PREPARATION OF IRON- REDUCED GRAPHENE OXIDE/ EPOXY RESIN COMPOSITE AND ITS FLAME RETARDANCY AND THERMAL STABILITY

In order to reduce flammability, smoke release and enhance thermal stability of epoxy resin (EP), iron powder is mixed with graphene oxide/ epoxy resin (GO/EP) composite by mechanical blending. The combustion performance of composite material is investigated through limiting oxygen index (LOI), Underwriters Laboratory (UL)-94 test, and cone calorimeter test (CCT). Thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) and scanning electron microscope (SEM) are also used to explore the mechanism of flame retardancy and smoke suppression. Results show that, with the addition of 0.5% mass fraction of GO and the corresponding iron powder combination (EP3 sample), the LOI value can achieve 32.5% while reaching the UL-94 V0 rating. Compare with EP0, the peaks of heat release rate, smoke production rate, and smoke factor values of EP3 are decreased by 42%, 60%, and 50%, respectively. The char and TG-FTIR data of EP3 reveal that it has a more compact structure, good thermal stability, and produce fewer toxic gases and smoke. Reduction of GO could inhibit the degradation of EP, and iron catalyzes the formation of carbonaceous char on the surface. Thus, the thermal stability and flame retardancy of EP are improved significantly. This study provides a suitable way to prepare graphene/EP composites that contain iron catalyst and can be extended to the industrial manufacture of flame retardant polymer composites. Keywords: iron powder; epoxy resin; graphene oxide; flame retardant; thermal stability

Bio-Based Rigid Polyurethane Foams Modified with Phosphorus Flame Retardants

Rigid polyurethane foams (RPURF) containing a bio-polyol from rapeseed oil and different phosphorus-based flame retardants were obtained. Triethyl phosphate (TEP), dimethyl propane phosphonate (DMPP) and cyclic phosphonates Addforce CT 901 (20 parts per hundred polyol by weight) were used in the synthesis of RPURF. The influence of used flame retardants on foaming process, cell structure, and physical–mechanical properties as well as flammability of RPURF were examined. The addition of flame retardants influenced the parameters of the cellular structure and decreased compressive strength. All obtained foam materials had a low thermal conductivity coefficient, which allows them to be used as thermal insulation. The research results of bio-based RPURF were compared with foams obtained without bio-polyol. All modified materials had an oxygen index above 21 vol%; therefore, they can be classified as self-extinguishing materials. The analysis of parameters obtained after the cone calorimeter test showed that the modified RPURF have a lower tendency to fire development compared to the reference foams, which was particularly noticeable for the materials with the addition of DMPP.

Synergistic effects of halloysite nanotubes with metal and phosphorus additives on the optimal design of eco-friendly sandwich panels with maximum flame resistance and minimum weight

The present work addresses the optimal design of sandwich panels made of flax fabric (FF)/vinyl ester (VE) composite face sheets and honeycomb VE core. The sandwich structures are first optimized in terms of flammability by obtaining the best combination of ammonium polyphosphate (APP), halloysite nanotube (HNT), and magnesium hydroxide (MH) as three flame retardants (FRs). Using the Taguchi method and horizontal burning test, it is shown that [6, 3, and 3%] and [1, 0.5, and 0%] are the optimal combinations of APP, HNT, and MH for the face sheets and core, respectively. Cone calorimeter test results indicate that the optimal FR combinations significantly decrease the mass lost rate (MLR), heat rate release (HRR), total smoke release (TSR), and maximum average release heat emission (MARHE). The FR sandwich structures are then geometrically optimized under compressive loads based on their weight. Different failure modes are considered as the design constraints of the optimization problem. Imperialist competitive algorithm (ICA), as a powerful meta-heuristic algorithm, is implemented to considerably reduce the computational cost of the optimization process. The results of this study show that proper combinations of FR additives can increase the flame retardancy while decreasing the weight of sandwich panels.

Comparative Study of Fire Resistance and Char Formation of Intumescent Fire-Retardant Coatings Reinforced with Three Types of Shell Bio-Fillers

Three types of shell bio-fillers, including eggshell (CES), conch shell (CHS) and clamshell (CMS), were prepared by cleaning, ultrasonication and pulverizing processes of biowastes, and then applied to intumescent fire-retardant coatings. The effects of shell bio-fillers with different polymorphs on the fire resistance and char-forming of intumescent fire-retardant coatings were investigated by cone calorimeter test, fire protection tests, smoke density test, thermogravimetric analysis (TG), and the fire resistance and char-forming mechanism of bio-fillers in intumescent fire-retardant coatings were proposed. The results show that three kinds of bio-fillers exert an excellent synergistic effect on enhancing the fire resistance and char-forming properties of the intumescent fire-retardant coatings, while clamshell has the best synergistic efficiency among the bio-fillers. Especially, IFRC-CMS coating containing 3 wt% clamshell shows the best fire protection performance and lowest smoke production and heat release, which offers an equilibrium backside temperature of 134.6 °C at 900 s, a flame-spread rating of 14.4, and a smoke density rating value of 22.8%. The synergistic efficiency of bio-fillers in the intumescent coatings depends on the polymorphs of CaCO3 in bio-fillers, and aragonite CaCO3 shows a higher synergistic efficiency compared to calcite CaCO3 and the mixture of aragonite and calcite CaCO3. The CMS composed of aragonite shows the best synergistic effect, CHS composed of aragonite and calcite comes second, and CES composed of calcite has the weakest synergistic effect.

Synergistic Flame-Retardant Effect of Aluminum Diethyl Phosphinate in PP/IFR System and the Flame-Retardant Mechanism

Synergistic flame-retardant effect of aluminum diethyl phosphinate (AlPi) in intumescent flame retardant polypropylene (PP/IFR) system and the flame-retardant mechanism were investigated. The flame retardancy of PP/IFR/AlPi (the mass ratio of IFR to AlPi is 2 : 1) was the best, which was proved by the results of the limiting oxygen index (LOI) test, UL-94 test, and cone calorimeter test ( CCT) test. Here, the LOI value of the sample was as high as 34% and passed the V–0 rating in UL–94 test. The peak heat release rate (PHRR) decreased by 92.57%, the total heat release (THR) reduced by 90.52%. Thermogravimetric (TGA) data showed that the introduction of AlPi improved thermal stability and changed the thermal degradation behavior of PP/IFR composites. Interestingly, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDXS) and laser Raman spectroscopy (LRS) proved that PP/IFR/AlPi had formed more residual carbon, but the flame retardancy was worse than PP/IFR/AlPi. This is because when the mass ratio of IFR to AlPi is 2 : 1, the synergy between IFR and AlPi was significant, gas-phase flame retardant and condensed-phase flame retardant reached a balance and obtained the best flame retardant effect.

A Novel Synergistic Flame Retardant of Hexaphenoxycyclotriphosphazene for Epoxy Resin

Hexaphenoxycyclotriphosphazene (HPCP) is a common flame retardant for epoxy resin (EP). To improve the thermostability and fire safety of HPCP-containing EP, we combined UiO66-NH2 (a kind of metal-organic frame, MOF) with halloysite nanotubes (HNTs) by hydrothermal reaction to create a novel synergistic flame retardant (H-U) of HPCP for EP. For the EP containing HPCP and H-U, the initial decomposition temperature (T5%) and the temperature of maximum decomposition rate (Tmax) increased by 11 and 17 °C under nitrogen atmosphere compared with those of the EP containing only HPCP. Meanwhile, the EP containing HPCP and H-U exhibited better tensile and flexural properties due to the addition of rigid nanoparticles. Notably, the EP containing HPCP and H-U reached a V-0 rating in UL-94 test and a limited oxygen index (LOI) of 35.2%. However, with the introduction of H-U, the flame retardant performances of EP composites were weakened in the cone calorimeter test, which was probably due to the decreased height of intumescent residual char.

Fire Performance of Intumescent Waterborne Coatings with Encapsulated APP for Wood Constructions

In this work, intumescent coatings were prepared for protection of wood from fire. The fire-retardant chemical ammonium polyphosphate (APP) is known to have poor resistance to water and high humidity as it is hygroscopic in nature. To improve the water resistance, durability and fire resistance of the intumescent coating, APP was modified using a hybrid organic-inorganic polysiloxane encapsulation shell prepared by the sol–gel method. The physical and chemical properties of the intumescent mix containing microencapsulated ammonium polyphosphate (EAPP) particles were characterized by X-ray fluorescence (XRF), Fourier transform infrared spectroscopy (FTIR), water absorption, dynamic vapor sorption (DVS) and thermogravimetric analysis (TGA). The EAPP mix showed 50% reduction in water absorption, 75% reduction in water vapor sorption and increased thermal stability when compared to the APP mix. The intumescent coatings were applied on wood samples, and their fire performance was evaluated using a cone calorimeter test. The intumescent coatings containing EAPP mix showed better fire retarding properties with longer time to ignition, lower heat release rate and shorter heat release peak when compared to the coating without EAPP mix. The prepared intumescent coating shows higher resistance to water and moisture, and it has great potential to be used in bio-based construction industry for enhancing the fire resistance of wood.

Transparent low-flammability epoxy resins using a benzoguanamine-based DOPO derivative

We successfully prepared a highly effective flame-retardant additive called hsalbenzoguanamine phosphaphenanthrene (HDPD) through salicylaldehyde and nitrogen-rich benzoguanamine. The introduction of HDPD into epoxy resin (EP) sharply enhanced the flame retardancy of EP/HDPD thermosets. The introduction of 6 wt% HDPD into EP succeeded in reaching the V-0 rating. Limited oxygen index results revealed the high flame-retarding performance of HDPD. Cone calorimeter test data revealed that heat and smoke released from EP/6 wt% HDPD thermoset were significantly restrained. In addition, EP/6 wt% HDPD thermoset demonstrated excellent transmittance and mechanical strength. The transmittance of EP/6 wt% HDPD was assessed from 520 to 800 nm. The results showed that transmittance of EP/6 wt% HDPD were nearly 90% of the control group.

Investigating the Effect of Aluminum Diethylphosphinate on Thermal Stability, Flame Retardancy, and Mechanical Properties of Poly(butylene succinate)

Poly(butylene succinate) is one of the most promising biodegradable polymers, but its applications are limited by poor flame retardancy. In this work, poly(butylene succinate)/diethylphosphinate (PBS/AlPi) composites were fabricated to investigate the effect of AlPi on their thermal stability, flame retardancy, and mechanical properties. It was found that the high content of AlPi decreased the thermal stability of PBS, and the decrease became stronger under the air atmosphere. When the content of AlPi reached 25wt%, the flame retardancy was improved with limited oxygen index (LOI) of 29.5%, V0 rating in UL-94 vertical burning test, and 49.3% reduction on the peak of heat release rate (PHRR) in cone calorimeter test. Meanwhile, the addition of AlPi could improve the mechanical properties of PBS with high tensile strength and Young’s modulus, which was ascribed to the compatible effect of maleic anhydride-grafted poly(butylene succinate) (PBS-g-MA) with good filler dispersion and strong matrix-particles interaction. Thus, the AlPi was an effective flame retardant to PBS, so that PBS/AlPi composites displayed excellent flame retardancy without seriously sacrificing other comprehensive performances.

Rigid Polyurethane Foams Containing Modified Ammonium Polyphosphate Having Outstanding Charring Ability and Increased Flame Retardancy

Ammonium polyphosphate (APP) with different polymerization degrees were modified by a novel phosphorus-containing organosilicon compound (PCOC), and the products obtained were coded as MAPP-30 and MAPP-1000. Then they were applied to prepare flame-retardant rigid polyurethane foam (RPUF) separately. The impact of modified APP (MAPP) on the flame-retardant properties of RPUF was investigated by the limited oxygen index (LOI) test, horizontal burning test, and cone calorimeter test. The morphologies of the char residues were observed by SEM. Furthermore, the mechanical properties of RPUF composites were measured by the compressive strength test. The results showed that whether the degree of polymerization of MAPP is 30 or 1000, they both had greater charring ability and better flame-retardant properties than unmodified APP. The residual char yield of RPUF/MAPP-30 (37.3%) and RPUF/MAPP-1000 (36.5%) were both significantly higher than RPUF/APP-30 (22.8%) and RPUF/APP-1000 (24.9%). The peak heat release rate value of RPUF/MAPP-30 was 29.9% lower than that of RPUF/APP-30, and the drop of RPUF/MAPP-1000 was 50.9% compared to RPUF/APP-1000. Moreover, the total heat release of RPUF/MAPP-1000 (9.7 MJ/m2) was much lower than that of RPUF/MAPP-30 (11.3 MJ/m2). In summary, MAPP-1000 has the best flame-retardant properties among all RPUF composites. In addition, the results also showed that flame-retardant performance and the mechanical properties dramatically decreased with the increase in the addition of MAPP-1000, and the RPUF composite had the best comprehensive performance with 20% content of MAPP-1000.