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.

Optical and Flame-Retardant Properties of a Series of Polyimides Containing Side Chained Bulky Phosphaphenanthrene Units.

Among the multitude of polymers with carbon-based macromolecular architectures that easily ignite in certain applications where short circuits may occur, polyimide has evolved as a class of polymers with high thermal stability while exhibiting intrinsic flame retardancy at elevated temperatures via a char-forming mechanism. However, high amounts of aromatic rings in the macromolecular backbone are required for these results, which may affect other properties such as film-forming capacity or mechanical properties; thus, much work has been done to structurally derivatize or make hybrid polyimide systems. In this respect, flexible polyimide films (PI(1-4)) containing bulky 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) units have been developed starting from commercial dianhydrides and an aromatic diamine containing two side chain bulky DOPO groups. The chemical structure of PI(1-4)) was characterized by 1H NMR, 13C NMR and 31P NMR spectroscopy. The optical properties, including absorption and luminescence spectra of these polymers, were analyzed. All polyimides containing DOPO derivatives emitted blue light with an emission maxima in the range of 340-445 nm, in solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, chloroform, and N,N-dimethylacetamide, while green light emission (λem = 487 nm for PI-4) was evidenced in a thin-film state. The thermal decomposition mechanism and flame-retardant behavior of the resulting materials were investigated by pyrolysis-gas-chromatography spectrometry (Py-GC), scanning electron microscopy (SEM), EDX maps and FTIR spectroscopy. The residues resulting from the TGA experiments were examined by SEM microscopy images and FTIR spectra to understand the pyrolysis mechanism.

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.

Evaluation of the Antibacterial Properties of Polyvinyl Alcohol-Pullulan Scaffolds Loaded with Nepeta racemosa Lam. Essential Oil and Perspectives for Possible Applications.

Essential oil of Nepeta racemosa Lam. was extracted and characterized to determine its antimicrobial activity and potential use in applications. The essential oil was loaded on polyvinyl alcohol-pullulan films and gels and characterized by optical microscopy, scanning electron microscopy, and UV-Vis spectroscopy before having its antimicrobial capacities assessed. The essential oil extracted from Nepeta racemosa Lam. was characterized using gas chromatography coupled with mass spectroscopy, which indicated that the most abundant component was nepetalic acid (55.5%), followed by eucalyptol (10.7%) and other compounds with concentrations of about 5% or less. The essential oil, as well as the loaded films and gels, exhibited good antibacterial activity on both gram-positive and gram-negative strains, with growth inhibition zones larger in some cases than for gentamicin, indicating excellent premises for using these essential-oil-loaded materials for applications in the food industry or biomedicine.

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.

Antimicrobial Activity of Artemisia dracunculus Oil-Loaded Agarose/Poly(Vinyl Alcohol) Hydrogel for Bio-Applications.

In this study, the potential use of Artemisia dracunculus essential oil in bio-applications was investigated. Firstly, the phytochemicals from Artemisia dracunculus were analyzed by different methods. Secondly, the Artemisia dracunculus essential oil was incorporated into the hydrogel matrix based on poly(vinyl alcohol) (PVA) and agar (A). The structural, morphological, and physical properties of the hydrogel matrix loaded with different amounts of Artemisia dracunculus essential oil were thoroughly investigated. FTIR analysis revealed the successful loading of the essential oil Artemisia dracunculus into the PVA/A hydrogel matrix. The influence of the mechanical properties and antimicrobial activity of the PVA/A hydrogel matrix loaded with different amounts of Artemisia dracunculus was also assessed. The antimicrobial activity of Artemisia dracunculus (EO Artemisia dracunculus) essential oil was tested using the disk diffusion method and the time-kill assay method after entrapment in the PVA/A hydrogel matrices. The results showed that PVA/agar-based hydrogels loaded with EO Artemisia dracunculus exhibited significant antimicrobial activity (log reduction ratio in the range of 85.5111-100%) against nine pathogenic isolates, both Gram-positive (S. aureus, MRSA, E. faecalis, L. monocytogenes) and Gram-negative (E. coli, K. pneumoniae, S. enteritidis, S. typhimurium, and A. salmonicida). The resulted biocompatible polymers proved to have enhanced properties when functionalized with the essential oil of Artemisia dracunculus, offering opportunities and possibilities for novel applications.

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.

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.

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.

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.

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.

Tunable Properties via Composition Modulations of Poly(vinyl alcohol)/Xanthan Gum/Oxalic Acid Hydrogels.

The design of hydrogel networks with tuned properties is essential for new innovative biomedical materials. Herein, poly(vinyl alcohol) and xanthan gum were used to develop hydrogels by the freeze/thaw cycles method in the presence of oxalic acid as a crosslinker. The structure and morphology of the obtained hydrogels were investigated by means of scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and swelling behavior. The SEM analysis revealed that the surface morphology was mostly affected by the blending ratio between the two components, namely, poly(vinyl alcohol) and xanthan gum. From the swelling study, it was observed that the presence of oxalic acid influenced the hydrophilicity of blends. The hydrogels based on poly(vinyl alcohol) without xanthan gum led to structures with a smaller pore diameter, a lower swelling degree in pH 7.4 buffer solution, and a higher elastic modulus. The antimicrobial activity of the prepared hydrogels was tested and the results showed that the hydrogels conferred antibacterial activity against Gram positive bacteria (Staphylococcus aureus 25923 ATCC) and Gram negative bacteria (Escherichia coli 25922 ATCC).

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.

Electrospun Polyvinyl Alcohol Loaded with Phytotherapeutic Agents for Wound Healing Applications.

In this paper, hydroalcoholic solutions of Thymus vulgaris, Salvia officinalis folium, and Hyperici herba were used in combination with poly (vinyl alcohol) with the aim of developing novel poly (vinyl alcohol)-based nanofiber mats loaded with phytotherapeutic agents via the electrospinning technique. The chemical structure and morphology of the polymeric nanofibers were investigated using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The addition of Thymus vulgaris, Salvia officinalis folium, and Hyperici herba extracts to the pure polyvinyl alcohol fibers led to changes in the morphology of the fibers and a reduction in the fibers' diameter, from 0.1798 µm in the case of pure polyvinyl alcohol to 0.1672, 0.1425, and 0.1369 µm in the case of polyvinyl alcohol loaded with Thymus vulgaris, Salvia officinalis folium, and Hyperici herba, respectively. The adapted Folin-Ciocalteu (FC) method, which was used to determine the total phenolic contents, revealed that the samples of PVA-Hyperici herba and PVA-Thymus vulgaris had the highest phenol contents, at 13.25 µgGAE/mL and 12.66 µgGAE/mL, respectively. Dynamic water vapor measurements were used in order to investigate the moisture sorption and desorption behavior of the developed electrospun materials. The antimicrobial behavior of these products was also evaluated. Disk diffusion assay studies with Escherichia coli, Staphylococcus aureus, and Methicillin-resistant Staphylococcus aureus were conducted on the developed nanofibers in order to quantify their phytotherapeutic potential.

Functional Polyimide-Based Electrospun Fibers for Biomedical Application.

The current study focuses on the application of cytotoxicity tests upon one membrane matrix based on electrospun polyimide fibers, appealing for biomedical application, such as scaffolds for cell growth, patches or meshes for wound healing, etc. Assays were performed in order to determine the viability and proliferation of L929 murine fibroblasts after they were kept in direct contact with the studied electrospun polyimide fibers. Increased cell viability and proliferation were detected for cells seeded on electrospun polyimide fibers membrane, in comparison with the control system, either after two or six days of evaluation. The number of live cells was higher on the studied material compared to the control, after two and six days of cell seeding. The tendency of the cells to proliferate on the electrospun polyimide fibers was revealed by confocal microscopy. The morphological stability of electrospun polyimide membrane was evaluated by SEM observation, after immersion of the samples in phosphate buffer saline solution (PBS, 7.4 at 37 °C) at various time intervals. Additionally, the easy production of electrospun polyimide fibers can facilitate the development of these types of matrices into specific biomedical applications in the future.