Search Results (28)

Polyamide 6,6 (PA6,6) fabrics are widely used in textiles due to their high mechanical strength and chemical stability. However, their inherent flammability and melting behavior under fire pose significant safety challenges. In this study, a dual-layer flame-retardant system was developed by integrating atomic layer deposition (ALD) of ZnO with a phosphorus–silane-based flame retardant (DOPO-ETES). ALD allowed precise control of ZnO layer thickness (50, 84, and 199 nm), ensuring uniform coating. Thermal analysis (TGA) and microscale combustion calorimetry (MCC) revealed that ZnO altered the degradation pathway of PA6,6 through catalytic effects, promoting char formation and reducing heat release. The combination of ZnO and DOPO-ETES resulted in further reductions in heat release rates. However, direct flame tests showed that self-extinguishing behavior was not achieved, emphasizing the limitations related to the melting of PA6,6. TG-IR and cone calorimetry confirmed that ZnO coatings suppressed the release of smoke-related volatiles and incomplete combustion products. These findings highlight the potential of combining metal-based catalytic flame retardants like ZnO with phosphorus-based coatings to improve flame retardancy while addressing the specific challenges of polyamide textiles. This approach may also be adapted to other fabric types and integrated with additional flame retardants, broadening its relevance for textile applications. Full article

In this study, a solvent-free, slow-curing, inherently flame-retardant polyurea coating was successfully developed through an optimized formulation. The novel polyurea was synthesized using mixed Schiff base latent curing agents derived from terminal polyether amines with different-number average molecular weights (D2000 and D400), methyl isobutyl ketone, and polyethyl phosphate glycol ester (OP550). Subsequently, polyurea/meta-aramid (PUA/AF) composite fabrics were fabricated via a scraping coating technique. Thermogravimetric analysis revealed enhanced char formation and reduced decomposition temperatures due to the incorporation of OP550. Comprehensive flame retardant performance was demonstrated through vertical flame testing, limiting oxygen index, and micro-scale combustion calorimetry, with results showing significantly reduced heat release rates, lower total heat release, and increased residual char. Mechanical evaluations indicated marked improvements in tearing, tensile, single-yarn tensile, and bursting forces, attributed to strong fiber–polyurea interfacial interactions, as confirmed by detailed SEM morphological analyses. Moreover, the PUA/AF composites exhibited excellent static puncture resistance and effective self-healing capability. Collectively, these advancements highlight the potential of PUA/AF composite fabrics as promising candidates for advanced protective textiles, integrating superior flame retardancy, mechanical strength, puncture resistance, and self-repairing functionality. Full article

This study explores how functionalized aromatic P-FRs, specifically phenyl- and phenoxy-based phosphoric acid derivatives, influence the flame retardancy of cotton textiles. By systematically investigating derivatives with varying degrees of phenyl, phenoxy, and acidic hydroxyl terminations, alongside ortho-phosphoric acid as a reference, this work aimed to elucidate the role of aromaticity and functional group composition on both gas- and condensed-phase flame retardant efficacy. Cotton fabrics were treated with comparable phosphorus loadings (~3 g/m²), quantified using inductively coupled plasma optical emission spectroscopy (ICP-OES), to evaluate the gas- and condensed-phase efficacy of the flame retardants. Notably, derivatives with a higher number of acidic hydroxyl terminations exhibited the best flame retardant performance, enhancing char formation through dehydration and condensation reactions during combustion. Thermal analysis (TGA) and microscale combustion calorimetry (MCC) confirmed that phenoxy systems catalyze cotton decomposition more effectively, promoting dehydration through the hydrolysis of phenoxy groups. Furthermore, IR analysis of evolved gases revealed a significant reduction in volatile emissions for phenoxy systems, while this was not observed for phenyl derivatives. These findings underscore the importance of robust condensed-phase mechanisms for achieving effective flame retardancy in cotton textiles. Full article

The intumescent flame retardant (IFR) technique is an alternative to halogen-based flame retardants for reducing fire hazards in polymers. However, IFR has drawbacks like unsatisfactory flame-retardant efficiency and high loading requirements. In this study, MIL-125 (Ti-based metal–organic framework) is added to ABS/IFR composites to improve flame retardancy and reduce smoke emissions. Thermogravimetric analysis (TGA) results indicate that combining ammonium polyphosphate (APP) and expandable graphite (EG) increases charred residue and slows mass loss compared with the original ABS resin. The ABS/IFR/MIL-125 system stabilizes the char layer, serving as a protective shield against combustible gases during combustion. Additionally, MIL-125 enhances performance in microscale combustion calorimetry (MCC) flammability testing. In fire tests (UL-94, limiting oxygen index (LOI), and cone calorimeter), the ABS/IFR/MIL-125 system achieves a UL-94 V0 rating and the highest LOI value of 31.5% ± 0.1%. Peak heat lease rate (PHRR) values in the cone calorimeter are reduced by 72% with 20 wt.% of additives, and smoke production decreases by 53% compared with neat ABS. These results demonstrate the efficient synergistic effects of MIL-125 and IFR additives in improving the formation and stability of the intumescent char layer, thereby protecting ABS from intense burning. Full article

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. Full article

In this work, a novel bio-based high-performance bisbenzoxazine resin was synthesized from daidzein, 2-thiophenemethylamine and paraformaldehyde. The chemical structure was confirmed using nuclear magnetic resonance spectroscopy (NMR) and Fourier-transform infrared spectroscopy (FT-IR). The polymerization process was systematically studied using differential scanning calorimetry (DSC) and in situ FT-IR spectra. It can be polymerized through multiple polymerization behaviors under the synergistic reaction of thiophene rings with benzopyrone rather than a single polymerization mechanism of traditional benzoxazines, as reported. In addition, thermogravimetric analysis (TGA) and a microscale combustion calorimeter (MCC) were used to study the thermal stability and flame retardancy of the resulting polybenzoxazine. The thermosetting material showed a high carbon residue rate of 62.8% and a low heat release capacity (HRC) value of 33 J/gK without adding any flame retardants. Based on its outstanding capability of carbon formation, this newly obtained benzoxazine resin was carbonized and activated to obtain a porous carbon material doped with both sulfur and nitrogen. The CO₂ absorption of the carbon material at 0 °C and 25 °C at 1 bar was 3.64 mmol/g and 3.26 mmol/g, respectively. The above excellent comprehensive properties prove its potential applications in many advanced fields. Full article

In this study, an analysis of the influence of extractives, suberin and lignocellulosic components on the pyrolysis decomposition and fire reaction mechanisms of a cork oak powder from Quercus suber L. is presented. The summative chemical composition of cork powder was determined. Suberin was the main component at 40% of the total weight, followed by 24% of lignin, 19% of polysaccharides and 14% of extractives. The absorbance peaks of cork and its individual components were further analyzed by means of ATR-FTIR spectrometry. Thermogravimetric analysis (TGA) showed that the removal of extractives from cork slightly increased the thermal stability between 200 °C and 300 °C and led to the formation of a more thermally stable residue at the end of the cork decomposition. Moreover, by removing suberin, a shift of the onset decomposition temperature to a lower temperature was noticed, indicating that suberin plays a major role in enhancing the thermal stability of cork. Furthermore, non-polar extractives showed the highest flammability with a peak of heat release rate (pHRR) of 365 W/g analyzed by means of micro-scale combustion calorimetry (MCC). Above 300 °C, the heat release rate (HRR) of suberin was lower than that of polysaccharides or lignin. However, below that temperature it released more flammable gases with a pHRR of 180 W/g, without significant charring ability, contrary to the mentioned components that showed lower HRR due to their prominent condensed mode of action that slowed down the mass and heat transfer processes during the combustion process. Full article

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. Full article

Three-dimensional simulations of laminar flame propagating downwards the vertical surface of a rigid polyurethane slab heated by a radiative panel are presented and compared with the measurement data. The gas-phase model (ANSYS Fluent) allows for finite-rate volatile oxidation, soot formation and oxidation, emission, transfer, and absorption of thermal radiation. The solid-phase model Pyropolis considers heat transfer across the material layer and generation of combustible volatiles in thermal decomposition of the material. Kinetic model of material decomposition is derived to obey the microscale combustion calorimetry data for different heating rates. Transient behavior of propagating flame and pyrolysis zone, as well as spatial distributions of heat flux components, temperature, and mass burning rates over the specimen surface are examined. Variation of the thermal properties of the material during its thermal decomposition, as well as the specimen surface emissivity and reradiation are shown to be the important issues strongly affecting model predictions. Two distinct modes of counterflow flame spread, thermal and kinetic, are identified. In the thermal mode corresponding to fast chemistry in the gaseous flame, the flame propagation velocity is governed by the heating rate of the combustible material ahead of the flame front. Alternatively, in the kinetic mode, it is limited by the burning velocity of the volatile-air mixture forming ahead of the flame front. Simulation results are favorably compared with the measured propagation velocity. Full article

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. Full article

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. Full article

Driven by concerns over the health and environmental impacts of currently used fire retardants (FRs), recent years have seen strong demand for alternative safer and sustainable bio-based FRs. In this paper, we evaluated the potential of nitrogen-modified biopolyphenols as FRs for cellulosic natural fibres that could be used in low-density cellulose insulations. We describe the preparation and characterisation of nitrogen-modified lignin and tannin containing over 10% nitrogen as well as the treatment of cellulose pulp fibres with combinations of lignin or tannin and adsorption-enhancing retention aids. Combining lignin or tannin with a mixture of commercial bio-based flocculant (cationised tannin) and anionic retention chemical allowed for a nearly fourfold increase in lignin adsorption onto cellulosic pulp. The nitrogen-modified biopolyphenols showed significant improvement in heat release parameters in micro-scale combustion calorimetry (MCC) testing compared with their unmodified counterparts. Moreover, the adsorption of nitrogen-modified lignin or tannin onto cellulose fibres decreased the maximum heat release rate and total heat release compared with cellulose reference by 15–23%. A further positive finding was that the temperature at the peak heat release rate did not change. These results show the potential of nitrogen-modified biopolyphenols to improve fire-retarding properties of cellulosic products. Full article

We studied the effects of silicon carbide (SiC) and SiC hybrid systems with different conventional fillers (silica, carbon black, graphene, hydrotalcite, halloysite) on the rheometric measurements, crosslink density, mechanical performance, aging stability, morphology, thermal behaviour, and flammability of ethylene-propylene-diene (EPDM) rubber composites. The hybrid filler systems showed technically promising synergetic effects on the performance of the EPDM composites. A pronounced reinforcing effect in EPDM composites filled with hybrid SiC filler systems was noted. Tensile strength increased in the systems with carbon black, silica, and graphene nanoplatelets, by 21%, 37%, and 68%, respectively, compared to the neat EPDM. Dynamic-mechanical analysis (DMA) revealed a shift of the glass transition temperature (Tg) of EPDM composites towards higher values following the incorporation of hybrid SiC fillers, indicating that the mobility of the macromolecule chains was restricted by the presence of filler particles. Importantly, the application of SiC as a filler in EPDM rubber composites contributed to a considerable reduction in flammability, as demonstrated by microscale combustion calorimetry (MCC). The most promising results were obtained for HAL/SiC and LDH/SiC hybrid systems, which produced final composites with high flame retardancy and good mechanical performance. The study highlights the significant potential of SiC and SiC hybrid systems as effective fillers improving the properties of elastomer composites. Full article

To improve on the poor strength and flame retardancy of a chitosan (CS)-based functional film, cellulose nanofiber (CNF) was taken as the reinforced material and both ammonium polyphosphate (APP) and branched polyethyleneimine (BPEI) as the flame-retardant additives in the CS matrix to prepare the CS/CNF/APP/BPEI composite film by simple drying. The resulting composite film showed good mechanical strength, with a tensile strength reaching 71.84 Mpa due to the high flexibility of CNF and the combination of CS, CNF and BPEI through strong hydrogen bonding interactions. The flame retardant-performance of the composite film greatly enhanced the limit oxygen index (LOI), up to 32.7% from 27.6% for the pure film, and the PHRR intensity decreased to 28.87 W/g from 39.38% in the micro-scale combustion calorimetry (MCC) test due to the ability of BPEI to stimulate the decomposition of APP, releasing non-flammable gases such as CO₂, N₂, NH₃, etc., and forming a protective phosphating layer to block the entry of O₂. Based on the good flame retardancy, mechanical strength and transparency, the CS/CNF/APP/BPEI composite film has a great potential for future applications. Full article

To study the practicability of a micro combustion calorimeter to analyze the calorimetry kinetics of wood, a micro combustion calorimeter with 13 heating rates from 0.1 to 5.5 K/s was used to perform the analysis of 10 kinds of common hardwood and softwood samples. As a microscale combustion measurement method, MCC (microscale combustion calorimetry) can be used to judge the flammability of materials. However, there are two methods for measuring MCC: Method A and Method B. However, there is no uniform standard for the application of combustible MCC methods. In this study, the two MCC standard measurement Methods A and B were employed to check their practicability. With Method A, the maximum specific heat release rate, heat release temperature, and specific heat release of the samples were obtained at different heating rates, while for Method B, the maximum specific combustion rate, combustion temperature and net calorific values of the samples were obtained at different heating rates. The ignition capacity and heat release capacity were then derived and evaluated for all the common hardwood and softwood samples. The results obtained by the two methods have significant differences in the shape of the specific heat release rate curves and the amplitude of the characteristic parameters, which lead to the differences of the derived parameters. A comparison of the specific heat release and the net calorific heat of combustion with the gross caloric values and heating values obtained by bomb calorimetry was also made. The results show that Method B has the potentiality to evaluate the amount of combustion heat release of materials. Full article