Structural, Optical and Dielectric Properties of Some Nanocomposites Derived from Copper Oxide Nanoparticles Embedded in Poly(vinylpyrrolidone) Matrix.

Polymer nanocomposite films based on poly(vinyl pyrrolidone) incorporated with different amounts of copper oxide (CuO) nanoparticles were prepared by the solution casting technique. The PVP/CuO nanocomposites were analyzed by X-ray diffractometry (XRD), scanning electron microscopy, UV-Visible absorption spectroscopy and dielectric spectroscopy. The XRD analysis showed that the monoclinic structure of cupric oxide was maintained in the PVP host matrix. The key optical parameters, such as optical energy gap Eg, Urbach energy EU, absorption coefficient and refractive index, were estimated based on the UV-Vis data. The optical characteristics of the nanocomposite films revealed that their transmittance and absorption were influenced by the addition of CuO nanoparticles in the PVP matrix. Incorporation of CuO nanoparticles into the PVP matrix led to a significant decrease in band gap energy and an increase in the refractive index. The dielectric and electrical behaviors of the PVP/CuO nanocomposites were analyzed over a frequency range between 10 Hz and 1 MHz. The effect of CuO loading on the dielectric parameters (dielectric constant and dielectric loss) of the metal oxide nanocomposites was also discussed.

Effects of Atmospheric Pressure Plasma Jet on 3D-Printed Acrylonitrile Butadiene Styrene (ABS).

Polymers are essential in several sectors, yet some applications necessitate surface modification. One practical and eco-friendly option is non-thermal plasma exposure. The present research endeavors to examine the impacts of dielectric barrier discharge atmospheric pressure plasma on the chemical composition and wettability properties of acrylonitrile butadiene styrene surfaces subject to the action of additive manufacturing. The plasma source was produced by igniting either helium or argon and then adjusted to maximize the operational conditions for exposing polymers. The drop in contact angle and the improvement in wettability after plasma exposure can be due to the increased oxygen-containing groups onto the surface, together with a reduction in carbon content. The research findings indicated that plasma treatment significantly improved the wettability of the polymer surface, with an increase of up to 60% for both working gases, while the polar index increased from 0.01 up to 0.99 after plasma treatment. XPS measurements showed an increase of up to 10% in oxygen groups at the surface of He-plasma-treated samples and up to 13% after Ar-plasma treatment. Significant modifications were observed in the structure that led to a reduction of its roughness by 50% and also caused a leveling effect after plasma treatment. A slight decrease in the glass and melting temperature after plasma treatment was pointed out by differential scanning calorimetry and broadband dielectric spectroscopy. Up to a 15% crystallinity index was determined after plasma treatment, and the 3D printing process was measured through X-ray diffraction. The empirical findings encourage the implementation of atmospheric pressure plasma-based techniques for the environmentally sustainable manipulation of polymers for applications necessitating higher levels of adhesion and specific prerequisites.

Atmospheric Pressure Plasma Jet Exposure of Polylactic Acid Surfaces for Better Adhesion: Plasma Parameters towards Polymer Properties.

Polymers play a crucial role in multiple industries; however, surface modification is necessary for certain applications. Exposure to non-thermal plasma provides a viable and environmentally beneficial option. Fused deposition molding utilizes biodegradable polylactic acid, although it encounters constraints in biomedical applications as a result of inadequate mechanical characteristics. This study investigates the effects of atmospheric pressure plasma generated by a dielectric barrier discharge system using helium and/or argon on the modification of polylactic acid surfaces, changes in their wettability properties, and alterations in their chemical composition. The plasma source was ignited in either He or Ar and was tailored to fit the best operational conditions for polymer exposure. The results demonstrated the enhanced wettability of the polymer surface following plasma treatment (up to 40% in He and 20% in Ar), with a marginal variation observed among treatments utilizing different gases. The plasma treatments also caused changes in the surface topography, morphology, roughness, and hydrophilicity. Plasma exposure also resulted in observable modifications in the dielectric characteristics, phase transition, and structure. The experimental findings endorse the utilization of plasma technologies at normal air pressure for environmentally friendly processing of polymer materials, specifically for applications that necessitate enhanced adhesion and have carefully selected prerequisites.

Hybrid green bionanocomposites based on chitosan/starch/gelatin and metallic nanoparticles for biological applications.

Multicomponent composites based on natural biopolymers: chitosan, starch and gelatin in two different ratios (0.5:1:1 and 1:1:1) were in situ crosslinked by intermolecular interactions and used as matrices for zinc oxide and magnetite fillers. The bionanocomposite films have been evaluated by spectral and microscopy methods: Fourier-Transform Infrared spectrometry (FT-IR), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) confirming the electrostatic and hydrogen bonding interactions between the components of the polymeric matrices and the inorganic fillers and the crosslinking process. AFM and SEM images showed a compact, non-porous and homogenous morphology of the hybrid films, proving a good miscibility of the blends. At lower concentrations of embedded filler, the composites were less hardened and more ductile due to the interaction with the polymeric matrix. Increased amounts of inorganic NPs led to the reduced mechanical properties of the prepared materials and increased thermal stability. The bionanocomposites revealed a similar behavior of the dielectric constant with frequency and increased values at higher temperatures. The wettability of the films' surface and the values of the water sorption capacity revealed a slight hydrophilicity of the bionanocomposites as compared with the initial matrices. The biocompatibility, evaluated by means of the surface free energy components and the interfacial tension with blood, and the hemolysis analysis demonstrated that the bionanocomposites possess a low risk of thrombosis, being promising materials for in vivo biomedical applications.

Novel Bio-Based Materials: From Castor Oil to Epoxy Resins for Engineering Applications.

The paper presents the synthesis and thermal behavior of novel epoxy resins prepared from epoxidized castor oil in the presence of or without trimethylolpropane triglycidyl ether (TMP) crosslinked with 3-hexahydro-4-methylphtalic anhydride (MHHPA) and their comparison with a petroleum-based epoxy resin (MHHPA and TMP). Epoxidized castor oil (ECO) was obtained via in situ epoxidation of castor oil with peroxyacetic acid. The chemical structures of castor oil (CO), ECO, and epoxy matrix were confirmed using FT-IR and 1H-NMR spectroscopy. The morphological and thermal behavior of the resulting products have been investigated. Compared to petroleum-based resins, castor oil-based ones have a lower Tg. Anyway, the introduction of TMP increases the Tg of the resins containing ECO. The morphological behavior is not significantly influenced by using ECO or by adding TMP in the synthesis of resins. The dielectric properties of epoxy resins have been analyzed as a function of frequency (1 kHz-1 MHz) and temperature (-50 to 200 °C). The water absorption test showed that as Tg increased, the percent mass of water ingress decreased.

Testing the Performance of the Azo-Polyimide Supramolecular Systems as Substrate for Sensors Based on Platinum Electrodes.

Azo-polyimide films with supramolecular structure were obtained by casting onto glass plates a mixture based on polyamidic acid and different quantities of azochromophore, followed by thermal treatment to realize the final azo-polyimide structure. The dielectric characteristics of the supramolecular structure of polymer films were investigated by broad-band dielectric spectroscopy measurements at different temperatures and frequencies. The free-standing films proved to be flexible and tough and maintained their integrity after repeated bending. The work of adhesion at the polymer/platinum interface was calculated after the evaluation of the surface energy parameters before and after plasma treatment. Atomic force microscopy was used to image the surface morphology, the evolution of the roughness parameters, and the adhesion force between the platinum-covered tip and the polymer surface, registered at the nanoscale with the quantity of the azo dye introduced in the system. The simulation of the columnar growth of a platinum layer was made to provide information about the deposition parameters that should be used for optimal results in the deposition of platinum electrodes for sensors.

Thermal and Dielectric Investigations of Polystyrene Nanoparticles as a Viable Platform-Toward the Next Generation of Fillers for Nanocomposites.

Nanoparticles are often used as fillers for enhancing various properties of polymer composites such as mechanical, electrical, or dielectric. Among them, polymer nanoparticles are considered ideal contenders because of their compatibility with a polymer matrix. For this reason, it is important that they are synthesized in a surfactant-free form, to obtain predictable surface and structural properties. Here, we synthesized a series of polystyrene nanoparticles (PS NPs), by emulsion polymerization of styrene, using varying amounts of divinylbenzene as a crosslinking agent and sodium 4-vinylbenzenesulfonate as a copolymerizing monomer surfactant-"surfmer". Using "surfmers" we obtained surfactant-free nanoparticles that are monodisperse, with a high degree of thermal stability, as observed by scanning electron microscopy and thermogravimetric investigations. The prepared series of NPs were investigated by means of broadband dielectric spectroscopy and we demonstrate that by fine-tuning their chemical composition, fine changes in their dielectric and thermal properties are obtained. Further, we demonstrate that the physical transformations in the nanoparticles, such as the glass transition, can be predicted by performing the first derivative of dielectric permittivity for all investigated samples. The glass transition temperature of PS NPs appears to be inversely correlated with the dielectric permittivity and the average diameter of NPs.

Novel Insight into the Photophysical Properties and 2D Supramolecular Organization of Poly(3,4-ethylenedioxythiophene)/Permodified Cyclodextrins Polyrotaxanes at the Air-Water Interface.

Two poly(3,4-ethylenedioxythiophene) polyrotaxanes (PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD) end-capped by pyrene (Py) were synthesized by oxidative polymerization of EDOT encapsulated into TMe-ßCD or TMe-γCD cavities with iron (III) chloride (FeCl3) in water and chemically characterized. The effect of TMe-ßCD or TMe-γCD encapsulation of PEDOT backbones on the molecular weight, thermal stability, and solubility were investigated in depth. UV-vis absorption, fluorescence (FL), phosphorescence (PH), quantum efficiencies, and lifetimes in water and acetonitrile were also explored, together with their surface morphology and electrical properties. Furthermore, dynamic light scattering was used to study the hydrodynamic diameter (DH) and z-potential (ZP-ζ) of the water soluble fractions of PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD. PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD exhibited a sharp monodisperse peak with a DH of 55 ± 15 nm and 122 ± 32 nm, respectively. The ZP-ζ value decreased from -31.23 mV for PEDOT∙TMe-ßCD to -20.38 mV for PEDOT∙TMe-γCD, indicating that a negatively charged layer covers their surfaces. Surface pressure-area isotherms and Brewster angle microscopy (BAM) studies revealed the capability of the investigated compounds to organize into sizeable and homogeneous 2D supramolecular assemblies at the air-water interface. The control of the 2D monolayer organization through the thermodynamic parameters of PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD suggests potential for a wide range of optoelectronic applications.

Cobalt Ferrite/Polyetherimide Composites as Thermally Stable Materials for Electromagnetic Interference Shielding Uses.

The progress of the automated industry has introduced many benefits in our daily life, but it also produces undesired electromagnetic interference (EMI) that distresses the end-users and functionality of electronic devices. This article develops new composites based on a polyetherimide (PEI) matrix and cobalt ferrite (CoFe2O4) nanofiller (10-50 wt%) by mixing inorganic phase in the poly(amic acid) solution, followed by film casting and controlled heating, to acquire the corresponding imide structure. The composites were designed to contain both electric and magnetic dipole sources by including highly polarizable groups (phenyls, ethers, -CN) in the PEI structure and by loading this matrix with magnetic nanoparticles, respectively. The films exhibited high thermal stability, having the temperature at which decomposition begins in the interval of 450-487 °C. Magnetic analyses indicated a saturation magnetization, coercitive force, and magnetic remanence of 27.9 emu g-1, 705 Oe, and 9.57 emu g-1, respectively, for the PEI/CoFe2O4 50 wt%. Electrical measurements evidenced an increase in the conductivity from 4.42 10-9 S/cm for the neat PEI to 1.70 10-8 S/cm for PEI/CoFe2O4 50 wt% at 1 MHz. The subglass γ- and ß-relaxations, primary relaxation, and conductivity relaxation were also examined depending on the nanofiller content. These novel composites are investigated from the point of view of their EMI shielding properties, showing that they are capable of attenuating the electric and magnetic parts of electromagnetic waves.

All-Polymer Piezo-Composites for Scalable Energy Harvesting and Sensing Devices.

Silicone elastomer composites with piezoelectric properties, conferred by incorporated polyimide copolymers, with pressure sensors similar to human skin and kinetic energy harvester capabilities, were developed as thin film (<100 micron thick) layered architecture. They are based on polymer materials which can be produced in industrial amounts and are scalable for large areas (m2). The piezoelectric properties of the tested materials were determined using a dynamic mode of piezoelectric force microscopy. These composite materials bring together polydimethylsiloxane polymers with customized poly(siloxane-imide) copolymers (2−20 wt% relative to siloxanes), with siloxane segments inserted into the structure to ensure the compatibility of the components. The morphology of the materials as free-standing films was studied by SEM and AFM, revealing separated phases for higher polyimide concentration (10, 20 wt%). The composites show dielectric behavior with a low loss (<10−1) and a relative permittivity superior (3−4) to pure siloxane within a 0.1−106 Hz range. The composite in the form of a thin film can generate up to 750 mV under contact with a 30 g steel ball dropped from 10 cm high. This capability to convert a pressure signal into a direct current for the tested device has potential for applications in self-powered sensors and kinetic energy-harvesting applications. Furthermore, the materials preserve the known electromechanical properties of pure polysiloxane, with lateral strain actuation values of up to 6.2% at 28.9 V/µm.

Investigating the Vibrational, Magnetic and Dielectric Properties, and Antioxidant Activity of Cerium Oxide Nanoparticles.

Dielectric, magnetic and Raman measurements of cerium oxide nanoparticles obtained by the precipitation method are discussed. Morphological study was performed by scanning electron microscopy, confirming the formation of nanoparticles of 5-27 nm. The Raman spectra exhibited a strong band around 465 cm-1, corresponding to the symmetrical stretching mode of the Ce-O8 vibrational unit. The nature of the room temperature ferromagnetism of cerium oxide nanoparticles was analyzed, taking into account the oxygen defects at the surface or interface of the nanoparticles. The evolution of dielectric constant, ε', and dielectric loss, ε″ was studied as a function of frequency at different temperatures. Additionally, the variation of the electric conductivity versus temperature was investigated. Finally, complex impedance study of the cerium oxide nanoparticles was performed.

Tailoring Thermal and Electrical Properties of Jeffamine Segmented Polyetherimide Composite Films Containing BaTiO3 particles.

The continuous advancement of materials science has highlighted the ongoing need for additional studies on the main composite materials topics, particularly in the field of multifunctional nano-composites, towards improving their capability to meet multifaceted requirements in order to stimulate both scientific and technological development. In this study, we report the preparation and characterization of polyetherimides (PEIs) derived from 4,4'-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) following a two-step polycondensation reaction using either 4,4'-(1,3-phenylenedioxy) dianiline, or Jeffamine ED-600 as comonomers, or a mixture of the two diamines. Based on the PEI containing flexible Jeffamine segments, polymer composite films were developed by incorporating BaTiO3 particles. The chemical structure and morphology of the composite films were investigated by FTIR spectroscopy and scanning electron microscopy. Thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. The influence of Jeffamine segments on the thermal decomposition process was investigated by TG/MS/FTIR measurements under air and nitrogen atmospheres. Based on the obtained data, the thermal decomposition mechanism was established and is discussed in accordance with the chemical structures of the polymers. The surface properties of the PEI and PEI-composite films were characterized by performing contact angle measurements. The addition of BaTiO3 increased the wettability of the surfaces. The dielectric characteristics of polymer composite films were investigated by broad band dielectric spectroscopy measurements. It was noticed that the addition of BaTiO3 nanoparticles to the copolymer matrix gradually enhanced the dielectric constant of the composites.

Multi-Functional Materials Based on Cu-Doped TiO2 Ceramic Fibers with Enhanced Pseudocapacitive Performances and Their Dielectric Characteristics.

In this work, pure TiO2 and Cu (0.5, 1, 2%)-doped TiO2 composites prepared by electrospinning technique followed by calcination at 900 °C, and having high pseudocapacitive and dielectric characteristics were reported. These nanocomposites were characterized by scanning electron microscopy, X-ray diffraction, and dynamic water sorption vapor measurements. The structural characterization of these nanostructures highlighted good crystallinity including only the rutile phase. The electrochemical characteristics were investigated by cyclic voltammetry and galvanostatic charge-discharge measurements, which were performed in a KOH electrolyte solution. Among the Cu-doped TiO2 nanostructures that were prepared, the one containing 0.5% Cu exhibited superior electrochemical properties, including high specific gravimetric capacitance of 1183 F·g-1, specific capacitance of 664 F·g-1, energy density of 45.20 Wh·kg-1, high power density of 723.14 W·kg-1, and capacitance retention of about 94% after 100 cycles. The dielectric investigation shows good dielectric properties for all materials, where the dielectric constant and the dielectric loss decreased with the frequency increase. Thus, all the interconnected studies proved that these new materials show manifold ability and real applicative potential as pseudocapacitors and high-performance dielectrics. Future work and perspectives are anticipated for characterizing electrochemical and dielectric properties for materials including larger amounts of Cu dopant.

Homologous Series of Polyaniline Derivatives Block Copolymers with Amphiphilic and Semiconducting Properties.

Semiconducting polymers with amphiphilic properties can play an increasing role in future organic and unimolecular electronic devices, especially due to their excellent processability and ease of self-assembly into thin films, but they could also be used as intermediate layers to improve electron transport in metal-organic junctions. In this work, we synthesized a homologous series of amphiphiles by copolymerization of aniline with aniline-N-propanesulfonic acid. The polymerization was first initiated with aniline, and the latter monomer was added at different time intervals: 2, 10, 20, 30, 40, and 60 min, spaced from the time of initiation. Thus, the poly(aniline-co-aniline-N-propanesulfonic acid) (PANi-co-PANs) homologous series of copolymers obtained had the same length of the water soluble PANs chain, and a variable length of the water insoluble PANi chain. We demonstrated that there is a strong structure-activity relationship in the homologous series of PANi-co-PANs copolymers, evidenced in the tensiometry and wettability studies, as well as in-depth conductivity with frequency and temperature investigations. We observed a gradual change in solubility, interfacial activity, and conductivity in the homologous series of amphiphiles within the boundaries set by the electrically insulating, hydrophilic PANs chain and the semiconducting, hydrophobic PANi chains; representing a viable platform toward designing polymers with tunable conductivity.

The effect of PbS quantum dots on molecular dynamics and conductivity of PTB7:PC71BM bulk heterojunction as revealed by dielectric spectroscopy.

A ternary photovoltaic blend containing the PTB7 donor component, the PC71BM acceptor component, and colloidal quantum dots of lead sulfide (PbS QDs) was investigated using broadband dielectric spectroscopy. In the dielectric loss spectrum of PTB7:PC71BM:PbS QDs, γ- and ß-relaxation processes in PTB7 were recognized and analyzed in terms of Arrhenius-type equations. To elucidate the effect of PbS QDs on molecular dynamics of PTB7, the activation energies of both processes were evaluated and compared with those obtained for the binary PTB7:PC71BM blend. Using the CELIV method, the charge carrier mobility was estimated. The PbS QD incorporation into the binary blend was shown to decrease both electron and hole mobility in the ternary PTB7:PC71BM:PbS QD blend. For evaluating the charge carrier lifetime in the ternary blend, the Cole-Cole diagrams derived from the dc conductivity data were plotted. The charge carrier lifetime was found to be much less than the hole extraction time, thus providing effective accumulation of charge carries at the electrodes in the ternary blend under investigation.

Dual crystalline-amorphous salen-metal complexes behave like nematic droplets with AIEgens vistas.

A series of metal salen complexes, original in view of the presence in their structure of a highly flexible and hydrophobic spacer, were prepared on the basis of the reaction of 1,3-bis(3-aminopropyl)tetramethyldisiloxane with 3,5-dichloro-, 3,5-dibromo- and 3-hydroxy-salicylaldehyde and various metal ions (Co2+, Ni2+, Cu2+ and Zn2+). The isolated products were completely characterized from the structural point of view by FTIR, NMR, elemental analysis and single crystal X-ray diffraction, and further investigated from the perspective of the behavior induced mainly by the structural peculiarities. Emphasis is placed on self-assembly properties, both in bulk and in solution, depending on temperature, solvent nature and concentration, including thermotropic and lyotropic liquid crystals (LC). LCs that appear in the form of nematic toroidal droplets have been fully demonstrated by polarized optical microscopy (POM), differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and fluorescence anisotropy studies. The fluorescence analysis results revealed the aggregation-induced emission (AIE) phenomenon, where the emission occurs only for liquid crystals, with a few exceptions. Because these complexes can exist in both amorphous and crystalline states, it raised the question of how properties, such as electrical, change when switching from one state to another. These were well highlighted by DSC, BDS, PXRD, FTIR and fluorescence anisotropy.

Dielectric, Thermal and Water Absorption Properties of Some EPDM/Flax Fiber Composites.

This paper deals with the dielectric and sorption properties of some flax fiber-reinforced ethylene-propylene-diene monomer (EPDM) composites containing different fiber loadings as well as their behavior after exposure to different doses of electron beam irradiation. Three relaxation processes were evinced, a weak relaxation ß at sub-Tg temperatures and two α-type relaxations above the Tg. The EPDM/flax composites exhibited higher values of dielectric constant, dielectric loss and conductivity as compared to a pristine EPDM sample. Using thermogravimetric analysis (TG) coupled with Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS) (TG/FTIR/MS system), the degradation products can be identified. The water uptake increased as the flax fiber level increased in composites. The water uptake tests of irradiated composites showed that the highest water content was obtained for a flax fiber level of 20 phr.

Novel Polyimide/Copper-Nickel Ferrite Composites with Tunable Magnetic and Dielectric Properties.

Heat-resistant magnetic polymer composites were prepared by incorporating cerium-doped copper-nickel ferrite particles, having the general formula Ni1-xCuxFe1.92Ce0.08O4 (x: 0.0, 0.3, 0.6, 1.0), into a polyimide matrix. The effects of particle type and concentration on the thermal, magnetic, and electrical properties of the resulting composites were investigated. The samples were characterized by FTIR, scanning electron microscopy, X-ray diffractometry, thermogravimetric analysis, differential scanning calorimetry, vibrating sample magnetometer, and broadband dielectric spectroscopy. The composites exhibited high thermal stability, having initial decomposition temperatures between 495 and 509 °C. Saturation magnetization (Ms), magnetic remanence (Mr), and coercivity (Hc) were found in range of 2.37-10.90 emu g-1, 0.45-2.84 emu g-1, and 32-244 Oe, respectively. The study of dielectric properties revealed dielectric constant values of 3.0-4.3 and low dielectric losses of 0.016-0.197 at room temperature and a frequency of 1 Hz.

Chitosan-Sulfated Titania Composite Membranes with Potential Applications in Fuel Cell: Influence of Cross-Linker Nature.

Chitosan-sulfated titania composite membranes were prepared, characterized, and evaluated for potential application as polymer electrolyte membranes. To improve the chemical stability, the membranes were cross-linked using sulfuric acid, pentasodium triphosphate, and epoxy-terminated polydimethylsiloxane. Differences in membranes' structure, thickness, morphology, mechanical, and thermal properties prior and after cross-linking reactions were evaluated. Membranes' water uptake capacities and their chemical stability in Fenton reagent were also studied. As proved by dielectric spectroscopy, the conductivity strongly depends on cross-linker nature and on hydration state of membranes. The most encouraging results were obtained for the chitosan-sulfated titania membrane cross-linked with sulfuric acid. This hydrated membrane attained values of proton conductivity of 1.1 × 10-3 S/cm and 6.2 × 10-3 S/cm, as determined at 60 °C by dielectric spectroscopy and the four-probes method, respectively.