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The development of high-strength and intrinsic flame-retardant natural fiber-reinforced green composite (NFRGC) is a landmark for high-performance structural applications. This paper reports a biobased, high-performance, flame-retardant composite material based on diverse bio-resources. Tough and strong cellulose long filaments (CLFs) are combined with vanillin-derived epoxy (VDE) resin to achieve high strength and flame-retardant NFRGC. The green composite was fabricated using a simple hand lay-up and compression molding technique. The green composite showed a noteworthy increment of 100.9 % flexural strength and 346 % flexural modulus compared to the neat VDE resin. Interestingly, despite the highly flammable nature of CLF, the green composite passes a V-0 rating under the UL-94 test, indicating excellent flame-retardant characteristics. Additionally, the green composite demonstrated outstanding hydrophobicity with a water contact angle of 104.2° and good chemical stability in various acidic and organic solvents. The green composite's excellent mechanical and physical properties show its potential for high-strength and flame-retardant structural applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that have influenced the study reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Biodegradable composites were prepared from polylactic acid (PLA) and bamboo charcoal (BC) by melt blending and hot pressing. The effects of BC addition on the mechanical properties, water absorption, DMA, TGA, DSC, and CONE of BC/PLA composites were investigated. The microscopic morphology of the composites was analyzed by SEM. The results showed that for BC addition of 40 wt%, the mechanical strength, thermal properties, and flame retardant properties of the composites were improved compared with those of PLA, with a 2.24 % increase in flexural strength and a 1535 % increase (500 °C) in TG mass retention rate. The crystallinity increased by 129.66 %, the peak loss factor decreased by 31.15 %, the time required for combustion was delayed by 168 s, the peak heat release rate decreased by 29.40 %, the carbon residue rate detected by cone calorimetry increased by 48.50 %, and the peak mass loss rate decreased by 48.82 %. The addition of BC enhanced the crystallization capacity of PLA, and improved the thermal properties and flame retardant properties of the prepared composites. The results showed that materials prepared with a BC content of 40 wt% exhibited the best overall performance., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Currently, it is still a huge challenge to prepare high performance eco-friendly poly(lactic acid) (PLA) with high thermal stability, good processability, excellent crystallization behavior, good transparency and highly-efficient fire safety. In this paper, a novel bio-based nucleation agent N-(furan-2-ylmethyl)-P,P-diphenylphosphinic amide (FPPA) was prepared and used for the fabrication of fire safety PLA/FPPA composites. The chemical structure of FPPA was measured by FTIR, NMR and MS. Further, the crystallization behavior, thermal stability, fire safety and mechanical properties of PLA/FPPA composites were performed by TGA, DSC, polarization microscope, LOI, UL94, cone calorimeter, DMA and, SEM, Raman, GC-MS, and TGA-FTIR. The results showed that the multifunctional FPPA not only had a high thermal stability and was a good nucleation agent for PLA. Moreover, only loading of 3 wt% FPPA increased the LOI of PLA from 19.0 to 33.8 % with UL-94 V-0 classification. Furthermore, the heat release rate and total heat release values of PLA/3%FPPA composite reduced by 6.3 % and 15.3 % in cone-calorimeter test. Such high fire safety was mainly attributed to specific fire safety radicals due to thermal degradation of FPPA to interrupt composites burning in gas phase. Besides, transparency and mechanical properties were almost not changed because of low loading of FPPA in PLA. This multifunctional bio-based fire-retardant for PLA with good comprehensive performance promises broad application in engineering electronics, automobiles, 3D printing and construction materials., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Lyocell fabrics are widely applied in textiles, however, its high flammability increases the risk of fire. Therefore, to resolve the issue, a novel biomass-based flame retardant with phosphorus and nitrogen elements was designed and synthesized by the reaction of arginine with phosphoric acid and urea. It was then grafted onto the lyocell fabric by a dip-dry-cure technique to prepare durable flame-retardant lyocell fabric (FR-lyocell). X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) analysis demonstrated that the flame retardant was successfully introduced into the lyocell sample. Thermogravimetric (TG) and Raman analyses confirmed that the modified lyocell fabric featured excellent thermal stability and significantly increased char residue. Vertical combustion results indicated that FR-lyocell before and after washing formed a complete and dense char layer. Thermogravimetric Fourier-transform infrared (TG-FTIR) analysis suggested that incombustible substances (such as H 2 O and CO 2 ) were produced and played a significant fire retarding role in the gas phase. The cone calorimeter test corroborated that the peak of heat release rate (PHRR) and total heat release (THR) declined by 89.4% and 56.4%, respectively. These results indicated that the flame retardancy of the lyocell fabric was observably ameliorated.

Epoxy resins (EP) have great chemical and physical properties, but their poor flame retardant properties have prevented their widespread use. To improve the flame retardancy properties of EP, an active P/N/Si flame retardant (KDC) containing a double bond was successfully synthesized in this work by using a typical aldehyde amine condensation reaction. This flame retardant not only can form a large molecule flame retardant in situ by double bond reaction and increase the tightness with EP matrix, but also has the advantage of P/N/Si three elements synergistic flame retardant, and at the same time play the flame retardant performance of each element, can achieve excellent flame retardant performance and low smoke and toxicity with low addition amount. Subsequently, the performance of the flame retardants was tested. When 7 wt% of KDC was added, the pHRR and TSR of the EP composites were reduced by 51.7% and 29.8%, respectively. More importantly, the addition of KDC inhibited the release of toxic fuels and smoke from EP, where the TSP values of EP/3‐KDC were 18.14% below those of neat EP and increased the residual amount of charcoal, while the inhibition of CO and CO2 release was particularly pronounced with the presence of KDC. [ABSTRACT FROM AUTHOR]

Poly(lactic acid) (PLA) is derived from crops, and has a broad application prospect in electronics and electrical, automotive industries due to its biodegradability and good physical and mechanical properties. However, PLA's flammability and serious melt dripping cannot meet the requirements of terminal products, thus limiting its application. Over the past decade, much research on flame retardant PLA has emerged. This paper reviews the development of PLA flame retardants in recent years, focusing on phosphorus‐based, phosphorus–nitrogen‐based, bio‐based, nanoparticles, intumescent flame retardants, and their combinations. Besides that, the efficiency of flame retardant and its loading on the thermal and mechanical properties of PLA is also thoroughly reviewed. Finally, the future development of flame‐retardant PLA is briefly summarized and prospected. [ABSTRACT FROM AUTHOR]

• Tannic acid is neither a good flame retardant nor a highly swelling material. • TA combined with CLS reduces flammability of biocomposite by 30 % compared to PLA. • Mixing of TA with CLS in melt doesn't allow for PHRR reduction of more than 20 %. The purpose of this study was to determine the quantitative and qualitative effects of the form of natural phenolic compounds (NPCs) on the decomposition of polylactide (PLA) under different measurement conditions. For this purpose, thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), and pyrolysis-combustion flow calorimetry (PCFC) analyses were carried out not only on individual raw materials like calcium lignosulfonate (BX), tannic acid (TA), BX chemically modified with TA (BMT), but also on PLA/BX, PLA/TA, and PLA/BMT composites with 3, 6, and 9 wt.% of filler. Moreover, the work checked whether to obtain satisfactory results it is necessary to carry out chemical modification lasting many hours, or whether simple physical mixing of ingredients (TABX) is enough, e.g. in proportions 1:2, 2:4, 3:6. The results of these analyses showed that TA is neither a good flame retardant nor a highly swelling material, but when combined with BX physically or chemically, it can produce an interesting synergistic effect. This work proves that chemically obtained BMT hybrid material allows to reduce flammability by 30 % compared to PLA which cannot be achieved by physically mixing these components in a polymer melt. On the other hand, the addition of TABX is sufficient to achieve a good thermal stabilization effect under processing conditions. [Display omitted] [ABSTRACT FROM AUTHOR]

The selected functional properties of rice husk/wood blended particleboards which include thermal analysis, limiting oxygen index, morphological analysis, and mechanical properties have been investigated. Rice husk/wood particleboards were produced with one step hot press casting technique using citric acid to improve the compatibility in the particleboards with calcium oxide and aluminum oxide as flame retardants. The results showed improvement in the mechanical properties, flame retardancy, and thermal stability with the addition of flame retardants to the particleboards. The aluminum oxide synergy with citric acid in rice husk/wood particleboards gave the best flame retardancy.

Nowadays, increasing attention is devoted to the search for polymeric composite materials that are characterized by reduced flammability. In this work, the layer-by-layer (LbL) technique was applied to form multilayered protective coatings for polyamide 6/montmorillonite (PA6/MMT) hybrid nanocomposites. This time, the double layers LbL deposition was used in order to improve the thermal properties or flammability of PA6 materials. Our goal was to check how five, 10, and 15 triple-layer deposition onto the surface of PA6 and PA6/MMT composites influenced these relevant properties. For this reason, disodium H-phosphonate, sodium montmorillonite, and iodo-bis(triphenylphosphino)copper were used for polyelectrolyte solution preparation. It was found that the LbL method could be successfully used to improve the flammability characteristics of polyamide 6-based composites. Nevertheless, the deposition of the copper complex should be combined with other flame retardants—preferentially containing phosphorus—which enable synergistic effects to occur. Moreover, microscopic observations confirmed that the surfaces on which the formation of interwoven fibrous crystal structures was observed had a tendency to protect the entire material against the destructive effects of heat, contributing, among other things, to reduce the maximum point of heat release rate (PHRR). [ABSTRACT FROM AUTHOR]

Phosphorus-containing polyol applications in polyurethane synthesis can prevent volatilization of flame retardants and their migration on the surface of a material. In this work, novel cast polyurethanes were prepared by a one-step method with the use of different amounts of phosphorus-containing polyol, 4,4′–diphenylmethane diisocyanate and 1,4-butanediol. The chemical structure, thermal, physicochemical and mechanical properties and flame resistance of the prepared materials were investigated. The results obtained for cast flame-retarded polyurethanes were compared with cast polyurethane synthesized with commonly known polyether polyol. It has been shown that with an increasing amount of phosphorus content to polyurethane’s chemical structure, an increased flame resistance and char yield were found during combustion tests. Phosphorus polyol worked in both the condensed (reduced heat and mass exchange) and gas phase (inhibition of flame propagation during burning). The obtained materials contained phosphorus polyol, indicating higher thermal stability in an oxidative environment than an inert atmosphere.

Epoxy resin DER 671X75 cured with hardener T31. Epoxy polymer composite materials DER 671X75/T31 were improved the mechanical properties, thermal stability by triphenyl phosphate (TPP) and nanosilica (fumed silica S5505). Triphenyl phosphate and nanosilica were dispersed in epoxy resin DER 671X75 by mechanical stirring and ultrasonic vibration. The structural morphology of materials was characterized by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The thermal stability and thermal properties of materials were characterized by Thermo Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). The results showed that triphenyl phosphate with a content of 5 wt % in epoxy resin DER 671X75 improved the mechanical properties of epoxy polymer coating film DER 671X75/T31 with an impact strength increased 25%. The contents of 5 wt % triphenyl phosphate and 1 wt % nanosilica in epoxy resin DER 671X75 improved the impact strength of epoxy polymer coating film DER 671X75/T31 by 125%. The thermal stability of epoxy nanocomposite materials DER 671X75/5% triphenyl phosphate/1% nanosilica/T31 increased 45.35%. Epoxy coatings based on epoxy resin DER 671X75/5% triphenyl phosphate/1% nanosilica/pigments/fillers/additives/hardener T31 achieved mechanical properties, physical chemistry properties for coating and, had thermal degradation over 500 °C.

In this study, azomethine polyphosphonates were synthesized by solution polycondensation of phenylphosphonic dichloride with various azomethine diols such as [4-(4-hydroxy phenyl) iminomethyl] phenol, [(4-(4-hydroxy-3-methoxy phenyl) iminomethyl)] phenol and [4-(4-hydroxy-3-ethoxy phenyl) iminomethyl] phenol using triethylamine catalyst at ambient temperature. The structure of the synthesized polymers was confirmed by Fourier transform infrared and 1H-, 13C- and 31P- nuclear magnetic resonance spectroscopic techniques. Thermal properties of the polymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry under nitrogen atmosphere. The TGA data showed that the synthesized polyphosphonates produce high char yield at 600°C due to the presence of phosphorous atom in the polymer chain and hence have good flame-retardant properties. One of the synthesized polyphosphonate was blended with commercial diglycidyl ether of bisphenol-A (DGEBA) resin in various weight percentage and cured with commercial curing agent triethylene tetramine (TETA). The polyphosphonates-blended epoxy thermosets have tensile strength in the range of 5–41 MPa and the percentage of elongation at breaks was 4–18. It was found that the incorporation of polyphosphonates into epoxy thermoset decreased the tensile strength from 41 MPa to 5 MPa, whereas the elongation at break value increased with increase in the weight percentage of polyphosphonate. The influence of polyphosphonates on the flame retardancy of blended thermosets was examined by limiting oxygen index (LOI) and vertical burning (UL-94) tests and found that the polymer samples achieved an increased UL-94 rating and the LOI values were in the range of 24–26. Broido and Horowitz–Metzger methods have been used to study the thermal degradation kinetic parameters. [ABSTRACT FROM AUTHOR]

Nowadays, increasing attention is devoted to the search for polymeric composite materials that are characterized by reduced flammability. In this work, the layer-by-layer (LbL) technique was applied to form multilayered protective coatings for polyamide 6/montmorillonite (PA6/MMT) hybrid nanocomposites. This time, the double layers LbL deposition was used in order to improve the thermal properties or flammability of PA6 materials. Our goal was to check how five, 10, and 15 triple-layer deposition onto the surface of PA6 and PA6/MMT composites influenced these relevant properties. For this reason, disodium H-phosphonate, sodium montmorillonite, and iodo-bis(triphenylphosphino)copper were used for polyelectrolyte solution preparation. It was found that the LbL method could be successfully used to improve the flammability characteristics of polyamide 6-based composites. Nevertheless, the deposition of the copper complex should be combined with other flame retardants—preferentially containing phosphorus—which enable synergistic effects to occur. Moreover, microscopic observations confirmed that the surfaces on which the formation of interwoven fibrous crystal structures was observed had a tendency to protect the entire material against the destructive effects of heat, contributing, among other things, to reduce the maximum point of heat release rate (PHRR).

The aim of present study was to investigate the thermal properties and flame retardancy behavior of flame retardant (FR) epoxy nanocomposites from chemically treated (bromine water and tin chloride) oil palm empty fruit bunch (OPEFB) nano filler at different filler loading (1, 3, 5%). Thermal properties were evaluated through thermogravimetry analyzer, derivative thermogravimetry and differential scanning calorimetry. FR properties of nanocomposites are evaluated through UL-94 vertical burning test and limiting oxygen index (LOI). The functional group analysis of all composites was made by FTIR spectroscopy. Thermal analysis shows that degradation temperature of epoxy composites shifts from 370 to 410 °C and char yield also increases for 3% loading. Furthermore LOI value of 29% and UL-94 rating of V-0 with no flame dripping and cotton ignition, revealed that 3% oil palm nano filler filled epoxy nanocomposites display satisfactory flame retardancy. The superior flame retardancy of epoxy nanocomposites are attributed to the chemical reactions occurred in the gaseous phases and the profound synergistic flame retardation effect of tin with bromine in the treated nano OPEFB filler. All the epoxy nanocomposites displayed almost similar FTIR spectra with the characteristics metal-halogen bond supporting the synergism. Homogeneous dispersion of 3% oil palm nano filler act as highly effective combustion chain terminating agent compared with 1 and 5% nano OPEFB/epoxy nanocomposites. [ABSTRACT FROM AUTHOR]

The inhibition of a double-base solid propellant is used to control and prevent the burning degree of the exposed area, which is due to longer burning time. In recent years, inhibition with cellulose derivatives has become popular, but these monolithic systems usually suffer from the drawback of a high erosion rate and demand high thickness and low burning time. In this research two composite inhibitors based on natural fibers were manufactured by filament winding technique and their physical, thermal, and thermomechanical properties were compared. In addition, a chlorinated flame retardant (CFR) as well as antimony trioxide were added in inhibitor compositions to control their burning processes. It was found that the cotton/epoxy composite inhibitor displays a compatible thermal expansion coefficient with the propellant and a high amount of residual char compared to cotton/vinyl ester composite. Also, it was understood that the moisture absorption resistance and thermal stability, i.e., initial decomposition temperature of cotton/vinyl ester specimen were better than cotton/epoxy specimen. Furthermore, density and the flame retardant performance of both composite inhibitors were similar. Additionally, the tan(δ) value obtained for cotton/epoxy composite was higher than that of cotton/vinyl ester composite indicating its good dissipation of vibrational energy. [ABSTRACT FROM AUTHOR]

Chemical modification based on incorporation of flame retardants (FR) into the polymer backbone was used in order to reduce polystyrene flammability. Boronated styrenes such as 4-vinylphenylboronic acid (StB(OH)2) and 6-methyl-2-(4-vinylphenyl)-1,3,6,2-dioxazaborocane-4,8-dione (StBcyclo) were applied as reactive FR. Homo- and copolymers of boronated styrenes and styrene (St) were synthesized with different feed ratios using free radical polymerization. It yielded in series of (co)polymers with various amounts of StB(OH)2 and StBcyclo (5-20% mol/mol of St). Copolymer compositions were determined by 1H NMR. The relative reactivity ratios of system St-StBcyclo were determined by applying the Jaacks method. Glass transition temperature and thermal stability of obtained (co)polymers were determined from DSC and TGA analysis, respectively. The pyrolysis combustion flow calorimeter was applied as a tool for assessing the flammability of the synthesized (co)polymers. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Natural fibers are low-cost fibers with low density and high specific properties. These fibers are biodegradable and non-abrasive. The natural fiber composites offer unique properties comparable to those of conventional synthetic fiber composites. However, development of these composites is often hampered by weak compatibility between fibers and polymer matrix and poor thermal resistance, which often reduce their performance. This paper reports thermal properties and flammability of cotton/vinyl ester composites containing some flame retardant materials such as ammonium molybdate, aluminum trihydroxide, antimony trioxide and Chlorez tested by thermogravimetric analysis and flame retardancy. Addition of flame retardants to cotton/vinyl ester composites reduced burning rate and produced a self-extinguishing flame in some flame-resistant systems. In addition, alkali treatment of cotton fibers using 15% NaOH solution was conducted to improve compatibility of cotton fibers and vinyl ester resin. Tensile test indicated that the treated cotton fibers improved the interfacial bonding and enhanced elongation-at-break of the composites. [ABSTRACT FROM PUBLISHER]

Abstract: Engineering thermoplastic polymers such as polyamides, polycarbonates, semi-crystalline aromatic polyesters and their blends are widely used as insulating materials in electrical and electronic appliances. Flame retardants are often employed in the formulation of these materials, since good performance in terms of ignition and tracking resistance, evaluated by Glow Wire Tests (GWIT) and Comparative Tracking Index (CTI) are required in these applications. In this paper, a comparative evaluation of GWIT and CTI performances has been simultaneously performed for a wide set of glass fibre filled materials chosen among engineering thermoplastics and their blends. Some flame retarded formulations have been also tested, in order to screen the effects of various additives. Useful indications have been obtained on the effect of each polymer and additives on GWIT and CTI properties. In addition, interesting synergies have been observed, especially by blending polyesters and polyamides. Thermogravimetric measurements of char yields have been successfully related with CTI behaviour. The presence of additives changes the structure of the carbonaceous residue, hence the conductivity of the tracks. Neat polycarbonate passed the GWIT test but not CTI, while poly(butylene terephthalate) showed the best balance of GWIT and CTI performance among the pure resins tested. Blending polycarbonate with polyester did not improve significantly GWIT performance, but had a negative effect on tracking resistance. Polyesters/polyamide blends were dominated by polyester in GWIT, but they showed synergistic effects in CTI. [Copyright &y& Elsevier]

Phosphorus-containing polyol applications in polyurethane synthesis can prevent volatilization of flame retardants and their migration on the surface of a material. In this work, novel cast polyurethanes were prepared by a one-step method with the use of different amounts of phosphorus-containing polyol, 4,4′–diphenylmethane diisocyanate and 1,4-butanediol. The chemical structure, thermal, physicochemical and mechanical properties and flame resistance of the prepared materials were investigated. The results obtained for cast flame-retarded polyurethanes were compared with cast polyurethane synthesized with commonly known polyether polyol. It has been shown that with an increasing amount of phosphorus content to polyurethane's chemical structure, an increased flame resistance and char yield were found during combustion tests. Phosphorus polyol worked in both the condensed (reduced heat and mass exchange) and gas phase (inhibition of flame propagation during burning). The obtained materials contained phosphorus polyol, indicating higher thermal stability in an oxidative environment than an inert atmosphere. [ABSTRACT FROM AUTHOR]