Polymer Films Research Articles

Synergetic Improvement of Flexoelectric Coefficient in liquid Crystal Embedded Flexible PVDF Polymer Composite for Energy Harvesting Applications.

Flexoelectricity is the universal electric polarization of dielectrics upon exertion of a non-uniform strain gradient. With the advancement of nano-technology and miniaturization of electronic devices, flexoelectricity holds the promise to address the power requirements for such device operation. The direct flexoelectric effect in liquid crystal (LC) embedded Poly(vinylidene fluoride) (PVDF) polymer films is examined for the first time by the application of external strain on the films. Physical characterizations such as DSC, dielectric spectroscopy, XRD and FESEM are carried out to study the composite films' intrinsic and extrinsic properties like dielectric, crystallinity and morphologies. The value of the flexoelectric coefficient (μ12) increases with the concentration of LC incorporation. At 3wt%, μ12 attains a maximum value of 68 nC/m, which is more than a three-fold increase compared to that of the pure PVDF film. The role of Maxwell Wagner Sillars (MWS) polarization in determining flexoelectric polarization in polymer composites is also discussed. Moreover, the influence of the microstructure and domain size formation in determining the flexoelectric response are discussed in detail to infer the behaviour of the flexoelectric coefficients of the films. Potential device applications based on this phenomenon have been proposed for future research in sensing and actuation. This article is protected by copyright. All rights reserved.

Resistive Memristors Using Robust Electropolymerized Porous Organic Polymer Films as Switchable Materials.

Porous organic polymers (POPs) with inherent porosity, tunable pore environment, and semiconductive property are ideally suitable for application in various advanced semiconductor-related devices. However, owing to the lack of processability, POPs are usually prepared in powder forms, which limits their application in advanced devices. Herein, we demonstrate an example of information storage application of POPs with film form prepared by an electrochemical method. The growth process of the electropolymerized films in accordance with the Volmer-Weber model was proposed by observation of atomic force microscopy. Given the mechanism of the electron transfer system, we verified and mainly emphasized the importance of porosity and interfacial properties of porous polymer films for memristor. As expected, the as-fabricated memristors exhibit good performance on low turn-on voltage (0.65 ± 0.10 V), reliable data storage, and high on/off current ratio (104). This work offers inspiration for applying POPs in the form of electropolymerized films in various advanced semiconductor-related devices.

A Study on the Dilational Modulus Measurement of Polyacrylic Acid Films at Air–Water Interface by Pendant Bubble Tensiometry

The dilational modulus (E) of polymer films has been commonly measured using the oscillating ring/bubble/drop methods with an external force, and often without specifying the state of the adsorbed film. This study explores an approach where E was determined from the relaxations of surface tension (ST) and surface area (SA) of natural perturbations, in which ST and SA were monitored using a pendant bubble tensiometer. The E of the adsorbed film of PAA (polyacrylic acid) was evaluated for aqueous solutions at CPAA = 5 × 10−4 g/cm3, [MW = 5, 25, and 250 (kDa)]. The E (=dγ/dlnA) was estimated from the surface dilational rate (dlnA/dt) and the rate of ST change (dγ/dt) of the bubble surface from the natural perturbation caused by minute variations in ambient temperature. The data revealed that (i) a considerable time is required to reach the equilibrium-ST (γeq) and to attain the saturated dilational modulus (Esat) of the adsorbed PAA film, (ii) both γeq and Esat of PAA solutions increase with MW of PAA, (iii) a lower MW solution requires a longer time to reach its γeq and Esat, and (iv) this approach is workable for evaluating the E of adsorbed polymer films.

Enhanced Performance of Complementary Electrochromic Device with Hierarchical‐Porous NiO x Decorated ITO Glasses as the Transparent Conductive Electrodes

To pursuit advancing electrochromic technology, the preparation of a novel hierarchical‐porous NiOx‐decorated ITO transparent conductive electrode was developed through the vapor‐assisted conversion and subsequent calcination processes. The modified transparent electrode exhibited advantages in the electrodeposition of conductive polymer films, which significantly enhanced electrochromic cycling stability. Moreover, the complementary electrochromic device based on NiOx‐decorated ITO transparent electrode was fabricated, demonstrating rapid response time (1.75 s for coloration and 0.87 s for bleaching), high optical contrast (53.4%), and remarkable cycling stability (90% optical contrast retention over 2000 cycles). This finding holds prominent potential for applications in related fields.

Antibacterial, Biodegradable Polymeric Films Loaded with Co-MOF/ZnS Nanoparticles for Food Packaging and Photo-Degradation Applications

Antibacterial, Biodegradable Polymeric Films Loaded with Co-MOF/ZnS Nanoparticles for Food Packaging and Photo-Degradation Applications

Synthesis of New Ruthenium Complexes and Their Exploratory Study as Polymer Hybrid Composites in Organic Electronics

Polymeric hybrid films, for their application in organic electronics, were produced from new ruthenium indanones in poly(methyl methacrylate) (PMMA) by the drop-casting procedure. Initially, the synthesis and structural characterization of the ruthenium complexes were performed, and subsequently, their properties as a potential semiconductor material were explored. Hence hybrid films in ruthenium complexes were deposited using PMMA as a polymeric matrix. The hybrid films were characterized by infrared spectrophotometry and atomic force microscopy. The obtained results confirmed that the presence of the ruthenium complexes enhanced the mechanical properties in addition to increasing the transmittance, favoring the determination of their optical parameters. Both hybrid films exhibited a maximum stress around 10.5 MPa and a Knoop hardness between 2.1 and 18.4. Regarding the optical parameters, the maximum transparency was obtained at wavelengths greater than 590 nm, the optical band gap was in the range of 1.73–2.24 eV, while the Tauc band gap was in the range of 1.68–2.17 eV, and the Urbach energy was between 0.29 and 0.50 eV. Consequently, the above comments are indicative of an adequate semiconductor behavior; hence, the target polymeric hybrid films must be welcomed as convenient candidates as active layers or transparent electrodes in organic electronics.

Integrating Electrochemically Grown Nano‐Oxide and Polymer Films for Electrochromic Device: Achieving Near‐Infrared Shielding and Four‐Digit Efficiency

Electrochemically deposited thin films yield high uniformity, a property which is quite vital to in the context of electrochromic (EC) coatings and devices. Tungsten oxide and polyaniline are two such materials that show superior EC properties individually. However, when combined into a solid‐state device structure, they yield a device where the efficiency increases multifolds. This device combination, being thoroughly characterized in the domain of EC parameters such as high switching speeds, rich color contrast, and stability, is found to be an excellent complementary EC pair. The unique property of the said device is that it can reduce the transmission of wavelengths in the near‐infrared region of the electromagnetic spectrum, providing an edge over other such combinations. In addition, a four‐digit value of coloration efficiency makes this device stand out in the family of its contemporaries. Overall, the hybrid nature of the device prompts it to be an excellent combination indicating its high performance in terms of increased endurance and heat isolation capacity.

Discriminative spatial localisation in confocal reflectance and carbon dots-based fluorescence imaging using mixed-mode endoscopic scanner

Carbon dots (CDs)-based fluorescence imaging with confocal reflectance effectively localises labelled structures with clear sample visualization. Yet, integrating these modalities into single-fibre cantilever-based endoscopic scanners poses challenges. Thus, we present an endoscopic scanner with a mixed-mode fibre cantilever for dual modalities imaging. The cantilever features two-attached fibre construction for multiple illumination and detection channels without additional optical components. The measured lateral and axial resolutions are 5.81 and 6.52 µm, respectively with field-of-view of 408 × 488 µm. The fluorescence detection capability was first verified using fluorescent microspheres and CD-embedded polymer film, followed by confocal reflectance and CDs-based fluorescence imaging on labelled fibrous network and plant samples. The results demonstrate the complementary strengths of confocal reflectance, which extracts surface profiles, and CDs-based fluorescence, which captures fluorescence signals, leading to precise localization of fluorescence signals within the sample. Switching modality schemes at the scanner’s back-end enables implementation of different modalities.

Amplified Circularly Polarized Luminescence Behavior in Chiral Co-assembled Liquid Crystal Polymer Films via the Strategic Manipulation of Chiral Inducers.

One of the most important factors for the future application of circularly polarized luminescence (CPL) materials is their high dissymmetry factors (gem), and more and more studies are working tirelessly to focus on increasing the gem value. Herein, we chose an achiral liquid crystal polymer (LC-P) and two chiral binaphthyl-based inducers (R/S-3 and R/S-6) with different substitution positions (3,3' positions for R/S-3 and 6,6' positions for R/S-6) to construct chiral co-assemblies and explored their induced amplification CPL behaviors. Interestingly, after the thermal annealing treatment, this kind of chiral co-assembly (R/S-3)0.05-(LC-P)0.95 can emit a superior CPL signal (|gem| = 0.31 and λem = 424 nm), which achieves about 13-fold signal amplification in the spin-coated film, compared to (R/S-6)0.1-(LC-P)0.9 (|gem| = 0.023 and λem = 424 nm). This is because (R/S-3)0.05-(LC-P)0.95 could further co-assemble to form a more ordered arrangement LC state and generate regular helix nanofibers than that of (R/S-6)0.1-(LC-P)0.9. This work provides an efficient method for synthesizing high-quality CPL-active materials through the strategic manipulation of the structure of chiral binaphthyl-based inducers in chiral co-assembled LCP systems.

Self-oscillating polymeric refrigerator with high energy efficiency.

Electrocaloric1,2 and electrostrictive3,4 effects concurrently exist in dielectric materials. Combining these two effects could achieve the lightweight, compact localized thermal management that is promised by electrocaloric refrigeration5. Despite a handful of numerical models and schematic presentations6,7, current electrocaloric refrigerators still rely on external accessories to drive the working bodies8-10 and hence result in a low device-level cooling power density and coefficient of performance (COP). Here we report an electrocaloric thin-film device that uses the electro-thermomechanical synergy provided by polymeric ferroelectrics. Under one-time a.c. electric stimulation, the device is thermally and mechanically cycled by the working body itself, resulting in an external-driver-free, self-cycling, soft refrigerator. The prototype offers a directly measured cooling power density of 6.5 W g-1 and a peak COP exceeding 58 under a zero temperature span. Being merely a 30-µm-thick polymer film, the device achieved a COP close to 24 under a 4 K temperature span in an open ambient environment (32% thermodynamic efficiency). Compared with passive cooling, the thin-film refrigerator could immediately induce an additional 17.5 K temperature drop against an electronic chip. The soft, polymeric refrigerator can sense, actuate and pump heat to provide automatic localized thermal management.

Dynamic color‐tunable ultra‐long room temperature phosphorescence polymers with photo‐chromism and water‐stimuli response for multilevel anti‐counterfeiting

AbstractDeveloping dynamic color‐tunable ultra‐long room temperature phosphorescence (URTP) polymers with afterglow of over 1 s, photo‐chromism, and multi‐stimuli response for practical anti‐counterfeiting and information security applications is attractive but very challenging. Herein, by doping multicolor phosphorescence pyridinium bromide L block or viologen‐based photo‐chromic V block into polyvinyl alcohol matrixes, the water‐stimuli‐responsive color‐tunable URTP polymer films with afterglow of up to 8 s and the reversible viologen‐based photochromic polymer films have been developed. More significantly, a series of dynamic color‐tunable URTP polymer films with ultra‐long afterglow of over 6 s, photo‐chromism, and water‐stimuli response have been successfully exploited by integrating L and V blocks into one polymer system. Mechanistic investigations have revealed that their photo‐chromism mainly comes from the photo‐generated viologen free radicals. Furthermore, their dynamic multilevel anti‐counterfeiting applications have been demonstrated. These results pave the way to develop smarter multifunctional URTP materials for anti‐counterfeiting and optical sensing.

Femtosecond Laser-induced Nanoparticle Implantation into Flexible Substrate for Sensitive and Reusable Microfluidics SERS Detection

Abstract Surface-enhanced Raman spectroscopy (SERS) microfluidic system, which enables rapid detection of chemical and biological analytes, offers an effective platform to monitor various food contaminants and disease diagnoses. The efficacy of SERS microfluidic systems is greatly dependent on the sensitivity and reusability of SERS detection substrates to ensure repeated use for prolonged periods. This study proposed a novel process of femtosecond laser nanoparticle array (NPA) implantation to achieve homogeneous forward transfer of gold NPA on a flexible polymer film and accurately integrated it within microfluidic chips for SERS detection. The implanted Au-NPA strips show a remarkable electromagnetic field enhancement with the factor of 9×108 during SERS detection of malachite green (MG) solution, achieving a detection limit lower than 10 ppt, far better than most laser-prepared SERS substrates. Furthermore, Au-NPA strips show excellent reusability after several physical and chemical cleaning, because of the robust embedment of laser-implanted NPA in flexible substrates. To demonstrate the performance of Au-NPA, a SERS microfluidic system is built to monitor the online oxidation reaction between MG/NaClO reactants, which helps infer the reaction path. The proposed method of nanoparticle implantation is more effective than the direct laser structuring technique. It provides better performance for SERS detection, robustness of detection, and substrate flexibility and has a wider range of applications for microfluidic systems without any negative impact.

Tailoring the optical properties of dye–polymer composite films based on polyvinyl alcohol doped with phenol red toward flexible optoelectronic applications

The composite films of polyvinyl alcohol (PVA) incorporating varying concentrations of phenol red (PR) dye were fabricated using the solution casting method. Structural characteristics of the prepared films were explored through XRD and FTIR spectroscopy analyses. The inclusion of PR dye within the PVA matrix induced cross-linking, enhancing the amorphous nature of the doped PVA samples, as evidenced by XRD patterns. In the presence of PR dopants, the FTIR peaks for PVA exhibited altered intensities and increased width, indicating physical interactions between the functional groups of PVA and PR dopants. The impact of PR additives on the optical properties of PVA was investigated across the spectral range of 190–2500 nm. The PVA/phenol red composite demonstrated enhanced UV blocking in the 190–400 nm wavelength range, rendering it suitable for applications such as UV notch filters, including laser blocking filters. The indirect and direct optical band-gaps of PVA polymer films were reduced from 5.20 eV and 5.78 eV to 4.30 eV and 5.28 eV, respectively, with an increase in the PR filling ratio from 0 wt% to 1.8 wt%. The dispersion region of the refractive index was analyzed using the single oscillator model (Wemple-DiDomenico). Calculation and discussion of values such as dispersion and oscillation energies (Ed and Eo), permittivity at infinite frequency (ε ∞), and lattice contribution to the dielectric function (ε L) of PVA/PR composite films were conducted. These advancements position PVA/PR composite films for potential applications in flexible optoelectronic devices, including light-emitting diodes and photodetectors.

Transdermal Delivery of Niacin Through Polysaccharide Films Ameliorates Cutaneous Flushing in Experimental Wistar Rats.

Niacin, an established therapeutic for dyslipidemia, is hindered by its propensity to induce significant cutaneous flushing when administered orally in its unmodified state, thereby constraining its clinical utility. This study aimed to fabricate, characterize, and assess the in-vitro and in-vivo effectiveness of niacin-loaded polymeric films (NLPFs) comprised of carboxymethyl tamarind seed polysaccharide. The primary objective was to mitigate the flushing-related side effects associated with oral niacin administration. NLPFs were synthesized using the solvent casting method and subsequently subjected to characterization, including assessments of tensile strength, moisture uptake, thickness, and folding endurance. Surface characteristics were analyzed using a surface profiler and scanning electron microscopy (SEM). Potential interactions between niacin and the polysaccharide core were investigated through X-ray diffraction experiments (XRD) and Fourier transform infrared spectroscopy (FTIR). The viscoelastic properties of the films were explored using a Rheometer. In-vitro assessments included drug release studies, swelling behavior assays, and antioxidant assays. In-vivo efficacy was evaluated through skin permeation assays, skin irritation assays, and histopathological analyses. NLPFs exhibited a smooth texture with favorable tensile strength and moisture absorption capabilities. Niacin demonstrated interaction with the polysaccharide core, rendering the films amorphous. The films displayed slow and sustained drug release, exceptional antioxidant properties, optimal swelling behavior, and viscoelastic characteristics. Furthermore, the films exhibited biocompatibility and non-toxicity towards skin cells. NLPFs emerged as promising carrier systems for the therapeutic transdermal delivery of niacin, effectively mitigating its flushing-associated adverse effects.

Full color control and patterned display device from cyan/magenta/yellow water-dispersed electrochromic polymer nanoparticles systems.

Electrochromic polymers (ECPs) have great application potential in flexible displays, and there is an increasing expectation of using green methods to form ECP films. Herein, we propose a modified microemulsion method to prepare Cyan/Magenta/Yellow (C/M/Y) water-dispersed electrochromic polymer nanoparticles systems. Three polymer films (WDECP-C/M/Y) maintain similar electrochemical properties compared to their corresponding organic solvent-based polymer films. It is intriguing that WDECP-C/M/Y exhibit better electrochromic properties in terms of higher cycling stability (97.24%, 95.05%, and 52.84%, respectively) and faster switching time (0.94 s, 1.09 s, and 1.34 s for coloring time, respectively) due to the introduction of nanoparticles. In addition, it can achieve various desired colors by blending the C/M/Y water-dispersed electrochromic polymer nanoparticles systems in different ratios. The calculated chromaticity coordinates of the blending polymer films show close values to the experimental observation, and the calculated ΔE*ab values range from 2.6 to 10.3, which may provide theoretical guidance for precisely color control. Finally, large-scale and patterned devices were assembled, which can achieve colored-to-colorless reversible electrochromism at a low driving voltage of 0 to 1.5 V. This work puts forward a universal and environmentally sustainable strategy to prepare water-dispersed electrochromic polymer nanoparticles systems, demonstrating their wide range of applications in display devices and electronic tags.

D-π-A chromophores based on novel macroacceptors - Fused (azinylmethylene)malononitriles: Linear and nonlinear optical properties in solution and in poled polymer films

D-π-A chromophores based on novel macroacceptors − fused azinylmethylenemalononitriles (fused azine = pyrido [2,3-b]pyrazine, quinoline, quinoxaline and quinoxalin-2-one) − have been synthesized and their linear and nonlinear optical properties in gas, solution and in poled PMMA-based films have been investigated by DFT, UV–vis and second harmonic generation technique. The transition from chromophores with an azine acceptor to ones with azinylmethylenemalononitrile acceptors leads to a 10-fold increase in calculated μβ values. Poled polymer films doped with studied chromophores at 25 wt% load exhibit quadratic nonlinear optical activity with d33 values up to 42 pm/V.

270 MHz passively mode-locked Er-Doped fiber laser using single walled carbon nanotube polymer film

270 MHz passively mode-locked Er-Doped fiber laser using single walled carbon nanotube polymer film

Unraveling the Molecular Weight Dependence of High Magnetic Field to Manipulate the Semiconducting Polymer Molecular Orientation.

The magnetic alignment of molecules, which exploits the anisotropy of diamagnetic susceptibility, provides a clean and versatile approach to the structural manipulation of semiconducting polymers. Here, the magnetic-alignment dynamics of two molecular-weight (MW) batches of a diketopyrrolopyrrole (DPP)-based copolymer (PDVT-8) were investigated. Microstructural characterizations revealed that the magnetically aligned, high-MW (Mn = 53.7 kDa) PDVT-8 film exhibited a higher degree of backbone chain alignment and film crystallinity compared with the low-MW (Mn = 17.6 kDa) PDVT-8 film grown via the same magnetic alignment method. We found that as the MW increases, the degree of preaggregation of the polymer molecules in solution significantly increases and the aggregation mode changes from H-aggregation to J-aggregation through a cooperative assembly mechanism. These events improved the responsiveness of high-MW polymer molecules to magnetic fields. Field-effect transistors based on the magnetic aligned high-MW PDVT-8 films exhibited a 6.8-fold increase in hole mobility compared to the spin-coated films, along with a mobility anisotropy ratio of 12.6. This work establishes a significant correlation among chain aggregation behavior in solution, polymer film microstructures, magnetic responsiveness, and carrier transport performance in donor-acceptor polymer systems.

Design and research on sequentially controlled magnetic-driven actuators with high stiffness by changing local EGaIn structural density

Magnetic-driven actuators (MDAs) are attracting increasing attention due to fast response and harmless interaction with humans. However, due to their low stiffness and difficulties in sequential magnetic control, MDAs are difficult to complete high-load tasks, and overcoming these obstacles can enable them to be exploited for a wide range of novel applications. In this work, sequentially controlled MDAs (SC-MDAs) with high stiffness were prepared by embedding a polydimethylsiloxane/liquid metal (PDMS/EGaIn) heating layer between magnetic memory polymer (MSMP) films. The variation of EGaIn structural density between different regions leads to temperature discrepancies, resulting in selective activation of specific regions for sequence control. The modulus of the optimized MSMP film at room temperature is 2.21 GPa, which exceeds that of other materials (about 1 MPa) by three orders of magnitude, demonstrating a substantial increase in stiffness. When the content of NdFeB is adjusted to 80 wt%, driving performance is adjusted by optimizing the length-thickness ratio of SC-MDAs. Each claw of the mechanical gripper exhibits a remarkable increase in load capacity, being able to carry 54 times its own weight, which is significantly higher compared to actuators made from other materials (about its weight). A hand-like actuator realizes the sequential control deformation by combining “fingers” with different heating properties.

Infrared spectral features of the charge carriers in nickel salen polymeric complexes

A series of the polymeric complexes (PCs) of nickel(II) with N2O2 Schiff base ligands have been studied by in situ Fourier Transform Infrared (FTIR) spectroelectrochemistry. The molecular structure of the metal-salen complexes as starting materials for the polymer synthesis was modulated by various substituents in the phenolate moieties and diimine bridge. Two groups of the infrared-active vibration (IRAV) bands are obtained in the spectra depending on the oxidation level of the polymers. The assignment of the main IRAV bands was carried out and the electrochemically generated charge carriers were determined. Analysis of the spectroscopic features observed in the mid and near IR region provides information on the charge distribution within the polymer film.