Fabrication Of Composite Films Research Articles

Strategies for alkali-free synthesis, surface modification, and electrophoretic deposition of composite films for biomedical applications

This investigation addresses increasing interest in composites for biomedical applications and advanced methods for their synthesis and electrophoretic deposition (EPD). The feasibility of preparation of hydroxyapatite (HA), titania and zirconia particles using branched polyethylenimine polymer (BPEI) or L-arginine amino acid as organic alkalizers is demonstrated. In this new approach, BPEI and L-arginine are used as alkalizers-capping agents instead of inorganic alkalis. The use of BPEI facilitates synthesis of HA nanorods with reduced size. This approach opens an avenue for the fabrication of nanoparticles of other functional inorganic materials using alkalizers-capping agents. It offers advantages of simple procedure, environmental benefits and improved control of particle size. Composite films are obtained by cathodic EPD using linear polyethylenimine (LPEI) as a charging and film-forming agent. A conceptually new approach is developed for anodic EPD of alginic acid polymer (AlgH) and composite films containing drug molecules in AlgH matrix. This strategy involves the use of L-arginine as an alkalizer for solubilization of drugs, which exhibit poor solubility in water. AlgH and drug molecules are solubilized in water and deposited by anodic EPD. Testing results confirm the fabrication of composite films, containing drug molecules. This method allows reduced gas evolution at the electrode, elimination of film porosity, improved stabilization of bioceramic particles in polymer solutions and facilitates composite film formation from stable suspensions. The deposition methods developed in this investigation can be used for deposition of other cationic and anionic polymers and their co-EPD with bioceramics, drugs and other functional materials.

Sub-micron alkylated graphene oxide from coal

Sub-micron graphene oxide (GO) has emerged as a promising additive in the realms of composite films and fibers applications. Traditional GO preparation involves acid oxidation of high-purity graphite, yielding particles in micron scale. Achieving sub-micron dimensions typically demands rigorous conditions, leading to increased defects with low yield. In this study, the sp2 carbon domain from anthracite first undergoes graphitization, growing from nano to sub-micron scale, then sub-micron GO is extracted via oxidatively severing its bridging bonds. The resulting GO exhibits an average size of 800 nm, a thickness of 1-2 layers, and a yield of 107%. This methodology is applicable to bituminous and lignite as well. Furthermore, the broken bridging bonds act as alkyl danglings on sub-micron GO and serving as anchors in composites through hydrogen bonding. The reinforcing efficacy of sub-micron GO is demonstrated through the fabrication of composite films and fibers. This work pioneers cost-effective production of high-quality sub-micron GO, elevating coal’s value through advanced applications.

Visible light-responsive vitamin B2 functionalized ZnO with dual-mechanism bactericidal effects for perishable agrofood preservation

Recent advances in functionalized micro-nanostructures have enlightened promising non-thermal-dependent antibacterial strategies with broad applications in preventing agrofood spoilage, clinical infections, and environmental pollution caused by pathogens. These advances highlight the need for precise design of efficient and multi-mode bactericides. Herein, photosensitive vitamin B2 (VB2) was exploited to functionalize semiconductors with limited visible-light response and intrinsic antibacterial activity, while ZnO served as a paradigm for the fabrication of VB2-functionalized zinc oxide (VB2-ZnO) with persistent antibacterial effects. The enhanced visible photocatalytic activity and the released Zn2+ in VB2-ZnO contribute to potent antibacterial and anti-biofilm effects by disrupting bacterial structures and inducing oxidative stress. Furthermore, the successful fabrication of composite films incorporating VB2-ZnO and natural locust bean gum (LBG) exhibited improved physicochemical properties and persistent antibacterial effects, resulting in the shelf-life extension of perishable berries. This work pioneers a novel approach to functionalizing semiconductor photocatalysts with VB2 photosensitizer, offering novel solutions for ensuring agrofood safety through multi-mechanism antibacterial materials.

Application of Cyrene solvent for the fabrication of polymethyl methacrylate, polyethyl methacrylate and composite films containing hydroxyapatite and diamonds

AbstractCyrene is a new biodegradable solvent, which represents a green alternative to many traditional toxic solvents for advanced polymers. Therefore, this investigation is motivated by interest in applications of Cyrene for polymer processing. The feasibility of solubilization of polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) in Cyrene is demonstrated. The ability to form relatively concentrated solutions of the high molecular mass polymers is an important factor for the formation of PMMA and PEMA films by a dip coating method. It was found that the polymer coatings provide corrosion protection of stainless steel in 30 g L−1 NaCl solutions. Another important finding is that the use of Cyrene facilitates the fabrication of stable suspensions of hydroxyapatite (HAp), microdiamond, and nanodiamond particles. Therefore, the problems of the dispersant selection for dispersion of chemically inert diamond and development of biocompatible dispersants are avoided using Cyrene. For the fabrication of composite films, HAp nanorods with reduced particle size are obtained using rutin as a chelating capping agent. Composite films containing HAp, microdiamond and nanodiamond in the PMMA or PEMA matrix are obtained. The composite films are promising for biomedical applications. It was found that the film morphology, composition and microstructure are influenced by the solvent–particle–polymer interactions and processing conditions.

Antibacterial PVDF Coral-Like Hierarchical Structure Composite Film Fabrication for Self-Cleaning and Radiative Cooling Effect.

Passive radiative cooling (PRC) is a zero-energy-consumption technology that reflects sunlight and radiates heat to cold outer space. In this work, a porous poly(vinylidene fluoride)-poly(methyl methacrylate) (PVDF-PMMA) composite film is fabricated by decorating zinc-imidazolate metal-organic framework (MOF) (ZIF-8) particles obtained by phase inversion. Due to the competent scattering via the coral-like hierarchical structures and the vibration excitations of specific functional groups, the prepared film exhibits good solar reflectance (92.6%) and intermediate infrared emittance (99.1%), with an average sub-ambient cooling of 10.4 °C under a solar radiation intensity of 0.6 AM1.5. Additionally, poly(vinylidene fluoride) has a low surface energy, while the ZIF-8 particles and coral-like hierarchical structures enhance the surface roughness, endowing the surface with significant superhydrophobicity characterized by a water contact angle (WCA) of 157.5° and a sliding angle (SA) of 2°. These films exhibit excellent antibacterial properties. When the content of ZIF-8 particles in the film is 300 mg·L-1, the antibacterial rate reaches 100% after 1 h of treatment. Thus, the ZIF-8 porous poly(vinylidene fluoride)-poly(methyl methacrylate) composite (ZPPP) film has potential application prospects in areas with high health and environmental requirements, such as cold chain transportation and public spaces.

Utilization of peanut shell for the fabrication of composite films: a novel biomaterial

Utilization of peanut shell for the fabrication of composite films: a novel biomaterial

A SANS investigation of silk-stabilized aqueous poly(3-hexylthiophene): phenyl-C61-butyric acid methyl ester nanoparticle dispersions

Regenerated silk fibroin (RSF) protein comprising both hydrophilic and hydrophobic chain segments offer great potential for interfacial interaction and stabilization of organic nanoparticles (NPs) in aqueous medium. In this work, aqueous dispersion of poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) NPs of 1:1 weight ratio were prepared using RSF as surfactant for the first time via the mini-emulsion method. The size, morphology, internal structure, interface and hierarchical organization of RSF-stabilized P3HT:PCBM NPs was investigated using UV–visible spectroscopy, contrast-variation small-angle neutron scattering (CV-SANS) and ultra-small-angle neutron scattering (CV-USANS). The P3HT:PCBM NPs were established to be stabilized in the matrix of RSF colloidal microparticles in water. Unlike the commonly used surfactant sodium dodecyl sulfate which produces core–shell (PCBM–P3HT) NPs, the RSF molecules generated P3HT:PCBM NPs with internal structure that resemble phase-separated solvent-cast films. The as-prepared dispersion has good film-forming ability and has been demonstrated for fabrication of composite films comprising graphene oxide.

Facile fabrication of composite film modified electrodes based on vanadium-substituted tungstophosphate with Fe3O4@Au for electrochemical detection of sodium nitrite

The [P2W17V/PEI]n/Fe3O4@Au/GCE composite film was fabricated successfully and displayed improved electrochemical detection of sodium nitrite compared to the single component.

Fabrication of Highly Conductive Porous Fe3O4@RGO/PEDOT:PSS Composite Films via Acid Post-Treatment and Their Applications as Electrochemical Supercapacitor and Thermoelectric Material.

As a remarkable multifunctional material, ferroferric oxide (Fe3O4) exhibits considerable potential for applications in many fields, such as energy storage and conversion technologies. However, the poor electronic and ionic conductivities of classical Fe3O4 restricts its application. To address this challenge, Fe3O4 nanoparticles are combined with graphene oxide (GO) via a typical hydrothermal method, followed by a conductive wrapping using poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic sulfonate) (PEDOT:PSS) for the fabrication of composite films. Upon acid treatment, a highly conductive porous Fe3O4@RGO/PEDOT:PSS hybrid is successfully constructed, and each component exerts its action that effectively facilitates the electron transfer and subsequent performance improvement. Specifically, the Fe3O4@RGO/PEDOT:PSS porous film achieves a high specific capacitance of 244.7 F g-1 at a current of 1 A g-1. Furthermore, due to the facial fabrication of the highly conductive networks, the free-standing film exhibits potential advantages in flexible thermoelectric (TE) materials. Notably, such a hybrid film shows a high electric conductivity (σ) of 507.56 S cm-1, a three times greater value than the Fe3O4@RGO component, and achieves an optimized Seebeck coefficient (S) of 13.29 μV K-1 at room temperature. This work provides a novel route for the synthesis of Fe3O4@RGO/PEDOT:PSS multifunctional films that possess promising applications in energy storage and conversion.

Effects of polyvinyl alcohol incorporation on the physical and antioxidant properties of soy protein isolate/Xanthoceras sorbifolia husk extract active films

The design and development of biomass-based films have attracted extensive attention with the increasing demand for novel biodegradable food packaging materials. Herein, soy protein isolate (SPI) and the extracts of the waste Xanthoceras sorbifolia husk were mixed to fabricate composite films via a casting method. Polyvinyl alcohol (PVA) was further incorporated to establish ternary composite films, and the influence of PVA content (0%, 0.2%, 0.4%, 0.6%, and 0.8% w/v) on the film performance was well evaluated. The characterizations including scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FT-IR), and X-ray diffraction (XRD) demonstrated the excellent compatibility and intermolecular interactions among the components after introducing appropriate PVA. Compared with the control film, the water barrier, mechanical and UV-blocking properties of the composite films were greatly improved due to the presence of PVA, especially at 0.6%. The tensile strength and the water vapor permeability of the reinforced films with 0.6% PVA addition was 10.83 MPa and 0.95 × 10−10 g m m−2 s−1 Pa−1, increased by 47% and reduced by 16%, respectively. The composite films also exhibited excellent DPPH and ABTS radical scavenging capacity. Thus, the functional SPI-based films provide a feasible route for the fabrication of composite films applied for potential active packaging applications.

Composites Based on Poly(ε-caprolactone) and Graphene Oxide Modified with Oligo/Poly(Glutamic Acid) as Biomaterials with Osteoconductive Properties.

The development of new biodegradable biomaterials with osteoconductive properties for bone tissue regeneration is one of the urgent tasks of modern medicine. In this study, we proposed the pathway for graphene oxide (GO) modification with oligo/poly(glutamic acid) (oligo/poly(Glu)) possessing osteoconductive properties. The modification was confirmed by a number of methods such as Fourier-transform infrared spectroscopy, quantitative amino acid HPLC analysis, thermogravimetric analysis, scanning electron microscopy, and dynamic and electrophoretic light scattering. Modified GO was used as a filler for poly(ε-caprolactone) (PCL) in the fabrication of composite films. The mechanical properties of the biocomposites were compared with those obtained for the PCL/GO composites. An 18-27% increase in elastic modulus was found for all composites containing modified GO. No significant cytotoxicity of the GO and its derivatives in human osteosarcoma cells (MG-63) was revealed. Moreover, the developed composites stimulated the proliferation of human mesenchymal stem cells (hMSCs) adhered to the surface of the films in comparison with unfilled PCL material. The osteoconductive properties of the PCL-based composites filled with GO modified with oligo/poly(Glu) were confirmed via alkaline phosphatase assay as well as calcein and alizarin red S staining after osteogenic differentiation of hMSC in vitro.

Lignin self-assembly and auto-adhesion for hydrophobic cellulose/lignin composite film fabrication

Large amounts of lignin are produced as a by-product of paper pulping, resulting in a tremendous waste of natural resources with potential uses across various areas. To achieve the value-added utilization of agricultural waste and lignin, we developed a method for the fabrication of a lignin structure-designed hydrophobic film (LSHF) directly through solvent/anti-solvent self-assembly (acetic acid aqueous solution/n-hexane) and auto-adhesion of acetic acid lignin (AL) on the surface of a lignocellulose film (LCF). As the morphology structure revealed, the LSHF had a rough surface composed of lignin colloidal spheres, which significantly improved the water contact angle (WCA) from ~80° to ~130°. Furthermore, benefiting from the auto-adhesion of lignin, the WCA was more stable in 240 s, demonstrating that the LSHF had a lower WCA decrease (15.53 % – 25.55 % decrease) than the LCF (41.97 % – 61.11 % decrease) and the sample without auto-adhesion (100 % decrease). Simultaneously, auto-adhesion endowed the LSHF with a ~50 % increase in tensile strength. This work provides a novel strategy for the fabrication of hydrophobic cellulose/lignin composite films via lignin self-assembly and auto-adhesion.

LOW-TEMPERATURE CATALYZED GROWTH AND PLASMONIC PROPERTIES OF COLUMNAR Au-SiOx NANOCOMPOSITE THIN FILMS

The optical properties of noble metal nanoparticles (NPs) can be efficiently controlled by their incorporation into host matrix films. Here, we report on the fabrication of composite films of gold NPs in a silicon suboxide matrix by a novel approach using a combination of pulsed laser deposition for NP production and gas-jet, electron-beam plasma chemical vapor deposition for low-temperature (300°C) synthesis of a SiO<sub>x</sub> (x = 0.38-1.55) thin film as a matrix for the NPs. The produced nanocomposite exhibits unexpected plasmonic properties, non-monotonically dependent on the matrix thickness, due to a porous columnar matrix structure grown from the NPs with variable oxygen content along the columns. This implies that low-temperature, gold-catalyzed oxidation of silicon occurs during the structure growth. Calculations based on Mie theory show that the refractive index of the obtained SiO<sub>x</sub> matrix can be as low as 1.2 at certain film thicknesses. Mechanisms of the columnar structure formation at different deposition stages are discussed. The synthesis approach can be used for the fabrication of optical thin-film materials with controllable low refractive index.

Biodegradable, Flexible and Ultraviolet Blocking Nanocellulose Composite Film Incorporated with Lignin Nanoparticles

The exploration of functional films using sustainable cellulose-based materials to replace plastics has been of much interest. In this work, two kinds of lignin nanoparticles (LNPs) were mixed with cellulose nanofibrils (CNFs) for the fabrication of composite films with biodegradable, flexible and ultraviolet blocking performances. LNPs isolated from p-toluenesulfonic acid hydrolysis was easily recondensed and deposited on the surface of composite film, resulting in a more uneven surface; however, the composite film consisting of CNFs and LNPs isolated from maleic acid hydrolysis exhibited a homogeneous surface. Compared to pure CNF film, the composite CNF/LNP films exhibited higher physical properties (tensile strength of 164 MPa and Young's modulus of 8.0 GPa), a higher maximal weight loss temperature of 310 °C, and a perfect UVB blocking performance of 95.2%. Meanwhile, the composite film had a lower environmental impact as it could be rapidly biodegraded in soil and manmade seawater. Overall, our results open new avenues for the utilization of lignin nanoparticles in biopolymer composites to produce functional and biodegradable film as a promising alternative to petrochemical plastics.

A W-Band High Radiation Efficiency With BCB-Air Cavity-Backed Antenna Based on Through Silicon Ring Trench

The design of a W-band BCB-air cavity-backed antennas is presented in this letter. The three-dimensional (3-D) capacitance model of the cavity-backed structure is analyzed and the design methodology is illustrated in detail. The proposed antenna is fabricated by using our in-house silicon-based MEMS photosensitive composite film fabrication process by combining localized backside etching technology and through silicon ring trench. The measured impedance bandwidth (−10 dB) of the antenna is from 88.9 to 93.7 GHz with a maximum gain 8.2 dBi and 95% radiation efficiency at 91 GHz, higher the gain and radiation efficiency by 2.2 dB and 35%, respectively, as compared with the case without TSRT. The measured results show close agreement with the simulated results. The proposed antenna can be further 3-D heterogeneously integrated with other components because of low interconnection loss to enhance the high-frequency performance for future millimeter wave radar and communication systems.

Preparation and Physiochemical Characterization of Bitter Orange Oil Loaded Sodium Alginate and Casein Based Edible Films.

Biopolymers-based composite edible films are gaining interest in the food packaging industry due to their sustainable nature and diverse biological activities. In the current study, we used sodium alginate (SA) and casein (CA) for the fabrication of composite film using the casting method. We also added orange oil to the edible film and assessed its impact on the biological, chemical, physical, and barrier properties of the films. The fabricated films were analyzed using X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). It was observed that CA–SA films loaded with 1.5% OEO had better visual attributes, and a further increase in oil concentration was not found to be as favorable. Mechanical assessment of the films revealed that CA–SA-OEO (1.5%) film showed lower puncture deformation and higher puncture force values. XRD data showed that all samples exhibited peaks at similar positions (21° of 2θ) with different intensities. In FTIR analysis, characteristic peaks of the film components (sodium alginate, casein, and orange oil) were reported at corresponding positions. The thermal stability of films was enhanced after the addition of the OEO (1.5%), however, a greater increase in OEO caused a decrease in the thermal stability, observed during TGA analysis. Moreover, the surface of the blank CA–SA film (FL1) was found to be rough (with cracks) compared to CA–SA films (FL2) containing 1.5% OEO. Additionally, FL2 was found to be relatively better than the other samples in terms of swelling degree (SD), thickness, water solubility (WS), oxygen permeability (OP), water vapor permeability (WVP), moisture content (MC), and transparency (T).

Biomimetic strategy for electrophoretic deposition of composite ferroelectric poly(vinylidene, fluoride-co-hexafluoropropylene) – ferrimagnetic NiFe2O4 films

This investigation is motivated by interest in fabrication of composite films combining ferrimagnetic properties of spinel ferrites with multifunctional properties of ferroelectric polymers. It addresses the need in the development of surface modification techniques for inorganic materials and polymers and their electrophoretic deposition (EPD) for the fabrication of composite films. This article describes for the first time the fabrication of composite ferroelectric poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) - ferrimagnetic NiFe2O4 films by EPD. The approach is based on feasibility of fabrication, surface modification and EPD of PVDF-HFP particles using natural biosurfactants, such as catecholate-type caffeic acid (CA) and bile acid-type cholic acid (ChA). The analysis of chemical structure of CA and ChA provides an insight into the surface modification mechanisms and EPD efficiency. Film morphologies and corrosion protection properties are analyzed. An important finding is the ability of CA to act as a charging dispersant for materials of different types, such as PVDF-HFP polymer particles and inorganic nanoparticles of NiFe2O4 spinel and fabrication of composite films by EPD. The film deposition yield, morphology and composition of PVDF-HFP - NiFe2O4 films are analyzed. NiFe2O4 content and magnetic properties of the composites are varied by variation of EPD bath composition. This investigation provides a platform for EPD of composite films combining ferrimagnetic properties of spinel ferrites with multifunctional properties of ferroelectric polymers.

Edible film fabrication modified by freeze drying from whey protein isolate and sunflower oil: Functional property evaluation

The objective of the study was to simplify the composite film fabrication process. Different sunflower oil (SO) concentrations, 0.05, 0.10 and 0.15 (g/100 mL) were incorporated into whey protein isolate (WPI) matrix. The obtained WPI-SO solutions were dried using a freeze dryer to get a new composite powder. The powder was just mixed with water and glycerol; then it was cast to form WPI-SO based edible films. The effects of freeze drying and SO concentration on the optical, physical, thermal, barrier, mechanical and morphological properties of the novel WPI films were investigated. It was observed that films formed from reconstituted powder had enhanced barrier properties. Oil incorporation into the film matrix resulted in decreased lipid droplet size and increased opacity. In conclusion, edible films were produced successfully with improved functional properties. This situation proved that film production method, modified with freeze drying, has promising potential for biodegradable packaging industry.

A Versatile Strategy for the Fabrication of Poly(ethyl methacrylate) Composites

Poly(ethyl methacrylate) (PEMA) is dissolved in ethanol, known to be a non-solvent for PEMA, due to the solubilizing ability of an added bile acid biosurfactant, lithocholic acid (LA). The ability to avoid traditional toxic and carcinogenic solvents is important for the fabrication of composites for biomedical applications. The formation of concentrated solutions of high molecular weight PEMA is a key factor for the film deposition using the dip coating method. PEMA films provide corrosion protection for stainless steel. Composite films are prepared, containing bioceramics, such as hydroxyapatite and silica, for biomedical applications. LA facilitates dispersion of hydroxyapatite and silica in suspensions for film deposition. Ibuprofen and tetracycline are used as model drugs for the fabrication of composite films. PEMA-nanocellulose films are successfully prepared using the dip coating method. The microstructure and composition of the films are investigated. The conceptually new approach developed in this investigation represents a versatile strategy for the fabrication of composites for biomedical and other applications, using natural biosurfactants as solubilizing and dispersing agents.

The effects of cellulose nanocrystal and cellulose nanofiber on the properties of pumpkin starch-based composite films

Pumpkin starch (PS) was extracted from Cucurbita maxima and utilized to prepare films in combination with cellulose nanocrystal (CNC) and cellulose nanofiber (CNF), using a solvent casting strategy. The PS was characterized to contain 26.6% of amylose, exhibiting a “B”-type crystalline structure and high stability against thermal degradation. PS/CNF films showed better thermal stability than PS/CNC films, whereas the CNC was more effective than CNF for enhancing the tensile strength (TS) of the films. The nanocomposite films containing 1% CNC showed the highest TS of 30.32 MPa. Fourier transform infrared spectra revealed stronger hydrogen bonding in the PS/CNC films, likely contributing to the observed high mechanical strength. CNC and CNF both decreased the transparency of PS films, by 5.2% and 13.1%, respectively. Overall, the properties of PS composite films can be effectively modified by incorporating CNC and CNF, as PS/CNC films with high mechanical strength and PS/CNF films with good thermal stability. Our results indicate that PS is a suitable material for CNC/CNF composite film fabrication. These films are expected to be especially useful in food packaging applications.