Sensing of Co2+ and Cu2+ Ions Using Dimethylamino-functionalized Poly(azomethine-1,3,4-oxadiazole)s.

The ability of OxT and OxFl azomethines to recognize metal ions in THF solutions was investigated using UV-vis absorption techniques. Various metal ions, including Cd2+, Hg2+, Co2+, Sn2+, Cu2+, Ni2+, Zn2+ and Ag+, were tested. The absorption spectra revealed two distinct π-π* transition bands in the 273-278 nm and 330-346 nm wavelength ranges. Additionally, OxFl displayed an absorption peak at 309 nm, attributed to the fluorene group. Spectral titrations were used to study the fluorescence behavior in the presence of these metal ions. The results showed significant quenching with Co2+ and Cu2+ ions, while other metal ions had minimal effects on the fluorescence intensity. The quenching mechanism was further analyzed using the Stern-Volmer and Lehrer equations, and the binding constants ( K b fl ) were calculated using the Benesi-Hildebrand relations. The results confirm that Co2+ has a 1:2 stoichiometry and Cu2+ has a 1:1 stoichiometry, indicating the strong affinity of OxFl and OxT for these ions. The negative values of ΔG (Gibbs free energy) suggest that complex formation occurs spontaneously at room temperature.

Simultaneous Enhancement of Flame Resistance and Antimicrobial Activity in Epoxy Nanocomposites Containing Phosphorus and Silver-Based Additives.

The design and manufacture of innovative multifunctional materials possessing superior characteristics, quality and standards, rigorously required for future development of existing or emerging advanced technologies, is of great importance. These materials should have a very low degree of influence (or none) on the environmental and human health. Adjusting the properties of epoxy resins with organophosphorus compounds and silver-containing additives is key to the simultaneous improvement of the flame-resistant and antimicrobial properties of advanced epoxy-based materials. These environmentally friendly epoxy resin nanocomposites were manufactured using two additives, a reactive phosphorus-containing bisphenol derived from vanillin, namely, (4-(((4-hidroxyphenyl)amino)(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)methyl)-2-methoxyphenyl) phenylphosphonate (BPH), designed as both cross-linking agent and a flame-retardant additive for epoxy resin; and additional silver-loaded zeolite L nanoparticles (Ze-Ag NPs) used as a doping additive to impart antimicrobial activity. The effect of BPH and Ze-Ag NPs content on the structural, morphological, thermal, flame resistance and antimicrobial characteristics of thermosetting epoxy nanocomposites was investigated. The structure and morphology of epoxy nanocomposites were investigated via FTIR spectroscopy and scanning electron microscopy (SEM). In general, the nanocomposites had a glassy and homogeneous morphology. The samples showed a single glass transition temperature in the range of 166-194 °C and an initiation decomposition temperature in the range of 332-399 °C. The introduction of Ze-Ag NPs in a concentration of 7-15 wt% provided antimicrobial activity to epoxy thermosets.

Flame-Resistant Poly(vinyl alcohol) Composites with Improved Ionic Conductivity.

Flame-resistant polymer composites were prepared based on polyvinyl alcohol (PVA) as a polymer matrix and a polyphosphonate as flame retardant. Oxalic acid was used as crosslinking agent. LiClO4, BaTiO3, and graphene oxide were also incorporated into PVA matrix to increase the ionic conductivity. The obtained film composites were investigated by infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and microscale combustion tests. Incorporating fire retardant (PFRV), BaTiO3, and graphene oxide (GO) into a material results in increased resistance to fire when compared to the control sample. A thermogravimetric analysis revealed that, as a general trend, the presence of PFRV and BaTiO3 nanoparticles enhances the residue quantity at a temperature of 700 °C from 7.9 wt% to 23.6 wt%. Their dielectric properties were evaluated with Broad Band Dielectric Spectroscopy. The electrical conductivity of the samples was determined and discussed in relation to the LiClO4 content. The electrical properties, including permittivity and conductivity, are being enhanced by the use of LiClO4. Additionally, a relaxation peak has been observed in the dielectric losses at frequencies exceeding 103 Hz. The electrical properties, including permittivity and conductivity, are being enhanced by the use of LiClO4. Additionally, a relaxation peak has been observed in the dielectric losses at frequencies exceeding 103 Hz. Out of the various composites tested, the composite containing 35 wt% of LiClO4 exhibits the highest alternating current (AC) conductivity, with a measured value of 2.46 × 10-3 S/m. Taking into consideration all the aspects discussed, these improved composites are intended for utilization in the manufacturing of Li-Ion batteries.

Organophosphorus Reinforced Poly(vinyl alcohol) Nanocomposites Doped with Silver-Loaded Zeolite L Nanoparticles as Sustainable Materials for Packaging Applications.

The sustainable development of innovative eco-friendly multifunctional nanocomposites, possessing superior characteristics, is a noteworthy topic. Novel semi-interpenetrated nanocomposite films based on poly(vinyl alcohol) covalently and thermally crosslinked with oxalic acid (OA), reinforced with a novel organophosphorus flame retardant (PFR-4) derived from co-polycondensation in solution reaction of equimolar amounts of co-monomers, namely, bis((6-oxido-6H-dibenz[c,e][1,2]oxaphosphorinyl)-(4-hydroxyaniline)-methylene)-1,4-phenylene, bisphenol S, and phenylphosphonic dichloride, in a molar ratio of 1:1:2, and additionally doped with silver-loaded zeolite L nanoparticles (ze-Ag), have been prepared by casting from solution technique. The morphology of the as prepared PVA-oxalic acid films and their semi-interpenetrated nanocomposites with PFR-4 and ze-Ag was investigated by scanning electron microscopy (SEM), while the homogeneous distribution of the organophosphorus compound and nanoparticles within the nanocomposite films has been introspected by means of energy dispersive X-ray spectroscopy (EDX). It was established that composites with a very low phosphorus content had noticeably improved flame retardancy. The peak of the heat release rate was reduced up to 55%, depending on the content of the flame-retardant additive and the doping ze-Ag nanoparticles introduced into the PVA/OA matrix. The ultimate tensile strength and elastic modulus increased significantly in the reinforced nanocomposites. Considerably increased antimicrobial activity was revealed in the case of the samples containing silver-loaded zeolite L nanoparticles.

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.

Electrospun Nanofibers Based on Polymer Blends with Tunable High-Performance Properties for Innovative Fire-Resistant Materials.

The main concern of materials designed for firefighting protective clothing applications is heat protection, which can be experienced from any uncomfortably hot objects or inner spaces, as well as direct contact with flame. While textile fibers are one of the most important components of clothing, there is a constant need for the development of innovative fire-retardant textile fibers with improved thermal characteristics. Lately, inherently fire-resistant fibers have become very popular to provide better protection for firefighters. In the current study, the electrospinning technique was applied as a versatile method to produce micro-/nano-scaled non-woven fibrous membranes based on various ratios of a poly(ether-ether-ketone) (PEEK) and a phosphorus-containing polyimide. Rheological measurements have been performed on solutions of certain ratios of these components in order to optimize the electrospinning process. FTIR spectroscopy and scanning electron microscopy were used to investigate the chemical structure and morphology of electrospun nanofiber membranes, while thermogravimetric analysis, heat transfer measurements and differential scanning calorimetry were used to determine their thermal properties. The water vapor sorption behavior and mechanical properties of the optimized electrospun nanofiber membranes were also evaluated.

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.

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.

Thermal Properties and Flammability Characteristics of a Series of DGEBA-Based Thermosets Loaded with a Novel Bisphenol Containing DOPO and Phenylphosphonate Units.

Despite a recent sustained preoccupation for developing biobased epoxies with enhanced applicability, such products have not been widely accepted for industry because of their inferior characteristics compared to classic petroleum-based epoxy thermosets. Therefore, significant effort is being made to improve the flame retardance of the most commonly used epoxies, such as diglycidyl ether-based bisphenol A (DGEBA), bisphenol F (DGEBF), novalac epoxy, and others, while continuously avoiding the use of hazardous halogen-containing flame retardants. Herein, a phosphorus-containing bisphenol, bis(4-(((4-hydroxyphenyl)amino)(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)methyl)phenyl) phenylphosphonate (BPH), was synthesized by reacting bis(4-formylphenyl)phenylphosphonate with 4-hydroxybenzaldehyde followed by the addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to the resulting azomethine groups. Environmentally friendly epoxy-based polymer thermosets were prepared by using epoxy resin as polymer matrix and a mixture of BPH and 4,4'-diaminodiphenylsulfone (DDS) as hardeners. A hyperbranched phthalocyanine polymer (HPc) and BaTiO3 nanoparticles were incorporated into epoxy resin to improve the characteristics of the final products. The structure and morphology of epoxy thermosets were evaluated by infrared spectroscopy and scanning electron microscopy (SEM), while the flammability characteristics were evaluated by microscale combustion calorimetry. Thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. The surface morphology of the char residues obtained by pyrolysis was studied by SEM analysis.

Effects of Phosphorus and Boron Compounds on Thermal Stability and Flame Retardancy Properties of Epoxy Composites.

While plastics are regarded as the most resourceful materials nowadays, ranging from countless utilities including protective or decorating coatings, to adhesives, packaging materials, electronic components, paintings, furniture, insulating composites, foams, building blocks and so on, their critical limitation is their advanced flammability, which in fire incidents can result in dramatic human fatalities and irreversible environmental damage. Herein, epoxy-based composites with improved flame-resistant characteristics have been prepared by incorporating two flame retardant additives into epoxy resin, namely 6-(hydroxy(phenyl)methyl)-6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide (PFR) and boric acid (H3BO3). The additional reaction of 9,10-dihydro-oxa-10-phosphophenanthrene-10-oxide (DOPO) to the carbonyl group of benzaldehyde yielded PFR, which was then used to prepare epoxy composites having a phosphorus content ranging from 1.5 to 4 wt%, while the boron content was 2 wt%. The structure, morphology, thermal stability and flammability of resulted epoxy composites were investigated by FTIR spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis, differential scanning calorimetry, and microscale combustion calorimetry (MCC). Thermogravimetric analysis indicated that the simultaneous incorporation of PFR and H3BO3 improved the thermal stability of the char residue at high temperatures. The surface morphology of the char residues, studied by SEM measurements, showed improved characteristics in the case of the samples containing both phosphorus and boron atoms. The MCC tests revealed a significant reduction in flammability as well as a significant decrease in heat release capacity for samples containing both PFR and H3BO3 compared to the neat epoxy thermoset.

Effect of Hardener Type on the Photochemical and Antifungal Performance of Epoxy and Oligophosphonate S-IPNs.

Due to their highly reactive character and multiple crosslinking capacity, epoxy resins are one of the worldwide market-dominating classes of thermosetting polymers and are present in a wide range of technical applications, including structural adhesives, coatings and polymer matrices for composite materials. Despite their excellent features, epoxy resins are known to be highly flammable and possess low thermal stability and a brittle character and crack easily under impact forces. An efficient approach towards eliminating such drawbacks resides in obtaining epoxy-based semi-interpenetrating polymer networks, which possess excellent control over the morphology. The article describes the comparative effect of three hardeners (aromatic, cycloaliphatic and aliphatic) in the presence of an oligophosphonate (-R-O-PO(C6H5)-O-) (2 wt.% phosphorus) on the photochemical, fire and antifungal performance of bisphenol A diglycidyl ether semi-interpenetrating polymer networks. The networks are designed as future potential outdoor protective coatings for different substrates. The fire resistance capacity of the networks was undertaken with microscale combustion calorimetry before and after photochemical aging. Structural changes during photoirradiation were monitored via color modification studies, Fourier-transform infrared spectroscopy, differential scanning calorimetry, morphological assessment through scanning electron microscopy and mass loss measurements in order to propose the action mode of the hardeners and the oligophosphonate on the material properties. Microbiological testing was also undertaken with the aid of three specific wood decaying fungi as a first substrate.

Phosphorylated Poly(vinyl alcohol) Electrospun Mats for Protective Equipment Applications.

The development of intelligent materials for protective equipment applications is still growing, with enormous potential to improve the safety of personnel functioning in specialized professions, such as firefighters. The design and production of such materials by the chemical modification of biodegradable semisynthetic polymers, accompanied by modern manufacturing techniques such as electrospinning, which may increase specific properties of the targeted material, continue to attract the interest of researchers. Phosphorus-modified poly(vinyl alcohol)s have been, thus, synthesized and utilized to prepare environmentally friendly electrospun mats. Poly(vinyl alcohol)s of three different molecular weights and degrees of hydrolysis were phosphorylated by polycondensation reaction in solution in the presence of phenyl dichlorophosphate in order to enhance their flame resistance and thermal stability. The thermal behavior and the flame resistance of the resulting phosphorus-modified poly(vinyl alcohol) products were investigated by thermogravimetric analysis and by cone calorimetry at a micro scale. Based on the as-synthesized phosphorus-modified poly(vinyl alcohol)s, electrospun mats were successfully fabricated by the electrospinning process. Rheology studies were performed to establish the optimal conditions of the electrospinning process, and scanning electron microscopy investigations were undertaken to observe the morphology of the phosphorus-modified poly(vinyl alcohol) electrospun mats.

Fabrication of Poly(vinyl alcohol)/Chitosan Composite Films Strengthened with Titanium Dioxide and Polyphosphonate Additives for Packaging Applications.

Eco-innovation through the development of intelligent materials for food packaging is evolving, and it still has huge potential to improve food product safety, quality, and control. The design of such materials by the combination of biodegradable semi-synthetic polymers with natural ones and with some additives, which may improve certain functionalities in the targeted material, is continuing to attract attention of researchers. To fabricate composite films via casting from solution, followed by drying in atmospheric conditions, certain mass ratios of poly(vinyl alcohol) and chitosan were used as polymeric matrix, whereas TiO2 nanoparticles and a polyphosphonate were used as reinforcing additives. The structural confirmation, surface properties, swelling behavior, and morphology of the xerogel composite films have been studied. The results confirmed the presence of all ingredients in the prepared fabrics, the contact angle of the formulation containing poly(vinyl alcohol), chitosan, and titanium dioxide in its composition exhibited the smallest value (87.67°), whereas the profilometry and scanning electron microscopy enlightened the good dispersion of the ingredients and the quality of all the composite films. Antimicrobial assay established successful antimicrobial potential of the poly(vinyl alcoohol)/chitosan-reinforced composites films against Staphylococcus aureus, Methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli, Pseudomonas aeruginosa, and Candida albicans. Cytotoxicity tests have revealed that the studied films are non-toxic, presented good compatibility, and they are attractive candidates for packaging applications.

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.

Metal ions sensing properties of some phenylquinoxaline derivatives.

The sensitivity and selectivity properties of three phenylquinoxaline derivatives to different metal ions were investigated by absorption and fluorescence spectroscopy. The absorption and fluorescence responses of the phenylquinoxaline derivatives were examined towards the following metal ions Ag+, Mg2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+, in THF solution. All investigated samples exhibit sensitivity and selectivity to Ag+, Co2+ and Cu2+ ions compared to other metal ions (Mn+ = Mg2+, Ni2+, Zn2+, Cd2+ and Hg2+). The gradual addition of Ag+, Co2+ and Cu2+ ions to a Q-Ox sample solution generates new absorption bands (with maxima at 244, 675 and 294 nm, in presence of the Ag+, Co2+ and Cu2+ ions, respectively) while the emission intensities were weakly quenched, except in presence of Ag+ ions, when the emission was almost completely quenched (quenching efficiency at 426 nm, (I0 - I) / I0 × 100% = 91%). Absorption and fluorescence results show the formation of 1:2 metal complexes with Ag+ ions and 1:1 stoichiometry for a complexation between Q-Ox and Co2+ or Cu2+ ions. The following characteristics of these phenylquinoxaline derivatives have been calculated and discussed: the effects of the interfering ions, the binding constants and the detection limit of Ag+, Co2+ and Cu2+ ions.

Photophysical Properties of some 1,3,4-Oxadiazole Derivatives Containing Phenolphtalein, Fluorene and Bisphenol A Units.

The photophysical properties of the three 1,3,4-oxadiazole derivatives containing fluorene (Ox-FL); fluorene and phenolphtaleine (Ox-FL-FF); or fluorene and bisphenol A (Ox-FL-BPA) moieties in the main chain were investigated by the fluorescence and absorption spectroscopy in different solvents and in the solid state. The electronic absorption spectra included a strong absorption band located in the 270-395 nm region, with a maxima around at 302 nm. The fluorescence excitation spectra were also characterized by one broad band, appearing in the wavelength range of 220-340 nm. All samples displayed the emission bands around 356-373 nm and exhibit high quantum yields ranged from 31.61 to 90.77%, in chloroform solution. The sensitivity of the emission spectra on medium characteristics (polarity, acidity and basicity) were evaluated by using the Catalan solvent scale and the fluorescence titration with a dilute acid solution.

Optical Properties of Some Fluorinated Poly(1,3,4-Oxadiazole-Ether)s in Homogeneous and Heterogeneous Media. Changes Induced by SnO2, NiO and SnO2/NiO Mixed-Oxide Nanoparticles.

Optical characteristics of some fluorinated poly(1,3,4-oxadiazole-ether)s in presence of SnO2, NiO and SnO2/NiO mixed-oxide nanoparticles (NPs) was investigated. The interactions between polymers and metal oxide NPs were studied by steady-state UV-Vis absorption and fluorescence spectroscopy techniques. The absorption and fluorescence signals of all investigated polymers was modified by presence of both pure and mixed-oxide nanoparticles. The moderate values of Stern-Volmer quenching constant and non-linear trend of Scott plot indicate the less affinity between metal oxide NPs and polymers. The solvation behavior of some fluorinated poly(1,3,4-oxadiazole-ether)s in chloroform-N,N-dimethylformamide and N,N-dimethylformamide-dimethylsulfoxide mixtures was discussed.