Experimental study on the thermal behaviors of lithium-ion batteries under discharge and overcharge conditions

Iron oxide modified montmorillonite (MMT) as flame retardant was used to polyvinyl chloride (PVC), and the flame retardant and smoke-suppressant properties of the PVC were investigated by the smoke density rating and cone calorimeter tests (CONE), and the thermal degradation behaviors of PVC were studied by thermogravimetric analysis (TG) in air atmosphere. The activation energies for the first stage of thermal degradation were obtained following the equation of Kissinger. The mechanical properties testing resultant data showed that iron oxide modified MMT had little effect on the tensile strength of the sample. The CONE result indicated that iron oxide modified MMT could reduce the heat release rate in flame retardant PVC: a more compact char residue formed on the surface of the sample including iron oxide modified MMT during the combustion process. The TG result showed that the sample with modified iron oxide MMT had higher thermal stability than the pure PVC. Besides, the PVC treated with modified MMT showed high activation energy.     

The potential of ferric pyrophosphate for influencing the thermal degradation of cotton fabrics

Ferric pyrophosphate (FePP) was used as additive to study its synergistic effect of thermal degradation on cotton fabrics. The microscale combustion calorimetry (MCC), thermogravimetric analysis (TG), Raman spectroscopy and Real Time Fourier transform infrared spectroscopy (RT-FTIR) were utilized to evaluate the synergistic effects of FePP on cotton/DIA. The MCC results revealed that cotton/DIA/FePP generated less combustion heat during heating than that of cotton/DIA. TG results showed that presence of FePP improved the thermal stability of materials. The Raman spectroscopy test showed that FePP can ameliorate the structural organization level of the carbon and the graphitization degree of the char. RT-FTIR data revealed the mechanism of the influence of FePP, which can catalyze the break of the flame retardant as well as promote the char forming.     

Mechanical and fire retardant properties of EVA/clay/ATH nanocomposites - Effect of particle size and surface treatment of ATH filler

Mechanical and flame retardant properties of ethylene vinyl acetate (EVA) copolymer/organoclay/alumina trihydrate (ATH) nanocomposites have been studied. ATH with different particle sizes, ATH1 (2.2-5.2 μm) and ATH2 (1.5-3.5 μm), and three different surface treatments, uncoated, fatty acid coated and silane coated, have been used. A synergistic effect was observed in EVA/organoclay/ATH nanocomposites with the total heat evolved (THE) and the heat release rate (HRR) lower than that of EVA/ATH composite. It was also found that mechanical and flame retardant properties are affected in different ways by the particle size and the surface treatment of ATH fillers. Improvements in tensile and flame retardant properties were observed in nanocomposites when uncoated ATH fillers and fatty acid coated ATH2 filler were used. On the other hand, silane coating on ATH1 and ATH2 improves limiting oxygen index (LOI) and leads to higher t_ignition and the best char stability after cone calorimeter test.     

Synthesis and thermal degradation behaviors of hyperbranched polyphosphate

A novel epoxy-terminated hyperbranched polyphosphate (E-HBPP) was synthesized by employing an A₂ + B₃ polycondensation and characterized by FTIR, ¹H NMR and GPC. E-HBPP was used as a reactive-type flame retardant for diglycidyl ether of bisphenol-A/m-phenylene diamine (DGEBA/mPDA) system. A series of flame retardant resins were prepared and their flame retardancy was monitored by the limiting oxygen index (LOI). The results showed that the LOI value of the cured samples and the degree of expansion of the formed char after burning increased along with the E-HBPP content. Their thermal degradation behaviors were investigated by thermogravimetric analysis and in situ FTIR and showed that the phosphate group of E-HBPP first degraded to form poly(phosphoric acid)s at around 300 °C, which had a major contribution to form the compact char to protect the sample from further degradation. The dynamic mechanical thermal properties were studied by dynamic mechanical thermal analysis (DMTA) and the results showed a good miscibility between E-HBPP and DGEBA. The mechanical properties of the cured films were also investigated. Less than 20% E-HBPP addition improved both the tensile strength and elongation at break.     

Preparation of a novel phosphorus‐containing organosilicon and its effect on the flame retardant and smoke suppression of polyethylene terephthalate

A novel phosphorus‐containing silicone flame retardant (PDPSI) was prepared by Mannish reaction, and a series of PDPSI/PET composites were prepared by melt blending method. The nuclear magnetic resonance (¹H NMR), Fourier transformation infrared (FTIR), and the thermogravimetric analyzer (TGA) results indicated that PDPSI showed network structure and owned good thermal stability, with the char residue of 62.2% at 800°C. The flame retardancy of PDPSI/PET composites was characterized by limiting oxygen index (LOI), vertical burning tests (UL‐94), and cone calorimeter (CCT). The results revealed that the addition amount of PDPSI was 5%, the LOI value of PDPSI/PET composites increased to 27.3%, and UL‐94 test passed V‐0 rating. When the PDPSI loading was 3%, PET composites showed excellent flame retardancy and smoke suppression, with a decrease in the peak heat release rate (PHRR) by 71.19% and the total smoke release (TSP) reduced from 14.4 to 11.1m². The scanning electron microscopy (SEM) and FTIR results of char residue demonstrated that the flame‐retardant mechanism of PDPSI was solid phase flame retardant. PDPSI catalyzed the aromatization reaction of PET to promote the formation of a dense and continuous carbon layer, finally improving the flame retardancy and smoke suppression properties of PET.     

Effect of a novel flame retardant containing silicon and nitrogen on the thermal stability and flame retardancy of polycarbonate

A novel flame retardant (PSiN), containing silicon and nitrogen, was synthesized using N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and diphenylsilanediol through solution polycondensation and it was added to polycarbonate (PC). The structure and thermal properties of PSiN were characterized by fourier transform infrared spectroscopy and thermogravimetric analysis (TG) tests. The effect of PSiN on the flame retardancy and thermal behaviors of PC was investigated by limited oxygen index (LOI), vertical burning test (UL-94), and TG tests. The results showed that the flame retardancy and the thermal stability of PC are improved with the addition of PSiN. When 1 mass% PSiN and 0.5 mass% diphenylsulfone sulfonate (KSS) are incorporated, the LOI value of PC is found to be 46, and class V-0 of UL-94 test is passed. The char structure observed by scanning electron microscopy indicated that the surface of the char for PC/KSS/PSiN system holds a firmer and denser char structure when compared with neat PC and PC/KSS system.     

Flammability, structure and mechanical properties of PP/OMMT nanocomposites

Polypropylene/organoclay (PP/OMMT) nanocomposites were prepared in a twin-screw corotating extruder using two methods. The first method was the dilution of commercial (PP/50% Nanofil SE3000) masterbatch in PP (or PP with commercial flame retardant). The second method consists of two stages was the extrusion of maleic anhydride grafted polypropylene (PP-g-MAH) with commercially available organobentonite masterbatch in first stage and dilution of the masterbatch in PP (or PP with commercial flame retardant) in second stage. XRD results showed no intercalation in composites obtained from commercial masterbatch without compatibilizer and semi - delamination for compatibilized systems. Tensile tests revealed that nanocomposites with 5% of organoclay have a slightly higher tensile modulus and tensile strength than pristine PP, however addition of the commercial flame retardant (FR) reduces mechanical parameters to roughly the level of those for neat PP. PP/OMMT composites have approx. 25% higher oxygen index than pristine PP, and this changes slightly after the addition of FR. The cone calorimeter tests showed a decrease of a heat release rate (HRR) and a mass loss rate (MLR) after the addition of FR.     

Highly efficient multielement flame retardant for multifunctional epoxy resin with satisfactory thermal,flame‐retardant,and mechanical properties

Multifunctional epoxy resins with excellent, thermal, flame‐retardant, and mechanical properties are extremely important for various applications. To solve this challenging problem, a novel highly efficient multielement flame retardant (PMSBA) is synthesized and the flame‐retardant and mechanical properties of modified epoxy resins are greatly enhanced without significantly altering their and thermal properties by applying the as‐synthesized PMSBA. The limiting oxygen index value reaches up to 29.6% and could pass the V‐0 rating in the UL‐94 test with even low P content (0.13%). Furthermore, cone calorimetry results demonstrate that 30.3% reduction in the peak heat release rate for the sample with 10.0 wt% PMSBA is achieved. X‐ray photoelectron spectroscopy and scanning electron microscopy indicate that Si‐C, Si‐N, and phosphoric acid derivative can be transformed into a multihole and intumescent char layer as an effective barrier, preserving the epoxy resin structure from fire. More importantly, mechanical properties such as impact strength, tensile strength, and flexural strength are also increased by 63.86%, 33.54%, and 15.65%, respectively, which show the incorporation of PMSBA do not deteriorate the mechanical properties of modified epoxy resins. All the results show that PMSBA is a promising strategy for epoxy resin with satisfactory, thermal, flame‐retardant, and mechanical properties.     

Effect of a Nanoclay on the Mechanical,Thermal and Flame Retardant Properties of Rigid Polyurethane Foam

Water blown rigid polyurethane foams (PUF) with organoclay/organically modified nanoclay (ONC) were prepared and their properties such as density, mechanical, morphological, insulation, thermal and flame retardant properties were studied. In this investigation, the ONC content was varied from 1 to 10 parts per hundred of polyol (php) by weight. It was observed that the compressive strength of ONC filled PUF increased up to 3 php of ONC loading and then it decreased. Wide angle X-ray diffraction and transmission electron microscopy studies indicated the exfoliated dispersion of ONC in PUF. The thermal conductivity of ONC filled PUF decreases up to 5 php and then increases. The glass transition temperature (Tg) of PUF decreases on loading of ONC. The TGA analysis shows that there is slight increase in degradation temperature with increase in ONC loading. The flame retardant properties (LOI and flame spread rate) are improved slightly on addition (3 php) of ONC filled PUF.     

Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant

An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR.     

Synthesis of a novel polyphosphazene/triazine bi‐group flame retardant in situ doping nano zinc oxide and its application in poly (lactic acid) resin

A novel polyphosphazene/triazine bi‐group flame retardant in situ doping nano ZnO (A4‐d‐ZnO) was synthesized and applied in poly (lactic acid) (PLA). Fourier transform infrared (FTIR), solid state nuclear magnetic resonance (SSNMR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscope (TEM), and energy dispersive spectrometer (EDS) were used to confirm the chemical structure of A4‐d‐ZnO. The thermal stability and the flame‐retardant properties of the PLA composites were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), limiting oxygen index (LOI), vertical burning test (UL‐94), and micro combustion calorimeter (MCC) test. The results of XPS showed that A4‐d‐ZnO has been synthesized, and the doping ratio of ZnO was 7.2% in flame‐retardant A4‐d‐ZnO. TGA results revealed that A4‐d‐ZnO had good char forming ability (40 wt% at 600°C). The results of LOI, vertical burning test, and MCC showed that PLA/5%A4‐d‐ZnO composite acquired a higher LOI value (24%), higher UL94 rating, and lower pk‐HRR (501 kW/m²) comparing with that of pure PLA. It indicated that a small amount of flame‐retardant A4‐d‐ZnO could achieve great flame‐retardant performance in PLA composites. The catalytic chain scission effect of A4‐d‐ZnO could make PLA composites drip with flame and go out during combustion, which was the reason for the good flame‐retardant property. Moreover, after the addition of A4‐d‐ZnO, the impaired mechanical properties of PLA composites are minimal enough.     

The Effect of Glass Fibre and a Phosphorus-Containing Flame Retardant on the Flammability of Recycled PET

The availability of scrap poly(ethylene terephthalate) (PET) from post-consumer bottles is increasing as the post-consumer collecting systems are becoming more usual in daily life. PET is well known as a high-performance engineering thermoplastic because of its good thermal stability, chemical resistance, and excellent mechanical properties. Many efforts have been carried out to use this material in housings of electronic applications. However, the flammability of PET is a shortcoming in some of these applications. In this study, our attempt is to incorporate a non-halogenated flame retardant, in form of a phosphorus-containing compound, together with a commercial glass fibre grade to achieve UL94 test V-0 rating for PET. An investigation of thermal stability and flammability (HDT, UL94 V-test) and mechanical (tensile, flexural and impact tests) properties of glass fibre filled PET samples is reported as a function of fraction of flame retardant. This work shows the influence of the filler content and the interfacial filler/matrix adhesion on the flame retardant and the mechanical properties.     

Fire Retardancy of Aluminum Hydroxide Reinforced Flame Retardant Modified Epoxy Resin Composite

A novel phosphorous containing flame retardant epoxy resin is synthesized by modifying the epoxy resin initially with phosphoric acid and further with aluminum hydroxide (ATH) to enhance the fire retardancy of the modified epoxy resin. The several phosphorous modified epoxy resin to ATH mass ratios were used to study the effect of ATH addition on epoxy. Thermal and mechanical properties. The structure of the modified flame retardant epoxy resin was characterized using Fourier-transform infrared spectroscopy (FTIR) while thermal degradation behavior and flame retardant properties were examined using thermo-gravimetric analysis (TGA) and UL-94 testing. Furthermore, ultimate tensile strength and young modulus were analyzed to study the effect of ATH addition on mechanical properties. The findings indicated that fire retardancy of ATH reinforced modified ep oxy resin is higher than virgin and phosphorous modified epoxy resin and depicted eminent flame retardant properties with suitable mechanical properties.

     

Construction of crosslinking network structures by adding ZnO and ADR in intumescent flame retardant PLA composites

Different proportion of nano zinc oxide (nano ZnO) and chain extender (ADR) were combined with the intumescent flame retardant and then added into the PLA matrix. The thermal stability, flame retardant performance, and mechanical properties were studied. The gel content results showed that crosslinking structures were obtained after the addition of nano ZnO and ADR, which were generated by the catalytic chain scission effect of nano ZnO and chain extension effect of ADR. With addition of 1% nano ZnO and 1.6% ADR, the gel content of flame retardant PLA composite reached the highest value (14.2%). Meanwhile, the corresponding flame retardant PLA composite with 1% nano ZnO and 1.6% ADR, named FRPLA/ZnO/ADR-1, exhibited an overall improved properties including the flame retardant properties and mechanical performance, which passed the UL94 V-0 level with a limiting oxygen index value of 40.1%. Compared to FRPLA (flame retardant PLA without ZnO and ADR), the peak heat release rate and the total smoke production of FRPLA/ZnO/ADR-1were reduced by 60% and 67% respectively, and the final mass improved from 12% to 38%. In addition, the tensile strength and elongation at break of FRPLA/ZnO/ADR-1 increased by 25%, 14% compared with that of FRPLA. The impact strength was 15.1 kJ/m², which is similar to the pure PLA (15.6 kJ/m²). It indicated that the addition of nano ZnO and ADR could balance the flame retardant performance and the mechanical properties of the flame retardant PLA.     

Modified montmorillonite combined with intumescent flame retardants on the flame retardancy and thermal stability properties of unsaturated polyester resins

Modified montmorillonite‐containing phytic acid (PA‐MMT) has been prepared by acid treatment and then introduced into unsaturated polyester resin (UPR) with an intumescent flame retardant (IFRs). The flame retardancy and thermal degradation of UPR/IFRs/PA‐MMT were evaluated by a limiting oxygen index (LOI) test, a vertical burning test (UL‐94), a thermogravimetric analysis (TGA), and a cone calorimeter test (CCT). Besides, the mechanical properties were studied by a universal testing machine. The LOI value of UPR/IFRs/PA‐MMT composites was increased to 29.2%. The CCT results indicated that the incorporation of PA‐MMT and IFRs significantly improved the combustion behavior of UPR. The results of the mechanical properties indicated that 1.5 wt% loading of PA‐MMT in UPR/IFRs showed the highest improvement in flexural strength and tensile strength. The flame‐retardant mechanism of PA‐MMT/IFRs was examined and discussed based on the results of combustion behavior and char analysis.     

Fire retarded polyurethane foam composites based on steel slag/ammonium polyphosphate system: A novel strategy for utilization of metallurgical solid waste

A series of FR-RPUF composites were prepared by a one-step water foaming process with ammonium polyphosphate (APP) and steel slag (SS) as flame retardants. Thermogravimetric analysis (TG), limiting oxygen index (LOI), UL-94 vertical combustion test, microscale combustion calorimetry (MCC), TG-Fourier transform infrared spectrometry (TG-FTIR), scanning electron microscopy (SEM), Raman spectra and FTIR were used to investigate the thermal stability, flame retardancy, combustion performance, gas phase products, and char residue morphology of FR-RPUF composites. TG test results showed that the initial decomposition temperature (T_-5wt%) and char residue rate at 700°C of RPUF/APP/SS composites were significantly enhanced by the addition of APP and SS, and the thermal stability of the composites was improved. Flame retardant test results confirmed the significantly increased LOI values of RPUF/APP/SS composites with V-0 rating. TG-FTIR also confirmed the obviously decreased release of toxic gases and flammable gases in the combustion of RPUF/APP/SS composites. SEM and Raman spectra of char residues for the composites suggested that APP/SS system improved the compactness and graphitization degree of char layer for RPUF/APP/SS composite. The above researches provide a new strategy for the utilization of SS in fire safety engineering.     

Thermal stability and flame retardancy of LDPE/EVA blends filled with synthetic hydromagnesite/aluminium hydroxide/montmorillonite and magnesium hydroxide/aluminium hydroxide/montmorillonite mixtures

The combination of organophillised montmorillonite (MMT), synthetic hydromagnesite and aluminium hydroxide (ATH) as flame retardant system for polyethylene-based materials was studied and compared with a similar system with magnesium hydroxide, ATH and MMT. The thermal stability and the flame retardant properties were evaluated by thermogravimetric analysis (TGA), differential thermal analysis (DTA), limiting oxygen index (LOI) and cone calorimeter tests. The results indicated that the addition of montmorillonite makes it possible to reduce the total filler content to achieve the flame retardant requirements. The thermal stability of filled LDPE/EVA blends increases to a higher extent for the samples containing MMT. In the cone calorimeter tests we observed a reduction of the peak heat release rate for the sample containing montmorillonite in comparison with a sample with higher filler loading without this nanoclay. An increase of the stability of the char formed could be responsible for this favourable behaviour when montmorillonite is added.In addition, mechanical properties significantly improved for the composites containing montmorillonite both for the filler loading reduction and the reinforcement effect of the nanoclay.     

Effect of surface chemical modification for aluminum hypophosphite with hexa‐(4‐aldehyde‐phenoxy)‐cyclotriphosphazene on the fire retardancy,water resistance,and thermal properties for polyamide 6

The surface chemical modified aluminum hypophosphite (AHP) defined as MAHP was successful prepared through P–H bonds on AHP surface reacted with the aldehyde groups in hexa‐(4‐aldehyde‐phenoxy)‐cyclotriphosphazene made in our lab. The wettability of the flame retardants was evaluated by water contact angle tests, and the water contact angle of the prepared MAHP dramatically increased from 0° for AHP to 145°, which indicated the surface modification made the superhydrophilic AHP into superior hydrophobic MAHP. The prepared MAHP and AHP, respectively, incorporated into polyamide 6 (PA6) matrix to prepare flame retardant PA6 composites and the fire retardancy and thermal degradation behavior of flame retardant PA6 composites were investigated by limiting oxygen index, vertical burning test (UL‐94), cone calorimeter, and thermogravimetric analysis tests. The morphologies and chemical compositions of the char residues for PA6 composites were investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy, respectively. The water resistant properties of flame retardant PA6 composites were evaluated by putting the samples into distilled water at 70°C for 168 hr, and the mechanical properties for flame retardant PA6 composites were investigated by the tensile, flexural, and Izod impact strength tests. The results demonstrated that the PA6/MAHP composites successfully passed UL‐94 V‐0 flammability rating, and the limiting oxygen index value was 27.6% when the loading amount of MAHP was 21 wt%. However, there is no rating in vertical burning tests for PA6/AHP composite with the same amount of AHP, which indicated the surface modification of AHP enhanced the flame retardancy efficiency for PA6 composites. The morphological structures and analysis of X‐ray photoelectron spectroscopy of char residues revealed that the surface modification of AHP benefited to the formation of a sufficient, flame retardant elements rich, more compact and homogeneous char layer on the materials surface during combustion, which prevented the heat transmission and diffusion, limit the production of combustible gases, inhibit the emission of smoke and then led to the reduction of the heat release rate and smoke produce rate. The mechanical properties results revealed that the surface modification of AHP enhanced the mechanical properties, especially the Izod impact strength comparing with that of PA6/AHP composites with the same amount of flame retardant. After water resistance tests, the PA6/MAHP composites remained superior flame retardancy and presented continuous and compact char layer after cone calorimeter tests; however, the fire retardancy for PA6/AHP composite obviously decreased, and the char layer was discontinuous with big hole caused by the extraction of AHP by water during water resistance tests. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation and characterization of a water resistance flame retardant and its enhancement on charring–forming for polycarbonate

Hexakis(4-nitrophenoxy) cyclotriphosphazene (HNTP) was synthesized and was added into polycarbonate (PC) functioned as intumescent flame retardant and charring agent. The chemical structure of HNTP was confirmed by hydrogen and phosphorus nuclear magnetic resonance (¹H-NMR, ³¹P-NMR), energy-dispersive spectroscopy and Fourier transform infrared (FTIR). Flame retardancy and charring–forming behaviors of HNTP- and PC-based composites were extensively investigated with the limiting oxygen index, UL-94 vertical burning test, microscale combustion calorimeter (MCC) and thermogravimetric analysis. The water resistance of PC-based composites was studied by stationary water contact angle measurements. Furthermore, TG/FTIR was used to research their gaseous products and their releasing intensity during the decomposition. The morphology and chemical structure of residual char were used to study scanning electron microscopy (SEM) analyses and FTIR spectroscopy. The mechanical properties of samples were compared by tensile and impact tests.     

Microencapsulation of bisphenol-A bis (diphenyl phosphate) and influence of particle loading on thermal and fire properties of polypropylene and polyethylene terephtalate

Microencapsulated flame retardant, bisphenol-A bis (diphenyl phosphate) (BDP), with a silane shell was prepared by sol–gel process with the goal of incorporating them in polymeric matrices by melt blending to improve the flame retardancy of isotactic polypropylene (iPP) and polyethylene terephtalate (PET). The influence of the loading content on thermal transitions has been studied by differential scanning calorimetry (DSC), the thermal stability of the polymer/microcapsules composites has been assessed by thermogravimetric analysis (TGA) and cone calorimetry has been used to study the fire reaction. It was noticed that the microcapsules have a limited influence on the thermal transitions of iPP matrix, but a decrease of the melting and glass transition temperatures was detected for the PET microcomposites. TGA results showed that the addition of microcapsules could improve char formation of the PET systems both in nitrogen and in air atmospheres, whereas only a small improvement of the thermal stability was detected in oxidative atmosphere for the iPP samples. Furthermore, cone calorimeter experiments show that the incorporation of microcapsules in the iPP gives almost no improvement in the iPP fire reaction. However, the microcapsules act as flame retardant in PET reducing the heat release rate during the combustion and the total heat evolved. Therefore, microcapsules can act as a char promoter agent to enhance the fire resistance in the case of PET.