Fabrication Of Polymer Research Articles

Fabrication and adapting the optical, and dielectric performance of PVC/ MnFe2O4/ZnMn2O4 nanocomposite films for optoelectronic applications

The current study focuses on the fabrication of hybrid flexible polymers composed of MnFe2O4/ZnMn2O4 nanocomposites doped polyvinyl chloride (PVC). The doped polymers show great potential for utilization in a wide range of optoelectronics applications. PVC/(1-x)MnFe2O4/xZnMn2O4 were made using the casting and sol gel processes. The effect of (1-x)MnFe2O4/xZnMn2O4 nanocomposite samples on the optical parameters of PVC polymer has been explored using ultraviolet–visible diffused reflectance measurements. Doped polymers might be useful as protective barriers against ultraviolet radiation of various wavelengths (UVA, UVB, UVC) and as excellent absorber materials for solar cells. The direct and indirect bandgaps (Eg) of PVC are 4.26 and 4.08 eV. The direct/indirect optical band gap lowered to their lowest 3.97/3.45 eV as the PVC doped with nanofillers contained 50 %/80 % ZnMn2O4, respectively. Different models were used to extracted the refractive index (n) of different polymers based on the obtained optical band gaps (direct/indirect). Doped polymers containing 50 and 80 % ZnMn2O4 had the highest n values using direct and indirect Eg values, respectively. The n value (obtained from the direct optical bandgap energy) of PVC increased from 2.209 to the maximum value (2.262) as x = 0.5. The n value (obtained from the indirect optical bandgap energy) of PVC increased from 2.349 to the maximum value (2.367) as x = 0.8. All linear and nonlinear optical parameters of PVC polymer were improved as it doped with the nanocomposite fillers. The fluorescence (FL) intensity of PVC was reduced as it was doped with (1-x)MnFe2O4/xZnMn2O4 and this intensity reduced as the content of ZnMn2O4. The standard (CIE) color space chromaticity diagram was used to analysis the FL spectra for different samples. The effect of nanocomposite samples on the AC conductivity, dielectric constants and electric modulus of the PVC was studied. At 1 kHz, the dielectric constant of PVC was increased from 11.745 to 12.906 and 12.096 for polymers with x = 0 and x = 0.2, respectively. The enhanced optical and dielectric properties of the PVC/(1-x)MnFe2O4/xZnMn2O4 polymers nanocomposites suggest that these materials are suitable for smart electronic devices.

Precise Construction of Nitrogen-Enriched Porous Ionic Polymers as Highly Efficient Sulfur Dioxide Adsorbent.

Porous ionic polymers with unique features have exhibited high performance in various applications. However, the fabrication of functional porous ionic polymers with custom functionality and porosity for efficient removal of low-concentration SO2 remains challenging. Herein, a novel nitrogen-enriched porous ionic polymer NH2Py-PIP is prepared featuring high-content nitrogen sites (15.9wt.%), adequate ionic sites (1.22mmolg-1), and a hierarchical porous structure. The proposed construction pathway relies on a tailored nitrogen-functionalized cross-linker NH2Py, which effectively introduces abundant functional sites and improves the porosity of porous ionic polymers. NH2Py-PIP with a well-engineered SO2-affinity environment achieves excellent SO2/CO2 selectivity (1165) and high SO2 adsorption capacity (1.13mmolg-1 at 0.002bar), as well as enables highly efficient and reversible dynamic separation performance. Modeling studies further elucidate that the nitrogen sites and bromide anions collaboratively promote preferential adsorption of SO2. The unique design in this work provides new insights into constructing functional porous ionic polymers for high-efficiency separations.

Facile and scalable synthesis of functionalized hierarchical porous polymers for efficient uranium adsorption

Efficient uranium capture from wastewater holds great importance for the environmental remediation and sustainable development of nuclear energy, but it is a tremendous challenge. Herein, a facile and scalable approach is reported to fabricate functionalized hierarchical porous polymers (PPN-3) decorated with high density of phosphate groups for uranium adsorption. The as-constructed hierarchical porous structure could allow rapid diffusion of uranyl ions, while abundant phosphate groups that serve as adsorption sites could provide the high affinity for uranyl. Consequently, PPN-3 shows a high uranium adsorption uptake of 923.06 mg g−1 and reaches adsorption equilibrium within simply 10 min in uranium-spiked aqueous solution. Moreover, PPN-3 affords selective adsorption of uranyl over multiple metal ions and possesses a rapid and high removal rate of U(VI) in real water systems. Furthermore, this study offers direct polymerization strategy for the cost-effective fabrication of phosphate-functionalized porous organic polymers, which may provide promising application potential for uranium extraction.

Advanced Smart Biomaterials for Regenerative Medicine and Drug Delivery Based on Phosphoramidite Chemistry: From Oligonucleotides to Precision Polymers.

Over decades of development, while phosphoramidite chemistry has been known as the leading method in commercial synthesis of oligonucleotides, it has also revolutionized the fabrication of sequence-defined polymers (SDPs), offering novel functional materials in polymer science and clinical medicine. This review has introduced the evolution of phosphoramidite chemistry, emphasizing its development from the synthesis of oligonucleotides to the creation of universal SDPs, which have unlocked the potential for designing programmable smart biomaterials with applications in diverse areas including data storage, regenerative medicine and drug delivery. The key methodologies, functions, biomedical applications, and future challenges in SDPs, have also been summarized in this review, underscoring the significance of breakthroughs in precisely synthesized materials.

Fabrication of SU-8 polymer micro/nanoscale nozzle by hot embossing method

Electrohydrodynamic-jet printing (E-jet printing) is a direct-writing technology for manufacturing micro-nano devices. To further reduce the inner diameter of the nozzle to improve the printing resolution, a large-scale manufacturing method of SU-8 polymer micro/nanoscale nozzle by means of a process combining UV exposure and hot embossing was proposed. To improve the adhesive strength between the UV mask and SU-8, the influence of the oxygen plasma treatment parameters on the water contact angles of the UV mask was analyzed. The effect of hot embossing time and temperature on the replication precision was studied. The influence of UV exposure parameters and thermal bonding parameters on the micro and nanochannel pattern was investigated. The SU-8 polymer nozzles with 188 ± 3 nm wide and 104 ± 2 nm deep nanochannels were successfully fabricated, and the replication precision can reach to 98.5%. The proposed manufacturing method of SU-8 polymer nozzles in this study will significantly advance the research on the transport properties of nanoscale channels in E-jet nozzles and facilitate further advancements in E-jet based applications.

Strategies for Improving Sustainability in the Development of High-Performance Styrenic Block Copolymers by Developing Blends with Cellulose Derivatives.

Next-generation high-performance polymers require consideration as sustainable solutions. Here, to satisfy these criteria, we propose to combine high-performance styrenic block copolymers, a class of thermoplastic elastomer, with cellulose derivatives as a reinforcing agent with the aim of maintaining and/or improving structural and surface properties. A great advantage of the proposed blends is, besides their biocompatibility, a decrease in environmental impact due to blending with a natural polymer. Particularly, we focus on identifying the effect of different blending compounds and blend ratios on the morphological, structural, thermal, mechanical, electrical and cytotoxic characteristics of materials. This research provides, together with novel material formulations, practical guidelines for the design and fabrication of next-generation sustainable high-performance polymers.

The power of light - From dental materials processing to diagnostics and therapeutics.

Harnessing the power of light and its photonic energy is a powerful tool in biomedical applications. Its use ranges from biomaterials processing and fabrication of polymers to diagnostics and therapeutics. Dental light curable materials have evolved over several decades and now offer very fast (≤ 10 s) and reliable polymerization through depth (4-6 mm thick). This has been achieved by developments on two fronts: (1) chemistries with more efficient light absorption characteristics (camphorquinone [CQ], ~30 L mol-1 cm1 [ʎmax 470 nm]; monoacylphosphine oxides [MAPO], ~800 L mol-1 cm-1 [ʎmax 385 nm]; bisacylphosphine oxide [BAPO], ~1,000 L mol-1 cm-1 [ʎmax 385 nm]) as well mechanistically efficient and prolonged radical generation processes during and after light irradiation, and; (2) introducing light curing technologies (light emitting diodes [LEDs] and less common lasers) with higher powers (≤ 2 W), better spectral range using multiple diodes (short: 390-405 nm; intermediate: 410-450 nm; and long: 450-480 nm), and better spatial power distribution (i.e. homogenous irradiance). However, adequate cure of materials falls short for several reasons, including improper selection of materials and lights, limitations in the chemistry of the materials, and limitations in delivering light through depth. Photonic energy has further applications in dentistry which include transillumination for diagnostics, and therapeutic applications that include photodynamic therapy, photobiomodulation, and photodisinfection. Light interactions with materials and biological tissues are complex and it is important to understand the advantages and limitations of these interactions for successful treatment outcomes. This article highlights the advent of photonic technologies in dentistry, its applications, the advantages and limitations, and possible future developments.

Facile fabrication of high thickness hydrophilic polymer brushes via Surface-Initiated Microliter-Scale copper mediated PhotoATRP toward antifouling surfaces

The recent development of sustainable chemistry motivates scientists to develop economically favourable, highly efficient, and environmentally friendly polymerization techniques. This contribution demonstrates a facile fabrication of hydrophilic polymer brushes via surface-initiated photochemically induced atom transfer radical polymerization using a copper catalyst in low concentrations and microlitre volume of polymerization mixture (SI-μL-CuPhotoATRP). The fabrication proceeds by sandwiching of μL reaction solution between a Si-wafer modified with ATRP-initiator and a glass slide under atmospheric and ambient conditions. Optimization of reaction conditions was realized on hydrophilic monomer such as 2-hydroxyethyl methacrylate (HEMA). Effect of various experimental parameters such as light intensity, solvents, ligands, the volume of the reaction solution, size of the Si-wafers, amount of CuBr2, and CuBr2/ligand ratio in kinetics, linear increase of polymer layer thickness, final thickness and profile of unmodified edges were investigated. The successful fabrication of hydrophilic polymer brushes is confirmed via Fourier transfer infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), profilometry and water contact angle. A linear thickness increase with time up to at least 300 nm was achieved, compared to polymethacrylate layers with thickness up to approximately 100 nm previously published by using photoATRP. The general applicability of the optimized conditions for SI-μL-CuPhotoATRP was further proved for two additional hydrophilic monomers, such as glycidyl methacrylate and 2-hydroxypropyl methacrylate. Furthermore, sequential homo and block copolymerization demonstrated the living character of fabrication conditions, permitting facile fabrication of well-controlled tetra block homo/copolymer brushes with a pyramid-like pattern on Si-wafer. Poly(2-hydroxyethyl methacrylate) (PHEMA) brushes-grown surfaces exhibit excellent antifouling properties and long-term structural stability. The facile, affordable, and environmentally friendly SI-μL-CuPhotoATRPapproachprovides avenues for various surface modifications, such as biomedical, soft robotic, and coating applications.

Low-cost and convenient fabrication of polymer micro/nanopores with the needle punching process and their applications in nanofluidic sensing.

Solid-state micro/nanopores play an important role in the sensing field because of their high stability and controllable size. Aiming at problems of complex processes and high costs in pore manufacturing, we propose a convenient and low-cost micro/nanopore fabrication technique based on the needle punching method. The thin film is pierced by controlling the feed of a microscale tungsten needle, and the size variations of the micropore are monitored by the current feedback system. Based on the positive correlation between the micropore size and the current threshold, the size-controllable preparation of micropores is achieved. The preparation of nanopores is realized by the combination of needle punching and chemical etching. First, a conical defect is prepared on the film with the tungsten needle. Then, nanopores are obtained by unilateral chemical etching of the film. Using the prepared conical micropores, resistive-pulse detection of nanoparticles is performed. Significant ionic current rectification is also obtained with our conical nanopores. It is proved that the properties of micro/nanopores prepared by our method are comparable to those prepared by the track-etching method. The simple and controllable fabrication process proposed here will advance the development of low-cost micro/nanopore sensors.

Amphiphilic ionic liquids as catalysts for efficient synthesis of novel isosorbide-based optical polymers with good biocompatibility and tunable properties

Accurate design and green synthesis of sustainable optical materials from renewable biomass has become vital in polymer science, especially in field of corneal contact lenses or intraocular lens (IOLs). Here we demonstrate the structure design of monomers and efficient synthesis of novel optical poly(isosorbide thioethers) (PITEs) with methyl, alicyclic or aromatic side-groups for high-performance biomedical optical materials. To regulate and control the polymerization process accurately, ionic liquids (ILs) were selected as catalysts and evaluated systematically. Since the presence of hydroxyl in anion improved proton-accepting ability combined with cations functionalized with dual activation sites, the IL tetraethylammonium lactate [TEA][Lac] in trace amount was discovered to show outstanding catalytic performance, better than the reported catalysts. According to experimental results, NMR analysis and DFT calculations, the anion-cation synergistic catalytic mechanism for nucleophilic hydrothiolation was proposed at molecular level. The activation barriers of transition structures decreased significantly from 211.1 to 16.7 kJ·mol−1 after using IL catalyst. The novel PITEs exhibited excellent biocompatibility for L929 cells, good optical transparency (>90 %) and higher refractive index (nD = 1.57 ∼ 1.61) than commercial IOLs (nD = 1.46 ∼ 1.55). Meanwhile, the PITEs possessed not only tunable mechanical properties (strain at break of 1.6 %∼367 %, storage modulus of 2.5 ∼ 4.3 GPa), but also suitable glass-transition temperature (Tg = 41.6 ∼ 92.9 °C) and good thermal stability for polymer melting or moulding process. This work provides a versatile approach for convenient fabrication of novel isosorbide-based polymers with adjustable properties for biomedical optical lenses, which are promising to achieve scale-up and application in future.

Fabrication of second auxiliary ligand-induced copper-based coordination polymers as urease inhibitors

Urease inhibitors (UIs) can improve soil nutrients, reduce soil nitrogen loss, increase nitrate nitrogen content, and help soil maintain nutrients. Because the already available inhibitors were harmful and inefficient, it was critical to develop and manufacture a new family of UIs with high efficiency. In this paper, two copper-based coordination polymers (Cu-CPs) were prepared and served as UIs, which showed that the Cu-CPs had good inhibitory effects on urease and the inhibitory rates were 0.83 ± 0.01 μM and 4.22 ± 0.51 μM. The kinetics of the UIs were determined that the Cu-CPs were anti-competitive inhibition modes with corresponding dissociation constants Ki of 1.52 μM and 5.32 μM. The results of molecular docking show that the two series of active compounds have obvious binding effect on the active site of urease. Furthermore, the oxygen atoms of –COO and μ2-OH groups play critical roles in urease inhibition action.

Fabrication of Substituent-Regulated Two-Dimensional Copper-Based Coordination Polymers as Urease Inhibitors

Fabrication of Substituent-Regulated Two-Dimensional Copper-Based Coordination Polymers as Urease Inhibitors

Shrinking Devices: Shape-Memory Polymer Fabrication of Micro-and Nanostructured Electrodes.

The front cover artwork is provided by Prof. Jose Moran-Mirabal's group at McMaster University in Hamilton, Ontario, Canada. The image shows a 3D rendering and electron microscopy images of micro/nanostructured electrodes, fabricated through thermal shrinking of a shape memory polymer. Read the full text of the Review at 10.1002/cphc.202300535.

Interlaminar Adhesion Study of Fused Filament Fabrication (FFF)-Printed Soft and Rigid Bilayer Structure with Composites

Multi-material Additive manufacturing (AM) has opened new opportunities for the creation of multifunctional structures that enables value-added structural product designs. Among the multi-material AM techniques, multi-nozzle fused filament fabrication which is a type of material extrusion technique is found to be the more popular choice for multi-material polymer fabrication. One major challenge of multi-material additive manufacturing of polymers is the poor mechanical strength at the interface of the dissimilar materials such as polylactic acid (PLA) and thermoplastic polyurethane (TPU) due to the lack of chemical affinity. Therefore, understanding the mechanical strength at the interface of these dissimilar materials becomes an important topic as it allows product designers to do necessary tweak to the design to compensate for the weaker link in the structural design. In this work, we investigated the tensile strength and the shear strength of different combinations of PLA and TPU and their respective nanocomposites, as well as the fatigue analysis of the bi-layer structures made of these dissimilar materials in a 3-point bending test configuration. Generally, when functional fillers or particles are added to the polymer in composites, they tend to adversely affect the interlaminar adhesion property and fatigue life of the soft-rigid bilayer structure. It was found, that the interlaminar tensile strength and the interlaminar shear strength can reduce as high as 44% and 78%, respectively, compared to the baseline samples with no fillers.

Biodegradable photo-crosslinked polycaprolactone/polydopamine elastomers with excellent light driven programmable shape memory and chemical degradation properties

Fabrication of biodegradable shape memory polymer with remotely controllable shape actuation is of great significance in the biomedical field but remains challenging. Herein, we present a simple strategy to fabricate a monolayer-based stretchable and mechanically robust polycaprolactone/polydopamine elastomer via efficient thiol-ene click chemistry. The resultant elastomers exhibit desirable photothermal transfer efficiency and can enable rapid temperature increase over the melting temperature of polymeric matrix, and quantitative results demonstrate that the crosslinked film exhibited excellent shape memory properties with shape fixity (Rf) and shape recovery ratios (Rr) approaching 92.3 % and 95.6 %, respectively. Combined with photo stimuli, anisotropic polymer chain relaxation of the prestretched film can generate asymmetric contractions and eventually give rise to ut out-of-plane bending actuations upon photo stimulation, meanwhile, numerical simulation reveals the interaction mechanism of light with film. Beyond this, we further demonstrate that the bending angle is correlated with the parameters of prestretch strain, film thickness as well as irradiation time, and the maximum value can reach 158° with prestretch strain of 200 % and film thickness of 0.3 mm. In particular, the bent structures could be reversibly deformed into plane state via photo-directed corresponding opposite surfaces. Remarkably, the in vitro degradation properties of the elastomers on PBS-T buffer solutions demonstrated that the degradation was composed of induction stage and acceleration stage. This work will pave way for designing biodegradable light-induced shape memory materials toward biomedical device fields and so on.

Self-poled piezoelectric polymer composites via melt-state energy implantation

Lightweight flexible piezoelectric polymers are demanded for various applications. However, the low instinctively piezoelectric coefficient (i.e. d33) and complex poling process greatly resist their applications. Herein, we show that introducing dynamic pressure during fabrication is capable for poling polyvinylidene difluoride/barium titanate (PVDF/BTO) composites with d33 of ~51.20 pC/N at low density of ~0.64 g/cm3. The melt-state dynamic pressure driven energy implantation induces structure evolutions of both PVDF and BTO are demonstrated as reasons for self-poling. Then, the porous material is employed as pressure sensor with a high output of ~20.0 V and sensitivity of ~132.87 mV/kPa. Besides, the energy harvesting experiment suggests power density of ~58.7 mW/m2 can be achieved for 10 N pressure with a long-term durability. In summary, we not only provide a high performance lightweight, flexible piezoelectric polymer composite towards sustainable self-powered sensing and energy harvesting, but also pave an avenue for electrical-free fabrication of piezoelectric polymers.

Three-Dimensional Optical Imaging of Internal Deformations in Polymeric Microscale Mechanical Metamaterials.

Recent advances in two-photon polymerization fabrication processes are paving the way to creating macroscopic metamaterials with microscale architectures, which exhibit mechanical properties superior to their bulk material counterparts. These metamaterials typically feature lightweight, complex patterns such as lattice or minimal surface structures. Conventional tools for investigating these microscale structures, such as scanning electron microscopy, cannot easily probe the internal features of these structures, which are critical for a comprehensive assessment of their mechanical behavior. In turn, we demonstrate an optical confocal microscopy-based approach that allows for high-resolution optical imaging of internal deformations and fracture processes in microscale metamaterials under mechanical load. We validate this technique by investigating an exemplary metamaterial lattice structure of 80 × 80 × 80 μm3 in size. This technique can be extended to other metamaterial systems and holds significant promise to enhance our understanding of their real-world performance under loading conditions.

Capillary-Assisted Assembly of Soft Conductive Polymer Nanopillar/Tube Arrays and Applications.

Nanopillar/tube arrays have emerged as encouraging platforms, possessing remarkable advantages, including large specific areas and highly aligned orientations. Despite the progress of nano/microfabrication technologies, facile and controllable fabrication of conductive polymer nanopillar/tube arrays remains challenging. In this study, we demonstrate that the air-liquid interfacial self-assembly can be extended to obtain three-dimensional nanostructured arrays. A smart and novel method is proposed for preparing uniform conductive polymer nanopillar/tube arrays by a template-mediated interfacial synthesis approach. By utilizing capillary force, precise control processes of the nanostructure and patterned structure can be easily realized. Furthermore, a transfer strategy is devised, allowing for scalable fabrication and expansion of the applicability. Applications, including antibacterial surfaces and actuators, have been demonstrated. We extend the air-liquid interfacial synthesis technique as a powerful and universal strategy for producing ordered nanopillar/tube arrays and show the great potential of soft nanostructured arrays as advanced platforms in diverse applications.

Fabrication of lidocaine-loaded polymer dissolving microneedles for rapid and prolonged local anesthesia.

There is an urgent need for research into effective interventions for pain management to improve patients' life quality. Traditional needle and syringe injection were used to administer the local anesthesia. However, it causes various discomforts, ranging from brief stings to trypanophobia and denial of medical operations. In this study, a dissolving microneedles (MNs) system made of composite matrix materials of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and sodium hyaluronate (HA) was successfully developed for the loading of lidocaine hydrochloride (LidH). The morphology, size and mechanical properties of the MNs were also investigated. After the insertion of MNs into the skin, the matrix at the tip of the MNs was swelled and dissolved by absorption of interstitial fluid, leading to a rapid release of loaded LidH from MNs' tips. And the LidH in the back patching was diffused into deeper skin tissue through microchannels created by MNs insertion, forming a prolonged anesthesia effect. In addition, the back patching of MNs could be acted as a drug reservoir to form a prolonged local anesthesia effect. The results showed that LidH MNs provided a superior analgesia up to 8h, exhibiting a rapid and long-lasting analgesic effects. Additionally, tissue sectioning and in vitro cytotoxicity tests indicated that the MNs patch we developed had a favorable biosafety profile.

Shrinking Devices: Shape-Memory Polymer Fabrication of Micro-and Nanostructured Electrodes.

Since their discovery in the 1940s, shape memory polymers (SMPs) have been used in a broad spectrum of applications for research and industry.[1] SMPs can adopt a temporary shape and promptly return to their original form when submitted to an external stimulus. They have proven useful in fields such as wearable and stretchable electronics,[2] biomedicine,[3] and aerospace..[4] These materials are attractive and unique due to their ability to "remember" a shape after being submitted to elastic deformation. By combining the properties of SMPs with the advantages of electrochemistry, opportunities have emerged to develop structured sensing devices through simple and inexpensive fabrication approaches. The use of electrochemistry for signal transduction provides several advantages, including the translation into inexpensive sensing devices that are relatively easy to miniaturize, extremely low concentration requirements for detection, rapid sensing, and multiplexed detection. Thus, electrochemistry has been used in biosensing,[5] pollutant detection,[6] and pharmacological[7] applications, among others. To date, there is no review that summarizes the literature addressing the use of SMPs in the fabrication of structured electrodes for electrochemical sensing. This review aims to fill this gap by compiling the research that has been done on this topic over the last decade.