High-Temperature Resistant Polyborosilazanes with Tailored Structures

Boron-containing organosilicon polymers are widely used under harsh environments as preceramic polymers for advanced ceramics fabrication. However, harmful chemicals released during synthesis and the complex synthesis routes have limited their applications. To solve the problems, a two-component route was adopted to synthesize cross-linked boron-containing silicone polymer (CPBCS) via a solventless process. The boron content and CPBCSs’ polymeric structures could be readily tuned through controlling the ratio of multifunctional boron hybrid silazane monomers (BSZ12) and poly[imino(methylsilylene)]. The CPBCSs showed high thermal stability and good mechanical properties. The CPBCS with Si-H/C=C ratio of 10:1 showed 75 wt% char yields at 1000 °C in argon, and the heat release capacity (HRC) and total heat release (THR) are determined to be 37.9 J/g K and 6.2 KJ/g, demonstrating high thermal stability and flame retardancy. The reduced modulus and hardness of CPBCS are 0.30 GPa and 2.32 GPa, respectively. The novel polysilazanes can be potentially used under harsh environments, such as high temperatures or fire hazards.

Review of new requirements for smoke ventilation system for road tunnels in NFPA 502 published in 2020

Одним из нормативных документов, содержащих основные требования к системам противодымной вентиляции автодорожных тоннелей, является NFPA 502 «Standard for Road Tunnels, Bridges and Limited Access Highways». Стандарт обобщает накопленный опыт, полученный в результате экспериментальных исследований, проводимых как в США, так и за их пределами. В августе 2019 г. была опубликована его новая редакция (2020 Edition), в которой значительно изменился подход к определению требуемых параметров противодымной вентиляции, основанной на продольной схеме. The article presents an analysis of the new edition of NFPA 502 “Standard for Road Tunnels, Bridges, and Limited Access Highways” regarding the method for determining the critical value of the longitudinal air flow velocity generated by smoke ventilation based on longitudinal scheme. The classification of road tunnels introduced by NFPA 502 is described, taking into account the occupancy of tunnels by vehicles during rush hour, as well as the length of the tunnel. The data concerning protection of tunnel by fire protection systems taking into account the introduced classification are presented. There are analysed the schemes of smoke ventilation, including longitudinal, semi-transverse and transverse, containing different number of concentrated and distributed smoke receiving and air intake devices introduced by NFPA 502. There is described the effect of trapping air from under the smoke layer, that is called as “Plugholing” effect in the standard. The data on heat release capacity from fire source are presented taking into account various types of burning vehicles, as well as the equipment of tunnel with automatic fire extinguishing systems. There is performed the comparison of results of the calculated determination of critical velocity, determined by the dependencies of NFPA 502 in 2017 and 2020 editions. The significant discrepancy in required values is found.

Impact of melamine and its derivatives on the properties of poly(vinyl acetate)-based composite wood adhesive

A fire retardant composite adhesive for bonding wood and wood-based elements has been developed and characterized. To obtain the enhanced fire-proof properties of the wood adhesive dispersion based on the poly(vinyl acetate) (PVAc), ceramic fillers (17.5 wt% total)—alumina, silica, kaolin and glass fibers were applied. Moreover, fire retardants such as melamine, melamine phosphate and melamine polyphosphate (up to 7 wt%) were also used. Thermal analysis (TG-DSC), strength tests, rheology, pH and flammability measurements (PCFC) were performed. The best properties of the adhesive were achieved for ceramic additives supported by melamine phosphate. A slight improvement of shear strength, shift of the last decomposition step of PVAc (residue degradation) towards higher temperatures by about 50 °C, reduction in mass loss from 100 wt% to less than 70 wt% and about 30–40% improvement of flammability parameters such as heat release capacity, total heat release or peak heat release rate were found compared to the pure poly(vinyl acetate) adhesive.

Nacre-Mimetic Green Flame Retardant: Ultra-High Nanofiller Content, Thin Nanocomposite as an Effective Flame Retardant

A nacre-mimetic brick-and-mortar structure was used to develop a new flame-retardant technology. A second biomimetic approach was utilized to develop a non-flammable elastomeric benzoxazine for use as a polymer matrix that effectively adheres to the hydrophilic laponite nanofiller. A combination of laponite and benzoxazine is used to apply an ultra-high nanofiller content, thin nanocomposite coating on a polyurethane foam. The technology used is made environmentally friendly by eliminating the need to add any undesirable flame retardants, such as phosphorus additives or halogenated compounds. The very-thin coating on the polyurethane foam (PUF) is obtained through a single dip-coating. The structure of the polymer has been confirmed by proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The flammability of the polymer and nanocomposite was evaluated by heat release capacity using microscale combustion calorimetry (MCC). A material with heat release capacity (HRC) lower than 100 J/Kg is considered non-ignitable. The nanocomposite developed exhibits HRC of 22 J/Kg, which is well within the classification of a non-ignitable material. The cone calorimeter test was also used to investigate the flame retardancy of the nanocomposite’s thin film on polyurethane foam. This test confirms that the second peak of the heat release rate (HRR) decreased 62% or completely disappeared for the coated PUF with different loadings. Compression tests show an increase in the modulus of the PUF by 88% for the 4 wt% coating concentration. Upon repeated modulus tests, the rigidity decreases, approaching the modulus of the uncoated PUF. However, the effect of this repeated mechanical loading does not significantly affect the flame retarding performance.

Synthesis of ortho-methyltetrahydrophthalimide functional benzoxazine containing phthalonitrile group: Thermally activated polymerization behaviors and properties of its polymer

Two novel benzoxazine monomers, oHMTI-a and oHMTI-pn, have been obtained via the modified Mannich condensation from ortho-4-methyltetrahydrophalimide functional phenol, paraformaldehyde, and aniline/4-aminophthalonitrile, respectively. The chemical structures of both benzoxazine monomers have been studied by Fourier transform infrared (FT-IR) and 1H and 13C nuclear magnetic resonance (NMR) spectra. Their polymerization processes are investigated using in-situ FT-IR and different scanning calorimetry (DSC). Specifically, the phthalonitrile group in oHMTI-pn can react at a relatively lower temperature without adding any catalysts, which suggests the presence of the thermal synergistic polymerization effect in this benzoxazine monomer. In addition, the thermal and fire related properties of the resulting polybenzoxazines are evaluated by thermogravimetric analysis (TGA) and micro-scale combustion calorimetry (MCC). The polybenzoxazine derived from oHMTI-pn shows both high thermal stability and outstanding flame retardancy, with a T g of 350°C, a T d10 value of 417°C, a high char yield value of 65%, and a very low heat release capacity value of 35.2 J/(g·K).

Application of Adaptive Neuro-Fuzzy Inference System in Flammability Parameter Prediction

The fire behavior of materials is usually modeled on the basis of fire physics and material composition. However, significant strides have been made recently in applying soft computing methods such as artificial intelligence in flammability studies. In this paper, multiple linear regression (MLR) was employed to test the degree of non-linearities in flammability parameter modeling by assessing the linear relationship between sample mass, heating rate, heat release capacity (HRC) and total heat release (THR). Adaptive neuro-fuzzy inference system (ANFIS) was then adopted to predict the HRC and THR of the extruded polystyrene measured from microscale combustion calorimetry experiments. The ANFIS models presented excellent predictions, showing very low mean training and testing errors as well as reasonable agreements between experimental and predicted datasets. Hence, it can be inferred that ANFIS can handle the non-linearities in flammability modeling, making it apt as a modeling technique for accurate and effective flammability assessments.

New fire-resistant epoxy thermosets: nonisothermal kinetic study and flammability behavior

New fire-resistant thermosets are prepared based on a bisphenol A-epoxy resin which is thermally crosslinked in the presence of dicyandiamide and two phenols containing phosphorus atoms. The thermosets are characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis (TGA), and microscale combustion calorimetry (MCC) tests. A nonisothermal kinetic study is performed based on processing of TGA data applying the method proposed by Vyazovkin. The lifetime prediction analyses establish that the phosphorus-containing polymers could be used at a constant temperature of 200°C up to 200–780 min. The MCC tests reveal an improvement of the flammability behavior, as well as a significant heat release capacity reduction for phosphorus-containing samples compared to the sample which has no phosphorus component.

Exploring the Contribution of Two Phosphorus-Based Groups to Polymer Flammability via Pyrolysis–Combustion Flow Calorimetry

From a set of around 100 phosphorus-containing polymers tested in pyrolysis–combustion flow calorimetry, the contributions to flammability of two phosphorus-containing pendant groups (called 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and PO3) were calculated using an advanced method previously proposed and validated. The flammability properties include total heat release (THR) and heat release capacity (HRC) measured in standard conditions, i.e., anaerobic pyrolysis and complete combustion. The calculated contributions are in good agreement with the main modes of action of both phosphorus groups, i.e., flame inhibition for DOPO and char promotion for PO3. Moreover, the results provide first conclusions about the cooperative interaction between phosphorus and nitrogen, as well as the influence of the architecture of tested co-polymers.