Search Results (14)

Hybrid aluminum dialkylphosphinates were synthesized from mixed diethyl-, ethylisobutyl-, and diisobutylphosphinates and Al³⁺ in water. The XRD, DSC, and TGA results of these Al phosphinates established that phosphinate ligands are randomly distributed in the species. The thermal and thermoxidative stabilities of the hybrid phosphinates were easily adjustable by varying the ratio of phosphinate ligands, a desirable feature for efficient flame retardants. The hybrid aluminum dialkylphosphinates with a relatively low ratio of diethylphosphinate demonstrated higher efficiency than Al diethylphosphinate and Al diisobutylphosphinate in flame-retarding polyamide 66. Detailed investigations on the thermal and thermoxidative stabilities of Al dialkylphosphinates and the morphologies of char obtained in UL-94 tests revealed that timely vaporization of degradation products of hybrid dialkylphosphinates at a temperature which closely matches the degradation temperature of polyamides and their ability to promote char formation of polyamides are two key factors which contribute to the excellent performance of hybrid aluminum dialkylphosphinates. Full article

A synergistic multi-material flame retardant system based on expandable graphite (EG), aluminum diethylphosphinate (AlPi), melamine polyphosphate (MPP), and montmorillonite (MMT) has been studied in glass-fiber-reinforced polyamide 6 (PA6). Analytical evaluations and fire performances were evaluated using coupled thermogravimetric analysis (TGA) and Fourier-transform infrared spectroscopy (FTIR) as well as cone calorimetry, UL-94 fire testing, and limiting oxygen index (LOI). A combination of EG/AlPi/MPP/MMT has been shown to provide superior flame-retarding properties when integrated at 20 wt.% into glass-fiber-reinforced PA6 (25 wt.%), achieving UL-94 V0 classification and an oxygen index of 32%. Strong residue formation resulted in low heat development overall, with a peak heat release rate (pHRR) of 103 kW/m², a maximum of average heat release rate (MAHRE) of 33 kW/m², and deficient total smoke production (TSP) of 3.8 m². Particularly remarkable was the structural stability of the char residue. The char residue could easily withstand an areal weight of 35 g/cm², showing no visible deformation. Full article

BDE-47, a flame retardant that is frequently detected in environmental compartments and human tissues, has been associated with various toxic effects. In turn, information about the effects of aluminum diethyl-phosphinate (ALPI), a halogen-free flame retardant from a newer generation, is limited. This study aims to assess and compare the toxicity of BDE-47 and ALPI to zebrafish by analyzing the tail coiling, locomotor, acetylcholinesterase activities, and oxidative stress biomarkers. At 3000 µg/L BDE-47, the coiling frequency increased at 26–27 h post-fertilization (hpf), but the burst activity (%) and mean burst duration (s) did not change significantly. Here, we considered that the increased coiling frequency is a slight neurotoxic effect because locomotor activity was impaired at 144 hpf and 300 µg/L BDE-47. Moreover, we hypothesized that oxidative stress could be involved in the BDE-47 toxicity mechanisms. In contrast, only at 30,000 µg/L did ALPI increase the catalase activity, while the motor behavior during different developmental stages remained unaffected. On the basis of these findings, BDE-47 is more toxic than ALPI. Full article

Herein, we developed polyacrylonitrile (PAN)-based nanoporous composite membranes incorporating aluminum diethylphosphinate (ADEP) for use as a heat-resistant and flame-retardant separator in high-performance and safe lithium-ion batteries (LIBs). ADEP is phosphorus-rich, thermally stable, and flame retardant, and it can effectively suppress the combustibility of PAN nanofibers. Nanofibrous membranes were obtained by electrospinning, and the content of ADEP varied from 0 to 20 wt%. From the vertical burning test, it was demonstrated that the flame retardancy of the composite membranes was enhanced when more than 5 wt% of ADEP was added to PAN, potentially increasing the safety level of LIBs. Moreover, the composite membrane showed higher ionic conductivity and electrolyte uptake (0.83 mS/cm and 137%) compared to those of commercial polypropylene (PP) membranes (Celgard 2400: 0.65 mS/cm and 63%), resulting from interconnected pores and the polar chemical composition in the composite membranes. In terms of battery performance, the composite membrane showed highly stable electrochemical and heat-resistant properties, including superior discharge capacity when compared to Celgard 2400, indicating that the PAN/ADEP composite membrane has the potential to be used as a heat-resistant and flame-retardant separator for safe and high-power LIBs. Full article

A flame retardant system based on expandable graphite (EG), aluminum diethylphosphinate (AlPI) and melamine polyphosphate (MPP) was investigated in glass fiber- (GF) reinforced polyamide 6 (PA6). Burning characteristics were evaluated via cone calorimeter, limiting oxygen index (LOI) and UL-94 tests. Thermogravimetric analysis (TGA) and coupled Fourier transform infrared spectroscopy (FTIR) was used to investigate the decomposition process as well as flame retardant modes of actions. Specifically, in the cone calorimeter tests, formulations containing EG showed excellent flame retardant properties for non-reinforced and reinforced PA6. The best performance was achieved for 25 wt.% glass fiber-reinforced PA6 containing solely 20 wt.% EG, corresponding to a measured pHRR of 134 kW/m² and a total smoke production of 1.2 m². Higher glass fiber contents of 45 wt.% (30 vol.%) revealed a lower char volume, which was attributed to both the limited space available for expansion and the sheer-induced reduction in particle size during processing. All of the reinforced PA6 formulations only achieved V2 classifications, but this was at low filling degrees (10 wt.%) for both net EG or EG/AlPi/MPP combinations. For GF-reinforced PA6 containing EG/AlPi/MPP mixtures, a synergistic effect was found to improve the oxygen index up to 30.6%. Full article

In this work, polyamide 66/polyphenylene oxide (PA66/PPO) composites, including the flame retardants 98 wt% aluminum diethylphosphinate + 2 wt% polydimethylsiloxane (P@Si), Al(OH)₃-coated red phosphorus (RP*), and glass fiber (GF), were systematically studied, respectively. The limiting oxygen index (LOI), UL-94 vertical burning level, and thermal and mechanical properties of the PA66/PPO composites were characterized. The results showed that the P@Si and RP flame retardants both improved the LOI value and UL-94 vertical burning level of the PA66/PPO composites, and PA66/PPO composites passed to the UL-94 V-0 level when the contents of P@Si and RP* flame retardants were 16 wt% and 8 wt%. On the other hand, the mechanical properties of the PA66/PPO composites were reduced from a ductile to a brittle fracture mode. The addition of GF effectively made up for these defects and improved the mechanical properties of the PA66/PPO composites containing the P@Si and RP*, but it did not change the fracture mode. P@Si and RP* flame retardants improved the thermal decomposition of PA66/PPO/GF composites and reduced the maximum mass loss rates, showing that the PA66/PPO/GF composites containing the P@Si and RP* flame retardants could be used in higher-temperature fields. Full article

Aluminum tris-(diethylphosphinate) (AlPi) is known to have an efficient flame-retardant effect when used in poly(butadiene terephthalates) (PBT). Additionally, better flame-retardant effects can be achieved through the partial substitution of AlPi by boehmite in multi-component systems, which have been shown to be an effective synergist due to cooling effects and residue formation. Although the potential of beneficial effects is generally well known, the influence of particle sizes and behavior in synergistic compositions are still unknown. Within this paper, it is shown that the synergistic effects in flammability measured by limiting oxygen index (LOI) can vary depending on the particle size distribution used in PBT. In conducting thermogravimetric analysis (TGA) measurements, it was observed that smaller boehmite particles result in slightly increased char yields, most probably due to increased reactivity of the metal oxides formed, and they react slightly earlier than larger boehmite particles. This leads to an earlier release of water into the system enhancing the hydrolysis of PBT. Supported by Fourier transformation infrared spectroscopy (FTIR), we propose that the later reactions of the larger boehmite particles decrease the portion of highly flammable tetrahydrofuran in the gas phase within early burning stages. Therefore, the LOI index increased by 4 vol.% when lager boehmite particles were used for the synergistic mixture. Full article

In this work, functionalized multi-walled carbon nanotubes (MWCNT) were synthesized by the reaction between acylated MWCNT and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (ODOPB). The obtained MWCNT-ODOPB was well dispersed into epoxy resins together with aluminum diethylphosphinate (AlPi) to form flame-retardant nanocomposites. The epoxy resin nanocomposite with phosphorus content of 1.00 wt % met UL 94 V-0 rating, exhibited LOI value of 39.5, and had a higher T_g compared to neat epoxy resin, which indicates its excellent flame retardant performance. These experimental results indicated that MWCNT-ODOPB was a compatible and efficient flame retardant for epoxy resins. Moreover, cone calorimeter analysis showed that the peak heat release rate (pHRR), total heat release (THR) values, and CO₂ production profiles of the composites decreased with an increase in the additional amount of phosphorus. Full article

A series of novel flame retardants (aluminum diethylphosphinate and melamine) were used to improve the fire performance of phenolic resin. Fourier transform infrared spectroscopy (FTIR) was used to characterize the modification results. Thermo-gravimetric analysis (TGA) was used to study the thermal decomposition of phenolic resin system, and the flame retardancy of phenolic resin system was tested by vertical combustion test (UL-94) and limiting oxygen index (LOI). The combustion properties of modified phenolic resin were further tested with a cone calorimeter(CCT). Finally, the structure of carbon residue layer was measured by scanning electron microscopy (SEM). The results show that with the introduction of 10 wt % aluminum diethylphosphinate in phenolic resin, the LOI reaches 33.1%, residual carbon content increase to 55%. The heat release rate (HRR) decreased to 245.6 kW/m², and the total heat release (THR) decreased to 58.6 MJ/m². By adding 10 wt % aluminum diethylphosphinate and 3 wt % melamine, the flame retardancy of the modified resin can pass UL-94 V-0 flame retardant grade, LOI reaches 34.6%, residual carbon content increase to 59.5%. The HRR decreases to 196.2 kW/m² at 196 s, relatively pure phenolic resin decreased by 35.5%, and THR decreased to 51 MJ/m². Compared with pure phenolic resin, the heat release rate and total heat release of modified phenolic resin decreased significantly. This suggests that aluminum diethylphosphinate and melamine play a nitrogen-phosphorus synergistic effect in the phenolic resin, which improves the thermal stability and flame retardancy of the phenolic resin. Full article

In this work, polyamide 6 (PA6) composites with improved flame retardancy and thermal conductivity were prepared with different thermal conductive fillers (TC fillers) such as aluminum nitride (AlN) and boron nitride (BN) in a PA6 matrix with aluminum diethylphosphinate (AlPi) as a fire retardant. The resultant halogen-free flame retardant (HFFR) and thermal conductive (TC) PA6 (HFFR-TC-PA6) were investigated in detail with a mechanical property test, a limiting oxygen index (LOI), the vertical burning test (UL-94), a cone calorimeter, a thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The morphology of the impact fracture surface and char residue of the composites were analyzed by scanning electron microscopy (SEM). It was found that the thermal conductivity of the HFFR-TC-PA6 composite increased with the amount of TC fillers. The TC fillers exerted a positive effect for flame retardant PA6. For example, the HFFR-TC-PA6 composites with the thickness of 1.6 mm successfully passed the UL-94 V-0 rating with an LOI of more than 29% when the loading amount of AlN-550RFS, BN-SW08 and BN-NW04 was 30 wt%. The morphological structures of the char residues revealed that TC fillers formed a highly integrated char layer surface (without holes) during the combustion process, as compared to that of flame retardant PA6/AlPi composites. In addition, the thermal stability and crystallization behavior of the composites were studied. Full article

The thermal stabilities, flame retardancies, and physico-mechanical properties of rice husk-reinforced polyurethane (PU–RH) foams with and without flame retardants (FRs) were evaluated. Their flammability performances were studied by UL94, LOI, and cone calorimetry tests. The obtained results combined with FTIR, TGA, SEM, and XPS characterizations were used to evaluate the fire behaviors of the PU–RH samples. The PU–RH samples with a quite low loading (7 wt%) of aluminum diethylphosphinate (OP) and 32 wt% loading of aluminum hydroxide (ATH) had high thermal stabilities, excellent flame retardancies, UL94 V-0 ratings, and LOIs of 22%–23%. PU–RH did not pass the UL94 HB standard test and completely burned to the holder clamp with a low LOI (19%). The cone calorimetry results indicated that the fireproof characteristics of the PU foam composites were considerably improved by the addition of the FRs. The proposed flame retardancy mechanism and cone calorimetry results are consistent. The comprehensive FTIR spectroscopy, TG, SEM, and XPS analyses revealed that the addition of ATH generated white solid particles, which dispersed and covered the residue surface. The pyrolysis products of OP would self-condense or react with other volatiles generated by the decomposition of PU–RH to form stable, continuous, and thick phosphorus/aluminum-rich residual chars inhibiting the transfer of heat and oxygen. The PU–RH samples with and without the FRs exhibited the normal isothermal sorption hysteresis effect at relative humidities higher than 20%. At lower values, during the desorption, this effect was not observed, probably because of the biodegradation of organic components in the RH. The findings of this study not only contribute to the improvement in combustibility of PU–RH composites and reduce the smoke or toxic fume generation, but also solve the problem of RHs, which are abundant waste resources of agriculture materials leading to the waste disposal management problems. Full article

A way to suppress the deterioration in mechanical properties of polyamide 6 (PA6) is required, especially with high loading of flame retardants in the matrix. In this study, a novel aromatic Schiff base diepoxide (DES) was synthesized. It exhibited an efficient chain extension effect on PA6 and a synergistic flame-retardant effect with aluminum diethylphosphinate (AlPi) for PA6. The PA6 composite with 16 wt.% AlPi only passed UL-94 V-0 rating at 1.6 mm thickness, while the combination of 1.5 wt.% DES with 13 wt.% AlPi induced PA6 to achieve a UL-94 V-0 rating at 0.8 mm thickness. The tensile, flexural, and Izod notched impact strengths were increased by 16.2%, 16.5%, and 24.9%, respectively, compared with those of V-0 flame-retarded PA6 composites with 16 wt.% AlPi. The flame-retarded mechanism of PA6/AlPi/DES was investigated by cone calorimetry and infrared characterization of the char residues and pyrolysis products. These results showed that DES had a synergistic effect with AlPi in condensed-phase flame retardation by promoting the production of aluminum phosphorus oxides and polyphosphates in the char residues. Full article

An aromatic macromolecular polyimide (API) was synthesized and characterized, and used as a synergistic charring flame retardant in glass fiber reinforced polyamide 6 (GF/PA6). API and aluminum diethylphosphinate (ADP) exhibited better flame inhibition behavior and synergistic charring flame retardant behavior compared with ADP alone. The 5%API/7%ADP/GF/PA6 sample achieved the lower peak value of the heat release rate (pk-HRR) at 497 kW/m² and produced higher residue yields of 36.1 wt.%, verifying that API and ADP have an outstanding synergistic effect on the barrier effect. The API/ADP system facilitated the formation of a carbonaceous, phosphorus and aluminum-containing compact char layer with increased barrier effect. FTIR spectra of the residue and real-time TGA-FTIR analysis on the evolved gases from PA6 composites revealed that API interacted with ADP/PA6 and locked in more P–O–C and P–O–Ar content, which is the main mechanism for improving flame inhibition and charring ability. In addition, the API/ADP system improved the mechanical properties and corrosion resistance of GF/PA6 composites compared to ADP alone. Full article

The present work deals with the study of phosphorus flame retardant microcellular acrylonitrile–butadiene–styrene (ABS) parts and the effects of weight reduction on the fire and mechanical performance. Phosphorus-based flame retardant additives (PFR), aluminum diethylphosphinate and ammonium polyphosphate, were used as a more environmentally friendly alternative to halogenated flame retardants. A 25 wt % of such PFR system was added to the polymer using a co-rotating twin-screw extruder. Subsequently, microcellular parts with 10, 15, and 20% of nominal weight reduction were prepared using a MuCell^® injection-molding process. The results indicate that the presence of PFR particles increased the storage modulus and decreased the impact energy determined by means of dynamic-mechanical-thermal analysis and falling weight impact tests respectively. Nevertheless, the reduction of impact energy was found to be lower in ABS/PFR samples than in neat ABS with increasing weight reduction. This effect was attributed to the lower cell sizes and higher cell densities of the microcellular core of ABS/PFR parts. All ABS/PFR foams showed a self-extinguishing behavior under UL-94 burning vertical tests, independently of the weight reduction. Gradual decreases of the second peak of heat release rate and time of combustion with similar intumescent effect were observed with increasing weight reduction under cone calorimeter tests. Full article