Phosphorus-Based Flame-Retardant Acrylonitrile Butadiene Styrene Copolymer with Enhanced Mechanical Properties by Combining Ultrahigh Molecular Weight Silicone Rubber and Ethylene Methyl Acrylate Copolymer.

The present work proposes to investigate the effect of an ultrahigh molecular weight silicone rubber (UHMW-SR) and two ethylene methyl acrylate copolymers (EMA) with different methyl acrylate (MA) content on the mechanical and fire performance of a fireproof acrylonitrile butadiene styrene copolymer (ABS) composite, with an optimum amount of ammonium polyphosphate (APP) and aluminum diethyl phosphinate (AlPi). ABS formulations with a global flame retardant weight content of 20 wt.% (ABS P) were melt-compounded, with and without EMA and UHMW-SR, in a Brabender mixer. During this batch process, ABS P formulations with UHMW-SR and/or EMA registered lower torque values than those of ABS P. By means of scanning electron microscopy (SEM), it was possible to observe that all ABS composites exhibited a homogenous structure without phase separation or particle agglomeration. Slightly improved interfacial interaction between the well-dispersed flame-retardant particles in the presence of EMA and/or UHMW-SR was also noticed. Furthermore, synergies in mechanical properties by adding both EMA and UHMW-SR into ABS P were ascertained. An enhancement of molecular mobility that contributed to the softening of ABS P was observed under dynamic mechanical thermal analysis (DMTA). An improvement of its flexibility, ductility and toughness were also registered under three-point-bending trials, and even more remarkable synergies were noticed in Charpy notched impact strength. Particularly, a 212% increase was achieved when 5 wt.% of EMA with 29 wt.% of MA and 2 wt.% of UHMW-SR in ABS P (ABS E29 S P) were added. Thermogravimetric analysis (TGA) showed that the presence of EMA copolymers in ABS P formulations did not interfere with its thermal decomposition, whereas UHMW-SR presence decreased its thermal stability at the beginning of the decomposition. Although the addition of EMA or UHMW-SR, as well as the combination of both in ABS P increased the pHRR in cone calorimetry, UL 94 V-0 classification was maintained for all flame-retarded ABS composites. In addition, through SEM analysis of cone calorimetry sample residue, a more cohesive surface char layer, with Si-O-C network formation confirmed by Fourier transform infrared (FTIR), was shown in ABS P formulations with UHMW-SR.

Enhancing char formation of flame retardant epoxy composites: Onigiri-like ZIF-67 modification with carboxymethyl ß-cyclodextrin crosslinking.

To enhance char formation of flame retardant epoxy (EP) composites, carboxymethyl ß-cyclodextrin (CM-ß-CD) is employed as an etchant for or ZIF-67 derivatives. In the early stage, etching plays a dominant role. The mismatch in size between CM-ß-CD opening and ZIF-67 pore leads to the stacking of carboxyl cobalt complexes on the shell. When the reaction time is prolonged, crosslinking occurs between carboxyl and hydroxyl groups. Crosslinked CM-ß-CD weakens and eventually stops the etching process. Triethyl phosphate (TEP), an additive to improve flame retardancy, is also absorbed on the shell in this one-pot synthesis. Herin, the synthesis of metal-organic framework (MOF) derivatives can impart multiple functions to MOF. This novel nanohybrid significantly improved flame retardancy of EP composites with only 2.0 wt% loading. The peak heat release rate (pHRR) and total smoke production (TSP) were reduced by 54.8 and 46.9%, respectively. The integrated multi-element system resulted in an expanded and reinforced char layer. This study proposes a simple and precise method for controlling the structure of MOF-carbohydrate hybrids through competition between chemical reactions.

A Gas-Steamed Route to Mesoporous Open Metal-Organic Framework Cages Enhancing Flame Retardancy and Smoke Suppression of Polyurea.

Up to now, metal-organic frameworks (MOFs) with open nanostructures have shown outstanding capabilities in trapping smoke particles compared to the original MOFs. However, only a few MOF-based strategies have been reported to synthesize hierarchical porous cages thus far, which are mainly restricted to environmentally unfriendly wet-chemical liquid methods. Herein, as a proof-of-concept, a gas-steamed metal-organic framework approach was designed to fabricate a series of cheeselike open cages with hierarchical porosity. Briefly, zeolitic imidazolate framework-67 (ZIF-67) and phytic acid were employed as precursor and etchant, respectively. Abandoning the conventional wet-chemical method, the coordination bond of ZIF-67 was cleaved by acidic steam, forming an open framework with a high specific surface area and a hierarchical porous structure. The universality of this method was also confirmed by the selection of different etchants. Impressively, they also show outstanding fume-toxic adsorption capability and labyrinth effects based on abundant and complex porous channels. At only 5 wt % loading, Co3O4@open ZIF-67 cage-2 (Co3O4@OZC-2) imparted polyurea (PUA) composites with a 21.2% limiting oxygen index, and the peak of heat release rate, total heat release, and total smoke production were reduced by around 37.5, 25.5, and 40.4%, respectively, compared to neat PUA. This work will shed light on the advanced structural design of polymer composites with high fire safety, especially smoke suppression performance, so as to obtain more feasible applications.

The Components' Roles in Thermal Stability and Flammability of Cork Powder.

In this study, an analysis of the influence of extractives, suberin and lignocellulosic components on the pyrolysis decomposition and fire reaction mechanisms of a cork oak powder from Quercus suber L. is presented. The summative chemical composition of cork powder was determined. Suberin was the main component at 40% of the total weight, followed by 24% of lignin, 19% of polysaccharides and 14% of extractives. The absorbance peaks of cork and its individual components were further analyzed by means of ATR-FTIR spectrometry. Thermogravimetric analysis (TGA) showed that the removal of extractives from cork slightly increased the thermal stability between 200 °C and 300 °C and led to the formation of a more thermally stable residue at the end of the cork decomposition. Moreover, by removing suberin, a shift of the onset decomposition temperature to a lower temperature was noticed, indicating that suberin plays a major role in enhancing the thermal stability of cork. Furthermore, non-polar extractives showed the highest flammability with a peak of heat release rate (pHRR) of 365 W/g analyzed by means of micro-scale combustion calorimetry (MCC). Above 300 °C, the heat release rate (HRR) of suberin was lower than that of polysaccharides or lignin. However, below that temperature it released more flammable gases with a pHRR of 180 W/g, without significant charring ability, contrary to the mentioned components that showed lower HRR due to their prominent condensed mode of action that slowed down the mass and heat transfer processes during the combustion process.

Effects of a Phosphorus Flame Retardant System on the Mechanical and Fire Behavior of Microcellular ABS.

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.

Porous Membranes Based on Polypropylene-Ethylene Copolymers. Influence of Temperature on Extrusion, Annealing and Uniaxial Strain Stages.

In this study, block and random copolymers of polypropylene⁻ethylene are selected to prepare porous membranes through the melt extrusion-annealing-uniaxial stretching technique (MEAUS), at a constant draw ratio. In some cases, these copolymers were blended with a homopolymer grade. The variation of temperature in the stages of extrusion, annealing and uniaxial strain was analysed. Several characterisation techniques were employed to study this influence. The crystalline orientation was analysed by polarised infrared spectroscopy (FT-IR), and crystalline features were studied by differential scanning calorimetry (DSC). The thermal stability of the membranes was checked by thermogravimetric analysis (TGA). Tensile tests were performed to ascertain the stiffness and ductility of the produced samples. The results were correlated with the porous morphology, global porosity, and permeability to air. A close relationship was found between crystalline characteristics, porous morphology and the trends registered. An improved pore distribution along the membrane surface was found when copolymers were employed.