Cast Films Research Articles

Autohomogenization of Polybenzimidazole Composites with Enhanced Mechanical Performance by Air Incorporation.

Polybenzimidazoles are one of the most thermally and chemically stable polymers due to their rigid chemical structure with π-π stacking and conjugated bonding. Poly(2,5-benzimidazole) (ABPBI), the simplest structure of polybenzimidazole, was synthesized, but the cast film was not homogeneous and featured thick brown areas, which limited their further application. Silica nanospheres were adapted as porogen to generate nanopores in the ABPBI film by successive etching with hydrofluoric acid. As a result of air-composite formation, the ABPBI film became homogeneous and its surface roughness was reduced from 10.0 to 2.5 nm. The obtained air-composite ABPBI film had more favorable mechanical properties than the original film. An air-composite film prepared with 50 wt % silica content had a tensile strength of 128 MPa and an elongation at break of 23%, both of which values were approximately twice as high as the corresponding values of the original film.

Screening of Polymers for Oral Ritonavir Amorphous Solid Dispersions by Film Casting

Background/Objectives: Drug–polymer interactions and miscibility promote the formation and performance of amorphous solid dispersions (ASDs) of poorly soluble drugs for improved oral bioavailability. The objective of this study was to employ drug–polymer interaction calculations and small-scale experimental characterization to screen polymers for potential ASDs of ritonavir. Methods: Seven polymers across four polymer types were screened as follows: an enteric one (EudragitS100), amphiphilic ones (HPMCAS-L, HPMCAS-H, and their 1:1 combination), hydrophilic ones (PEG-6000, PVP-VA), and a surfactant (Soluplus), including PVP-VA as a positive control, as the commercial ASD employs PVP-VA. Drug–polymer interaction calculations were performed for Hansen solubility parameter, Flory–Huggins parameter, and glass transition temperature. ASDs were prepared via film casting. Experimental characterizations included drug solubility in polymer solutions, polymer inhibition of drug precipitation, polarized light microscopy, differential scanning calorimetry, solubilization capacity, and dissolution studies. Results: HPMCAS-L, HPMCAS L:H, and Soluplus, along with the positive control PVP-VA, were identified as polymers for potential ASDs of ritonavir, with HPMCAS-L and PVP-VA being preferable. HPMCAS-L and the positive control PVP-VA were always viable for both 20% and 40% drug loads across all tests. Films with each of these four polymers showed improved dissolution compared to amorphous ritonavir without polymer. Drug–polymer interaction calculations anticipated the unfavorable small-scale experimental results for PEG-6000 and EudragitS100. Conclusion: Overall, the results contribute towards a resource-sparing approach to identify polymers for ASDs.

Mechanically strong, transparent polyimide composite thin films with a low dielectric constant

Aromatic polyimide is widely used in microelectronics as dielectric packaging layers. There is a high demand to reduce its dielectric constant to meet the fast development of communication technology. Here we report a simple and eco-friendly approach to preparing polyimide films with a lowered dielectric constant by adding silica hollow nanospheres with an average size of 100 nm in an aqueous solution of poly(amic acid) salt, and subsequent film casting and thermal imidization. The silica hollow nanospheres present a uniform distribution in polyimide matrix after surface modification with 3-aminopropyltriethoxysilane. The dielectric constant of the resulting composite films decreases linearly with particle loading till 15 wt% and reaches the lowest value of 2.5. The surface hardness and elastic modulus of the films improve by adding hollow nanospheres, while maintaining high optical transparency, high flexibility and a low coefficient of thermal expansion.

Dual-mode draw resonance instability regulated by concentration fluctuation in the polymer solutions casting

Based on the two-fluid model, we successfully simulated the film casting process of the polymer solution system and observed the unique response wave of the film thickness and the concentration via applying perturbation. We identify that this instability pattern is essentially the product under the coupling effect of viscoelastic stress and osmotic pressure from fluctuations on different scales, which causes it to exhibit biperiodic characteristics. We call this new instability mode known as dual-mode draw resonance instability. Among them, the concentration oscillation predominates, thereby limiting the critical draw ratio Drc of the system. Through sorting out the molecular image of the polymer concentration response to perturbation, the relevant parameters are extracted, and the law of their influence on the Drc further verifies our conclusion and provides guidance for actual production.

Debbie McWilliams and the Elusive Role of the Casting Director in the Bond Franchise

Who will be the next 007, villain or ‘Bond girl’ remains a perennial topic of lively discussion. Yet the casting of Bond films as a professional process is not well understood. This is illustrated well by our relative lack of knowledge about one of the longest standing women behind James Bond, Debbie McWilliams, who has been the casting director of the Bond franchise since the early 1980s. Putting McWilliams at the centre of the casting discussion moves it away from the business of substituting one actor for another towards the day-to-day work of the casting department, where auditioning and selecting of actors represents just a small part of the job. Drawing on interviews and production histories, this article argues that the longevity and global scale of the Bond series has shaped the casting profession in important ways that have been overlooked.

Printable embedded pattern designs affect mechanical performance of cold-water fish gelatin cast films

Edible films made of cold-water fish gelatin suffer from suboptimal mechanical strength, limiting their use for sustainable packaging applications. In this study, the use of 3D-printable embedded patterns is investigated as reinforcement for gelatin cast films, aiming for cast films with customizable and enhanced mechanical strength. Various combinations of patterns (i.e. lines, grids, and triangles) and inks (varying concentrations of sodium caseinate, sodium alginate, and cellulose fibers) were 3D-printed. The 3D-printed structures were embedded into cast films and the mechanical properties were subsequently tested. Our results show that films with embedded patterns had an overall higher tensile strength at different stretching directions (i.e. parallel, perpendicular, and diagonal), compared to the plain gelatin films. The strongest mechanical anisotropy was found using the line pattern and the grid showed anisotropy in the parallel and perpendicular direction, highlighting the influence of printing path. Microscopical analysis revealed that embedded patterns affected the fracture mechanics of films. Interestingly, cellulose fibers showed alignment in the printed filaments along the printing direction, which contributes to an increased tensile strength of films after drying. Thus, by using printable embedded pattern design, edible films with customized mechanical performance can be made, contributing to future developments of sustainable packaging solutions.

Thin-film fabrication of polythiophene block copolymer via friction transfer

Abstract A thin film of thiophene block copolymer composed of 3-dodecylthiophene and 3-benzenesulfonato–thiophene was fabricated by using the friction-transfer method. The benzenesulfonato moiety was transformed by heating to the corresponding sulfonic acid, which induced self-doping. The obtained friction-transfer film showed different morphology from the related cast film. It was also revealed that the film indicated anisotropy parallel/perpendicular toward the drawing direction, which induced absorption dichroism and anisotropy of electric conductivity.

Facile In Situ Building of Sulfonated SiO2 Coating on Porous Skeletons of Lithium-Ion Battery Separators.

Polyolefin separators with worse porous structures and compatibilities mismatch the internal environment and deteriorate lithium-ion battery (LIB) combination properties. In this study, a sulfonated SiO2 (SSD) composited polypropylene separator (PP@SSD) is prepared to homogenize pore sizes and in situ-built SSD coatings on porous skeletons. Imported SSD uniformizes pore sizes owing to centralized interface distributions within casting films. Meanwhile, abundant cavitations enable the in situ SSD coating to facilely fix onto porous skeleton surfaces during separator fabrications, which feature simple techniques, low cost, environmental friendliness, and the capability for continuous fabrications. A sturdy SSD coating on the porous skeleton confines thermal shrinkages and offers a superior safety guarantee for LIBs. The abundant sulfonic acid groups of SSD endow PP@SSD with excellent electrolyte affinity, which lowers Li+ transfer barriers and optimizes interfacial compatibility. Therefore, assembled LIBs give the optimal C-rate capacity and cycling stability, holding a capacity retention of 82.7% after the 400th cycle at 0.5 C.

Electrical Conductivity, Thermo-Mechanical Properties, and Cytotoxicity of Poly(3,4-Ethylenedioxythiophene):Poly(Styrene Sulfonate) (PEDOT:PSS)/Sulfonated Polyurethane Blends.

Electrically conductive polymeric materials have recently garnered significant interest from researchers due to their potential applications in the biomedical field, including medical implants, tissue engineering, flexible electronic devices, and biosensors. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is considered the most successful conducting polymer due to its higher electrical conductivity and chemical stability, but it suffers from limited solubility in common organic solvents, poor mechanical properties, and low biocompatibility. An area of tremendous interest is in combining PEDOT:PSS with another polymer to form a blend or composite material in order to access the beneficial properties of both materials. However, the hydrophilic nature of PEDOT:PSS makes it difficult to produce composites with non-polar polymers. In order to overcome these problems, we have specifically designed and synthesized two new sulfonated polyurethanes (PUS) with high sulfonic acid functionality. The two polyurethanes, one water-soluble (PUS1) and one water-insoluble (PUS2), were used to make blends with two commercially available PEDOT:PSS formulations (CleviosTM FET and PH1000). Solvent cast films on glass substrates were made from water-soluble PEDOT:PSS/PUS1 blends while free-standing films of PEDOT:PSS/PUS2 blends were fabricated by compression-moulding. Ethylene glycol was used as conductivity enhancer, which showed an increase in the conductivity by several orders of magnitude in most of the compositions investigated. The highest conductivity of 438 S cm-1 was achieved for the blend with 80 wt% of PEDOT:PSS (PH1000) in PUS1.

Enhancement of wound dressings through cerium canadate and hydroxyapatite-infused hyaluronic acide and PVA membranes: A comprehensive characterization and biocompatibility study

This study explores the emhancement of advanced wound dressings by enhancing traditional bandages with suitable biomedical materials. We utilized Hyaluronic Acid (HA) and Polyvinyl Alcohol (PVA) as a polymeric matrix to create a novel membrane. Employing a film casting technique, we incorporated varying ratios of biological nanoparticles—Hydroxyapatite (HAP) and Cerium Vanadate (Ce₃(VO₄)₄)—to improve the wound dressing's properties. Wettability assessments provided insights into the surface characteristics of the scaffolds, revealing a diverse range of contact angles that reflect varying hydrophilic properties. Notably, the pure PVA/HA sample exhibited a contact angle of approximately 31.2° ± 12.1°, indicating excellent hydrophilicity and a strong capacity for drug absorption. However, the doping of nanoparticles resulted in an raise in contact angles, suggesting a slight reduction in hydrophilicity. Specifically, the addition of HAP produced a contact angle of about 36.5° ± 6.7°, while the addition of Ce₃(VO₄)₄ resulted in a contact angle of approximately 38.6° ± 6.4°. A significant increase in contact angle to 42.23° ± 4.8° was observed when mixing the nanoparticles, though the introduction of Graphene Oxide (GO) reduced the angle to 37.4° ± 0.35°, enhancing the hydrophilic properties of the composite. Cell viability testing was conducted to confirm the biocompatibility and bioactivity of the fabricated scaffolds. The results confirmed the ability of the scaffolds to promote cell growth, with an increase of 88.4 % in cell growth ratio observed at a suitable drug concentration of approximately 0.68 μg/ml. These findings highlight the potential of the developed scaffolds to enhance the wound healing process.

Optimization and Characterization of Mucoadhesive Buccal Films using Mimosa Seed-based Natural Polymer for Controlled Drug Release: A Sustainable Approach

Background: The present study attempted to develop cost-effective, biocompatible and biodegradable mucoadhesive buccal films exploring and using Mimosa pudica seed polymer, marking its potential as a sustainable drug delivery in pharmaceutical development. Methods: The extracted polymer was characterized for solubility, viscosity, loss on drying, pH, swelling index, starch, and mucilage ingredients. Compatibility between the polymer, drug, and excipients was assessed using FTIR analysis. Buccal film trial batches were formulated using the film casting technique and were optimized using the 23 full factorial design. Optimized formulation was characterized for drug release, permeability, mucoadhesive study, similarity, and difference factor along with histological and stability study. Results: The polymer’s pH, loss on drying, swelling index, and viscosity were 6.2, 6.8%, 81.77%, and 50,000 cP respectively. FTIR studies showed the compatibility between natural polymer, the model drug metoprolol succinate, and the excipients used. The early trial batches of polymeric films showed an extended drug release comparable to the standard polymers with a good permeability flux of 0.4048 ± 0.081 mcg*cm-2*h-1. The optimized film provided a controlled release of 52.31 ± 0.035% for more than 8 h following zero order kinetics. Mucoadhesive strength was found to be 32.25 ± 0.29 g. The similarity factor f2 (90.2) and difference factor f1 (8.197) indicated no significant difference compared to the standard formulation. Histological study demonstrated the non-irritant nature of the films and stability was established from the stability studies. Conclusion: Thus, a sustainable approach using natural polymeric buccal films was found promising for mucoadhesion and controlled release.

Orientation Control of Perfluorosulfonic Acid Films via Addition of 1,2,4-Triazole during Casting.

Perfluorosulfonic acid (PFSA) polymers are used as electrolyte membranes in polymer electrolyte fuel cells. To investigate the effect on proton conductivity through structural orientation control, we added 1,2,4-triazole to PFSA films during casting to impart anisotropy to the ion-cluster structure of the films. The proton conductivities of the films were found to be high in the film-surface direction and low in the film-thickness direction. Structural analysis using small-angle X-ray scattering suggested that the anisotropy in proton conductivity was due to anisotropy in the ion-cluster structure, which in turn was attributed to the formation of a phase-separated structure via strong bonding between sulfonic acid groups and 1,2,4-triazole during cast film formation and the surface segregation of fluorine. We expect the findings of this study to aid in the fabrication of PFSA films with controlled ion clusters.

All-in-one fabrication of NiO nanorods/carbon-containing porous catalytic polymer membranes for persulfate-facilitated oxidation-adsorption of diclofenac in flow–through

We introduce a novel all-in-one fabrication method for porous catalytic polyethersulfone (PES) membranes containing NiO nanorods and carbon nanoparticles. This method is based on the sonochemical in situ solidification of a metal salt with NaBH4 in presence of carbon particles in a PES-containing casting-reaction solution, directly followed by membrane preparation via film casting cum phase separation. In the catalytic flow-through degradation of 20 mg/L aqueous diclofenac with persulfate as oxidant, an as-prepared NiO-carbon-PES membrane achieved a 99 % aromatic content removal degree at a residence time of only 1.6 s. In comparison, NiO and CuO membranes without carbon particles exhibited < 40 % aromatic removal degrees. The high performance was attributed to a degradation-induced adsorption, with a diclofenac removal capacity of 950 mg/g of incorporated carbon particles. We demonstrated that diclofenac is catalytically mineralized in the membrane at incorporated NiO nanorods, followed by adsorption of remaining degradation products at nearby carbon particles. Our data further suggests that reducing NiO to Ni(0) via a membrane pretreatment shifts the catalytic persulfate activation from a radicaltoa non-radical pathway, and that HCO3– can function as sacrificial electron donor for Ni(0). This completely mitigated nickel leaching from the membrane in contact to persulfate. Moreover, even in the presence of NaHCO3 and NaCl, a Ni(0)–carbon–PES membrane consistently eliminated ∼ 90 % of the total organic carbon (TOC) from a 2 mg/L diclofenac feed containing persulfate in single-pass flow-through mode (continuously for 5 h, respectively for 500 L/m2 permeate volume), with no detectable release of degradation products or any nickel leaching.

Mitigation of Dendrite Growth in Zinc-iodide Flow Battery with Tröger’s Base Anion Exchange Membrane

Tröger’s base anion exchange membrane (TB-AEM) was readily prepared by condensation polymerization of biphenyl diamine and dimethoxymethane in the presence of trifluoroacetic acid followed by quaternization with methyl iodide. The film cast from N-Methyl-2-Pyrrolidone (NMP) solvent displayed good mechanical strength, a tensile modulus of 1.18 GPa with elongation at break of 17%, and a glass transition temperature (Tg) at 248 °C. It exhibited OH− ion conductivity of 108 mS cm−1 by impedance measurement at 80 °C in 1M KOH. The membrane exhibited good affinity toward I2, resulting in the formation of I2Br− ions in the membrane matrix. Over 300 charge/discharge cycles at a 50 mA cm−2 current density, the battery exhibited 95.5% Coulombic efficiency (CE), 76.4% voltage efficiency (VE), and 74.0% energy efficiency (EE) and delivered a capacity of 24.8 Ah L−1. Over a span of 60 h, the open-circuit voltage (OCV) of the cell remained constant at 1.2 V. Collectively, our findings suggest that the anion exchange membrane's charge and porosity tuning are key factors in the design of new generation separators for zinc-iodide flow batteries.

A versatile steel belt casting equipment for in situ synchrotron radiation x-ray scattering measurement of polymer films.

A steel belt casting equipment, weighing approximately ∼6-7 tons and measuring ∼5m in length, has been designed and developed for simulating the industrial processing of polymer films and being combined with synchrotron radiation in situ x-ray scattering measurements. Through modification of its modules, it is feasible to implement two distinct film casting modes, namely the wet and the dry casting processes. The speed of a steel belt can span from 0.5 to 8 m/min. The highest experimental temperature and drying wind speed are 300 °C and 6m/s, respectively. All film casting parameters, such as extrusion speed, distance between die and steel belt, casting speed, temperature, and wind speed, can be adjusted independently. Especially, the control accuracy of the temperature and casting rate can reach ±0.1 °C and ±0.01 m/min, respectively. The feasibility of this equipment has been validated through in situ x-ray scattering tests at the BL10U1 industrial beamline of the Shanghai synchrotron radiation facility. With the assistance of this equipment, the understanding of the physical mechanism behind the film casting process should be improved so that the development of advanced functional polymer films.

Evaluating the strategies to improve strength and water-resistance of chitin nanofibril assembled structures: Molecule-bridging, heat-treatment and deacidifying.

Chitin nanofibril (ChiNF) is a promising building block used to fabricate chitin fibers, films or gels via self-assembly from its aqueous suspension. Although mechanical strengthening of its assembled structures has made great advances, the unsatisfactory water-resistance is still a crucial obstacle to practical application and even rarely referred to. Herein, ChiNF was prepared via deacetylation-ultrasonication treatment and the strategies of molecule-bridging, heat-treatment and deacidifying that aiming to improve the strength and water-resistance of its assembled films were evaluated. Molecule-bridging, including tannic acid (TA) or/and chitosan (CS), improved the mechanical properties to some extent, but had no obvious positive effects on water-resistance; heat-treatment was a useful route to enhance both strength and water-resistance; interestingly, deacidifying was more efficient than heat-treatment with respect to improving strength and water-resistance, implying the presence of acid was the major reason for deteriorating assembled structures. Combining molecule-bridging, deacidifying and heat-treatment produced a strong ChiNF-TA/CS cast film with excellent water-resistance. Different from the commonly-used approach of vacuum filtration, these strategies are very suitable for large-scale production of the ChiNF-based self-supported films or coatings via solution casting. Furthermore, the reverse dialysis deacidification simultaneously produced highly concentrated suspensions suitable for dry-spinning, and thus strong chitin macrofibers were successfully fabricated.

Curing and Failure Monitoring of Composite Material Single-Lap Joint Based on CNT/PSF Sensor

Abstract Composite bonded structures are widely used in the field of aerospace. The safety of composite structures can be ensured by the health monitoring and early warning of their whole life. In this paper, a composite CNT/PSF film sensor based on asymmetric porous PSF film was designed and prepared. Through integrated molding with epoxy film, in-situ monitoring of gel point (142.1°C) and curing time (36min) of epoxy film is realized. After optimization of curing process, tensile strength of epoxy film casting body is increased by 86.3%. The single lap shear strength of the composite is increased by 45.7%. The CNT/PSF film sensor with composite material has high response sensitivity (GF≈1.4) and linearity (0.998) to cyclic strain (0-3000με). In the shear experiment of composite single lap joint, the adhesive layer presents a typical cohesive failure mode of first compression, then tensile and finally failure. The resistance changes of CNT/PSF film sensor first decreases from 0 to -1‰, and then rises to 2.7‰. Finally, the fracture response is good, and the in-situ failure behavior monitoring of the joint can be fully realized.

High-performance cellulose/thermoplastic polyurethane composites enabled by interaction-modulated cellulose regeneration

Strong interfacial adhesion between cellulose and other polymers is critical to achieve the properties required for specific applications in composite materials. Here, we developed a method for the simultaneous homogeneous dissolution of cellulose and thermoplastic polyurethane (TPU) in 1,8-diazabicyclo (5.4.0) undec-7-ene levulinate/dimethyl sulfoxide ([DBUH]Lev/DMSO) solvent. This process is essential for preparing cellulose/TPU composite films and fibers through interaction-modulated cellulose regeneration. Both cellulose and TPU can be easily dissolved together in [DBUH]Lev/DMSO solvent under mild conditions. The resulting cellulose/TPU solutions exhibited strong temperature sensitivity, shear-thinning behavior and viscoelasticity, making them suitable for cast films and continuous spinning. More importantly, research findings, including density functional theory calculations and experimental characterization, confirmed the high compatibility and interaction modulability of cellulose and TPU in the composite films. The representative C90T10 sample (cellulose/TPU, 90/10) showed high transparency (90 % at 800 nm) and excellent mechanical properties (tensile strength: 176 MPa; elongation at break: 8.1 %). Additionally, the maximum tensile strength and elongation at the break of the composite fiber from C90T10 were 214 MPa and 48.1 %, respectively. This method may provide a feasible approach to design and produce homogeneous environmentally friendly composites of cellulose and other polymers at the molecular level.

Effect of the molar mass of chitosan and film casting solvents on the properties of chitosan films loaded with Mentha spicata essential oil for potential application as wound dressing

Chitosan based films endowed with antibacterial features have witnessed remarkable progress as potential wound dressings. The current study aimed at appraising the effects of the molar mass of chitosan (MM) and the film casting acids on the properties of unplasticized chitosan films and plasticized MSO-embedded chitosan films in order to provide best suited film formulation as a potential candidate for wound dressing application. The prepared films were functionally characterized in terms of their qualitative assessment, thickness, density, swelling behavior, water vapor barrier, mechanical and antibacterial properties. Overall, all chitosan films displayed thickness lower than the human dermis even though thicker and denser films were produced with lactic acid. Assessment of the swelling behavior revealed that only high molar mass (HMM) chitosan films may be regarded as absorbent dressings. Moreover, unplasticized HMM lactate (HMM-LA) films furnished lower stiffness and higher percent strain break as compared to acetate films, due to the plasticizing effect of the remaining lactic acid as alluded by the FTIR analysis. Meanwhile, they provided suitable level of moisture and indicated substantial antibacterial activity against S. aureus and E. coli, the most commonly opportunistic bacteria found in infected skin wound. Plasticized chitosan films doped with MSO were significantly thicker and more permeable to water compared to unplasticized films. Furthermore, MSO significantly potentiate the antibacterial effect of chitosan-based films. Therefore, plasticized HMM-LA/MSO chitosan film flashing good swelling behavior, adequate WVTR and WVP, suitable mechanical properties and antibacterial performances substantiated to be a promising antibacterial dressing material for moderately exuding wounds.

Characterization, processing, and modeling of industrial recycled polyolefins

AbstractThis study aims to establish a systematic approach for characterizing recycled polyolefins of unknown composition, with a specific focus on predicting their performance in film extrusion. We explore various characterization techniques, including differential scanning calorimetry (DSC), Fourier‐transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and rheometry to assess their effectiveness in identifying the polyethylene (PE) fractions within polypropylene (PP) recyclates. By integrating experimental data with modeling techniques, we aim to provide insights into the predictive capabilities of these techniques in determining processing behaviors. The research highlights the superior fidelity of DSC in predicting the relative fraction and type of PE in a PP recyclate. FTIR is also identified as a high‐fidelity approach, albeit requiring application‐specific calibration. TGA, capillary, and oscillatory rheometry are recognized for their ability to distinguish between grades of recycled polyolefins but provide aggregate behaviors rather than detailed constituent information. 3D flow simulation of the cast film extrusion investigated the effect of the viscosity characterization method, non‐isothermal assumption, and process settings but could not fully replicate the observed variations in the cast film processing of two industrial polyolefins with similar melt flow rates and viscosity behaviors. This underscores the practical challenge of predicting processing issues prior to actual processing, necessitating reliance on reliable instrumentation suites and human expertise for diagnosing and remedying variations.Highlights Two industrial recycled polypropylene materials having similar melt flow rates exhibit drastically different cast film processing behaviors. DSC and FTIR provide reasonable approaches for identifying constituent materials. Modeling of the melt viscosities characterized by capillary and parallel plate rheology suggests that viscosity variations relative to the power‐law behavior assumed in the coat hanger die design is a predominant driver of cast film instabilities.