Polymer Layer Research Articles

In situ co-electropolymerization of resorcinol/2-aminophenol on Au-Chitosan-electroreduced graphene oxide nanocomposite for electrochemical detection of Vandetanib

This research work represents the first report of an electrochemical sensor designed specifically for the detection of Vandetanib based on the molecular imprinted polymer technique. The production of a polymer layer on the electrode surface was achieved utilizing the in situ co-electropolymerization method, with two resorcinol and 2-aminophenol monomers serving as the functional monomers. The electrode used to make the sensor was glassy carbon, which was modified in the first step using the electrochemical deposition of gold nanoparticles. Then, in order to further improve, a mixture of graphene oxide dispersed in the chitosan polymer network was incubated on the electrode surface, and then graphene oxide was electrochemically reduced. Under optimised conditions, the accurate identification of Vandetanib can be achieved with a linear range of 0.01 to 0.12 μM and a detection limit of 0.003 μM.

Static and dynamic buckling analysis of two-layer shells include auxetic honeycomb core combined with laminated three-phase polymer/GNP/fiber surface resting on Kerr elastic medium in hygro-thermal environments

This article investigates the static and dynamic buckling behavior of a double-curved sandwich shell composed of two layers via improved first-order shear deformation theory without using the shear correction is utilized to model the sandwich shell. The sandwich two-layer shell are held together by elastic pins, each layer made from an ultra-light auxetic honeycomb core layer (negative Poisson’s ratio) and is reinforced by a layer of tri-phase polymer, graphene nanoplatelets (GNP), and fiber. The double-curved sandwich shell is supported by a Kerr elastic medium in hygro-thermal environment assuming that temperature and humidity only cause forces to be applied tangentially to the shell and do not change the mechanical properties of the shell material. The motion equations of sandwich two-layer shell are derived by Hamilton’s principle, then the finite element method and Bolotin method are used to derive the dynamic instability region of sandwich two-layer shell. The accuracy of these results is confirmed by a comparison with established statements within the specific conditions of the problem model. The influence of inputs on the static and dynamic stability of sandwich two-layer shell is fully explored and discussed. Additionally, this serves as a crucial foundation for the calculation and design of structures that can integrate a variety of materials with different properties with low cost and simplification.

High-energy computed tomography for inspection and monitoring of flexible riser

Flexible risers have been widely used in the offshore oil and gas industry and have many applications, such as production, gas lifting, or gas and water injection. The structure comprises several metal and polymer layers, which allow it to withstand a sizeable bending curve and high internal pressure. Therefore, guaranteeing the integrity of flexible risers throughout their useful life is extremely important. It requires developing and applying effective inspection and monitoring techniques, particularly emphasizing the tensile armor layers. This work evaluated the ability of the High-Energy Computed Tomography (CT) Technique to detect internal defects such as cracks, breaks, and fissures in the riser layers. A flexible riser sample of approximately 2 m in length and 281 mm in external diameter was scanned using a tomography system consisting of a 6 MeV Betatron and a set of 14-bit A-Si digital detectors. The images were acquired in 360° with angular steps of 2°. After acquisition, the images were reconstructed, and 3D models were built for qualitative and quantitative evaluation. Through the segmentation process, the metal layers of the flexible riser could be analyzed individually. Defects were found in the tensile armor layers, indicating ruptures and cracks and the onset of pitting. The results strongly suggest that computed tomography can be used as a non-destructive technique for inspecting flexible risers, with good efficiency in detecting defects, and that its application can be extended to field tests.

Optical Force Sensor Based on Plasmon Modulated Upconversion Luminescence

AbstractA novel force sensor exploiting the interaction between plasmonic nanostructures and upconversion nanoparticles (UCNPs) is reported. The nanosensor is composed of a gold nanodisk and UCNPs separated by a flexible polymer layer. The gold nanodisk is designed to exhibit a plasmon resonance that selectively enhances one of the emission bands of the UCNPs while leaving the other ones largely unaffected. As the nanosensor is compressed or stretched by an external force, the polymer layer thickness changes, modulating the plasmon‐UCNP coupling. The resulting changes in the luminescence intensity provide the basis for sensing. Furthermore, the nanosensor employs ratiometric sensing, which makes it highly robust against any environmental variations. The nanosensors exhibit two orders of magnitude higher responsivity than previously reported UCNP‐based force sensors. They can be prepared as an on‐chip sensor array or in a colloidal solution, making them suitable for a variety of applications in biology and robotics.

Facile Electret-Based Self-Powered Soft Sensor for Noncontact Positioning and Information Translation.

Noncontact sensors have demonstrated significant potential in human-machine interactions (HMIs) in terms of hygiene and less wear and tear. The development of soft, stable, and simply structured noncontact sensors is highly desired for their practical applications in HMIs. This work reports on electret-based self-powered noncontact sensors that are soft, transparent, stable, and easy to manufacture. The sensors contain a three-layer structure with a thickness of 0.34 mm that is fabricated by simply stacking a polymeric electret layer, an electrode layer, and a substrate layer together. The fabricated sensors show high charge-retention capability, keeping over 98% of the initial surface potential even after 90 h, and can accurately and repeatedly sense external approaching objects with impressive durability. The intensity of the detected signal shows a strong dependence on the distance between the object and the sensor, capable of sensing a distance as small as 2 mm. Furthermore, the sensors can report stable signals in response to external objects over 3000 cycles. By virtue of the signal dependence on distance, an intelligent noncontact positioning system is developed that can precisely detect the location of an approaching object. Finally, by integrating with eyeglasses, the transparent sensor successfully captures the movements of blinks for information translation. This work may contribute to the development of stable and easily manufactured noncontact soft sensors for HMI applications, for instance, assisting with communication for locked-in syndrome patients.

MASSTRANSFER FEATURES IN THE APPARATUSES WITH A MOVING NOZZLE IN A THREE-PHASE FOAM LAYER

The improvement of heat and mass exchange equipment for sorption processes in the countercurrent contact of gas and liquid in combined block elements with a weighted spherical nozzle, as well as a more in-depth study of this process, is an urgent task of chemical technology. A fundamentally new type of ball-shaped three-dimensional mesh fluidized nozzle was developed and researched, the bodies of which are made of polymer layers with holes, and a freely coiled metal or polymer mesh is located inside. The nozzle has a high specific surface area, developed free volume and low bulk density. The study of mass transfer in the liquid and gas phases was carried out and the corresponding calculation equations were obtained. Dependencies for the calculation of the mass transfer coefficients and the efficiency of the combined block element on the mode and design parameters are established. The results of calculations based on the obtained dependencies show a sufficient correlation with the experimental data. The proposed model of the desorption process of carbon dioxide from water, which allows predicting the values of the efficiency indicators of the decarbonization process. It was established that the use of a combined block element with a ball-shaped nozzle allows to increase the mass transfer coefficients compared to the failure plate. The industrial implementation of absorption processes in the foam layer and the use of the gas-liquid layer stabilization method significantly expands the scope of application of foam apparatuses and opens up new opportunities for intensifying technological processes. Previously expressed assumption about the perspective of using mesh materials for the manufacture of nozzle bodies was confirmed by experiments, but the peculiarity of the operation of devices with similar nozzles should be emphasized.

Implementation of bio-inspired organic/inorganic layer structures as interphase in carbon fiber reinforced concrete

Biological materials found in nacre or glass sponges reveal specific layered organic and inorganic structures known for their fracture toughness caused by crack deflection and bridging. This work aims to bio-mimic the brick-and-mortar (BnM) structure from nacre and the layer-by-layer (LbL) structure from the glass sponge filaments to incorporate these effects into the contact zone of carbon fiber-reinforced concrete (CFRC) in order to prevent brittle composite failure. To build up BnM- and LbL-structure materials such as nanoclays, sodium water glass, and polymer dispersions were selected since they are well-established low-cost materials in building. Nanoclays were analyzed regarding their size, dispersibility and exfoliation. Montmorillonite (MMT) was used to be mixed with polymers to produce self-assembled BnM-structured films and coatings. Also, LbL-structures were formed by alternating layers of sodium water glass and polymer. Scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to verify the morphology. The MMT-containing coatings demonstrated enhanced nucleation potential when exposed to cementitious eluate. Micromechanical pull-out tests on single carbon fibers with BnM- and LbL-coatings embedded in concrete demonstrate the potential to increase composite toughness. The successful implementation of the bio-inspired structures using affordable materials lays the groundwork for their scalability and integration into composite structures for building.

Super-slippery silicone-based gel coating with a regenerative oil layer for long-term prevention of surface contamination

Polymer-based gel-type coatings, in which oil molecules are absorbed within polymer networks, have drawn attention as functional coatings to address fouling problems. However, surface drought caused by lubricant depletion limits the longevity of conventional gel-type coatings. In this study, a super-slippery long-chain entangled polydimethylsiloxane (LEP) gel that can self-regenerate a low-viscosity oil layer is proposed to enhance its long-term anti-fouling performance in both indoor and marine habitats. The proposed LEP gel coating can effectively prevent contamination from numerous liquids and protect aluminum surfaces from corrosion in seawater. Even when it was incubated with Porphyridium purpureum, marine red algae that readily stick to the surface, no biofilm was formed on the coated samples for 37 weeks. In field tests, no biological adhesion was observed on the coating surface which was applied to port structures and left for two summer months. This enhanced anti-contamination performance is mainly attributed to the dual protective barrier comprising the underlying polymer layer and regenerative oil layer. Due to special property of continuous self-regeneration of oil layer, the proposed LEP gel surface demonstrates much enhanced sustainability, compared to conventional gel-type coatings. Consequently, the long-term anti-contamination performance of the super-slippery LEP gel coating would pave the way for novel approach to its practical applications.

High performance composite phase change materials enhanced via evaporation-induced hydrogen bond network refactoring

Composite phase change materials (CPCMs) with real-time thermal harvesting are in high demand in the solar-thermal energy conversion industry. However, poor heat conduction, lack of strength and leakage problem severely restrict its availability. In this study, we develop an evaporation-inspired, facile, and versatile strategy for manufacturing shape stable CPCMs from organohydrogels with enhanced thermal performances for advanced thermal energy storage and management. Organohyodrogels contained with graphene nanoplatelets (GNPs) served as the template. By oven-drying the organohydrogel, hydrogen bonding reconstruction would assist in the formation of a dense polymer layer to encapsulate PCMs, forming the non-leakage CPCMs. The strong capillary force generated during the oven-drying process would induce the alignment of GNPs, forming thermal conduction pathways. The as-prepared composite exhibits a high thermal conductivity (1.25 W m-1K−1), satisfactory latent heat storage (171.5 J g−1) and excellent Young’s modulus (8.3 MPa). When subjected to solar radiation, solar energy is converted to heat and stored inside the material, with a conversion efficiency as high as 95.8 %. The robust composite with high performance is expected to be an efficient and reliable thermal management material in solar-thermal energy conversion.

Laminated dihydrazone Zn(II) coordination polymer with prospects for sensory and multifunctional biomedical applications

This study introduces a new laminated coordination polymer, {[Zn3(HL)2(H2O)6](SO4)2⋅1.5dmf·2.5H2O}n (1), synthesized through the direct interaction of ZnSO4·7H2O with dihydrazone Schiff base ligand (H2L = 2,6-diacetylpyridine bis(isonicotinoylhydrazone)) at room temperature. Comprehensive characterization of the compound, employing various methods (SCXRD, PXRD, IR, TGA) revealed different coordination surrounding of metal atoms and a combination of photoluminescent properties and biological activity. The polymeric layers are corrugated along the b-axis, mutually intertwined forming channels filled with outer sphere anions (SO42-) and solvent molecules (water and dmf). It was shown that solvent molecules have a decisive influence on the photoluminescent properties of the compound. The partial removal of water molecules leads to increased photoluminescence, the intensity of which doubles compared to the synthesized crystals. Furthermore, the compound demonstrates robust antibacterial effects against four Gram+ positive and two Gram- negative bacteria. In addition, its impact on cell proliferation, both in cancerous and non-cancerous cells, reveals the compound's antiproliferative effect on breast cancer cells in vitro, coupled with biocompatibility with human fibroblasts. This multifaceted approach positions the synthesized polymer as a promising candidate with vast potential for applications in luminescent materials and biomedical research.

Geometric-phase-based phase-knife mask for stellar nulling and coronagraphy

Exoplanets can be detected very close to stars using single-mode cross-aperture nulling interferometry, a photonic technique that relies on the inability of an anti-symmetric stellar point-spread function to couple to the symmetric mode of a single-mode fiber. We prepared an asymmetric field distribution from a laboratory point source using a flat geometric-phase-based pupil-plane phase-knife mask comprised of a planar liquid crystal polymer layer with orthogonal optical axes on opposite sides of a linear pupil bisector. Our mask yielded an on-axis laboratory point-source rejection (i.e., an interferometric “null depth”) of 2.2 × 10−5. Potential mask modifications to better reject starlight are described that incorporate additional phase regions to spatially broaden the rejection area, and additional layers to spectrally broaden the rejection. Also discussed is a topological correspondence between the spatial configurations of separated-aperture nullers, cross-aperture nullers and full-aperture phase coronagraphs.

Toward coupling across inorganic/organic hybrid interfaces: polyaniline-coated gold nanoparticles with 4-aminothiophenol as gold-anchoring moieties

AbstractThe chemical binding between metal nanoparticles and (semi-)conductive polymer layers is essential to control the (opto-)electronic properties of such hybrid materials. Current approaches that achieve a conjugated binding of organic (semi-)conductive ligands to metal nanoparticles demonstrated promising functional properties, but are based on tedious multi-step organic synthesis to incorporate the required binding moieties at the chain ends of targeted macromolecular species. Herein, we explore the pre-functionalization of gold nanoparticles with p-aminothiophenol and subsequent surfactant-assisted formation of a poly(aniline) (PANI) shell as a means to access gold/PANI core–shell-type nanoparticles with enhanced conductive properties. Controlled surface deposition of these hybrid nanoparticles is achieved via template-assisted self-assembly. For these surface-deposited nanoparticles, charge transport properties are characterized at the nanoscale by conductive atomic force microscopy measurements and show a significant conductivity increase of our core–shell particles as compared to reference particles formed by conventional surfactant-assisted PANI-shell formation. Graphical Abstract

Sealing porous carbon via surface-initiated polymerization achieves low-surface-area Si-C microparticles for Li-ion batteries

Porous Si-carbon composite architecture represents an effective design for lithium-ion batteries (LIBs) anodes. However, the high specific surface area (SSA) greatly negates cell initial Coulombic efficiency (ICE), and the function of porous carbon is challenged by practical conditions such as calendaring and high-mass-loading cycling. Here, we report a crosslinked conductive polymer layer as sealing layer for porous Si-C particles to enable high ICE and stable cycling of densified Si-anodes. A surface-initiated polymerization was adopted to form a conformal polymeric skin that can greatly lower the SSA and improve ICE of porous Si-C particles (94.8 vs. 5.7 m2/g, and 77.3% vs. 84.4%). The “sealed” Si-C particle maintains desirable intraparticle porosity to digest the volume changes during Li insertion, while the polymeric skin is key to shield off electrolyte penetration into the particles interior and to mechanically package the porous secondary particles throughout calendaring and cycling. The Si-C graphite mixtures anode (650 mAh/g) retains 70.8% capacity after 500 cycles. Adopting high-mass-loading NCM622, the full cell with stringent electrode metrics (anode at 1.2 g/cm3, NCM622 at 3.1 g/cm3, 3.4 mAh/cm2) demonstrates 65.9% capacity retention after 100 cycles. This study opens up a pathway to produce low-SSA porous anodes for practical LIBs.

Construction of PDMS@ZIF-8 composite membrane on PVDF hollow fiber inner surface for ultrafast ethanol/water separation

Construction of ultra-thin and defect-free separation membrane on inner surface of hollow fiber supports is significant but challenging for molecular separation. In this study, the highly permeable PDMS@ZIF-8/PVDF composite membranes were successfully fabricated upon the inner-surface of polyvinylidene fluoride (PVDF) hollow fiber membrane for pervaporation (PV) ethanol/water separation. The efficient preparation of hierarchical PDMS@ZIF-8/PVDF composite membranes benefited from the precise regulation of ZIF-8 layer through interfacial synthesis and sequential coating of PDMS matrix. The thickness of the PDMS layer was only 16 ± 2 nm, which admirably eliminated the non-selective defects in ZIF-8 layer. Owning to the optimal combination of MOF layer and ultra-thin polymer layer, the as-prepared membrane exhibited the excellent ethanol flux of 1.34 kg m−2 h−1 with an ethanol concentration in permeate of 31.3 wt% for separating 5 wt% ethanol aqueous solution at 40 °C. The separation performance of the resultant membrane was superior to that of the other ethanol selective PV membranes. These findings herein provided a new way for preparing high-performance hollow fiber composite membranes for PV separation.

Electrochemical-repaired porous graphene membranes for precise ion-ion separation

The preparation of atom-thick porous lattice hosting Å-scale pores is attractive to achieve a large ion-ion selectivity in combination with a large ion flux. Graphene film is an ideal selective layer for this if high-precision pores can be incorporated, however, it is challenging to avoid larger non-selective pores at the tail-end of the pore size distribution which reduces ion-ion selectivity. Herein, we develop a strategy to overcome this challenge using an electrochemical repair strategy that successfully masks larger pores in large-area graphene. 10-nm-thick electropolymerized conjugated microporous polymer (CMP) layer is successfully deposited on graphene, thanks to a strong π-π interaction in these two materials. While the CMP layer itself is not selective, it effectively masks graphene pores, leading to a large Li+/Mg2+ selectivity from zero-dimensional pores reaching 300 with a high Li+ ion permeation rate surpassing the performance of reported materials for ion-ion separation. Overall, this scalable repair strategy enables the fabrication of monolayer graphene membranes with customizable pore sizes, limiting the contribution of nonselective pores, and offering graphene membranes a versatile platform for a broad spectrum of challenging separations.

Vibration characteristics of a cylindrical sandwich shell with an FG auxetic honeycomb core and nanocomposite face layers subjected to supersonic fluid flow

In this paper, the flutter analysis is studied for a cylindrical sandwich shell subjected to external supersonic fluid flow. The sandwich shell consists of a re-entrant auxetic honeycomb (AH) core made of functionally graded materials (FGMs) which is covered with two polymeric face layers enriched with either carbon nanotubes (CNTs), graphene nanoplatelets (GNPs), or graphene oxide powders (GOPs). The volume fraction (percentage) of the ceramic phase in the functionally graded auxetic honeycomb (FGAH) core varies from zero at the inner surface to one at the outer one based on either power-law function (P-FGM), exponential function (E-FGM), or sigmoid function (S-FGM). It is assumed that the nanofillers are distributed uniformly inside the face layers. The first-order shear deformation theory (FSDT) and the piston theory are employed to provide the mathematical models of the shell and the aerodynamic pressure, respectively. The governing equations and boundary conditions are derived via Hamilton’s principle. An exact solution is performed in the circumferential direction via harmonic trigonometric functions (sine and cosine) and an approximate solution is performed in the axial direction utilizing the differential quadrature method (DQM). The natural frequencies and corresponding damping ratios are attained through the presented semi-analytical solution and the impacts of several factors on the natural frequencies and the critical aerodynamic pressure of the shell are examined. These factors the type of the FGM, the material index, and inclined angle of the cells in the FGAH core, the thickness of the FGAH core, the type and mass fraction of the nanofillers in the nanocomposite face layers, and boundary conditions.

Dendrite-Free Li5.5PS4.5Cl1.5-Based All-Solid-State Lithium Battery Enabled by Grain Boundary Electronic Insulation Strategy through In Situ Polymer Encapsulation.

Sulfide-based all-solid-state lithium batteries (ASSLBs) have attracted unprecedented attention in the past decade due to their excellent safety performance and high energy storage density. However, the sulfide solid-state electrolytes (SSEs) as the core component of ASSLBs have a certain stiffness, which inevitably leads to the formation of pores and cracks during the production process. In addition, although sulfide SSEs have high ionic conductivity, the electrolytes are unstable to lithium metal and have non-negligible electronic conductivity, which severely limits their practical applications. Herein, a grain boundary electronic insulation strategy through in situ polymer encapsulation is proposed for this purpose. A polymer layer with insulating properties is applied to the surface of the Li5.5PS4.5Cl1.5 (LPSC) electrolyte particles by simple ball milling. In this way, we can not only achieve a dense electrolyte pellet but also improve the stability of the Li metal anode and reduce the electronic conductivity of LPSC. This strategy of electronic isolation of the grain boundaries enables stable deposition/stripping of the modified electrolyte for more than 2000 h at a current density of 0.5 mA cm-1 in a symmetrical Li/Li cell. With this strategy, a full cell with Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) as the cathode shows high performance including high specific capacity, improved high-rate capability, and long-term stability. Therefore, this study presents a new strategy to achieve high-performance sulfide SSEs.

Voltage-modulated polymer nanopore field-effect transistor for multi-sized nanoparticle detection

Solid-state nanopores offer a range of distinct advantages over biological nanopores, such as structural diversity and greater stability and durability; this makes them highly promising for high-resolution nanoparticle sensing. Biological nanopores can exhibit gating characteristics with stress-responsive switches and can demonstrate specificity toward particular molecules. Drawing inspiration from biological nanopores, this paper introduces a novel polymer nanopore with field-effect characteristics, leveraging a conductive polymer in its construction to showcase intriguing gating behavior. Notably, in this device, the polymer layer serves as the gate, enabling precise control over the source–drain current response inside and outside the pore by simply adjusting the gate voltage. This unique feature allows fine-tuning of the nanopore’s sensitivity to nanoparticles of varying sizes and facilitates its operation in multiple modes. Experimental results reveal that the developed polymer nanopore field-effect transistor demonstrates remarkable selectivity in detecting nanoparticles of various sizes under different applied voltages. The proposed single device demonstrates the exceptional ability to detect multiple types of nanoparticle, showcasing its immense potential for a wide range of applications in biological-particle analysis and medical diagnostics.

Magnetic quaternary ammonium polymer bearing porous agarose for selective extraction of Aristolochic acids in the plasma

Aristolochic acids (AAs) naturally occurring in the herbal genus Aristolochia are associated with a high risk of kidney failure, multiple tumors and cancers. However, approaches with high selectivity and rapidity for measuring AAs in biological samples are still inadequate. Inspired by the mechanism of AAs-induced nephrotoxicity, we designed a hybrid magnetic polymer-porous agarose (denoted as MNs@SiO2M@DNV-A), mimicking the effect of basic and aromatic residues of organic anion transporter 1 (OAT1) for efficient enriching aristolochic acid I (AA I) and aristolochic acid II (AA II) in the plasma. The monomers of vinylbenzyl trimethylammonium chloride (VBTAC), N-vinyl-2-pyrrolidinone (NVP) and divinylbenzene (DVB) were employed to construct the polymer layer, which provided a selective adsorption for AAs by multiple interactions. The porous agarose shell contributed to remove interfering proteins in the plasma samples. A magnetic solid-phase extraction (MSPE) based on the proposed composite enhanced the selectivity toward AA I and AA II in the plasma samples. In combination of HPLC analysis, the proposed method was proved to be applicable to fast and specific quantification of AAs in blood samples, which was characterized by a good linearity, high sensitivity, acceptable recovery, excellent repeatability and satisfactory reusability.

Ammonia-trapping multilayer polymer urease film amplifier coated surface plasmon resonance sensor for ultra-sensitive urea detection

In this paper, we have developed a new urea signal amplification technology based on a multilayer urease polymer film self-assembly structure for the first time, enabling the realization of ultra-accurate urea optical detection. We demonstrate the effectiveness of this technique based on surface plasmon resonance (SPR) platform. When the urea signal amplifier is combined with SPR sensors, multilayer urease polymer film contacts with urea molecules, the urea molecules are oxidated into NH3 and CO2, causing the pH increase, which weakens the electrostatic interaction between different polymer layers and induces the RI reduction of the multilayer urease film, thereby causing the shift of the SPR spectrum. Experiment results confirm that urea sensitivity has been improved 12-fold, and the limit of detection (LOD) has been optimized to less than 10−3 mmol/L. Furthermore, the anti-interference has been improved 22.8-fold and is kept even the interference signal strength increases by 100 times. Moreover, multilayered urease polymer leads to the increase of urease on the sensor surface, thus expanding the detection range of urea by 3.5 times. This provides a new way to solve the contradiction between high sensitivity and large measurement range of optical fiber biosensor. Importantly, the concept of using enzyme-loaded polymer films for signal amplification can be adapted for the detection of various other biomolecules by replacing the enzyme with a specific recognition element for the target molecule. This opens doors for developing highly sensitive and specific biosensors for diverse applications in healthcare, environmental monitoring, and food safety.