A Multi-Material Flame-Retarding System Based on Expandable Graphite for Glass-Fiber-Reinforced PA6.

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.

The Impact of ß-Radiation Crosslinking on Flammability Properties of PA6 Modified by Commercially Available Flame-Retardant Additives.

A comparative study was conducted investigating the influence of ß-radiation crosslinking (ß-RC) on the fire behavior of flame retardant-modified polyamide 6 (PA6). In order to provide a comprehensive overview, a variety of commercially available flame-retardant additives were investigated, exhibiting different flame retarding actions such as delusion, char formation, intumescence and flame poisoning. This study focused on the identification of differences in the influence of ß-RC on fire behavior. Coupled thermal gravimetrical analysis (TGA) and Fourier transformation infrared spectroscopy (FTIR) were used to conduct changes within the decomposition processes. Dynamic thermal analysis (DTA) was used to identify structural stability limits and fire testing was conducted using the limiting oxygen index (LOI), vertical UL-94 and cone calorimeter testing. Crosslinking was found to substantially change the fire behavior observed, whereas the observed phenomena were exclusively physical for the given formulations studied: warpage, char residue destruction and anti-dripping. Despite these phenomena being observed for all ß-RC formulations, the impact on fire resistivity properties were found to be very different. However, the overall fire protection properties measured in UL-94 fire tests were found to deteriorate for ß-RC formulations. Only ß-RC formulations based on PA6/EG were found to achieve a UL-94 V0 classification.

Expandable Graphite as a Multifunctional Flame-Retarding Additive for Highly Filled Thermal Conductive Polymer Formulations.

Expandable graphite (EG) and graphite (G) were assessed as multifunctional additives improving both flame retardancy and thermal conductivity in highly filled, thermal conductive polymeric materials based on polyamide 6 (PA6). Fire testing was conducted using modern UL-94, LOI and cone calorimeter test setups. It is demonstrated that thermal conductivity can significantly influence the time to ignition, although offering little fire resistance once ignited even in highly filled systems. Thus, for PA6 formulations containing solely 70 wt.% G, the peak heat release rate (pHRR) measured in cone calorimeter tests was 193 kW/m², whereas PA6 formulations containing 20 wt.% EG/50 wt.% G did not exhibit a measurable heat development. Particular attention was paid to effect separation between thermal conductivity and residue formation. Good thermal conductivity properties are proven to be particularly effective in test scenarios where the heat impact is comparatively low and the testing environment provides good heat dissipation and convective cooling possibilities. For candle-like ignition scenarios (e.g., LOI), filling levels of >50 wt.% (G or EG/G) are shown to be sufficient to suppress ignition exclusively by thermal conductivity. V0 classifications in UL-94 vertical burning tests were achieved for PA6 formulations containing ≥70 wt.% G, ≥25 wt.% EG and ≥20 wt.% EG/25 wt.% G.

Expandable Graphite, Aluminum Diethylphospinate and Melamine Polyphosphate as Flame Retarding System in Glass Fiber-Reinforced PA6.

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%.

A Synergistic Flame Retardant System Based on Expandable Graphite, Aluminum (Diethyl-)Polyphospinate and Melamine Polyphosphate for Polyamide 6.

Expandable graphite (EG), aluminum (diethyl)polyphosphinate (AlPi) and melamine polyphophate (MPP) was used as flame retardant multi-material additive in a polyamide 6 (PA6) matrix. Flame inhabitation performances were conducted by cone calorimeter, LOI and UL-94 tests, synergisms identified analyzed by TGA-FTIR and TGA-GC/MS and effects found were comprehensively discussed. SEM images were used for char residue characterization. For PA6 containing 20 wt.% EG and 5 wt.% AlPi/MPP (3:2), a well working synergism in limiting oxygen indices could be identified exhibiting the highest oxygen index (OI) measured: 46%. The study shows that the synergism due to the partial substitution of EG by AlPi/MPP can be attributed to two effects: (1) When PA6/AlPi/MPP mixtures decompose predominantly CO2 evaporates in early decomposition stages. CO2 evaporations was found to be sensitive to the heating rate applied, whereas specifically high heating rates increased the CO2 yield measured. (2) Solid decomposition products of AlPi/MPP act as "glue" between expanded graphite and thus increase the mechanical residue stability.

Expandable Graphite for Flame Retardant PA6 Applications.

A new expandable graphite (EG) type was studied as a flame retardant additive in Polyamide 6 (PA6). The fire behavior was characterized by a cone calorimeter using external heat fluxes of 35, 50 and 65 kW/m2, limiting the oxygen index (LOI) and UL-94 burning tests. Additionally, electric and thermal conductivity as well as rheological properties were characterized to provide a general property overview. Fire tests were conducted using dry and humid conditioned samples. Cone Calorimeter tests showed a minimum filling degree of 15 wt.% (8.6 vol.%) EG was required to achieve a significant fire inhibiting effect in PA6 independent of the sample condition. UL-94 fire tests show a V0 classification at filling degrees greater than 20 wt.% (humid) and 25 wt.% (dry), although the associated LOI values of 39% and 38% demonstrate good flammability inhibition. Correlation analyses were conducted to identify major influences given by the sample condition for most important key figures measured in cone calorimeter tests. Accordingly, humid-conditioned samples containing between 2.5 (PA6 + 25 wt.% EG) and 4.2 wt.% (PA6) water were found to reduce the total heat evolved (THE) on average by 16% and the total smoke production (TSP) on average by 22%.

Achieving a 3D Thermally Conductive while Electrically Insulating Network in Polybenzoxazine with a Novel Hybrid Filler Composed of Boron Nitride and Carbon Nanotubes.

To solve the problem of excessive heat accumulation in the electronic packaging field, a novel series of hybrid filler (BN@CNT) with a hierarchical "line-plane" structure was assembled via a condensation reaction between functional boron nitride(f-BN) and acid treated carbon nanotubes (a-CNTs). The reactions with different mass ratios of BN and CNTs and the effect of the obtained hybrid filler on the composites' thermal conductivity were studied. According to the results, BN@15CNT exhibited better effects on promoting thermal conductivity of polybenzoxazine(PBz) composites which were prepared via ball milling and hot compression. The thermally conductive coefficient value of PBz composites, which were loaded with 25 wt% of BN@15CNT hybrid fillers, reached 0.794 W· m-1· K-1. The coefficient value was improved to 0.865 W· m-1· K-1 with 15 wt% of BN@15CNT and 10 wt% of BN. Although CNTs were adopted, the PBz composites maintained insulation. Dielectric properties and thermal stability of the composites were also studied. In addition, different thermal conduction models were used to manifest the mechanism of BN@CNT hybrid fillers in enhancing thermal conductivity of PBz composites.

Particle Size Related Effects of Multi-Component Flame-Retardant Systems in Poly(Butadiene Terephthalate).

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.