Thickness Of Polymer Layer Research Articles

Effect of layer thickness on the thermoelectric properties of fully sprayed poly(3-hexylthiophene-2,5-diyl) thin films doped with chloroauric acid

AbstractThe thermoelectric properties of fully sprayed thin films of poly(3-hexylthiophen-2,5-diyl) (P3HT) doped with chloroauric acid are investigated for different film thicknesses. The film thickness increases logarithmically with increasing amount of deposited material on the surfaces. Both the electrical conductivity and measured Seebeck coefficients of the doped thin films show an optimal polymer layer thickness between 275 and 310 nm and yield a maximum power factor of $$(1.77\,\pm \,0.22) \frac{\mu \text {W}}{\text {m}\cdot \text {K}^2}$$ ( 1.77 ± 0.22 ) μ W m · K 2 . The optimum layer thickness results from the optimal amount of dopant molecules per monomer between 1.1 and 1.3 at these ratios of P3HT and HAuCl$$_4$$ 4 for the thin film fabrication.

The Impact of the Polymer Layer Thickness in the Foundation Shim on the Stiffness of the Multi-Bolted Foundation Connection

The Impact of the Polymer Layer Thickness in the Foundation Shim on the Stiffness of the Multi-Bolted Foundation Connection

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.

Preparation of Poly(Styrene-co-Acrylonitrile)-Grafted Attapulgite via Simultaneous Reverse and Normal Initiation Atom Transfer Radical Polymerization (SR&NI ATRP) and Its Effect on Polycarbonate/Acrylonitrile-Butadiene-Styrene Terpolymer Ternary Composites

To further improve the comprehensive properties of polycarbonate/acrylonitrile–butadiene–styrene terpolymer blends (PC/ABS), in this work, styrene–acrylonitrile copolymer [P(St-co-An)] was grafted on the surface of attapulgite particles (ATP) by simultaneous reverse and normal initiation ATRP (SR&NI ATRP) to yield ATP@P(St-co-An) hybrid particles. Then a series of PC/ABS/ATP@P(St-co-An) composites were prepared via the melt blending method. The effects of ATP@P(St-co-An) content on the morphological, mechanical, thermal and rheological properties of the composites were investigated in detail. The core-shell ATP@P(St-co-An) hybrid particles with the polymer layer thickness of 20-40 nm were synthesized successfully according to the results of X-ray photoelectron spectrometer (XPS), Fourier transform infrared spectrometer (FTIR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). The improvement in mechanical properties, reduced glass transition temperature (T g) difference between PC and ABS and micromorphology changes of the composites proved the compatibilization, strengthening, and toughening effect of the ATP@P(St-co-An). Compared with the PC/ABS blend, with strength and toughness of 50.8 MPa and 56.3 kJ/m2, when the ATP@P(St-co-An) content was 4 wt%, a reasonable balance (85.8 MPa and 86.2 kJ/m2) between strength and toughness was achieved with substantially enhanced thermal stability. Moreover, the composite showed more remarkable non-Newtonian behavior, and its processability was also improved. We believe this work provides an effective approach to optimize the compatibility and comprehensive properties of PC/ABS blends.

Preparation of a surface molecularly imprinted thermo-sensitive polymer for selective trypsin capture

Molecularly imprinted polymers (MIPs) are innovative porous materials created through polymerization templating methods for highly selective, sensitive detection and separation of the desired chemical species, known as template molecules. Surface imprinting over nano-sized substrates with special functional groups is an effective approach for improving the mass transfer and rebinding capacity. In this study, we successfully performed surface imprinting using methacrylic acid (MAA) and thermoresponsive N-isopropyl acrylamide (NIPAm) as functional monomers on acrylic-functionalized silica nanoparticles and served as a Trypsin artificial receptor. The resulting Trypsin imprinted polymer exhibited a binding capacity of 1022.44 mg/g, surpassing the non-imprinted polymer’s capacity of 292.41 mg/g within 45 min. Moreover, the imprinting factor, the main influence factor in MIP performance, was 3.5, demonstrating the significant selectivity of the polymeric products. In addition, due to the temperature sensitivity of NIPAm the template removing process was simply done by changing pore size. The silica nanoparticles and the synthesized MIP particles had diameters of approximately 95 nm and 105 nm, respectively, with the polymer layer thickness being around 5 nm. The MIP adsorption model followed the Freundlich isotherm and pseudo-second-order kinetics resulting in efficiencies of 93.0 % and 95.4 %, respectively. The developed Trypsin imprinted polymer was reusable for four consecutive uses,demonstrating both resilience and selectivity towards Trypsin.

Optimization of polymer coating thickness and strut width in drug Eluting stents using Magnetic field

The transport of drug/magnetic particle (MP) conjugates in the presence of a Magnetic Field (MF) in Drug Eluting Stents (DESs) is modeled numerically using the Finite Volume Method (FVM). The effects of physiological conditions corresponding to different degrees of calcification, drug particles sizes and hematocrit level, were analyzed by investigating the roles of the tissue permeability, its anisotropy and the plasma viscosity. It was found that both in the absence and presence of the MF, as the tissue permeability decreases or the plasma viscosity increases, the free-phase drug and Extracellular Matrix (ECM)-bound phase contents increase. Stronger tissue anisotropy leads to a decrease of the free-phase drug content and an increase of the ECM-bound phase content. Within the explored ranges, the Specific Receptor (SR)-bound phase of the drug was found to be insensitive to the tissue permeability and plasma viscosity, and to be larger in anisotropic tissues. The activation of the MF leads systematically to larger free-phase drug contents, with the increases most prominent at smaller tissue permeability, anisotropy and plasma viscosity. On the other hand, the effects on the ECM-bound phase content are found to be stronger at larger permeability, smaller plasma viscosity and lower tissue anisotropy. For an isotropic tissue, the MF induces a decrease of the ECM-bound phase content at early times, followed by an increase at later times. For the considered ranges of permeability and viscosity, the MF does not seem to have any noticeable effects on the SR-bound phase. However, this phase of the drug tends to increase with the activation of the MF in isotropic tissues and is unchanged in anisotropic ones. These reported effects of the MF hold promise for alleviating two factors contributing to In-Stent Restenosis, namely the polymer coating width and thickness. The study reveals that a narrower or thinner polymer layer, in combination with the MF, can mimic the drug release dynamics of a wider or thicker polymer layer in the absence of the MF. The corresponding width and thickness of the magnetized stents, that we referred to as the equivalent polymer width (EPW) and equivalent polymer thickness (EPT) were determined and their dependence on the tissue permeability, isotropy and the plasma viscosity, was investigated. The study shows that it is possible to achieve the same drug delivery with polymer coating of half the width or half the thickness of the non-magnetized stent when an electric intensity of 3A is used.

Manufacture and structural performance of modular hybrid FRP–timber thin-walled beams

Developed to fulfil the rising societal demand for sustainable constructions, Modular Hybrid Fibre-reinforced polymer-Timber (MHFT) thin-walled sections are lightweight timber-based composite structures manufactured through a modular assembly method. Motivated by prior research on MHFT columns characterized by efficient load-carrying capacity, this paper conducted a thorough investigation into the manufacture and structural performance of MHFT beams. Experimental, analytical and numerical studies were conducted for beams subjected to four-point bending load, with parametric analyses of four distinct beam types to investigate design parameter influence on flexural performance. The experimental study demonstrated the structural efficacy of MHFT beams, as evidenced by increased moment of inertia and enhanced resistance to edge split failures, as compared to previously studied folded HFT beams. MHFT beams also exhibited a comparable strength-to-weight ratio compared to their structural steel counterparts. Both numerical and analytical methods provided acceptable predictions for flexural strength and material failure modes of MHFT beams, with strength predictions varying by less than 22% compared to experimental averages. The numerical method reliably predicted flexural stiffness and load–displacement responses, with discrepancies within 12%. The parametric analyses further revealed that the thickness of glass fibre-reinforced polymer (GFRP) layers and cross-sectional geometric profile were most strongly influenced beam parameters. Specifically, the use of 3-layer GFRP material resulted in a strength increase of over 17% and a stiffness increase of over 19% compared to 1-layer material, effectively mitigating the occurrence of local buckling and edge split failures.

Optical force sensor based on plasmon modulated upconversion luminescence.

We report a novel force sensor exploiting the interaction between plasmonic nanostructures and upconversion nanoparticles (UCNPs). 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 provides the basis for sensing. Furthermore, the nanosensor employs ratiometric sensing which makes it highly robust against any environmental variations. Our 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.

Enhancing the MRI contrast and hyperthermic properties of magnetic nanoflowers by modulating magnetisation dynamics using poly(butyl cyanoacrylate) shells: Towards multi-functional clinical carriers

Magnetic-polymeric complexes have strong potential as theranostic tools; when prepared as stable suspensions in the nano-range they are functionalisable carriers which can provide MRI (magnetic resonance imaging) tracking, static-field targeting and localised hyperthermia (on AC-field irradiation). In this work the effect of the polymer layer thickness on the MRI and hyperthermic efficacies, in clinically relevant ranges, for poly(butyl cyanoacrylate) encapsulated multi-domain γ-Fe2O3 nanoparticles was investigated for the first time. A series of nanocomposites were prepared at varying particle/polymer ratios revealing that progressively thicker polymer shells maximised the carrier potential and improved the MRI and hyperthermic efficacy due to enhancement of the Néel and partial suppression of the Brownian contribution to the dynamics of the magnetic moments. The implications for the development of multifunctional theranostic agents with optimised efficacy for AC-field triggered release are discussed.

Fluorescent nanocomposites of Ag nanoclusters grown in anionic polymer layers grafted to plastic substrate: Preparation, characterization and evaluation in Hg2+ sensing and white light generation

AbstractFluorescent noble metal nanoclusters (NCs) are emerging optical nanomaterials with properties similar to those of quantum dots. Their applications can be expanded by combining them with polymer matrices to obtain flexible and transparent light‐emitting nanocomposites. However, achieving highly fluorescent nanocomposites of this type remains challenging due to phase separation and aggregation of NCs in polymer hosts leading to a strong reduction in fluorescence efficiency. We address this key issue by covalently grafting a layer of a specifically selected matrix polymer onto a transparent plastic film and photochemically synthesizing the fluorescent metal NCs directly in the grafted layer. The surface‐grafted matrix polymer effectively captures the noble metal (Ag) ions, photo‐reduces them to atoms, acts as a capping ligand for the growing Ag NCs, and immobilizes them on the substrate surface. The Ag NCs were produced by both wet and dry synthesis, and effects of synthesis method, reaction time, and matrix polymer layer thickness on the fluorescence properties of the resulting nanocomposites were investigated and discussed. Importantly, the fluorescence intensity of these nanocomposite films is sensitive to submicromolar concentrations of aqueous Hg2+ that makes them useful as fluorescent sensing materials for selective and ultrasensitive detection of Hg2+ ions in water. Besides, the nanocomposite films obtained by the dry synthesis of NCs exhibit an intensive emission covering the whole green to red range of the visible spectrum and, hence, produce bright white light under illumination with a blue LED that makes them attractive as down‐conversion materials in one‐phosphor‐converted white LEDs.

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.

Integrated behavioural analysis of FRP-confined circular columns using FEM and machine learning

This study investigates the structural behaviour of double-skin columns, introducing novel double-skin double filled tubular (DSDFT) columns, which utilise double steel tubes and concrete to enhance the load-carrying capacity and ductility beyond conventional double-skin hollow tubular (DSHT) columns, employing a combination of finite element model (FEM) and machine learning (ML) techniques. A total of 48 columns (DSHT+DSDFT) were created to examine the impact of various parameters, such as double steel tube configurations, thickness of fibre-reinforced polymer (FRP) layer, type of FRP material, and steel tube diameter, on the load-carrying capacity and ductility of the columns. The results were validated against the experimental findings to ensure their accuracy. Key findings highlight the advantages of the DSDFT configuration. Compared to the DSHT columns, the DSDFT columns exhibited remarkable 19.54 % to 101.21 % increases in the load-carrying capacity, demonstrating improved ductility and load-bearing capabilities. Thicker FRP layers enhanced the load-carrying capacity up to 15 %, however at the expense of the reduced axial strain. It was also observed that glass FRP wrapping displayed 25 % superior ultimate axial strain than aramid FRP wrapping. Four different ML models were assessed to predict the axial load-carrying capacity of the columns, with long short-term memory (LSTM) and bidirectional LSTM models emerging as superior choices indicating exceptional predictive capabilities. This interdisciplinary approach offers valuable insights into designing and optimising confined column systems. It sheds light on both double-tube and single-tube configurations, propelling advancements in structural engineering practices for new constructions and retrofitting. Further, it lays out a blueprint for maximising the performance of the confined columns under the axial compression.

Understanding of the flocculating performance in varying salinity solutions of Chi-g-CPAM and CPAM

In this work, the adsorption performance of a novel chitosan-based flocculant (Chi-g-CPAM) and a cationic flocculant (CPAM) onto the kaolinite surface as well as the interaction mechanisms have been investigated by settling tests, atomic force microscopy (AFM) and quartz crystal microbalance with dissipation (QCM-D). When the KCl concentration of the solution altered from 1 mM to 100 mM, the settling rate of kaolinite suspension using CPAM deteriorated from 2.73 m/h to 1.97 m/h. However, the Chi-g-CPAM exhibited salt resistance as the settling rate changed slightly from 2.34 m/h to 2.44 m/h. From the QCM-D results, the Δf of CPAM onto silica sensor changed from − 3.6 Hz to − 33.6 Hz and -ΔD/Δf × 106 increased from 0.167 to 0.223, confirming that the CPAM layer adsorbed on the silica surface was thicker and more dissipative in 100 mM KCl solution. Meanwhile, the Δf of Chi-g-CPAM onto silica sensor changed from − 14.3 Hz to − 33.9 Hz. The conformation of Chi-g-CPAM layer changed slightly as the -ΔD/Δf × 106 increased from 0.174 to 0.186. From the AFM measurements in 1 mM and 100 mM KCl solution, the distance of adhesion forces between the silica probe and CPAM expanded from approximately 20 nm to around 50 nm, and the adhesion force changed from 1.9 nN± 0.1 nN to 21.3 nN± 0.1 nN. The interaction forces with a long range (∼100 nm) maintained at about 3 nN between the silica probe and Chi-g-CPAM. Such difference was mainly attributed to the steric hindrance effect originating from the shorter molecular chain of Chi-g-CPAM. In 100 mM KCl solution, the CPAM molecules with long chains had a more coiled conformation than Chi-g-CPAM, which resulted a train-like flat adsorption conformation and larger adhesion, and formed a loose and thick polymer layer of CPAM in high salinity. The insights into the flocculating performance in varying salinity solutions of CPAM and Chi-g-CPAM will contribute to the molecular design of chitosan-based flocculants for efficient wastewater treatment.

Diblock bottlebrush polymer in a non-polar medium: Self-assembly, surface forces, and superlubricity

Whilst bottlebrush polymers have been studied in aqueous media for their conjectured role in biolubrication, surface forces and friction mediated by bottlebrush polymers in non-polar media have not been previously reported. Here, small-angle neutron scattering (SANS) showed that a diblock bottlebrush copolymer (oligoethyleneglycol acrylate/ethylhexyl acrylate; OEGA/EHA) formed spherical core–shell aggregates in n-dodecane (a model oil) in the polymer concentration range 0.1–2.0 wt%, with a radius of gyration Rg ∼ 7 nm, comprising 40–65 polymer molecules per aggregate. The surface force apparatus (SFA) measurements revealed purely repulsive forces between surfaces bearing inhomogeneous polymer layers of thickness L ∼ 13–23 nm, attributed to adsorption of a mixture of polymer chains and surface-deformed micelles. Despite the surface inhomogeneity, the polymer layers could mediate effective lubrication, demonstrating superlubricity with the friction coefficient as low as µ ∼ 0.003. The analysis of velocity-dependence of friction using the Eyring model shed light on the mechanism of the frictional process. That is, the friction mediation was consistent with the presence of nanoscopic surface aggregates, with possible contributions from a gel-like network formed by the polymer chains on the surface. These unprecedented results, correlating self-assembled polymer micelle structure with the surface forces and friction the polymer layers mediate, highlight the potential of polymers with the diblock bottlebrush architecture widespread in biological living systems, in tailoring desired surface interactions in non-polar media.

Plasmon Resonance Properties of Au, Cu and Ag Multi-layered Structures with P(VDF-TrFE)

The theoretical modeling of the optical response of layered metal-polymer structures, which can be employed as plasmonic sensors, is carried out. The calculation of their linearly polarized light reflection is performed with the use of the well-known matrix method, which describes the electromagnetic radiation propagation through a sequence of homogeneous flat-parallel media layers. In this way, the attenuated total reflection curves of the structures containing metal films (Au, Cu, or Ag) and a polymer dielectric are obtained and analyzed. A new sensor is proposed, which will utilize the ferroelectric P(VDF-TrFE) copolymer separating metal films. This might be a perspective idea for the creation of tunable plasmonic sensors. The dependencies of the angular position of a surface plasmon resonance versus the thicknesses of structure’s layers, as well as versus the refractive index of the medium contacting to the free surface of a sensor, are considered. This makes it possible to carry out the approximate search for optimal constructive parameters of a sensor, namely, the thicknesses of metal and polymer layers, and to make conclusion about its resulting sensitivity and working range. It is found that the sensors based on a single metal film and a couple of such films separated by a polymer differ 1 ... 1.3 times in the sensitivity (single metal film demonstrates a more rapid resonant angle shift with analyte refractive index variation). It is established that the employment of Au, Cu, or Ag gives no significant changes in the sensitivity of a two-metal-layer sensor with a polymer, but the widest refractive index registration range may be expected for a Cu-based sensor.

Complementary spectroscopic and electrochemical analysis of the sealing of micropores in hexamethyldisilazane plasma polymer films by Al2O3 atomic layer deposition

In the present study, the effects of oxygen plasma treatment and subsequent 2 nm thin Al2O3 film deposition by atomic layer deposition on about 30 nm thick hexamethyldisilazane polymer layers are investigated by using a combination of spectroscopic and electrochemical analysis. The investigations focus on the microporosity of the corresponding films and their structural changes. Upon oxygen plasma treatment, the surface near region of the films is converted into SiOx, and the microporosity is increased. Atomic layer deposition of Al2O3 on the plasma oxidized films leads to the decrease of pore sizes and an effective sealing. A correlation between the film microporosity and the change of hydroxyl groups of the films with the adsorption of water was established by ellipsometric porosimetry and in situ Fourier transform infrared (FTIR) spectroscopy. Moreover, electrochemical analysis provided complementary information on the electrolyte up‐take in the differently conditioned thin films.

Facile Synthesis of Catechol-Containing Polyacrylamide Copolymers: Synergistic Effects of Amine, Amide and Catechol Residues in Mussel-Inspired Adhesives.

The straightforward synthesis of polyamide-derived statistical copolymers with catechol, amine, amide and hydroxy residues via free radical polymerization is presented. In particular, catechol, amine and amide residues are present in natural mussel foot proteins, enabling strong underwater adhesion due to synergistic effects where cationic residues displace hydration and ion layers, followed by strong short-rang hydrogen bonding between the catechol or primary amides and SiO2 surfaces. The present study is aimed at investigating whether such synergistic effects also exist for statistical copolymer systems that lack the sequence-defined positioning of functional groups in mussel foot proteins. A series of copolymers is established and the adsorption in saline solutions on SiO2 is determined by quartz crystal microbalance measurements and ellipsometry. These studies confirm a synergy between cationic amine groups with catechol units and primary amide groups via an increased adsorptivity and increased polymer layer thicknesses. Therefore, the free radical polymerization of catechol, amine and amide monomers as shown here may lead to simplified mussel-inspired adhesives that can be prepared with the readily scalable methods required for large-scale applications.

Direct visualization of nanoparticle morphology in thermally sintered nanoparticle ink traces and the relationship among nanoparticle morphology, incomplete polymer removal, and trace conductivity

A key challenge encountered by printed electronics is that the conductivity of sintered metal nanoparticle (NP) traces is always several times smaller than the bulk metal conductivity. Identifying the relative roles of the voids and the residual polymers on NP surfaces in sintered NP traces, in determining such reduced conductivity, is essential. In this paper, we employ a combination of electron microscopy imaging and detailed simulations to quantify the relative roles of such voids and residual polymers in the conductivity of sintered traces of a commercial (Novacentrix) silver nanoparticle-based ink. High resolution transmission electron microscopy imaging revealed details of the morphology of the inks before and after being sintered at 150 °C. Prior to sintering, NPs were randomly close packed into aggregates with nanometer thick polymer layers in the interstices. The 2D porosity in the aggregates prior to sintering was near 20%. After heating at 150 °C, NPs sintered together into dense aggregates (nanoaggregates or NAgs) with sizes ranging from 100 to 500 nm and the 2D porosity decreased to near 10%. Within the NAgs, the NPs were mostly connected via sintered metal bridges, while the outer surfaces of the NAgs were coated with a nanometer thick layer of polymer. Motivated by these experimental results, we developed a computational model for calculating the effective conductivity of the ink deposit represented by a prototypical NAg consisting of NPs connected by metallic bonds and having a polymer layer on its outer surface placed in a surrounding medium. The calculations reveal that a NAg that is 35%–40% covered by a nanometer thick polymeric layer has a similar conductivity compared to prior experimental measurements. The findings also demonstrate that the conductivity is less influenced by the polymer layer thickness or the absolute value of the NAg dimensions. Most importantly, we are able to infer that the reduced value of the conductivity of the sintered traces is less dependent on the void fraction and is primarily attributed to the incomplete removal of the polymeric material even after sintering.

ВЛИЯНИЕ ЧАСТОТЫ ПЕРЕМЕННОГО ПОЛЯ НА ЭЛЕКТРОФИЗИЧЕСКИЕ СВОЙСТВА ПОЛИМЕРНЫХ ПЛЕНОК

The results of an experimental study of the frequency dependences of the impedance of metal-polymer-metal sandwich structures for different thicknesses of the polymer layer are presented. The voltage characteristics of the samples in various frequency ranges were measured. The general view of the amplitude-frequency characteristics graphs for all film thicknesses is well described by the theoretical model of the sequential RC circuit. On all graphs, you can notice the presence of a cutoff frequency, which can be interpreted as the beginning of the RC filter. However, there are also significant deviations from the theoretical characteristics. It is established that with a polymer layer thickness of 80 nm in the frequency range At 10-40 Hz, an abnormal decrease in impedance is observed, corresponding to an increase in current at the volt-ampere characteristics. The resulting charge instability is considered as a consequence of the volume-charge polarization, which, in turn, is due to the specifics of polymer-polymer interfaces that arise during the formation of the supramolecular structure of the polymer. The results of the work are interpreted within the framework of the resistive switching model, which assumes that in the case of submicron polymer films used in the metalpolymer-metal system, resistive switching is possible as a result of the sequential transformation of the energy electronic subsystem of the polymer film under the action of charge injection from the electrodes.

Protective Coating for the Lithium Metal Anode Prepared by Plasma Polymerization

The demand for batteries with higher energy densities for energy storage and electric vehicles motivates research for a stable and reversible lithium metal anode. The native passivation layer on commercial lithium foils does not enable stable cycling in liquid electrolytes due to inhomogeneities in the layer composition and impurities. These inhomogeneities and impurities result in locally varying current densities, which often lead to dendrite growth and ultimately cell failure. Artificial protection layers are one promising option to overcome these issues and enable the reversible operation of lithium metal anodes. In this study, we used plasma polymerization of 1.4 bis(trifluoromethyl)benzene to form an artificial passivation layer on top of plasma-cleaned lithium metal. The layer was characterized with time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy. The mechanical properties of the layer were examined by nanoindentation. Symmetric cell tests showed stable cycling behavior for over 300 h, with overpotentials below 0.1 V at current densities between 0.1 and 1 mA/cm2. 18O2 isotope exchange experiments were used to get an estimation of the diffusion coefficients of oxygen in the native passivation layer of lithium foils at room temperature and for oxygen in the plasma polymer at room temperature. The combination of layer thickness and diffusion coefficient of the plasma polymer is sufficient to protect the lithium metal against oxygen for at least 30 min, which makes it a suitable protective coating.