Free-standing Films Research Articles

Oxhide gelatin-regulated aramid nanofiber/liquid metal films with sandwiched structure for electromagnetic interference shielding

Liquid metal (LM) based electromagnetic interference (EMI) shielding materials with high conductivity and continuous deformation capacity are important needs for meeting modern advanced electronic equipment. However, an independent free-standing film with LM is difficult to achieve due to its unique fluidity properties. Here, a simple alternating filtration film-forming method was utilized to orderly construct a sandwiched EMI shielding film with LM stabilized by bio-based oxhide gelatin (gel) as the intermediate conductive layer, and two films of aramid nanofibers/oxhide gel (ANF/gel) as the external insulating protective layers. This design not only prevents LM from being exposed to environmental conditions, but also reduces the risk of chemical corrosion in practical applications. Under optimal LM addition conditions, the sandwiched film (0.3-3 L) exhibited better EMI shielding performance of 50.4 dB in the X-band than the blended film (0.7 dB), as well as excellent mechanical properties (tensile strength of 65.8 MPa, strain 8.6 %). More importantly, the sandwiched film still maintained reliable EMI shielding performance after being experienced largely physical deformation. This study provides a new solution for preparing LM-based EMI shielding composites, and is expected to arouse pursuit of high EMI shielding effects of bio-based gel while also paying attention to their safety.

Alignment of lyotropic liquid crystals using magnetic nanoparticles improves ionic transport through built-in peptide ion channels

Hypothesis: We hypothesize that simultaneous incorporation of ion channel peptides (in this case, potassium channel as a model) and hydrophobic magnetite Fe3O4 nanoparticles (hFe3O4NPs) within lipidic hexagonal mesophases, and aligning them using an external magnetic field can significantly enhance ion transport through lipid membranes.Experiments: In this study, we successfully characterized the incorporation of gramicidin membrane ion channels and hFe3O4NPs in the lipidic hexagonal structure using SAXS and cryo-TEM methods. Additionally, we thoroughly investigated the conductive characteristics of freestanding films of lipidic hexagonal mesophases, both with and without gramicidin potassium channels, utilizing a range of electrochemical techniques, including impedance spectroscopy, normal pulse voltammetry, and chronoamperometry.Findings: Our research reveals a state-of-the-art breakthrough in enhancing ion transport in lyotropic liquid crystals as matrices for integral proteins and peptides. We demonstrate the remarkable efficacy of membranes composed of hexagonal lipid mesophases embedded with K+ transporting peptides. This enhancement is achieved through doping with hFe3O4NPs and exposure to a magnetic field. We investigate the intricate interplay between the conductive properties of the lipidic hexagonal structure, hFe3O4NPs, gramicidin incorporation, and the influence of Ca2+ on K+ channels. Furthermore, our study unveils a new direction in ion channel studies and biomimetic membrane investigations, presenting a versatile model for biomimetic membranes with unprecedented ion transport capabilities under an appropriately oriented magnetic field. These findings hold promise for advancing membrane technology and various biotechnological and biomedical applications of membrane proteins.

Ultra-Mild Fabrication of Highly Concentrated SWCNT Dispersion Using Spontaneous Charging in Solvated Electron System.

The efficient dispersion of single-walled carbon nanotubes (SWCNTs) has been the subject of extensive research over the past decade. Despite these efforts, achieving individually dispersed SWCNTs at high concentrations remains challenging. In this study, we address the limitations associated with conventional methods, such as defect formation, excessive surfactant use, and the use of corrosive solvents. Our novel dispersion method utilizes the spontaneous charging of SWCNTs in a solvated electron system created by dissolving potassium in hexamethyl phosphoramide (HMPA). The resulting charged SWCNTs (c-SWCNTs) can be directly dispersed in the charging medium using only magnetic stirring, leading to defect-free c-SWCNT dispersions with high concentrations of up to 20 mg/mL. The successful dispersion of individual c-SWCNT strands is confirmed by their liquid-crystalline behavior. Importantly, the dispersion medium for c-SWCNTs exhibits no reactivity with metals, polymers, or other organic solvents. This versatility enables a wide range of applications, including electrically conductive free-standing films produced via conventional blade coating, wet-spun fibers, membrane electrodes, thermal composites, and core-shell hybrid microparticles.

Ferroelectric Order Evolution in Freestanding PbTiO3 Films Monitored by Optical Second Harmonic Generation.

The demand for low-dimensional ferroelectric devices is steadily increasing, however, the thick substrates in epitaxial films impede further size miniaturization. Freestanding films offer a potential solution by eliminating substrate constraints. Nevertheless, it remains an ongoing challenge to improve the stability in thin and fragile freestanding films under strain and temperature. In this work, the structure and ferroelectric order of freestanding PbTiO3 (PTO) films are investigated under continuous variation of the strain and temperature using nondestructive optical second harmonic generation (SHG) technique. The findings reveal that there are both out-of-plane and in-plane domains with polarization along out-of-plane and in-plane directions in the orthorhombic-like freestanding PTO films, respectively. In contrast, only out-of-plane domains are observed in the tetragonal epitaxial PTO films. Remarkably, the ferroelectricity of freestanding PTO films is strengthened under small uniaxial tensile strain from 0% up to 1.66% and well-maintained under larger biaxial tensile strain up to 2.76% along the [100] direction and up to 4.46% along the [010] direction. Moreover, a high Curie temperature of 630K is identified in 50nm thick freestanding PTO films by wide-temperature-range SHG. These findings provide valuable understanding for the development of the next-generation electronic nanodevices with flexibility and thermostability.

PERSPECTIVE: Interfacial stresses in thin film drainage: Subtle yet significant

Film drainage, essential in droplet and bubble coalescence and surface wetting, is influenced strongly by the stress boundary condition, in particular, when interfacial stresses are present. These stresses, caused by ubiquitous surface-active components, significantly impact the dynamics of liquid films. Through dynamic thin film balance experiments, we compare the effects of Marangoni stresses, interfacial viscosity, and interfacial viscoelasticity on the drainage of free-standing thin liquid films. These data serve to demonstrate that film deformation intricately depends on the interplay between these stresses and capillarity, resulting in widely varied drainage times. Seemingly subtle changes, especially in the local stress-carrying capacity of the interface, can lead to significant differences in film dynamics. This makes it a promising area for research into interfacial-rheologically active materials for stabilizing potentially more sustainable multiphase materials.

Strategic design of degradable polyurethanes: Site-specific depolymerization, film-forming behavior, and reprocessability

This paper reports on the rational design of linear sustainable polyurethanes with on-demand depolymerization capabilities and film-forming properties. In this molecular approach, self-immolative urethane motifs are engineered to not only induce rapid degradation in response to an external stimulus via sequential elimination but also provide sufficient inter-chain interactions to yield nanofibers or free-standing films. Amalgamation with various isocyanate or polyol components results in a range of degradable polyurethanes, while doping with europium complexes or carbon black leads to the formation of free-standing hybrid films with photoluminescent or conductive properties, respectively. These films can be reversibly cast using a facile dissolution process, and the predetermined depolymerization products can then be used to generate upcycled materials such as polyurea or polyacrylate films. We believe that our conceptual design for sustainable polyurethanes can be advanced further when combined with conventional engineering techniques to meet industrial and environmental requirements and create desirable materials for contemporary applications.

TiO2 Films with Macroscopic Chiral Nematic-Like Structure Stabilized by Copper Promoting Light-Harvesting Capability for Hydrogen Generation.

Cellulose nanocrystals (CNCs) have inspired the synthesis of various advanced nanomaterials, opening opportunities for different applications. However, a simple and robust approach for transferring the long-range chiral nematic nanostructures into TiO2 photocatalyst is still fancy. Herein, a successful fabrication of freestanding TiO2 films maintaining their macroscopic chiral nematic structures after removing the CNCs biotemplate is reported. It is demonstrated that including copper acetate in the sol avoids the epitaxial growth of the lamellar-like structure of TiO2 and stabilizes the chiral nematic structure instead. The experimental results and optical simulation demonstrate an enhancement at the blue and red edges of the Fabry-Pérot reflectance peak located in the visible range. This enhancement arises from the light scattering effect induced by the formation of the chiral nematic structure. The nanostructured films showed 5.3 times higher performance in the photocatalytic hydrogen generation, compared to lamellar TiO2, and benefited from the presence of copper species for charge carriers' separation. This work is therefore anticipated to provide a simple approach for the design of chiral nematic photocatalysts and also offers insights into the electron transfer mechanisms on TiO2/CuxO with variable oxidation states for photocatalytic hydrogen generation.

Elastic-Plastic Fully π-Conjugated Polymer with Excellent Energy Dissipation Capacity for Ultra-Deep-Blue Flexible Polymer Light-Emitting Diodes with CIEy = 0.04.

Emerging intrinsically flexible fully π-conjugated polymers (FπCPs) are a promising functional material for flexible optoelectronics, attributed to their potential interchain interpenetration and entanglement. However, the challenge remains in obtaining elastic-plastic FπCPs with intrinsic robust optoelectronic property and excellent long-term and cycling deformation stability simultaneously for applications in deep-blue flexible polymer light-emitting diodes (PLEDs). This study, demonstrates a series of elastic-plastic FπCPs (P1-P4) with an excellent energy dissipation capacity via side-chain internal plasticization for the ultra-deep-blue flexible PLEDs. First, the freestanding P1 film exhibited a maximum fracture strain of 34.6%. More interestingly, the elastic behavior is observed with a low strain (≤10%), and the stretched film with a high deformation (>10%) attributed to plastic processing revealed the robust capacity to realize energy absorption and release. The elastic-plastic P1 film exhibits outstanding ultra-deep-blue emission, with an efficiency of 56.38%. Subsequently, efficient PLEDs are fabricated with an ultra-deep-blue emission of CIE (0.16, 0.04) and a maximum external quantum efficiency of 1.73%. Finally, stable and efficient ultra-deep-blue electroluminescence are obtained from PLEDs based on stretchable films with different strains and cycling deformations, suggesting excellent elastic-plastic behavior and deformation stability for flexible electronics.

Application of Spray Coating in the Fabrication of Free Standing Nanocellulose Films and Barrier Coating on the Paper Substrates

Spray coating is a novel concept for fabricating free-standing film and producing barrier coating on paper substrates. The spraying gives comparable efficacy with vacuum filtration in terms of operation time, film quality, and process intensification approach. The smooth films created by spraying nanocellulose onto the polished impermeable surface could serve as a platform for a variety of sustainable functional devices. Finally, the application of spray-coating barriers and nanocellulose films on paper substrates is the focus of the spray-coating concept designed to create smooth nanocellulose films. One of the most important factors that affect the performance of different cellulose-based functional materials is the smoothness of nanocellulose film coated with sprays in the production of flexible and printed electronics. The uses of nanocellulose film as a high-performance barrier material and the possible replacement of synthetic plastic packaging are expanded by spray coatings. The process of creating a nanocellulose film using spray coating takes less than a minute. Compared to vacuum filtering, this method offers excellent speed potential for nanocellulose films. The wet layer of spray coating takes more than 24 hours to dry in a controlled laboratory environment, using air drying. Future research projects will improve the drying process of wet films. The film spray process serves as a proof of concept, and the quality of the film produced by this method contrasts with vacuum filtration. Studying spray coating wet film drying outside the scope of this research is not part of the scope of this study, and additional research is needed in this area. The shiny film that is created by spraying nanocellulose on the impermeable polished surface can serve as a platform for various sustainable functional devices.

A gas sensor based on free-standing SWCNT film for selective recognition of toxic and flammable gases under thermal cycling protocols

The widespread adoption of e-nose devices based on chemiresistive materials has been hindered by issues related to sensor device complexity and reliability, specifically sensor drift, necessitating frequent recalibration and retraining of pattern recognition models. This study introduces a method for thermocycling a single sensor based on a free-standing network of single-walled carbon nanotubes (SWCNTs) to acquire signal patterns for selective analyte detection. Additionally, it employs a data filtering technique to compensate for the sensor drift. A free-standing SWCNT film, only a few nanometers thick, is thermally cycled via Joule heating between room temperature and 120 °C. Under these conditions, the sensitivity was tested towards NO2, H2S, and acetone vapors (10–25 ppm) in the mixture with dry air. Signal patterns produced through thermocycling were processed using CatBoost and LSTM algorithms. The accuracy of detection reached 90 % in the classification task, and the average root mean squared error of analyte concentration detection in the multioutput regression task was below 4 ppm. By combining original sensor design, thermocycling, signal filtering for drift compensation, and advanced pattern recognition models, this work contributes to overcoming the challenges in multivariate sensing systems, paving the way for practical applications of the more reliable chemiresistive sensors.

Fractures of low-k materials in a RF package with integrated passive device based on TGV

The radio frequency (RF) chips and passive devices integrated on the through-glass-via (TGV) substrate meets the demands of miniaturization, high performance and low losses in the application. The RF chip and integrated passive devices (IPDs) are interconnected electrically by a redistribution layer (RDL) on the TGV substrate with the isolation low-k materials. The low-k materials, however, are susceptible to fracture during the thermal process in packaging due to their weak mechanical properties. In this study, the fractures of the low-k material were studied by experiments and the finite element analysis (FEA) for a RF package with integrated passive device based on TGV. The mechanical properties of the low-k material used in the FEA were tested by fabricating freestanding low-k films using microfabrication techniques. Then the fracture behaviors of the low-k material in the package and its impact factors under thermal loadings were examined. The impact factors, such as the initial defect location, direction and length, were investigated by evaluating the stress intensity factors (SIFs) at the defect tips. The results revealed that the most hazardous location in the low-k material is the region below the micro-joint of RF chip. The vertical defects along thickness in low-k film are more likely to propagate than horizontal ones. The SIF value increases linearly with the defect length both in heating and cooling conditions.

Transparent, plasticized cellulose-glycerol bioplastics for food packaging applications

Free-standing films have been obtained by drop-casting cellulose-glycerol mixtures (up to 50 wt% glycerol) dissolved in trifluoroacetic acid and trifluoroacetic anhydride (TFA:TFAA, 2:1, v:v). A comprehensive examination of the optical, structural, mechanical, thermal, hydrodynamic, barrier, migration, greaseproof, and biodegradation characteristics of the films was conducted. The resulting cellulose-glycerol blends exhibited an amorphous molecular structure and a reinforced H-bond network, as evidenced by X-ray diffraction analysis and infrared spectroscopy, respectively. The inclusion of glycerol exerted a plasticizing influence on the mechanical properties of the films, while keeping their transparency. Hydrodynamic and barrier properties were assessed through water uptake and water vapor/oxygen transmission rates, respectively, and obtained values were consistent with those of other cellulose-based materials. Furthermore, overall migration levels were below European regulation limits, as stated by using Tenax® as a dry food simulant. In addition, these bioplastics demonstrated good greaseproof performance, particularly at high glycerol content, and potential as packaging materials for bakery products. Biodegradability assessments were carried out by measuring the biological oxygen demand in seawater and high biodegradation rates induced by glycerol were observed.

A Tale of Two Separation Properties: Bulk and Thin Films of Mixed Matrix Materials

AbstractMixed matrix materials (MMMs) integrating excellent processability from polymers and distinct separation properties from nanofillers are of interest for membrane gas separations, and they are often made into freestanding films (>100 µm) to demonstrate superior gas separation properties. However, they are difficult to fabricate into thin‐film nanocomposite (TFN) membranes due to interfacial incompatibility between polymers and nanofillers. Here TFN membranes based on MMMs (as thin as 200 nm) are successfully developed comprising amorphous poly(ethylene oxide) (aPEO) and UiO‐66‐NH2 enabling strong hydrogen bonds between the two matrices. Increasing the UiO‐66‐NH2 loading unexpectedly decreases CO2 permeability in freestanding films, but it surprisingly leads to the best CO2/N2 separation properties in the membranes at a loading of 10 mass% (CO2 permeance of 2900 GPU and CO2/N2 selectivity of 48). Nanoconfinement significantly influences the morphological and gas separation properties of the MMM layer. The membrane with 10 mass% UiO‐66‐NH2 demonstrates mixed‐gas CO2 permeance of 1400 GPU and CO2/N2 selectivity of 76 in the presence of 1.2 mol% water vapor at ≈23 °C, surpassing Robeson's upper bound. The membrane also demonstrates stable CO2/N2 separation performance when challenged with real flue gas for 700 h continuously.

High‐Density and Freestanding Porous Carbon Film for Compact Sodium‐Ion Storage

AbstractPorous carbon materials are often difficult to achieve high density while possessing high porosity, which limits their application in compact energy storage. Here, a design of freestanding porous‐yet‐dense carbon films with a tunable density (1.08–1.33 g cm−3) and porosity (specific surface area of 0–423.8 m2 g−1) is presented through an assembly of porous carbon nanosheet with graphene oxide under vacuum filtration. The typical freestanding carbon films simultaneously deliver a high density of 1.08 g cm−3 and a high specific surface area of 423.8 m2 g−1 when the porous carbon nanosheet content is 75 wt.%. As anode materials for sodium‐ion batteries, the optimized freestanding carbon films deliver high volumetric capacity (270 mAh cm−3 at 20 mA g−1), high initial capacity efficiency (81 %) and superior long‐term cycling stability (1300 cycles with a capacity decay rate of 0.012 % per cycle). This study provides a promising direction for creating freestanding electrodes that meet both high‐porosity and high‐density requirements for compact sodium‐ion batteries.

Laser-induced 2D/0D graphene-nanoceria freestanding paper-based films for on-site hydrogen peroxide monitoring in no-touch disinfection treatments

A one-shot CO2 laser-based strategy to generate conductive reduced graphene oxide (rGO) decorated with nanoceria (nCe) is proposed. The 2D/0D rGO-nCe films, integrated as catalytic sensing layers in paper-based sensors, were employed for on-site monitoring of indoor fogging treatments against Listeria monocytogenes (Lm), a ubiquitous pathogenic bacterium. The rGO-nCe laser-assisted synthesis was optimized to preserve the rGO film morphological and electron-transfer features and simultaneously integrate catalytic nCe. The films were characterized by microscopical (SEM), spectroscopical (EDX, Raman, and FTIR), and electrochemical techniques. The most performing film was integrated into a nitrocellulose substrate, and the complete sensor was assembled via a combination of xurography and stencil printing. The rGO-nCe sensor's catalytic activity was proved toward the detection of H2O2, obtaining sensitive determination (LOD = 0.3 µM) and an extended linear range (0.5–1500 µM). Eventually, the rGO-nCe sensor was challenged for the real-time continuous monitoring of hydrogen peroxide aerosol during no-touch fogging treatment conducted following the EU’s recommendation for biocidal product use. Treatment effectiveness was proved toward three Lm strains characterized by different origins, i.e., type strain ATCC 7644, clinical strain 338, and food strain 641/6II. The sensor allows for discrimination and quantification treatments at different environmental biocidal amounts and fogging times, and correlates with the microbiological inhibition, promoting the proposed sensor as a useful tool to modulate and monitor no-touch treatments.Graphical

Oxygen diffusion in freestanding body centered cubic tantalum structural thin films in air and in high vacuum

Sensors and actuators constructed from freestanding tantalum thin films show promise for micromachining applications and for the study of thin film mechanical behavior. To assess this promise, it is necessary to gain further understanding of the performance of Ta as a structural material. We first evaluate the coefficient of thermal expansion, αTa, using micromachined bent beams, which amplify displacement compared to linear expansion. The value for αTa is 6.8 × 10−6 m/m °C, in good agreement with the bulk value. This validation enables the study of interstitial oxygen diffusion in Ta, for which literature values of activation energy vary widely, from 0.60 to 1.98 eV. Displacement in air due to oxygen diffusion becomes measurable after 30 min exposure at 180 °C. We extract an activation energy for interstitial oxygen in Ta of 0.53 eV/atom. Analysis indicates that lattice rather than grain boundary diffusion is the associated mechanism. To inhibit the oxidation, we construct a thermal stage that controls specimen temperature in 10−5 Pa vacuum. Then, after a 24 h hold, oxidation is suppressed up to 400 °C. This result is discussed in terms of O dissolution from its native oxide, coupled with further absorption from background gases.

A Fluorescent Polymer for Facile One‐Step Writing of Polychromic Hidden Information in Flexible Films

AbstractA poly(para)phenylene conjugated polymer is developed to store information via a quick and facile optical writing method. After exposure to UV light, co‐fluorescence (films with two or more written emission colors –, i.e., “double‐on”) and “on‐off” states are written into the flexible polymer films. The hidden information is invisible under ambient lighting and can only be read with an appropriate light source, optical filter, and/or magnifier, thus providing a level of security for information encoded into the films. The physical and chemical mechanisms are discussed responsible for the rapid fluorescence changes that occur under UV exposure and demonstrate microscale multi‐colored artwork and hidden QR codes written into pliable and freestanding films. Depending on the preparation, the written patterns remained easily visible and stable after exposure to water and to ambient levels of UV background radiation.

Large Area Film of Highly Crystalline, Cleavable, and Transferable Semi-Conducting 2D-Imine Covalent Organic Framework on Dielectric Glass Substrate.

Two dimensional (2D) imine-based covalent organic framework (COF), 2D-COF, is a newly emerging molecular 2D polymer with potential applications in thin film electronics, sensing, and catalysis. It is considered an ideal candidate due to its robust 2D nature and precise tunability of the electronic and functional properties. Herein, we report a scalable facile synthesis of 2D imine-COF with control over film thickness (ranging from 100 nm to a few monolayers) and film dimension reaching up to 2 cm on a dielectric (glass) substrate. Highly crystalline 2D imine polymer films are formed by maintaining a quasi-equilibrium (very slow, ∼15 h) in Schiff base condensation reaction between p-phenylenediamine (PDA) and benzene-1,3,5-tricarboxaldehyde (TCA) molecules. Free-standing thin and ultrathin films of imine-COF are obtained using sonication exfoliation of 2D-COF polymer. Insights into the microstructure of thin/ultrathin imine-COF are obtained using scanning and transmission electron microscopy (SEM and TEM) and atomic force microscopy (AFM), which shows high crystallinity and 2D layered structure in both thin and ultrathin films. The chemical nature of the 2D polymer was established using X-ray photoelectron spectroscopy (XPS). Optical band gap measurements also reveal a semiconducting gap. This is further established by electronic structure calculation using density functional theory (DFT), which reveals a semiconductor-like band structure with strong dispersion in bands near conduction and valence band edges. The structural characteristics (layered morphology and microscopic structure) of 2D imine-COF show significant potential for its application in thin film device fabrication. In addition, the electronic structure shows strong dispersion in the frontier bands, making it a potential semiconducting material for charge carrier transportation in electronic devices.

Bio-inspired surface structures promote optical transmittance and hydrophobicity in cellulose-based films for self-cleaning perovskite solar cells

Developing suitable light management layers can improve the lifetime and efficiency of solar cells and other optoelectronics. Here, a bioinspired approach to produce all-biobased films with high anisotropic light scattering and superhydrophobicity is presented as a route toward sustainable light management layers for photovoltaics. The multifunctional films are achieved by replicating leek leaves onto cellulose acetate, producing hierarchical surface structures. The free-standing films show a transmittance of ≈94% and a haze of ≈54% at the wavelength of 550 nm. Moreover, anisotropic advancing contact angles of up to 160° and 156° in cross directions are achieved through tailoring a carnauba wax coating. Using the replica as the light management layer on perovskite solar cells improved the power conversion efficiency by 6 ± 0.3%. Meanwhile, the surface water repellency facilitates self-cleaning, ensuring maximum incident light over time by tackling dirt accumulation. Furthermore, the method can be potentially employed to fabricate substrates from virtually any leaf or patterned surface as the initial replication template.

The 4-inch free-standing diamond film prepared by MPCVD at 10kW

The plasma emission spectrum and polycrystalline diamond growth within 4 inches was studied by using a microwave plasma chemical vapor deposition (MPCVD) equipment with a microwave frequency of 2.45 GHz and a power of 10 kW, a 4-inch free-standing diamond thick film was prepared, and the growth uniformity, crystal quality at different positions, room temperature thermal conductivity, ultraviolet-visible-near infrared spectral transmittance and dielectric properties of diamond film were characterized. The results show that the freestanding diamond films are prepared with good uniformity and crystallinity at 10 kW power with high concentration and chemical activity of carbon and hydrogen active particles within the plasma diameter of about 100 mm. The thermal conductivity at room temperature reaches more than 1894 W/m·K, the infrared transmittance reaches more than 70%, the dielectric constant is 5.5, and the dielectric loss is 5.9 × 10−5. This study provides a theoretical possibility for the preparation of large-area high-quality diamond films in low-power MPCVD equipment.