Polymer Films Research Articles

Achieving Significantly Boosted Dielectric Energy Density of Polymer Film via Introducing a Bumpy Gold/Polymethylsilsesquioxane Granular Blocking Layer.

Polymer dielectrics are the key materials for pulsed energy storage systems, but their low energy densities greatly restrict the applications in integrated electronic devices. Herein, a unique bumpy granular interlayer consisting of gold nanoparticles (Au NPs) and polymethyksesquioxane (PMSQ) microspheres is introduced into a poly(vinylidene fluoride) (PVDF) film, forming trilayered PVDF-Au/PMSQ-PVDF films. Interestingly, the Au/PMSQ interlayer arouses a dielectric enhancement of 47% and an ultrahigh breakdown strength of 704MVm-1, which reaches 153% of pure PVDF. It is revealed that the greatly enhanced breakdown strength originated from the Coulomb-blockade effect of Au NPs and the excellent insulating properties of PMSQ microspheres with a special molecular-scale organic-inorganic hybrid structure. Benefiting from the concurrently enhanced dielectric and breakdown performances, an outstanding energy density of 22.42Jcm-3 with an efficiency of 67.1%, which reaches 249% of that of the pure PVDF, is achieved. It is further confirmed that this design strategy is also applicable to linear dielectric polymer polyethyleneimine. The composites exhibit an energy density of 8.91Jcm-3 with a high efficiency of ≈95%. This work offers a novel and efficient strategy for concurrently enhancing the dielectric and breakdown performances of polymers toward pulsed power applications.

Photocurable Hypervalent Fluorinated Sulfur Containing Thin Films with Remarkable Hardness and Modulus

Novel tetrafluoro-λ6-sulfanyl-containing oligomers prepared by visible light-promoted addition of 1,4-(bis-chlorotetrafluoro-λ6-sulfanyl) benzene or 1,3-(bis-chlorotetrafluoro-λ6-sulfanyl) benzene to either 1,4-diethynyl benzene or the 1,3-diethynyl isomers form hard, stress resistant thin films on spin casting. The isomeric oligomers were utilized to establish a structure-function relationship for the mechanical properties of films prepared from the oligomers. The Young’s moduli of 145-nm-thick cured films could reach 60 GPa. The measured hardnesses, between 1.57 and 2.77 GPa, were more than double those of polymethyl methacrylate (PMMA) films. Curing of the tetrafluoro-λ6-sulfanyl-containing polymer films by UV irradiation resulted in coatings that exhibited remarkable hardness and modulus with good surface adhesion to silicon.

Investigating the Influence of the Substrate Temperature and the Organic Precursor on the Mechanical Properties of Low‐Pressure Plasma Polymer Films

ABSTRACTThis work aims to investigate the influence of the substrate temperature on low‐pressure plasma polymerization processes. Emphasis is placed on the mechanical properties and growth mechanism of the plasma polymer films (PPFs). For this purpose, two precursors are considered, differing only by their unsaturation degree: 2‐propen‐1‐ol (CH2═CH–CH2–OH) and propan‐1‐ol (CH3–CH2–CH2–OH). Although propan‐1‐ol‐based PPFs behave like hard elastic solids, 2‐propen‐1‐ol‐based coatings evolve from a liquid film to an elastic solid on increasing the substrate temperature. This behavior is understood considering the evolution of the glass transition temperature of PPFs. The latter is correlated with the cross‐linking degree of the polymeric network governed by the energy density of bombarding ions on the growing film.

Recent Advances in the Development of 1,4-Cyclohexanedimethanol (CHDM) and Cyclic-Monomer-Based Advanced Amorphous and Semi-Crystalline Polyesters for Smart Film Applications

Polyester-based advanced thin films have versatile industrial applications, especially in the fields of textiles, packaging, and electronics. Recent advances in polymer science and engineering have resulted in the development of advanced amorphous and semi-crystalline polyesters with exceptional performance compared to those of conventional polymeric films. Among these, 1,4-cyclohexanedimethanol (CHDM) and cyclic-monomer-based polyesters have gained considerable attention for their exceptional characteristics and potential applications in smart films. This review article provides a comprehensive overview of the recent advances in the synthesis, characterization, and applications of CHDM and cyclic-monomer-based advanced polymers for smart film applications. It discusses the structure–property relationships of these innovative polyesters and highlights their unique characteristics, including thermal, mechanical, and barrier characteristics. Furthermore, this article also emphasizes the solution, melt, and solid-state polymerizations of the polymers. Special emphasis is placed on the influence of the addition of a second diol or second diacid on the performance characteristics of synthesized polyesters/copolyesters to explore their versatile industrial applications. Additionally, the impact of the stereochemistry of the monomers is explored to optimize the characterization of polyesters suitable for industrial applications. Furthermore, this article explores the potential of these advanced polyesters to be considered as materials for smart film applications, especially in the field of flexible electronics. Finally, this article examines the challenges and future recommendations for the development of CHDM and cyclic-monomer-based polyesters for smart film applications. It discusses potential avenues for further research, including in-depth studies for the synthesis and characterization of polyesters, the development of sustainable and biodegradable alternatives to cyclic monomers, alternative green approaches for the synthesis of polymers, etc. This review article provides valuable insight for researchers in academia and industry who are working in the fields of polymer science and materials engineering.

Magnetic Induction Heating in a Conducting Polymer for Biomedical Applications.

In this study, we investigate the magnetic induction heating induced in a conducting polymer (CP) under alternative magnetic fields (AMFs). Experimental results and numerical simulations have proved that the magneto-thermal conversion of the CP is caused by the induced eddy current, which is related to the shape and intensity of the applied external AMF, and the intrinsic electrical conductivity, macrostructure and microstructure of the CP. By employing various fabrication methods, specific temperature distribution and control of thermal field within conducting polymer films and aerogels could be achieved. To exploit the potential of magnetic induction heating in CP for biomedical applications, we designed a conducting polymer aerogel-based self-adaptive heat patch and demonstrated its AMF-enabled localized heating of skin. In addition to the thermal ablation of tumor cells via magneto-thermal conversion of the CP, the promotion of neuronal differentiation at mild temperature by noninvasive magneto-electrical stimulation has also been demonstrated to be an effective strategy for tissue engineering.

Production of Thermoplastic Starch-Aloe Vera Gel Film Embedded with Polyethylene for Improved Tensile Strength and Water Absorption

The water absorption characteristics of thermoplastic starch (TPS) reveal its ability to interact with and absorb water, influencing its overall performance in various applications. The introduction of aloe vera (AV) gel into the TPS polymeric matrix film has proven beneficial in enhancing tensile strength but a notable deficiency is observed in lowering water absorption percentage. Therefore, this paper aims to reduce the water absorption of the TPS30AV polymer matrix film by utilizing polyethylene (PE) without reducing the tensile strength performance of the TPS30AV film. The TPS30AV film was produced using melt-blending and hot-press techniques. Six samples were presented consisting of a control film (TPS30AV) and TPS30AV film with different concentrations of PE resins (5%, 10%, 20%, 30%, and 40%). The film's performance was assessed by examining its mechanical properties, water absorption, and water solubility. The finding shows that TPS30AV with 40% PE has the highest improvement in water absorption percentage which reduces from 309.86% to 34.16% but a tremendous decrement in tensile strength performance. However, TPS30AV with 10% PE has the highest tensile strength, 9.65 MPa with a 20.99% improvement in water absorption reduction. The properties obtained for TPS30AV10PE were also good inYoung's modulus and water solubility percentage. It shows that the film formulated is comparable with previous studies, and improvement has been achieved. As a conclusion, adding PE improved the polymeric structure of TPS30AV and can be used as a biodegradable food-packaging film.

High‐Efficiency Circularly Polarized Luminescence Regulation of a Dye‐Doped Polymer Film by Acid/Aggregation

AbstractSmart materials with circularly polarized luminescence (CPL) tunable ability show great potential for advanced information storage and encryption. While an effective integration of high photoluminescence quantum yield (PLQY) and facile regulation of CPL property in thin films are of great significance, it is challenging due to the scarcity of suitable materials and complexity of systems. Herein, a novel acid‐responsive CPL tunable molecule is designed by combining an aggregation‐induced emission (AIE) component (TPE), an acid‐responsive luminophore (Rhodol), and a chiral aniline. Benefitting by the “AIE” effect of TPE and acid‐sensitive nature of Rhodol, the acidified molecule (S‐Rhodol‐TPE) exhibits a high PLQY even when doped in the polymer substrate at high concentrations. In addition, due to the fluorescence resonance energy transfer (FRET) process between TPE and Rhodol, the emission color of S‐Rhodol‐TPE can be easily regulated by the doped ratio and acidified degree of S‐Rhodol‐TPE in the polymer film. This work exhibits a unique approach to achieving smart CPL‐tunable films with high PLQYs and multiple emission color‐regulation properties, which can undoubtedly facilitate the progress of CPL tunable materials.

Application of interlayer perforation and installation of transparent elements in the technology of duplicated decorative polymer films

Application of interlayer perforation and installation of transparent elements in the technology of duplicated decorative polymer films

Intrinsically stretchable fully π-conjugated polymer film via fluid conjugated molecular external-plasticizing for flexible light-emitting diodes

Fully π-conjugated polymers with rigid aromatic units are promising for flexible optoelectronic devices, but their inherent brittleness poses a challenge for achieving high-performance, intrinsically stretchable fully π-conjugated polymer. Here, we are establishing an external-plasticizing strategy using semiconductor fluid plasticizers (Z1 and Z2) to enhance the optoelectronic, morphological, and stretchable properties of fully π-conjugated polymer films for flexible light-emitting diodes. The synergistic effect of hierarchical structure and optoelectronic properties of Z1 in poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) films enable excellent stretchable deformability (~25%) and good conductivity. PLEDs based on F8BT/Z1 films show stable electroluminescence and efficiency under 15% stretch and 100 cycles at 10% strain, revealing outstanding stress tolerance. This strategy is also improving the stretchable properties of polymers like poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) and poly(2-methoxy-5(2′-ethyl)hexoxy-phenylenevinylene) (Super Yellow), demonstrating its general applicability. Therefore, this strategy can provide effective guidance for designing high-performance stretchable fully π-conjugated polymers films for flexible electronic devices.

Prediction of the structure of polymer-coated cardboards produced by thermocompression using I-optimal design of experiment.

The production of contrasted polymer-coated cardboards is necessary to establish the structure/properties relationships and produce the « just necessary » packaging materials. For that purpose, the impact of the processing parameters on the resulting structure of polymer-coated cardboards was modeled using a statistical Design of Experiment (DOE) approach. Five independent factors were considered: three numeric continuous factors, the pressure, the temperature, and the duration of thermocompression, one numeric discrete factor, the initial polymer film thickness, and one categorical factor, the cardboard basis weight. Four responses were considered: the thicknesses of each of the three layers constituting polymer-coated cardboards (i.e., the free polymer, the impregnated, and the free cardboard) and the material’s curvature. The choice of the adequate DOE was first assessed using a Scoping Design and coupled with the characterization of the used polymer, i.e., poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV). The I-optimal DOE was found to be the most suitable and was therefore implemented. To validate the model, the DOE was then used to produce two targeted structures, one with no impregnation of the polymer and another one with a complete impregnation of the cardboard. The values of thicknesses and curvature were not significantly different from the model predictions, therefore verifying the model.

A Visible-Light-Responsive Fluorescent Diarylethene Having a Betaine Structure.

As a new molecular scaffold of photoswitchable fluorophore, we developed a photochromic diarylethene containing a betaine structure based on pyridinium N-enolate. A facile reaction of a pyridyl-substituted dithienylperfluorocyclopentene derivative with octafluorocyclopentene constructed the betaine structure. The introduction of the betaine moiety provided the diarylethene molecule with bathochromically shifted optical absorption and fluorescing ability, thus enabling the molecule to function as a visible-light-sensitive turn-off mode photoswitchable fluorophore. The molecule in the open-ring form emitted bright blueish green fluorescence. Upon irradiation with 405 nm light, the molecule underwent cyclization isomerization to form the closed-ring isomer and the fluorescence intensity significantly decreased. The turn-off mode fluorescence photoswitching was observed not only in solution but also in polymer films.

Optical and structural transformations in polyethylene terephthalate (PET) films subjected to Ag[formula omitted]-ion implantation and subsequent Au[formula omitted]-ion irradiation

We report on the dual effects of ion implantation and swift heavy ion on the optical and structural characteristics of polyethylene terephthalate (PET) films using UV–Vis spectrophotometry, FTIR and X-ray diffraction measurements. Samples were first implanted with 150 keV Ag+-ions at different fluences of 1 ×1016, 5 ×1016, and 1 ×1017 ions/cm2, and thereafter irradiated with 30 MeV Au7+-ions at different fluences, while analysing elemental depth profile in situ on the Time of Flight Heavy Ions Elastic Recoil Detection (ToF-Hi-ERDA) instrument. The elemental depth profile measurements showed considerable atomic depletion of hydrogen from 36% down to below 6% and oxygen from 18% to about 5%. The proportion of carbon increased from 45% to over 87%. The optical bandgap decreased with increasing ion implantation fluence and reduced even further on irradiation with 30 MeV 197Au7+-ions. The most notable outcome of the implantation was the onset of the precipitation of gold nanoparticles (Au-NPs) in the PET matrix, marked by Localised Surface Plasmon Resonance effects, coincided with a relatively significant drop in the bandgap energy. This latter effect could only be best explained as the result of these Au-NPs in the PET. This suggests that optical bandgap tuning in polymer films, usually achievable through high fluence implantation at low energy (i.e., keV), could also be realized through low fluence irradiation with MeV energy ions. It is surmised that, for the noble metals, NP-induced bandgap modification in PET precludes the need for high fluence to achieve the same. This has the obvious advantage of bandgap alterations at much lower structural damage to the target polymer. As reported by FTIR results, one can observe structural changes with the formation of new chemical bonds on thin films. X-ray diffraction results exhibited one prominent peak corresponding to the (100) plane, which varies in intensity with increased implantation fluence, suggesting a change in the crystallinity of the PET. The decrease in (100) peak or crystallinity was well connected with the presence and decrease of 847, 970, and 1471 cm−1 peaks, which were assigned to the ethylene glycol molecular groups.

Diffusive Memristor with CuS Nanoparticles Embedded in Polymeric Film as Artificial Nociceptor.

The threshold behavior and the ion diffusion dynamics in diffusive volatile memristors have a very uncanny resemblance to the transduction process of biological nociceptors. Hence, the diffusive memristors are considered the most suited for making artificial nociceptive systems. To facilitate their widespread adoption, it is imperative to develop polymeric or organic-inorganic hybrid material-based diffusive memristors that are economical, biocompatible, and easily processable. In this study, we present a cluster-type polymeric diffusive memristor where copper is used as the active top electrode. The switching medium comprises copper(II) sulfide (CuS) nanoparticles embedded in poly(ethylene oxide) (PEO). The devices show electrochemical metalization (ECM)-type and bidirectional diffusive volatile memory with high nonlinearity (104) and turn-on slope (5.6 mV/dec). They reliably remain diffusive volatile with up to 10 wt % CuS in PEO and for a wide range of compliance (10-6 to 10-2 A) without transitioning to the bipolar nonvolatile type. The low reduction potential of CuS and optimal segmental dynamics of PEO work synergistically to ensure stable and reproducible diffusive memory. The CuS nanoparticles act as bipolar electrodes, undergoing local oxidation and reduction under the influence of the bias. The switching of resistance states in the CuS-PEO memristors is attributed to the formation of cluster-type filaments between CuS nanoparticles within the PEO matrix supported by the participation of copper ions from the top Cu electrode. The observation of low filament temperature and the independence of on-state resistance with respect to the device area and temperature further corroborate the cluster-type filament in CuS-PEO memristors. Using a 5 wt % CuS-based device, an artificial nociceptor is realized, which successfully mimics most of the nociceptive plasticities such as threshold, relaxation, no adaptation, and sensitization.

Biomimetic bilayer phase change hydrogels with enhanced water adsorption and desorption for evaporative cooling

Hygroscopic hydrogels, reliable carriers for water-based evaporative materials, undergo shrinkage after evaporative cooling, and the consequent reduction in hygroscopic sites can significantly impair their recyclability in cooling period. To realize cyclic evaporative cooling for rapid regeneration and evaporation, bilayer phase change hydrogel (BPH) concept combining an upper layer of hygroscopic polymer film (CaCl2@ carboxymethyl cellulose/konjac glucomannan films, CaCl2@CMC/KGM, MAF) with a lower layer of hygroscopic hydrogel (CaCl2@poly(vinyl alcohol)/sodium tetraborate decahydrate hydrogel, CaCl2@PVA/Borax, PCH), is presented in this paper. The high liquid–vapor phase change enthalpy of BPH (1274 J/g) enables it to continuously and rapidly remove heat. Benefiting from the MAF hygroscopic porous skeleton, the saturated BPH exhibited a faster water evaporation rate (2.15 kg m−2 h−1) and comparable water vapor transmission rate (1.61 kg m−2 h−1) at 50 °C. After being heated at 50 °C for 1 h, BPH requires 9h to regain its initial mass at 25 °C, 90 % RH. Fifteen moisture adsorption–desorption cycles demonstrate the excellent cyclic regeneration capability of BPH. COMSOL Multiphysics simulation results indicate that evaporative cooling in BPH provides excellent heat dissipation (reduced by about 27 °C). BPH reduces the peak temperatures of a mobile phone by 7.8 °C while charging and 6.5 °C while gaming. This design will contribute to the future cooling of heat-related devices and global sustainability.

Proximity-induced FRET and charge-transfer between quantum dots and curcumin enable reversible thermochromic hybrid polymeric films.

This study introduces a novel strategy for developing reversible thermochromic fluorescent films by precisely controlling the nanoscale proximity of boron nitride quantum dots and curcumin molecules within a poly(3-hydroxybutyrate) matrix. The synergistic interaction and Förster resonance energy transfer between these fluorophores result in an energy transfer efficiency of ∼94%. This approach enables tunable color changes in response to temperature variations, governed by the segmental mobility of polymer chains. Practical applications of these films as temperature sensors for water bottles and electronic devices are demonstrated, highlighting their potential in temperature monitoring, smart packaging, and thermal management systems.

Capillary-Assisted Assembly of Polymer Gel-Supported Lipid Bilayers.

The polymer-supported lipid bilayer represents an attractive supramolecular assembly in numerous biophysical and bioanalytical applications. The assembly of polymer-supported membranes with a polymer layer thickness of just a few nanometers is now well-established, but bilayer properties in such a membrane architecture are still influenced by the nearby solid substrate. Polymer-supported lipid bilayer systems with a several micrometers thick polymer layer will overcome this shortcoming. However, formation of a fluid lipid bilayer on a fully hydrated, micrometer thick polymer film using traditional methods (e.g., vesicle fusion and lipid monolayer deposition techniques) remains a challenging task due to the rather unfavorable interfacial conditions for bilayer formation in such a system. Here, we report for the first time on the facile capillary-assisted formation of a lipid bilayer on the surface of a fully hydrated, several micrometers thick polyacrylamide (PAA) gel, in which forced molecular crowding of lipids at the air-water interface of the capillary results in monolayer instability and collapse, thereby forming a lipid bilayer on the top of the polymer gel inside the capillary. Stable bilayer attachment on the surface of the polymer gel can be achieved via physisorption or specific chemical linkages (tethering) on both cross-linked and non-cross-linked PAA films. Unlike the traditional solid-supported lipid bilayer (SLB), the lipid lateral diffusion in the polymer gel-supported lipid bilayer is not anymore perturbed by a solid substrate. Instead, more like a plasma membrane, it is mainly influenced by the properties of the underlying polymer and the nature/distribution of polymer-bilayer attachments. Polymer gel-supported lipid bilayers built using the capillary-assisted assembly approach show attractive self-healing properties, resulting in superior long-term stability relative to the SLB. We hypothesize that the described capillary-assisted assembly method can be applied to a wide range of polymeric materials and lipid compositions, opening exciting opportunities as an advanced model membrane system.

Physical Crosslinking of Aqueous Polymer Dispersions: A Perspective

AbstractColloidal polymers, and in particular aqueous polymer dispersions, are widely used in commercial applications such as coatings and adhesives. Historically, the solvent resistance and mechanical properties of these systems have been improved by covalently crosslinking the polymer chains after drying. More recently, work has been directed toward replacing this covalent crosslinking, which typically involves highly reactive functional groups, by physical crosslinking through the use of supramolecular interactions. While conceptually similar to the use of covalent crosslinking, physical crosslinking has a unique influence on the rheology of the polymer, which leads to substantial differences in the development of mechanical strength during drying, as well as the mechanical properties of the final polymer film. In this perspective, the advantages and challenges of this approach are outlined, and an outlook for future research in this direction is provided.

PVA-based formulations as a design-technology platform for orally disintegrating film matrices

In the majority of pharmaceutical applications, polymers are employed extensively in a diverse range of pharmaceutical products, serving as indispensable components of contemporary solid oral dosage forms. A comprehensive understanding of the properties of polymers and selection the appropriate methods of characterization is essential for the design and development of novel drug delivery systems and manufacturing processes. Orally disintegrating film (ODF) formulations are considered to be a potential substitute to traditional oral dosage forms and an alternative method of drug administration for children and uncooperative adult patients, including those with swallowing difficulties. A multitude of pharmaceutical formulations with varying mechanical and biopharmaceutical properties have emerged from the modification of the original polymeric bulk. Here we propose different formulation approaches, i.e. solvent casting (SC), 3D printing (3DP), electrospinning (ES), and lyophilization (LP) that enabled us to adjust the disintegration time and the release profile of poorly water soluble haloperidol (HAL, BCS class II) from PVA (polyvinyl alcohol) based polymer films while maintaining similar hydrogel composition. In this study, the solubility of haloperidol in aqueous solution was improved by the addition of lactic acid. The prepared films were evaluated for their morphology (SEM, micro-CT), physicochemical and biopharmaceutical properties. TMDSC, TGA and PXRD were employed for extensive thermal and structural analysis of fabricated materials and their stability. These results allowed us to establish correlations between preparation technology, structural characteristics and properties of PVA films and to adapt the suitable manufacturing technique of the ODFs to achieve appropriate HAL dissolution behaviour.

Low-cost immunosensing approach for Chagas disease: exploiting modified pencil graphite electrodes with polymer films

Low-cost immunosensing approach for Chagas disease: exploiting modified pencil graphite electrodes with polymer films

Shingled design lightweight photovoltaic modules using honeycomb sandwich structures as backsheets

The expanding scale of the photovoltaic (PV) market has intensified the focus on PV module designs for diverse applications. Research actively pursues lightweight PV modules, replacing front glass with polymer films as a suitable design solution. Lightweight PV modules with front-film structures require additional structures to compensate for their inadequate mechanical rigidity. Hence, we integrated honeycomb sandwich structures into lightweight PV modules, substituting them for traditional PV backsheets. It increased the mechanical rigidity of lightweight PV modules and effectively replaced the PV backsheet through a simple one-step lamination process. Consequently, we successfully fabricated lightweight PV modules with a shingled design, achieving a conversion power of 205.80 W in an area of 1.034 m2, facilitating the integration of more solar cells in a limited space. Additionally, standard reliability tests were performed on a PV module weighing only 6.2 kg/m2.