In situ prepared polyamide 6/DOPO-derivative nanocomposite for melt-spinning of flame retardant textile filaments

Abstract A novel flame retardant polyamide 6 (PA6)/bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-derivative (PHED) nanocomposite textile filament yarns were developed. The scalable production approach includes in situ water-catalyzed ring-opening polymerization of e-caprolactam in the presence of the flame retardant PHED followed by melt-spinning of nanocomposite filament yarns and production of knitted fabrics. The specific chemical structure of the PHED additive enabled its excellent miscibility with molten e-caprolactam and the uninterrupted polymerization of e-caprolactam. The produced PA6/PHED nanocomposite was characterized by the preserved molecular structure of the polyamide 6 and uniformly distributed nano-dispersed FR at concentrations of 10 and 15 wt %. The PA6/PHED nanocomposite structure was successfully preserved after the melt-spinning processing. The PA6 nanocomposite filament yarns at the applied 15 wt %. loading of PHED showed (a) increased thermo-oxidative stability compared to neat PA6 up to 500 °C, with a 43% higher residue at 500 °C and (b) self-extinguishment of fiber strand and knitted samples within 1 s in standard vertical flame spread tests (ASTM D6413), followed by the significant reduction of the melt-dripping and the melt-drop flammability. Additionally, 1.2 mm-tick PA6/PHED bar samples achieved a V0 rating in UL94 vertical burning test at the applied 10 wt % concentration of PHED. This innovative and scalable approach could pave the way for the production of new-generation nanocomposite PA6 filament yarns with self-extinguishing properties at the macro-scale, which would be highly beneficial for increasing fire safety, whilst maintaining the use of a DOPO derivative at the minimum level

Characterisation of melamine formaldehyde microspheres synthesised with prolonged microencapsulated reaction time

The aim of the research was to identify the influence of different microencapsulated reaction time on the morphology, size, infrared spectral, thermal and micromechanical properties of melamine formaldehyde microspheres, synthesised with modified in situ polymerisation. Microspheres are microencapsulated particles with a blurred boundary of the core and shell due to their same composition. The synthesis of microspheres was paused after 1, 3, 9 and 15 h, and stopped after 23 h. The scanning electron microscopy and granulometric analysis were used to study the morphology and size of microspheres. Regardless of the reaction time, the produced microspheres were spherical in shape and with a rough surface. The average size of microspheres was almost identical (0.709–0.790 µm), while the volume size distribution curve of the particles became narrower with prolonged reaction time. The curing mechanism of melamine formaldehyde resin was studied using the Fourier-transform infrared spectroscopy and thermal analysis, and nano-indentation identification. The results revealed a slightly more crosslinked structure: with minimal (neglected) increased thermal weight loss (only up to 0.5%) and minor increased Young’s modulus (up to 2.3%). Using a nano-indenter, the hardness of synthesised particles improved by up to 14.8% after 23 h reaction time

Properties of bacterial cellulose produced using white and red grape bagasse as a nutrient source

The purpose of the study is to investigate the possibility of using wine industry wastes, such as red and white grape bagasse, to produce bacterial cellulose (BC) instead of using a costly commercial medium. BC was produced using grape bagasse as a carbon source replacement and the sole nutrient in the medium. The BC films were evaluated for their productivity and waterholding capacity. The BC films were also investigated for their morphology using scanning electron microscopy (SEM), their viscoelastic properties using dynamic mechanical analysis (DMA), and their chemical composition using Fourier-transform infrared spectroscopy (FTIR). Although the use of grape bagasse as the sole nutrient was successful in the preparation of BC, the BC films had inferior viscoelastic properties to other produced BC films. White grape bagasse proved to be an excellent carbon substitute as the production of BC and its water-holding capacity were five times higher and the produced BC films were up to 72% more flexible than the bacterial cellulose produced using standard HS medium

Effect of SiO2_2 and TiO2_2 nanoparticles on the performance of UV visible fluorescent coatings

In the present research, the properties of ultraviolet (UV) visible (daylight invisible) fluorescent coatings modified by the addition of SiO$_2$ and TiO$_2$ nanoparticles were studied. Structural, surface, and mechanical properties and changes in the coatings caused by accelerated ageing were analyzed. The results showed that the addition of nanoparticles caused the changes in unaged and aged printed coatings. Reflectance measurements of modified coatings showed that addition of TiO$_2$ nanoparticles improved the visual effect of the unaged coatings. Furthermore, results have shown that the addition of SiO$_2$ did not diminish the reflectance of the modified coatings after ageing. The results of roughness measurements showed that the addition of SiO$_2$ decreased roughness after the ageing process, probably due to the degradation process indicated by Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy. The roughness of the coatings with TiO$_2$ nanoparticles was increased after the ageing on the samples with higher concentrations of TiO$_2$ due to the agglomerates of plastisol formed on the surface of the coatings, visible in SEM images. Surface analysis of coatings showed that TiO$_2$ caused an increase in the polarity of the surface coatings. Results of the bending stiffness showed that the addition of the nanoparticles to the coating, especially of SiO$_2$, significantly improved the bending stiffness of the unaged samples

Fibers obtained from invasive alien plant species as a base material for paper production

Invasive alien plant species (IAPS) are one of the biggest challenges in European ecosystems, displacing local vegetation, destroying agricultural land, and causing billions of dollars of damage to the European economy every year. Many of them are removed daily and mainly burned. In this work, we investigated the possibilities of using plants as feedstock for paper production. Papers made from three invasive alien plants, i.e., Knotweed, Goldenrod, and Black locust, were studied and compared with commercial office paper. The study included testing of: (1) structural properties— basic physical properties, grammage, thickness, density and specific volume, moisture content, and ash content(2) physical and dynamic mechanical properties—tensile strength, Clark stiffness, viscoelastic properties(3) colorimetric properties of prints(4) effect of UV light on ageingand (5) study of cellulose fiber structure and morphology by microscopy. The results suggested that the paper produced can be used as commercial office paper, considering that the paper is slightly dyed. Such papers can also be used for special purposes that present a natural style and connection to nature. The papers produced can also be used for printing documents that are meant to be kept

Quality of Fine Yarns from Modacrylic/Polyacrylate/Lyocell Blends Intended for Affordable Flame-Resistant Underwear

Flammability testing of undergarments is a topic that is often overlooked and rarely on the list of textiles to be tested for fire safety. However, it is particularly important for professionals exposed to fire risk to investigate the flammability of underwear as its direct contact with the skin can be critical to the extent and degree of skin burns. This research focuses on the suitability of affordable blends of 55 wt.% modacrylic, 15 wt.% polyacrylate, and 30 wt.% lyocell fibres that have the potential to be used for flame-resistant underwear. The influence of modacrylic fibre linear density (standard and microfibres), ring spinning processes (conventional, Sirospun, and compact), and knitted structure (plain, 2:1 rib, 2:1 tuck rib, single pique, and triple tuck) on their properties required for thermal comfort in high-temperature environments was investigated. Scanning electron and optical microscopy, FT-IR spectroscopy, mechanical testing, moisture regain, water sorption, wettability, absorption, DSC, TGA, and flammability were tested to assess the desired suitability. The wetting time (5–14.6 s) and water absorption time (4.6–21.4 s) of the knitted fabrics have shown excellent ability to transport and absorb water compared to the knitted fabrics created from a conventional blend of 65% modacrylic and 35% cotton fibres. The afterflame and afterglow times of less than 2 s met the criteria for non-flammability of the knitted fabrics according to the limited flame spread test method. The results show that the investigated blends have the potential to be used for affordable flame-retardant and thermally comfortable knitted fabrics for underwear

Colour fastness to various agents and dynamic mechanical characteristics of biocomposite filaments and 3D printed samples

The aim of the study was to analyse the colour fastness of 3D printed samples that could be used as decorative or household items. Such items are often fabricated with 3D printing. The colour of filaments affects not only the mechanical properties, but also the appearance and user satisfaction. Samples of biocomposite filaments (PLA and PLA with added wood and hemp fibres) were used. First, the morphological properties of the filaments and 3D printed samples were analysed and then, the colour fastness against different agents was tested (water, oil, detergent, light and elevated temperature). Finally, the dynamic mechanical properties of the filaments and 3D printed samples were determined. The differences in the morphology of the filaments and 3D printed samples were identified with SEM analysis. The most obvious differences were observed in the samples with wood fibres. All printed samples showed good resistance to water and detergents, but poorer resistance to oil. The sample printed with filaments with added wood fibres showed the lowest colour fastness against light and elevated temperatures. Compared to the filaments, the glass transition of the printed samples increased, while their stiffness decreased significantly. The lowest elasticity was observed in the samples with wood fibres. The filaments to which hemp fibres were added showed the reinforcement effect. Without the influence on their elasticity, the printed samples can be safely used between 60 and 65 °C

Analysis of PLA composite filaments reinforced with lignin and polymerised-lignin-treated NFC

Polylactic acid (PLA) is one of the most suitable materials for 3D printing. Blending with nanoparticles improves some of its properties, broadening its application possibilities. The article presents a study of composite PLA matrix filaments with added unmodified and lignin/polymerised lignin surface-modified nanofibrillated cellulose (NFC). The influence of untreated and surfacemodified NFC on morphological, mechanical, technological, infrared spectroscopic, and dynamic mechanical properties was evaluated for different groups of samples. As determined by the stereo and scanning electron microscopy, the unmodified and surface-modified NFCs with lignin and polymerised lignin were present in the form of plate-shaped agglomerates. The addition of NFC slightly reduced the filaments’ tensile strength, stretchability, and ability to absorb energy, while in contrast, the initial modulus slightly improved. By adding NFC to the PLA matrix, the bending storage modulus (E’) decreased slightly at lower temperatures, especially in the PLA samples with 3 wt% and 5 wt% NFC. When NFC was modified with lignin and polymerised lignin, an increase in E’ was noticed, especially in the glassy state

Characterization of Polyamide 6/Multilayer Graphene Nanoplatelet Composite Textile Filaments Obtained Via In Situ Polymerization and Melt Spinning

Studies of the production of fiber-forming polyamide 6 (PA6)/graphene composite material and melt-spun textile fibers are scarce, but research to date reveals that achieving the high dispersion state of graphene is the main challenge to nanocomposite production. Considering the significant progress made in the industrial mass production of graphene nanoplatelets (GnPs), this study explored the feasibility of production of PA6/GnPs composite fibers using the commercially available few-layer GnPs. To this aim, the GnPs were pre-dispersed in molten ε-caprolactam at concentrations equal to 1 and 2 wt %, and incorporated into the PA6 matrix by the in situ water-catalyzed ring-opening polymerization of ε-caprolactam, which was followed by melt spinning. The results showed that the incorporated GnPs did not markedly influence the melting temperature of PA6 but affected the crystallization temperature, fiber bulk structure, crystallinity, and mechanical properties. Furthermore, GnPs increased the PA6 complex viscosity, which resulted in the need to adjust the parameters of melt spinning to enable continuous filament production. Although the incorporation of GnPs did not provide a reinforcing effect of PA6 fibers and reduced fiber tensile properties, the thermal stability of the PA6 fiber increased. The increased melt viscosity and graphene anti-dripping properties postponed melt dripping in the vertical flame spread test, which consequently prolonged burning within the samples