Fractal conceptualization of intumescent fire barriers, toward simulations of virtual morphologies.
ABSTRACT: By limiting the heat spread during a fire hazard, intumescent coatings are important components of passive protection systems. They swell due to heat induced reactions of micro constituents and are transformed into carbonaceous porous-like media, known as intumescent chars. Their multiscale inner structures, key elements of performance, are costly to predict by recurrent and large scale fire testing while numerical simulations are challenging due to complex kinetics. Hence, we propose a novel approach using the fractal theory and the random nature of events to conceptualize the coating expansion. Experimental specimens were obtained from fire protective coatings exposed to bench scale hydrocarbon fire. Mass fractals were evidenced in the slices of 3D sample volumes reconstructed from X-ray microtomography. Consequently, geometrical building blocks were simulated by random walk, active walk, aggregation-like and site percolation: physical-chemical modes of action were inherent in the attribution of the randomness. It is a first demonstration to conceptualize different types of intumescent actions by a generalized approach with dimensionless parameters at multiscale, thus eliminating the simulation of complex kinetics to obtain a realistic morphology. Also, fractal results brought new evidence to former chemical analyses on fire test residues trying to explain the kinetics of expansion. Expected outcomes are to predict virtually the reaction of fire protective systems hence to speed-up the assessment of fire performance through computed properties of virtual volumes.
Project description:Thin coatings of crosslinked poly(vinylphosphonic acid), PVPA, display good adhesion and excellent intumescent, fire-retardant barrier properties when applied to the surfaces of a typical thermoplastic, such as poly(methyl methacrylate), but perform relatively poorly in water-soak tests. To strengthen and further improve the barrier properties of the intumescent char and to make the coating more hydrophobic, PVPA has been complexed with various inorganic and organic species. The chars formed from coatings of some of these hybrid materials are less friable than chars from coatings synthesized from crosslinked PVPA alone, and show higher levels of water tolerance with no significant reduction in dry adhesion to the substrate.
Project description:Intumescent coatings are commonly used as passive fire protection systems for steel structures. The purpose of this work is to explore whether these can also be used effectively on glass fibre-reinforced epoxy (GRE) composites, considering the flammability of the composites compared to non-flammable steel substrate. The thermal barrier and reaction-to-fire properties of three commercial intumescent coatings on GRE composites have been studied using a cone calorimeter. Their thermophysical properties in terms of heating rate and/or temperature dependent char expansion ratios and thermal conductivities have been measured and correlated. It has been suggested that these two parameters can be used to design coatings to protect composite laminates of defined thicknesses for specified periods of time. The durability of the coatings to water absorption, peeling, impact, and flexural loading were also studied. A strong adhesion between all types of coatings and the substrate was observed. Water soaking had a little effect on the fire performance of epoxy based coatings. All types of 1 mm thick coatings on GRE helped in retaining ~90% of the flexural property after 2 min exposure to 50 kW/m² heat flux whereas the uncoated laminate underwent severe delamination and loss in structural integrity after 1 min.
Project description:Flammability and combustion of softwood treated with intumescent coatings were studied in the present work. The formulations applied onto wood surfaces contained different ratios of industrial fillers, titanium dioxide TiO2 and aluminium trihydroxide Al(OH)3, and/or bio-fillers, eggshell and rice husk ash. Combustion behaviours of unprotected and protected wood samples have been examined with the aid of cone calorimetry performed under the varied levels of thermal flux ranging from 30 to 50 kW/m². The char residues obtained after the completion of cone calorimetry test at 40 kW/m² were analysed by the Raman spectroscopy. The fire protective properties of the studied coatings were strongly influenced by the nature of the fillers as well as by the intensity of thermal irradiance. The incorporation of bio-based fillers into the water-based intumescent formulations significantly improved fire resistance of wood substrates. For example, at 30 kW/m², the Effective Heat of Combustion was reduced by more than 40%, whilst the average Peak to Heat Release Rate had dropped from 193.2 to 150.3 kW/m² for the wood sample protected with the formulation incorporating two industrial and two bio-fillers. Moreover, an application of the studied coatings resulted in a notable reduction of the back surface temperature of the wood specimens.
Project description:Zinc oxide nanoparticles (ZnO NPs) were synthesized by a precipitation method, and a new charring-foaming agent (CFA) N-ethanolamine triazine-piperazine, melamine polymer (ETPMP) was synthesized via nucleophilic substitution reaction by using cyanuric chloride, ethanolamine, piperazine, and melamine as precursor molecules. FTIR and energy-dispersive X-ray spectroscopy (EDS) studies were employed to characterize and confirm the synthesized ETPMP structure. New intumescent flame retardant epoxy coating compositions were prepared by adding ammonium polyphosphate (APP), ETPMP, and ZnO NPs into an epoxy resin. APP and ETPMP were fixed in a 2:1 w/w ratio and used as an intumescent flame-retardant (IFR) system. ZnO NPs were loaded as a synergistic agent in different amounts into the IFR coating system. The synergistic effects of ZnO NPs on IFR coatings were systematically evaluated by limited oxygen index (LOI) tests, vertical burning tests (UL-94 V), TGA, cone calorimeter tests, and SEM. The obtained results revealed that a small amount of ZnO NPs significantly increased the LOI values of the IFR coating and these coatings had a V-0 ratings in UL-94 V tests. From the TGA data, it is clear that the addition of ZnO NPs could change the thermal degradation behaviors of coatings with increasing char residue percentage at high temperatures. Cone calorimeter data reported that ZnO NPs could decrease the combustion parameters including peak heat release rates (PHRRs), and total heat release (THR) rates. The SEM results showed that ZnO NPs could enhance the strength and the compactness of the intumescent char, which restricted the flow of heat and oxygen.
Project description:The objective of this study is to assess the efficiency of biobased carbonization agent in intumescent formulations (IFRs) to examine the flame retardant properties of polylactic acid (PLA) composites and to investigate their melt-spinnability. We used phosphorous-based halogen free flame retardant (FR) and kraft lignin (KL) as bio-based carbonization agent. After melt compounding and molding into sheets by hot pressing various fire related characteristics of IFR composites were inspected and were characterized by different characterization methods. It was fascinating to discover that the introduction of 5-20 wt% FR increased the limiting oxygen index (LOI) of PLA composites from 20.1% to 23.2-33.5%. The addition of KL with content of 3-5 wt% further increased the LOI up to 36.6-37.8% and also endowed PLA/FR/KL composites with improved anti-dripping properties. Cone calorimetry revealed a 50% reduction in the peak heat release rate of the IFR composites in comparison to 100% PLA and confirmed the development of an intumescent char structure containing residue up to 40%. For comparative study, IFR composites containing pentaerythritol (PER) as a carbonization agent were also prepared and their FR properties were compared. IFR composites were melt spun and mechanical properties of multifilament yarns were tested. The analysis of char residues by energy dispersive X-ray spectrometry (EDS) and SEM images confirmed that PLA/FR/KL composites developed a thicker and more homogeneous char layer with better flame retardant properties confirming that the fire properties of PLA can be enhanced by using KL as a carbonization agent.
Project description:The demand for eco-friendly poly (lactic acid) (PLA) nonwovens grows at a high rate in the past several decades, however, only a little attention has been received for flame retardant PLA nonwoven fabrics. In this work, a novel halogen-free self-intumescent polyelectrolyte tris (hydroxymethyl)-aminomethane polyphosphate (APTris) was synthesized by reacting ammonium polyphosphate with tris (hydroxymethyl) aminomethane, and was then used to improve the fire resistance of PLA nonwovens via a dip-nip process. The flammability characterization indicated the limiting oxygen index value was increased to 30.0% from 18.3%, and the damaged area in the vertical burning test was reduced by about 87.0% by the presence of APTris. The cone calorimeter test results revealed that the peak heat release rate and total heat release of the treated sample were decreased by 41.0% and 28.2% respectively compared with that of the control PLA nonwoven sample. The char residue was increased to 12.3 from 1.7 wt. % at 800 °C. It is suggested that the dense char barrier formed at the presence of APTris prevents heat, smoke, and gas transfer, and hence enhance thermal dilatability and flame retardancy of PLA nonwovens. This simple sustainable halogen-free treatment has great potential to produce cleaner commercialized flame-retardant PLA nonwovens.
Project description:To evaluate intraoperative complications during phacoemulsification of intumescent cataract using lens decompression technique.Participants with intumescent cataract scheduled for phacoemulsification were recruited and divided into two groups. In both groups, after the anterior capsule was stained with trypan blue, the anterior chamber was filled peripherally with a dispersive ophthalmic viscosurgical device (OVD) followed centrally by a higher viscosity cohesive OVD (Healon GV). In Group 2, a 25-gauge needle was then inserted into the lens center and liquid cortex aspirated by pulling back on the syringe plunger. The outcomes measured were the incidence of capsular radial tears and the incidence of conversion to extracapsular cataract extraction (ECCE).In Group 1 (20 eyes), capsular radial tears occurred in four eyes, and in two eyes, the procedure had to be converted to ECCE. In Group 2 (20 eyes), no capsular radial tears or conversion to ECCE was reported.Lens decompression technique reduced the risk of capsular radial tears and conversion to ECCE during phacoemulsification of intumescent cataract.
Project description:Synthesis of a novel phosphorus and triazole-functionalized flame-retardant (FR) monomer (PTFM) using azide-alkyne "click" reaction between triprop-2-ynyl phosphate and 2-azidoethanol that can impart intumescent FR property to polyurethane foams (PUFs) has been reported. Polyurethane triazole foams (PUTFs) were prepared using the as-synthesized PTFM and a hydroxylated castor polyol with a hydroxyl value of ?310 mg KOH/g for application as reactive FR rigid foams. PTFM and the castor polyol were characterized for structural elucidation using Fourier transform infrared and 1H, 13C, and 31P NMR. PUTFs with a varying loading content of PTFM were subjected to the lab-scale flame test, cone calorimetry test, Underwriters Laboratory 94 Vertical burning test (UL 94V), and limiting oxygen index (LOI) test. A significant increase in the char yields, reduction in heat release rates, V-1 rating, and 27% of LOI were observed for PUTFs compared to PUFs and proportional to the percentage loading of PTFM. The cumulative effect of nitrogen and phosphorus in PUTFs on their intumescent behavior was evident from the thermogravimetric analysis and scanning electron microscopy micrographs, which were further supplemented by X-ray photoelectron spectroscopy studies, indicating expulsion of N2 and overall improvement in compression strength as well. Such environment-friendly reactive FRs can be good replacements to the halogenated ones.
Project description:In this communication, we describe a technique for creation of a single stage, adequately sized capsulorrhexis in intumescent cataracts by depressurizing the anterior and posterior intralenticular compartments in a nonleaky anterior chamber (AC) to prevent capsulorrhexis extension and Argentina flag sign. Initially, an incomplete main-port incision is made by the partial entry of a 2.2-mm keratome. A cohesive dispersive ophthalmic viscosurgical device (OVD) is injected into AC. Standard side-port incisions are made, followed by anterior capsular staining. The fluid cortex in anterior intralenticular compartment is aspirated by puncturing anterior capsule in the center using a 30-gauge needle entered through a separate limbal stab incision. The nucleus edge is gently tipped posteriorly with the needle tip to release the fluid from posterior intralenticular compartment also and as much fluid aspirated as possible. OVD is again injected and capsulorrhexis is performed in a single stage using micro-capsulorrhexis forceps.
Project description:Motor activity possesses a multiscale regulation that is characterized by fractal activity fluctuations with similar structure across a wide range of timescales spanning minutes to hours. Fractal activity patterns are disturbed in animals after ablating the master circadian pacemaker (suprachiasmatic nucleus, SCN) and in humans with SCN dysfunction as occurs with aging and in dementia, suggesting the crucial role of the circadian system in the multiscale activity regulation. We hypothesized that the normal synchronization between behavioural cycles and the SCN-generated circadian rhythms is required for multiscale activity regulation. To test the hypothesis, we studied activity fluctuations of rats in a simulated shift work protocol that was designed to force animals to be active during the habitual resting phase of the circadian/daily cycle. We found that these animals had gradually decreased mean activity level and reduced 24-h activity rhythm amplitude, indicating disturbed circadian and behavioural cycles. Moreover, these animals had disrupted fractal activity patterns as characterized by more random activity fluctuations at multiple timescales from 4 to 12 h. Intriguingly, these activity disturbances exacerbated when the shift work schedule lasted longer and persisted even in the normal days (without forced activity) following the shift work. The disrupted circadian and fractal patterns resemble those of SCN-lesioned animals and of human patients with dementia, suggesting a detrimental impact of shift work on multiscale activity regulation.