Facile Synthesis of Phosphorus and Cobalt Co-Doped Graphitic Carbon Nitride for Fire and Smoke Suppressions of Polylactide Composite.
ABSTRACT: Due to the unique two-dimensional structure and features of graphitic carbon nitride (g-C3N4), such as high thermal stability and superior catalytic property, it is considered to be a promising flame retardant nano-additive for polymers. Here, we reported a facile strategy to prepare cobalt/phosphorus co-doped graphitic carbon nitride (Co/P-C3N4) by a simple and scalable thermal decomposition method. The structure of Co/P-C3N4 was confirmed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The carbon atoms in g-C3N4 were most likely substituted by phosphorous atoms. The thermal stability of polylactide (PLA) composites was increased continuously with increasing the content of Co/P-C3N4. In contrast to the g-C3N4, the Polylactide (PLA) composites containing Co/P-C3N4 exhibited better flame retardant efficiency and smoke suppression. With the addition of 10 wt % Co/P-C3N4, the peak heat release rate (PHRR), carbon dioxide (CO2) production (PCO2P) and carbon oxide (CO) production (PCOP) values of PLA composites decreased by 22.4%, 16.2%, and 38.5%, respectively, compared to those of pure PLA, although the tensile strength of PLA composites had a slightly decrease. The char residues of Co/P-C3N4 composites had a more compact and continuous structure with few cracks. These improvements are ascribed to the physical barrier effect, as well as catalytic effects of Co/P-C3N4, which inhibit the rapid release of combustible gaseous products and suppression of toxic gases, i.e., CO.
Project description:Biocompatible and biodegradable polylactide (PLA) composites with supertough mechanical property and sufficient flame retardancy were fabricated by employing a facile approach involving reactive blending of PLA and ethylene-acrylic ester-glycidyl methacrylate terpolymer (EGMA), with the addition of aluminum hypophosphite (AHP) as an effective flame retardant. In consideration of the balance between mechanical property and flame retardancy, the optimal formula was taking a PLA/EGMA 80/20 blend (supertough STPLA) as the matrix and adding 20 wt % of AHP (relative to the mass of STPLA) as the flame retardant, coded as STPLA/20AHP. The mechanical property test showed that for STPLA/20AHP the elongation at break was increased by about 22 times and the notched Izod impact strength was enhanced by approximately 11 times as compared to those for neat PLA. The flame-retardant property test showed that for STPLA/20AHP the limiting oxygen index value reached 26.6% and the UL-94 V0 rating test was passed. Thermogravimetric analysis, microscale combustion calorimetry, and cone calorimeter were further applied to reveal the thermal stability and combustion behaviors of STPLA/xAHP, respectively, where x indicated the mass content of AHP in percentage. The phase separation morphology, dispersion of AHP particles in STPLA matrix, and fracture surfaces and char residues after flame burning were examined by phase contrast optical microscopy and scanning electron microscopy, respectively, which helped comprehend the results obtained from the mechanical property and flame retardancy tests. The supertough STPLA/xAHP, with sufficient flame retardancy as prepared in this work, could have a potential for engineering applications.
Project description:A comparison of the influence of sepiolite and lignin as potential synergists for fire retardant (FR) systems based on ammonium polyphosphate (APP) has been carried out in polyurethane elastomer and polylactide. Different ratios of kraft lignin and sepiolite were tested in combination with APP in both polymers. The thermal stability and the fire behavior of the corresponding composites were evaluated using Thermogravimetric Analysis (TGA), a Pyrolysis Combustion Flow Calorimeter (PCFC) and Cone Calorimeter (CC). The mechanisms of flame retardancy imparted by APP and other components were investigated. Synergistic effects were highlighted but only for specific ratios between APP and sepiolite in polyurethane elastomer (PUE) and polylactide (PLA) on one hand, and between APP and lignin in PLA on the other hand. Sepiolite acts as char reinforcement but through the formation of new phosphorus compounds it is also able to form a protective layer. Conversely, only complementary effects on fire performance were noted for lignin in PUE due to a dramatic influence on thermal stability despite its action on char formation.
Project description:The objective of this study is to assess the efficiency of biobased carbonization agent in intumescent formulations (IFRs) to examine the flame retardant properties of polylactic acid (PLA) composites and to investigate their melt-spinnability. We used phosphorous-based halogen free flame retardant (FR) and kraft lignin (KL) as bio-based carbonization agent. After melt compounding and molding into sheets by hot pressing various fire related characteristics of IFR composites were inspected and were characterized by different characterization methods. It was fascinating to discover that the introduction of 5-20 wt% FR increased the limiting oxygen index (LOI) of PLA composites from 20.1% to 23.2-33.5%. The addition of KL with content of 3-5 wt% further increased the LOI up to 36.6-37.8% and also endowed PLA/FR/KL composites with improved anti-dripping properties. Cone calorimetry revealed a 50% reduction in the peak heat release rate of the IFR composites in comparison to 100% PLA and confirmed the development of an intumescent char structure containing residue up to 40%. For comparative study, IFR composites containing pentaerythritol (PER) as a carbonization agent were also prepared and their FR properties were compared. IFR composites were melt spun and mechanical properties of multifilament yarns were tested. The analysis of char residues by energy dispersive X-ray spectrometry (EDS) and SEM images confirmed that PLA/FR/KL composites developed a thicker and more homogeneous char layer with better flame retardant properties confirming that the fire properties of PLA can be enhanced by using KL as a carbonization agent.
Project description:In this work, few-layered molybdenum disulfide (MoS2) was functionalized with metal oxide (MxOy) nanoparticles which served as a catalyst for carbon nanotubes (CNT) growth in the chemical vapour deposition (CVD) process. The resulting MoS2/MxOy/CNT functionalized nanomaterials were used for flame retarding application in poly(lactic acid) (PLA). The composites were extruded with a twin-screw extruder with different wt% loading of the nanomaterial. Full morphology characterization was performed, as well as detailed analysis of fire performance of the obtained composites in relation to pristine PLA and PLA containing an addition of the composites. The samples containing the addition of MoS2/MxOy/CNT displayed up to over 90% decrease in carbon oxide (CO) emission during pyrolysis in respect to pristine PLA. Microscale combustion calorimetry testing revealed reduction of key parameters in comparison to pristine PLA. Laser flash analysis revealed an increase in thermal conductivity of composite samples reaching up to 65% over pristine PLA. These results prove that few-layered 2D nanomaterials such as MoS2 functionalized with CNT can be effectively used as flame retardance of PLA.
Project description:Expanding the application range of flame-retardant polymer biocomposites remains a huge challenge for a sustainable society. Despite largely enhanced flame retardancy, until now the resultant poly(lactic acid) (PLA) composites still suffer reduced tensile strength and impact toughness due to improper material design strategies. We, herein, demonstrate the design of a green flame retardant additive (ammonium polyphosphate (APP)@cellulose nanofiber (CNF)) via using the cellulose nanofibers (CNFs) as the green multifunctional additives hybridized with ammonium polyphosphate (APP). The results show that PLA composite with 5 wt % loading of APP@CNF can pass the UL-94 V-0 rating, besides a high limited oxygen index of 27.5%, indicative of a significantly enhanced flame retardancy. Moreover, the 5 wt % of APP@CNF enables the impact strength (?i) of the PVA matrix to significantly improve from 7.63 to 11.8 kJ/m2 (increase by 54%), in addition to a high tensile strength of 50.3 MPa for the resultant flame-retardant PLA composite. The enhanced flame retardancy and mechanical strength performances are attributed to the improved dispersion of APP@CNF and its smaller phase size within the PLA matrix along with their synergistic effect between APP and CNF. This work opens up a facile innovative methodology for the design of high-performance ecofriendly flame retardants and their advanced polymeric composites.
Project description:A novel flame-retardant composite material based on zinc alginate (ZnAlg) and nano-cuprous oxide (Cu2O) was prepared through a simple, eco-friendly freeze-drying process and a sol-gel method. The composites were characterized and their combustion and flammability behavior were tested. The composites had high thermal stability and achieved nearly non-flammability with a limiting oxygen index (LOI) of 58. The results show remarkable improvement of flame-retardant properties in the ZnAlg/Cu2O composites, compared to ZnAlg. Furthermore, the pyrolysis behavior was determined by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and the flame-retardant mechanism was proposed based on the combined experimental results. The prepared composites show promising application prospects in building materials and the textile industry.
Project description:Single-walled carbon nanotubes (SWCNTs) have recently been utilized as fillers that reduce the flammability and enhance the strength and thermal conductivity of material composites. Enhancing the thermal stability of SWCNTs is crucial when these materials are applied to high temperature applications. In many instances, SWCNTs are applied to composites with surface coatings that are toxic to living organisms. Alternatively, single-stranded DNA, a naturally occurring biological polymer, has recently been utilized to form singly-dispersed hybrids with SWCNTs as well as suppress their known toxicological effects. These hybrids have shown unrivaled stabilities in both aqueous suspension or as a dried material. Furthermore, DNA has certain documented flame-retardant effects due to the creation of a protective char upon heating in the presence of oxygen. Herein, using various thermogravimetric analytical techniques, we find that single-stranded DNA has a significant flame-retardant effect on the SWCNTs, and effectively enhances their thermal stability. Hybridization with DNA results in the elevation of the thermal decomposition temperature of purified SWCNTs in excess of 200 °C. We translate this finding to other carbon nanomaterials including multi-walled carbon nanotubes (MWCNTs), reduced graphene oxide (RGO) and fullerene (C60), and show similar effects upon complexation with DNA. The rate of thermal decomposition of the SWCNTs was also explored and found to significantly depend upon the sequence of DNA that was used.
Project description:Mycelium and mycelium-biomass composites are emerging as new sustainable materials with useful flame-retardant potentials. Here we report a detailed characterisation of the thermal degradation and fire properties of fungal mycelium and mycelium-biomass composites. Measurements and analyses are carried out on key parameters such as decomposition temperatures, residual char, and gases evolved during pyrolysis. Pyrolysis flow combustion calorimetry (PCFC) evaluations reveal that the corresponding combustion propensity of mycelium is significantly lower compared to poly(methyl methacrylate) (PMMA) and polylactic acid (PLA), indicating that they are noticeably less prone to ignition and flaming combustion, and therefore safer to use. The hyphal diameters of mycelium decrease following pyrolysis. Cone calorimetry testing results show that the presence of mycelium has a positive influence on the fire reaction properties of wheat grains. This improvement is attributable to the relatively higher charring tendency of mycelium compared to wheat grain, which reduces the heat release rate (HRR) by acting as a thermal insulator and by limiting the supply of combustible gases to the flame front. The mycelium growth time has been found to yield no significant improvements in the fire properties of mycelium-wheat grain composites.
Project description:The demand for eco-friendly poly (lactic acid) (PLA) nonwovens grows at a high rate in the past several decades, however, only a little attention has been received for flame retardant PLA nonwoven fabrics. In this work, a novel halogen-free self-intumescent polyelectrolyte tris (hydroxymethyl)-aminomethane polyphosphate (APTris) was synthesized by reacting ammonium polyphosphate with tris (hydroxymethyl) aminomethane, and was then used to improve the fire resistance of PLA nonwovens via a dip-nip process. The flammability characterization indicated the limiting oxygen index value was increased to 30.0% from 18.3%, and the damaged area in the vertical burning test was reduced by about 87.0% by the presence of APTris. The cone calorimeter test results revealed that the peak heat release rate and total heat release of the treated sample were decreased by 41.0% and 28.2% respectively compared with that of the control PLA nonwoven sample. The char residue was increased to 12.3 from 1.7 wt. % at 800 °C. It is suggested that the dense char barrier formed at the presence of APTris prevents heat, smoke, and gas transfer, and hence enhance thermal dilatability and flame retardancy of PLA nonwovens. This simple sustainable halogen-free treatment has great potential to produce cleaner commercialized flame-retardant PLA nonwovens.
Project description:Aqueous miscible organic layered double hydroxides (AMO-LDHs) can act as organophilic inorganic flame retardant nanofillers for unmodified non-polar polymers. In this contribution, AMO [Mg3Al(OH)8](CO3)0.5·yH2O LDH-oxidized carbon nanotube (AMO-LDH-OCNT) hybrids are shown to perform better than the equivalent pure AMO-LDH. A synergistic effect between the AMO-LDH and OCNT was observed; this endows the hybrid material with enhanced flame retardancy, thermal stability, and mechanical properties. The thermal stability of polypropylene (PP) was significantly enhanced by adding AMO-LDH-OCNT hybrids. For PP mixed with AMO-LDH-OCNT hybrids to produce a composite with 10 wt% LDH and 2 wt% OCNT, the 50% weight loss temperature was increased by 43?°C. Further, a system with 10?wt% of AMO-LDH and 1?wt% OCNT showed a peak heat release rate (PHRR) reduction of 40%, greater than the PHRR reduction with PP/20?wt% AMO-LDH (31%). The degree of dispersion (mixability) between AMO-LDH and OCNT has a significant effect on the flame retardant performance of the hybrids. In addition, the incorporation of AMO-LDH-OCNT hybrids led to better mechanical properties, such as higher tensile strength (27.5?MPa) and elongation at break (17.9%), than those composites containing only AMO-LDH (25.6?MPa and 7.5%, respectively).