Biodegradable, Strong, and Hydrophobic Regenerated Cellulose Films Enriched with Esterified Lignin Nanoparticles.

The scientific community is pursuing significant efforts worldwide to develop environmentally viable film materials from biomass, particularly transparent, high-performance regenerated cellulose (RC) films, to replace traditional plastics. However, the inferior mechanical performance and hydrophilic nature of RC films are generally not suitable for use as a substitute for plastics in practical applications. Herein, lignin homogenization is used to synthesize high-performance composite films. The esterified lignin nanoparticles (ELNPs) with dispersible and binding advantages are prepared through esterification and nanometrization. In the presence of ELNPs, RC films exhibit a higher tensile strength (110.4 MPa), hydrophobic nature (103.6° water contact angle, 36.6% water absorption at 120 min, and 1.127 × 10-12 g cm cm-2 s-1 Pa-1 water vapor permeability), and exciting optical properties (high visible and low ultraviolet transmittance). The films further display antioxidant activity, oxygen barrier ability, and thermostability. The films completely biodegrade at 12 and 30% soil moisture. Overall, this study offers new insights into lignin valorization and regenerated cellulose composite films as novel bioplastic materials.

An Asymmetric Layer Structure Enables Robust Multifunctional Wearable Bacterial Cellulose Composite Film with Excellent Electrothermal/Photothermal and EMI Shielding Performance.

Highly robust flexible multifunctional film with excellent electromagnetic interference shielding and electrothermal/photothermal characteristics are highly desirable for aerospace, military, and wearable devices. Herein, an asymmetric gradient multilayer structured bacterial cellulose@Fe3O4/carbon nanotube/Ti3C2Tx (BC@Fe3O4/CNT/Ti3C2Tx) multifunctional composite film is fabricated with simultaneously demonstrating fast Joule response, excellent EMI shielding effectiveness (EMI SE) and photothermal conversion properties. The asymmetric gradient 6-layer composite film with 40% of Ti3C2Tx possesses excellent mechanical performance with exceptional tensile strength (76.1 MPa), large strain (14.7%), and good flexibility. This is attributed to the asymmetric gradient multilayer structure designed based on the hydrogen bonding self-assembly strategy between Ti3C2Tx and BC. It achieved an EMI SE of up to 71.3 dB, which is attributed to the gradient "absorption-reflection-reabsorption" mechanism. Furthermore, this composite film also exhibits excellent low-voltage-driven Joule heating (up to 80.3 °C at 2.5 V within 15 s) and fast-response photothermal performance (up to 101.5 °C at 1.0 W cm-2 within 10 s), which is attributed to the synergistic effect of heterostructure. This work demonstrates the fabrication of multifunctional bacterial cellulose@Fe3O4/carbon nanotube/Ti3C2Tx composite film has promising potentials for next-generation wearable electronic devices in energy conversion, aerospace, and artificial intelligence.

Green Extraction of Reed Lignin: The Effect of the Deep Eutectic Solvent Composition on the UV-Shielding and Antioxidant Properties of Lignin.

Lignin, the second most abundant natural polymer, is a by-product of the biorefinery and pulp and paper industries. This study was undertaken to evaluate the properties and estimate the prospects of using lignin as a by-product of the pretreatment of common reed straw (Phragmites australis) with deep eutectic solvents (DESs) of various compositions: choline chloride/oxalic acid (ChCl/OA), choline chloride/lactic acid (ChCl/LA), and choline chloride/monoethanol amine (ChCl/EA). The lignin samples, hereinafter referred to as Lig-OA, Lig-LA, and Lig-EA, were obtained as by-products after optimizing the conditions of reed straw pretreatment with DESs in order to improve the efficiency of subsequent enzymatic hydrolysis. The lignin was studied using gel penetration chromatography, UV-vis, ATR-FTIR, and 1H and 13C NMR spectroscopy; its antioxidant activity was assessed, and the UV-shielding properties of lignin/polyvinyl alcohol composite films were estimated. The DES composition had a significant impact on the structure and properties of the extracted lignin. The lignin's ability to scavenge ABTS+• and DPPH• radicals, as well as the efficiency of UV radiation shielding, decreased as follows: Lig-OA > Lig-LA > Lig-EA. The PVA/Lig-OA and PVA/Lig-LA films with a lignin content of 4% of the weight of PVA block UV radiation in the UVA range by 96% and 87%, respectively, and completely block UV radiation in the UVB range.

Nacre-like Anisotropic Multifunctional Aramid Nanofiber Composites for Electromagnetic Interference Shielding, Thermal Management, and Strain Sensing.

Developing multifunctional flexible composites with high-performance electromagnetic interference (EMI) shielding, thermal management, and sensing capacity is urgently required but challenging for next-generation smart electronic devices. Herein, novel nacre-like aramid nanofibers (ANFs)-based composite films with an anisotropic layered microstructure were prepared via vacuum-assisted filtration and hot-pressing. The formed 3D conductive skeleton enabled fast electron and phonon transport pathways in the composite films. As a result, the composite films showed a high electrical conductivity of 71.53 S/cm and an outstanding thermal conductivity of 6.4 W/m·K when the mass ratio of ANFs to MXene/AgNWs was 10:8. The excellent electrical properties and multi-layered structure endowed the composite films with superior EMI shielding performance and remarkable Joule heating performance, with a surface temperature of 78.3 °C at a voltage of 2.5 V. Additionally, it was found that the composite films also exhibited excellent mechanical properties and outstanding flame resistance. Moreover, the composite films could be further designed as strain sensors, which show great promise in monitoring real-time signals for human motion. These satisfactory results may open up a new opportunity for EMI shielding, thermal management, and sensing applications in wearable electronic devices.

The Use of Photocycloaddition Reactions to Drive Mechanical Motions Resembling Humanoid Movements.

With the aim of producing a photomechanical material for incorporation in soft microrobots, a one-dimensional diene coordination polymer (CP) [Cd(F-bpeb)(3-CBA)2]n (CP1, F-bpeb=4,4'-((1E,1'E)-(2,5-difluoro-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine, 3-HCBA=3-chlorobenzoic acid) was synthesized and characterized. Irradiation of CP1 with ultraviolet (UV) or visible light causes [2+2] photocycloaddition reactions resulting in the introduction of crystal strain which triggers various types of crystal movements. Composite films of CP1-PVA (SC) fabricated by dispersing CP1 crystals into polyvinyl alcohol (PVA) solution allow amplification of the crystal movement so that the film strips exhibit fast and flexible curling upon photoirradiation. The composite films may be cut into long rectangular strips and folded to simulate soft microrobots which exhibit a variety of fast, flexible and continuous photomechanical movements resembling a human performing various gymnastic exercises.

Highly Thermally Conductive Aramid Nanofiber Composite Films with Synchronous Visible/Infrared Camouflages and Information Encryption.

The development of highly thermally conductive composites that combine visible light/infrared camouflage and information encryption has been endowed with great significance in facilitating the application of 5G communication technology in military fields. This work uses aramid nanofibers (ANF) as the matrix, hetero-structured silver nanowires@boron nitride nanosheets (AgNWs@BNNS) prepared by in situ growth as fillers, which are combined to fabricate sandwich structured thermally conductive and electrically insulating (BNNS/ANF)-(AgNWs@BNNS)-(BNNS/ANF) (denoted as BAB) composite films by "filtration self-assembly, air spraying, and hot-pressing" method. When the mass ratio of AgNWs@BNNS to BNNS is 1 : 1 and the total mass fraction is 50 wt %, BAB composite film has the maximum in-plane thermal conductivity coefficient (λ∥ of 10.36 W/(m ⋅ K)), excellent electrical insulation (breakdown strength and volume resistivity of 41.5 kV/mm and 1.21×1015â€…Ω â‹… cm, respectively) and mechanical properties (tensile strength of 170.9 MPa). 50 wt % BAB composite film could efficiently reduce the equilibrium temperature of the central processing unit (CPU) working at full power, resulting in 7.0 °C lower than that of the CPU solely integrated with ANF directly. In addition, BAB composite film boasts adaptive visible light/infrared dual camouflage properties on cement roads and jungle environments, as well as the function of fast encryption of QR code information within 24 seconds.

Atomic Origins of Enhanced Ferroelectricity in Nanocolumnar PbTiO3 /PbO Composite Thin Films.

Nanocomposite films hold great promise for multifunctional devices by integrating different functionalities within a single film. The microstructure of the precipitate/secondary phase is an essential element in designing composites' properties. The interphase strain between the matrix and secondary phase is responsible for strain-mediated functionalities, such as magnetoelectric coupling and ferroelectricity. However, a quantitative microstructure-dependent interphase strain characterization has been scarcely studied. Here, it is demonstrated that the PbTiO3 (PTO)/PbO composite system can be prepared in nano-spherical and nanocolumnar configurations by tuning the misfit strain, confirmed by a three-dimensional reconstructive microscopy technique. With the atomic resolution quantitative microscopy with a depth resolution of a few nanometers, it is discovered that the strained region in PTO is much larger and more uniform in nanocolumnar compared to nano-spherical composites, resulting in much enhanced ferroelectric properties. The interphase strain between PbO and PTO in the nanocolumnar structure leads to a giant c/a ratio of 1.20 (bulk value of 1.06), accompanied by a Ti polarization displacement of 0.48 Å and an effective ferroelectric polarization of 241.7 µC cm-2 , three times compared to the bulk value. The quantitative atomic-scale strain and polarization analysis on the interphase strain provides an important guideline for designing ferroelectric nanocomposites.

Multistage SrBaTiO3 /PDMS Composite Film-Based Hybrid Nanogenerator for Efficient Floor Energy Harvesting Applications.

Triboelectric nanogenerators are an emerging energy-scavenging technology that can harvest kinetic energy from various mechanical moments into electricity. The energy generated while humans walk is the most commonly available biomechanical energy. Herein, a multistage consecutively-connected hybrid nanogenerator (HNG) is fabricated and combined with a flooring system (MCHCFS) to efficiently harvest mechanical energy while humans walk. Initially, the electrical output performance of the HNG is optimized by fabricating a prototype device using various strontium-doped barium titanate (Ba1- x Srx TiO3 , BST) microparticles loaded polydimethylsiloxane (PDMS) composite films. The BST/PDMS composite film acts as a negative triboelectric layer that operates against aluminum. Single HNG operated in contact-separation mode could generate an electrical output of ≈280 V, ≈8.5 µA, and ≈90 µC m-2 . The stability and robustness of the fabricated HNG are confirmed and eight similar HNGs are assembled in a 3D-printed MCHCFS. The MCHCFS is specifically designed to distribute applied force on the single HNG to four nearby HNGs. The MCHCFS can be implemented in real-life floors with an enlarged surface area to harvest energy generated while humans walk into direct current electrical output. The MCHCFS is demonstrated as a touch sensor that can be utilized in sustainable path lighting to save enormous electricity waste.

UV-Blocking and Light-Responsive Poly (ϵ-Caprolactone)/ZIF-8 Multifunctional Composite Films for Efficient Antibacterial Activities.

Antibacterial photodynamic therapy (APDT) has received considerable attention owing to its superiority. ZIF-8 was used to address the poor stability of the photosensitizer Rose Bengal (RB) encapsulation to synthesize RB@ZIF-8 NPs, which were doped into a composite film with poly (ϵ-caprolactone) (PCL) and polyvinyl alcohol-quaternary ammonium chitosan (PVA-QCS) as substrates to form composite films (PQZ). The composite films exhibited excellent photodynamic sterilization and good resistance to bacterial adhesion. The tensile strength of the film increased to 43.4 MPa, which was approximately 1.8 times that of the PCL film. With the addition of SiO2 and RB@ZIF-8 NPs, the film exhibited water repellency and UV-blocking properties. RAW264.7 cells were selected using the MTT method to confirm that the composite films had excellent biocompatibility and had no significant inhibitory effect on cell growth and reproduction. PQZ multifunctional composite films show potential as novel APDT antimicrobial materials for food packaging.

Photocatalytic solid-phase degradation of polyethylene with fluoride-doped titania under low consumption ultraviolet radiation.

Photodegradation of plastic in solid-phase requires the polymer to be composited with an efficient photocatalyst. We report herein the successful synthesis and characterization of fluoride-doped-TiO2 and its applicability, for the first time, on solid-phase photodegradation of polyethylene films. Nearly half weight loss of polyethylene, containing only 2% of the photocatalyst, is eliminated after three weeks of ultraviolet A radiation using a low consumption light emitting diode lamp, defeating previously reported data. The half-life time of the plastic was around 3 weeks, highlighting the viability of this process for real applications. Results were compared to raw PE and PE composite with well-known TiO2, resulting in, respectively, 0 and 26% of weight loss. The degradation process was monitored by optical microscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, Fourier transform infrared and X-ray photoelectron spectroscopy, which revealed the formation of plastic cracks, loss of polyethylene crystallinity and thus stability, the oxidation of C-H bonds and the oxidized state of the surface compounds during photodegradation. The obtained results open a path for the future production of cleaner and self-photodegradable plastics, where the photocatalyst would be introduced in all the manufactured plastics, making possible the quicker photodegradation of the plastics that end up on the environment and the plastics reaching wastewater treatment plants.

Development and characterization of pectin and chitosan films incorporated with a new cross-linking agent.

BACKGROUND: In this study, a new crosslinking agent (CA) containing whey protein, papin, glycerin, and epigallocatechin gallate (EGCG), was prepared. The effects of CA content (0, 10, 20, 30, and 40%, v/v) on food packaging properties, crystallinity, microstructure, and antioxidant properties of pectin-CA and chitosan-CA composite films were analyzed. The results of this research offer a theoretical basis for engineering improved films for food packing. RESULTS: Pectin-CA (30%) and chitosan-CA (40%) composite films showed the best light transmission, water retention, breathability, plasticity, and antioxidant activity. Scanning electron microscopy revealed that these composite films exhibited a uniform and homogeneous structure without obvious pores. Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) indicated that the amino acids and EGCG in CA were bonded to the film substrate (pectin/chitosan) via electrostatic interactions, hydrogen bonding, and covalent bonding, which led to an improvement in the film's properties. CONCLUSION: The CA has broad application prospects in food packaging as a cross-linking agent and antioxidant. © 2022 Society of Chemical Industry.

Improvement of the UV-resistance capability of fish gelatin-oxidized starch film via inserting mycosporine-like amino acids.

BACKGROUND: Mycosporine-like amino acids (MAAs) are known as the strongest solar guardians in nature. RESULTS: In the present study, the extraction of MAAs from dried Pyropia haitanensis was achieved. Fish gelatin and oxidized starch composite films embedded with MAAs (0-0.3% w/w) were fabricated. The maximum absorption wavelength of the composite film appeared at 334 nm, which was consistent with MAA solution. Furthermore, the UV absorption intensity of the composite film was highly dependent on the concentration of MAAs. The composite film exhibited excellent stability during the 7-day storage period. The physicochemical features of composite film were demonstrated by the measurement of water content, water vapor transmission rate, oil transmission, and visual characteristics. Furthermore, in the actual anti-UV effect investigation, the increase in peroxide value and the acid value of grease under the films coverage was delayed. In the meantime, the decrease in ascorbic acid content in dates was postponed, and survivability of Escherichia coli was increased. CONCLUSION: Our results suggest that fish gelatin-oxidized starch-mycosporine-like amino acids film (FOM film) with biodegradable and anti-ultraviolet properties has a high potential for usage in food packaging materials. © 2023 Society of Chemical Industry.

Multifunctional Thermally Conductive Composite Films Based on Fungal Tree-like Heterostructured Silver Nanowires@Boron Nitride Nanosheets and Aramid Nanofibers.

Thermal conduction for electronic equipment has grown in importance in light of the burgeoning of 5G communication. It is imperatively desired to design highly thermally conductive fillers and polymer composite films with prominent Joule heating characteristics and extensive mechanical properties. In this work, "solvothermal & in situ growth" method is carried out to prepare "Fungal tree"-like hetero-structured silver nanowires@boron nitride nanosheet (AgNWs@BNNS) thermally conductive fillers. The thermally conductive AgNWs@BNNS/ANF composite films are obtained by the method of "suction filtration self-assembly and hot-pressing". When the mass fraction of AgNWs@BNNS is 50 wt%, AgNWs@BNNS/ANF composite film presents the optimal thermal conductivity coefficient of 9.44 W/(m ⋅ K) and excellent tensile strength of 136.6 MPa, good temperature-voltage response characteristics, superior electrical stability and reliability, which promise a wide application potential in 5G electronic devices.

Electric-Field-Induced Alignment of Functionalized Carbon Nanotubes Inside Thermally Conductive Liquid Crystalline Polyimide Composite Films.

The positive liquid crystals, 4'-heptyl-4-biphenylcarbonitrile (7CB), are used to functionalize carbon nanotubes (LC-CNT), which can be aligned in the liquid crystalline polyimide (LC-PI) matrix under an alternating electric field to fabricate the thermally conductive LC-CNT/LC-PI composite films. The efficient establishment of thermal conduction pathways in thermally conductive LC-CNT/LC-PI composite films with a low amount of LC-CNT is achieved through the oriented alignment of LC-CNT within the LC-PI matrix. When the mass fraction of LC-CNT is 15 wt %, the in-plane thermal conductivity coefficient (λ∥ ) and the through-plane thermal conductivity coefficient (λ⊥ ) of the LC-CNT/LC-PI composite films reach 4.02 W/(m ⋅ K) and 0.55 W/(m⋅K), which are 90.5 % and 71.9 % higher than those of the intrinsically thermally conductive LC-PI films respectively, also 28.8 % and 5.8 % higher than those of the CNT/LC-PI composite films respectively. Meanwhile, the thermally conductive LC-CNT/LC-PI composite films also possess excellent mechanical and heat resistance properties. The Young's modulus and the heat resistance index are 2.3 GPa and 297.7 °C, respectively, which are higher than the intrinsically thermally conductive LC-PI films and the thermally conductive CNT/LC-PI composite films under the same amount of CNT.

Reversible Hydration Composite Films for Evaporative Perspiration Control and Heat Stress Management.

Donning of personal protective equipment (PPE) in the healthcare sector has been intensified by the on-going COVID-19 pandemic around the globe. While extensive PPE provides protection, it typically limits moisture permeability and severely hinders the sweat evaporation process, resulting in greater heat stress on the personnel. Herein, a zinc-poly(vinyl alcohol) (Zn-PVA) composite film is fabricated by embedding a super-hygroscopic zinc-ethanolamine complex (Zn-complex) in the PVA matrix. By attaching the Zn-PVA composite film, the relative humidity (RH) inside the protective suit decreases from 91.0% to 48.2%. The reduced RH level, in turn, enhances evaporative cooling, hence bringing down the heat index from 64.6 to 40.0 °C at an air temperature of 35 °C, remarkably lowering the likelihood of heat stroke. The American Society for Testing and Materials tests conducted on a sweating manikin have also proven that the Zn-PVA composite films can significantly reduce the evaporative resistance of the protective suit by 90%. The low material cost, facile fabrication process, and reusability allow the Zn-PVA composition films to be readily available for healthcare workers worldwide. This application can be further extended to other occupations that are facing severe thermal discomfort and heat stress.

Vacuum-Vapor-Deposited 0D/3D All-Inorganic Perovskite Composite Films toward Low-Threshold Amplified Spontaneous Emission and Lasing.

Vacuum vapor deposition (VVD) is a promising way to advancing the commercialization of perovskite light sources owing to its convenience for wafer-scale mass production and compatibility with silicon photonics manufacturing infrastructure. However, the light emission performance of VVD-grown perovskites still lags far behind that of the conventional solution-processed counterparts due to their inferior luminescence properties. Here, a 0D/3D cesium-lead-bromide perovskite composite film is prepared on Si/SiO2 substrates through composition modulation with the VVD method, which exhibits an ultralow amplified spontaneous emission (ASE) threshold down to 14.3 µJ cm-2 in the optimal films, which is on par with that of the solution-processed counterparts. Meanwhile, they also display intriguing operational stability with negligible emission intensity decay under continuous excitation above ASE threshold for 4 h in the air. The outstanding ASE performance mainly originates from the reduced trap density and weakened electron-phonon coupling in the 3D CsPbBr3 phase enabled by the incorporation of the 0D Cs4 PbBr6 phase. Finally, by integrating the composite film with the distributed feedback (DFB) cavity, DFB lasing is achieved with a low threshold of 18.2 µJ cm-2 under nanosecond-pulsed laser pumping, which highlights the potential of VVD-processed perovskites for developing high-performance lasers.

Fucoidan-based nanomaterial and its multifunctional role for pharmaceutical and biomedical applications.

Fucoidans are promising sulfated polysaccharides isolated from marine sources that have piqued the interest of scientists in recent years due to their widespread use as a bioactive substance. Bioactive coatings and films, unsurprisingly, have seized these substances to create novel, culinary, therapeutic, and diagnostic bioactive nanomaterials. The applications of fucoidan and its composite nanomaterials have a wide variety of food as well as pharmacological properties, including anti-oxidative, anti-inflammatory, anti-cancer, anti-thrombic, anti-coagulant, immunoregulatory, and anti-viral properties. Blends of fucoidan with other biopolymers such as chitosan, alginate, curdlan, starch, etc., have shown promising coating and film-forming capabilities. A blending of biopolymers is a recommended approach to improve their anticipated properties. This review focuses on the fundamental knowledge and current development of fucoidan, fucoidan-based composite material for bioactive coatings and films, and their biological properties. In this article, fucoidan-based edible bioactive coatings and films expressed excellent mechanical strength that can prolong the shelf-life of food products and maintain their biodegradability. Additionally, these coatings and films showed numerous applications in the biomedical field and contribute to the economy. We hope this review can deliver the theoretical basis for the development of fucoidan-based bioactive material and films.

A comprehensive review on the nanocomposites loaded with chitosan nanoparticles for food packaging.

Chitosan is mainly derived from seafood by-products and the thereof chitosan nanoparticles (CNPs) are known as nontoxic, biocompatible, biodegradable and functionalized nanostructures. CNPs, as green fillers, showed an appropriate potential in reinforcement of various biodegradable composites for food packaging and biomedical applications. After evaluation of different fabrication approaches and characterization techniques of CNPs, the changes in physical, mechanical, thermal, structural, morphological, and antimicrobial attributes of nanobiocomposites as a result of CNPs addition are discussed. The influence of bioactive loaded-CNPs and hybrid CNPs with metal nanoparticles, graphene, and montmorillonite in nanocomposites is also presented. Finally, the safety aspects of CNPs-loaded structures are highlighted to evaluate their implementation in food packaging and biomedical systems. It can be concluded that regardless of a few drawbacks, CNPs are promising nanomaterials to improve various operational, structural and antimicrobial properties of biocomposites for various applications in food packaging, delivery systems and biomedical uses.

Highly anisotropic thermal conductivity and electrical insulation of nanofibrillated cellulose/Al2O3@rGO composite films: effect of the particle size.

Nanofibrillated cellulose (NFC) film has received tremendous attention due to its excellent electrical insulation, which shows great application prospects in the field of electronic devices. However, the low efficient heat dissipation of NFC film largely limits its use in advanced applications. In this work, the reduced graphene oxide hybrid fillers loaded alumina (Al2O3) particles with different sizes were synthesized by different drying methods, and then they were mixed with NFC to prepare a series of NFC-based composite films. The effect of Al2O3particle sizes on the thermal conductivity of NFC-based composite films was studied. The results showed that the surface areas of l-Al2O3particles were smaller than that of s-Al2O3particles, resulting in the smaller interface thermal resistance and superior thermal conductivity of the film containing l-Al2O3particles. The NFC-based composite films showed great potential for applications in thermal management by adjusting the particle size of fillers.

Layer-by-Layer Assembly of Multifunctional NR/MXene/CNTs Composite Films with Exceptional Electromagnetic Interference Shielding Performances and Excellent Mechanical Properties.

With the rapid advance of electronics, the light, flexible, and multifunctional composite films with high electromagnetic interference (EMI) shielding effectiveness and excellent thermal management are highly desirable for next-generation portable and wearable electronic devices. Herein, a series of flexible and ultrathin natural rubber/MXene/carbon nanotubes (NR/MXene/CNTs) composite films with sandwich structure are constructed layer by layer through a facile vacuum-assisted filtration method for EMI shielding and Joule heating application. The fabricated NR/MXene/CNTs-50 composite film, with NR/MXene as inner layer and NR/CNTs as out layers, not only has high EMI shielding efficiency, but also has excellent comprehensive mechanical properties at the thickness of only 200 µm. In addition, the superior environmental durability, high electrothermal conversion efficiency, hydrophobicity, and fine performance stability after periodic cyclic bending make the film possess more value in practical application.