.     

Effect of substrate interactions on the melting behavior of thin polyethylene films

Polymer films have been known to change their physical properties when film thickness is decreased below a certain value. The cause of this phenomenon is still unclear but it has been suggested that interactions and/or chain free-volume changes at the surface of the films are largely responsible for this behavior. In this paper, the effect of substrate interactions on the behavior of polymer thin films is evaluated quantitatively. The infrared spectra of nanothin polyethylene (PE) films were recorded as a function of temperature and amount of substrate covering the surface of the film. The evolution of specific bands in the CH₂ rocking region of the spectra was used to determine the melting temperature (T _m ) of the material. Results show different variations in T _m depending on the nature of the substrate, indicating that interactions dominate free-volume considerations in PE thin films. By varying the amount of surface coverage, a quantitative estimate of the heat of interaction was determined, which confirmed the importance of surface interactions.     

Preparation and Properties of Antimicrobial Poly(butylene adipate-co-terephthalate)/TiO2 Nanocomposites Films

Abstract

Poly(butylene adipate-co-terephthalate) (PBAT) nanocomposite films with various contents of nano-titanium dioxide (TiO₂) and titanium dioxide doped silver (Ag-TiO₂) were prepared by a solvent casting method. The TiO₂ and Ag-TiO₂ nanoparticles were surface-modified with silane coupling agents to improve their compatibility and dispersibility in the PBAT matrix. They were denoted as mTiO₂ and mAg-TiO₂, and were characrterized by Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). The morphology of the PBAT nanocomposite films was studied by field emission scanning electron microscopy (FE-SEM). The crystallinity of the PBAT film increased upon the introduction of the nano-TiO₂/Ag-TiO₂. Its mechanical properties and gas barrier properties were also significantly improved. In addition, the PBAT/mTiO₂ and PBAT/mAg-TiO₂ nanocomposite films showed a strong antibacterial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) food-borne pathogenic bacteria.     

Electrical,optical and mechanical properties of PS/GNP composite films

In this study, the electrical, optical and mechanical properties of polystyrene (PS) thin films added graphene nanoplatelet (GNP) have been investigated. Surface conductivity (σ), absorbance intensity (A) and tensile modulus of these composite films have increased with increasing the content of GNP in the composite. The increase in the electrical and optical properties of the PS/GNP composite films has been interpreted by site and classical percolation theory, respectively. The electrical and the optical percolation thresholds of PS/GNP composite films were determined as R_σ?=?23.0?wt.% and R_op?=?13.0?wt.%, respectively. While the conductivity results have been attributed to the classical percolation theory, the optical results have attributed to the site percolation theory. The electrical (β_σ) and the optical (β_op) critical exponents were calculated as 2.54 and 0.40, respectively. The tensile modulus and the tensile strength of the PS/GNP composites increased with the increasing of GNP content in the PS. But, the toughness of the composites fluctuated with GNP addition.     

Biomedical properties of laser prepared silver-doped hydroxyapatite

Thin films of hydroxyapatite (HA) and silver-doped HA were synthesized using KrF excimer laser deposition. Material was ablated from one target composed from silver and HA segments. Layers properties as silver content, structure, color, FTIR spectra and antibacterial properties (Gram-positive Bacillus subtilis) were measured. Silver concentration in HA layers of 0.06, 0.3, 1.2, 4.4, 8.3, and 13.7 at % was detected. The antibacterial efficacy changed with silver dopation from 71.0 to 99.9%. The focus is on investigation of minimum Ag concentration needed to reach a high antibacterial efficacy.     

Studies on Comonomer Compositional Distribution of Poly(propylene carbonate-propylene oxide) Copolymer and Its Effect on the Thermal,Mechanical and Oxygen Barrier Properties of Fractions

Poly(propylene carbonate) (PPC) was synthesized by the alternating copolymerization of carbon dioxide and propylene oxide (PO). However, during the polymerization, two by-products tended to produce cyclic propylene carbonate (CPC) and a polyether (PE) segment. The excess PO repeat units (PE segment) can easily insert into the PPC backbone and eventually produce the PPC–PO copolymer. The production of CPC and PE segments affected the increase of polymer chain length. In order to investigate the effects of the existence of PE segments, CPC, and molecular weight of fractions on the physical properties of PPC–PO copolymer, a series of fractions with narrow molecular weight distribution were obtained by repeated fractionation. Based on a solvent/non-solvent (chloroform/n-heptane) mixture, an original PPC–PO sample was fractionated into nine fractions with number–average molecular weights (M_n) from 0.34 × 10⁵ to 5.56 × 10⁵ and PE content from 0.4 to 15 mol%. The M_n of PPC–PO fractions decreased with the increase of PE content in the PPC–PO backbone, and the thermal and mechanical properties of the PPC–PO copolymers were affected by their M_n and PE contents. Furthermore, the lower the PE content, the higher the M_n value. Higher M_n means better tensile and lower oxygen permeability of PPC–PO copolymer.     

Morphology and mechanical properties of reconstituted wood board waste-polyethylene composites

The morphology and mechanical properties of reconstituted wood board waste-polyethylene composites were studied using virgin polyethylene (PE) and 2 wt% maleic anhydride (MA) modified polyethylene (MAPE) as matrices. Although the wood waste (WW) and PE are not compatible with each other, dynamic mechanical analyses (DMA) show considerable shifting in the α-transition temperature and crystallisation temperature (T _c) of PE in the unmodified composites, indicating physical interaction between PE and WW. The increase in crystallinity with increasing WW content up to 50 wt% indicates that WW is a potential nucleating agent for PE. However, the tensile strength of the unmodified composites gradually decreases with WW content, indicating that the improvement in interface adhesion is essential for WW to be used as reinforcing fillers. Fourier transform infrared spectroscopic (FTIR) results indicate that MAPE interacts with WW through esterification and hydrogen bonding to form good adhesion between the two phases. Inward shifting in glass transition temperature (T _g) for the MAPE-based composites containing less than 60 wt% WW indicates that WW and MAPE are partially compatible with each other. SEM micrographs of MAPE-based composites provide further evidence for this mechanism. The tensile strength of the MAPE-based composites is clearly higher than that of the virgin PE-based composites.     

Effect of Polyethylene Functionalization on Mechanical Properties and Morphology of PE/SiO2 Composites

In this study composites of high density polyethylene (HDPE) with various SiO₂ content were prepared by melt compounding using maleic anhydride grafted polyethylene (PE-g-MAH) as a compatibilizer. The composites containing 2, 4 and 6% by weight of SiO₂ particles were melt-blended in a co-rotating twin screw extruder. In all composites, polyethylene-graft-maleic anhydride copolymer (PE-g-MAH, with 0.85% maleic anhydride content) was added as a compatibilizer in the amount of 2% by weight. Morphology of inorganic silica filler precipitated from emulsion media was investigated. Mechanical properties and composite microstructure were determined by tensile tests and scanning electron microscopy technique (SEM). Tensile strength, yield stress, Young's modulus and elongation at break of PE/SiO₂ composites were mainly discussed against the properties of PE/PE-g-MAH/SiO₂ composites. The most pronounced increase in mechanical parameters was observed in Young's modulus for composites with polyethylene grafted with maleic anhydride. The increase in the E-modulus of PE/PE-g-MAH/SiO₂composites was associated with the compatibility and improvement of interfacial adhesion between the polyethylene matrix and the nanoparticles, leading to an increased degree of particle dispersion. This finding was verified on the basis of SEM micrographs for composites of PE/PE-g-MAH/4% by weight of SiO₂. The micrographs clearly documented that addition of only 2 wt% of the compatibilizer changed the composite morphology by reducing filler aggregates size as well as their number. Increased adhesion between the PE matrix and SiO₂ particles was interpreted to be a result of interactions taking place between the polar groups of maleic anhydride and silanol groups on the silica surface. These interactions are responsible for reduction of the size of silica aggregates, leading to improved mechanical properties.     

Interfacial structure analysis of polymer laminate using SPring-8 X-ray microbeam

Interfacial structure of laminated polyethylene (PE)/polypropylene (PP) films was investigated by synchrotron X-ray microbeam. The X-ray microbeam (0.9 μm (vertical) × 1.7 μm (horizontal)) formed using a phase zone plate was irradiated on the cross-section of the laminated films. In order to irradiate X-ray microbeam in the direction perpendicular to the cross-section of the film sample, adjustment of the sample setting was performed by Thomson scattering method. The Thomson scattering intensity is proportional to the number of the irradiated electrons, so the irradiated position of the X-ray microbeam could be determined from the intensity profile with high spatial resolution. By changing the sample position, diffraction patterns could be obtained from the laminated films across the PE/PP interfacial region. The thickness of the interfacial region of the annealed laminate was estimated as 5 μm judging from the changes of the diffraction intensities from the PE crystallites to the PP ones. The interfacial thickness depended on the thermal treatment of the film. It was found that the adhesion strength of the PE/PP laminate increased with increasing the interfacial thickness. Both of PE and PP chains entangled each other during laminate processing. The entangled molecular chains play important role as anchoring effect at the PE/PP interdiffusion region. However, the phase separation progressed with further crystallization by annealing. Thus, the adhesion strength of the PE/PP laminate was considered to be influenced by the interfacial thickness.     

Influence of the nitrogen contents on the permeability characteristics and soft magnetic properties of FeHfN films

High permeability magnetic films can enhance the inductance of thin-film inductors in DC-DC converters. In order to obtain high permeability, the uniaxial anisotropy and coercivity should be as low as possible. This study employed dc reactive magnetron sputtering to fabricate nanocrystalline FeHfN thin films. The influence of the nitrogen flow on the composition, microstructure, and permeability characteristics, as well as magnetic properties was investigated. Increasing the nitrogen content can alter FeHfN films from amorphous-like to crystalline phases. The magnetic properties and permeability depend on variations in the microstructure. With the optimum N₂/Ar flow ratio of 4.8% (N₂ flow: 1.2 sccm), low anisotropy (H_K = 18 Oe), low coercivity (H_C = 1.1 Oe) and high permeability (μ′ > 600 at 50 MHz) were obtained for fabrication of a nanocrystalline FeHfN film with a thickness of around 700 nm. Such as-fabricated FeHfN films with a permeability of over 600 should be a promising candidate for high-permeability ferromagnetic material applications.     

沉积参数对SiNx薄膜结构及阻透性能的影响

利用直流脉冲磁控溅射法在室温下制备无氢SiN_x薄膜.通过傅里叶变换红外光谱、台阶仪、紫外—可见分光光度计、接触角测量仪、透湿测试仪等表征技术,分析了N₂流量、Si靶溅射功率等实验参数对SiN_x薄膜成分、结构、及阻透性能、透光性能、接触角等性能的影响.研究结果表明,Si靶溅射功率固定时,在低N₂流量条件下,或N₂流量固定时,在高Si靶溅射功率条件下,制备的SiN _{关键词： x}')" href="#">SiN_x 磁控溅射 微观结构 阻透性能     

Preparation and characterization of anhydrous polymer electrolyte membranes based on poly(vinyl alcohol-<Emphasis Type="Italic">co</Emphasis>-ethylene) copolymer

Anhydrous polymer electrolyte membranes with cross-linked structure have been prepared based on poly(vinyl alcohol-co-ethylene) (PVA-co-PE) copolymer. The PVA units of copolymer served to induce thermal cross-linking with 4,5-imidazole dicarboxylic acid (IDA) via esterification while PE units controlled the membrane swelling and the mechanical properties of films. Upon doping with phosphoric acid (PA, H₃PO₄) to form imidazole-PA complexes, the proton conductivity of membranes continuously increased with increasing PA content. As a result, proton conductivity reached 0.01 S/cm at 100 °C under anhydrous conditions. X-ray diffraction analysis revealed that both the d-spacing and crystalline peak of membranes were reduced upon introduction of IDA/PA due to the cross-linking effect. The PVA-co-PE/IDA/PA membranes exhibited good mechanical properties, e.g., 150 MPa of Young’s modulus, as determined by a universal testing machine. Thermal gravimetric analysis also represented that the thermal stability of membranes was increased up to 200 °C upon introduction of IDA/PA.     

The physical,mechanical, thermal and barrier properties of starch nanoparticle (SNP)/polyurethane (PU) nanocomposite films synthesised by an ultrasound-assisted process

This article reports on the ultrasound-assisted acid hydrolysis for the synthesis and evaluation of starch nanoparticles (SNP) as nanofillers to improve the physical, mechanical, thermal, and barrier properties of polyurethane (PU) films. During the ultrasonic irradiation, dropwise addition of 0.25 mol L^-1 H₂SO₄ was carried out to the starch dispersion for the preparation of SNPs. The synthesized SNPs were blended uniformly within the PU matrix using ultrasonic irradiation (20 kHz, 220 W pulse mode). The temperature was kept constant during the synthesis (4 °C). The nanocomposite coating films were made with a regulated thickness using the casting method. The effect of SNP content (wt%) in nanocomposite coating films on various properties such as morphology, water vapour permeability (WVP), glass transition temperature (Tg), microbial barrier, and mechanical properties was studied. The addition of SNP to the PU matrix increased the roughness of the surface, and Tg by 7 °C, lowering WVP by 60% compared to the PU film without the addition of SNP. As the SNP concentration was increased, the opacity of the film increased. The reinforcement of the SNP in the PU matrix enhanced the microbial barrier of the film by 99.9%, with the optimal content of SNP being 5%. Improvement in the toughness and barrier properties was observed with an increase in the SNP content of the film.     

In Vitro Assessment of Poly (Vinyl Alcohol) Film Incorporating Aloe Vera for Potential Application as a Wound Dressing

Since skin tissue acts as a vital protective barrier between the body and the external atmosphere, the repair or regeneration of skin injuries serves as a great challenge in regenerative medicine. Herein, hydrogel films composed of poly vinyl alcohol (PVA) and aloe vera (AV) extracted gel were prepared and characterized for wound dressing application. The physical and morphological properties, water absorption capacity, biodegradation behavior, and water transmission rate were characterized for several variations in the AV content (0–50%). The cytocompatibility of the films, as well as cell morphology in response to different films, was assessed using MTT assay and SEM, respectively. According to the results, AV incorporation improved the surface morphology, water absorption capacity, in vitro degradation rate, and water vapor permeability of the PVA films. However, these properties were affected by the AV content. The mechanical properties of the films were enhanced by introducing AV up to 30%, and then decreased significantly with further AV increase. Evaluation of fibroblast proliferation showed that AV can positively improve the bioactivity of the films without any cytotoxicity. In conclusion, the results demonstrated that PVA/AV optimized hydrogel film can be suggested as promising wound dressings for improving wound treatment.     

Novel ocotillol-derived lactone derivatives: design,synthesis, bioactive evaluation,SARs and preliminary antibacterial mechanism

A new series of ocotillol-derived lactone derivatives were designed and synthesized to consider their antibacterial activity, structure–activity relationships (SARs), antibacterial mechanism and in vivo antibacterial efficacy. Compound 6d, which exhibited broad antibacterial spectrum, was found to be the most active with minimum inhibitory concentrations (MICs) of 1–2 μg/mL against Gram-positive bacteria and 8–16 μg/mL against Gram-negative bacteria. The subsequent synergistic antibacterial tests displayed that 6d had the ability to improve the susceptibility of MRSA USA300, B. subtilis 168, and E. coli DH5α to kanamycin and chloramphenicol. This active molecule 6d also induced bacterial resistance more slowly than norfloxacin and kanamycin. Furthermore, compound 6d was membrane active and low toxic against mammalian cells, and it could rapidly inhibit the growth of MRSA and E. coli and did not obviously trigger bacterial resistance. Compound 6d also displayed strong in vivo antibacterial activity against S. aureus RN4220 in murine corneal infection models. Additionally, absorption, distribution, metabolism, and excretion properties of this type of compounds have shown drug-likeness with good oral absorption and moderate blood–brain barrier permeability. The obtained results demonstrated that ocotillol-derived compounds are a promising class of antibacterial agents worthy of further study.

Graphic abstract

     

Fabrication and characterization chitosan/functionalized zinc oxide bionanocomposites and study of their antibacterial activity

This study deals with preparation and evaluation of properties of chitosan/zinc oxide bionanocomposites (CT/ZnO BNCs) with different amounts of modified zinc oxide nanoparticles (ZnO NPs) through ultrasonic irradiation technique. Due to the high surface energy and tendency for agglomeration, the surface ZnO NPs was modified by a coupling agent as 3-aminopropyltriethoxysilane (APS) to form APS–ZnO nanoparticles. Fourier transform infrared (FTIR) spectroscopy confirmed that APS was successfully grafted onto the ZnO nanoparticles surface. Thermogravimetric analysis (TGA) revealed a surface coverage of the coupling molecule of 2.6 wt%. The resulting bionanocomposites were characterized by FTIR spectra, X-ray diffraction patterns, and TGA. The antibacterial activity of bionanocomposite films was tested against gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). The results of CT/ZnO BNCs revealed that the thermal and antibacterial properties obviously improved the presence of ZnO NPs in comparison with the pure CT and that this increase is higher when the NP content increases. Further, it was observed that antibacterial activity of the resulting hybrid biofilms showed somewhat higher for gram-positive bacteria compared to gram-negative bacteria.     

Supermolecular structure and orientation of blown cellulosic films

N-Methylmorpholine-N-oxide (NMMO) technology provides new possibilities for shaping fibers and films from cellulose. We discuss a blow-extrusion technique can be applied to a cellulose-amine oxide dope, yielding blown cellulosie films. Process parameters, such as the draw down ratio and the blow ratio, can be used to control the mechanical film properties in both the machine and transverse directions. In this way, a wide range of properties is covered, and a completely balanced film can be manufactured. The film thickness can be made as small as 5 μm, and the membrane properties can be varied by the conditions of precipitation. The blown cellulosic films exhibit a partially crystalline supermolecular structure and, depending on the coagulation conditions, a symmetrical or asymmetrical homogeneous morphology and pore structure. Generally, a uniplanar orientation type was found, the chains being parallel to the film surface. Around the surface normal, the chain orientation can be varied from nearly random to strongly uniaxial, in this way determining the mechanical properties in the machine and transverse directions. As compared with the conventional viscose processing route of cellophane, the blown film's NMMO processing route is less complicated and friendlier to the environment. Blown films can be made much thinner, and the mechanical properties are superior to viscose films. Possible application fields of blown cellulose films are food casings, particularly small sausage casings, packaging, and membranes.     

New packaging solutions for high pressure treatments of food

Abstract

High pressure is a promising technology for developing new processes in food treatment. In most cases, pre-packaged foods are used in high pressure treatments (HP). Consequently, the behavior of the package under treatment conditions is an important factor. The following work was devoted to the evaluation of different packages under high pressure conditions in the presence of different substances used as simulants. Three main characterizations were carried out after HP treatment: mechanical resistance, barrier properties and integrity.

The experimental results using multilayer plastic films (PA/PE) have led to the selection of several solutions which may be used as packages for high pressure treatments.