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The mechanism of action and the synergistic effect of nitrogenand phosphorus-containing fire retardants in fire protection and wood and peat fire suppression
Abstract
The factors exerting a significant influence on the termination of the combustion of natural materials (wood and peat) were studied with the use of synthetic nitrogen- and phosphorus-containing fire retardants with different efficiencies. With the use of a mathematical experimental design method, it was confirmed that the inhibition of gas-phase radical processes by volatile nitrogen-containing products is the predominant process of combustion suppression. It was found that the synergism of the nitrogen–phosphorus flame retardants is determined by their complex action: phosphorus mainly enters into organomineral structures in a the condensed phase, and nitrogen inhibits reactions in a gas phase.
... Nitrogen-containing flame retardants absorb heat and produce non-combustible gases to dilute the concentration of combustibles during the decomposition process of polymers [58,[60][61][62]. ...
... Bogdanova, Kobets and Kirlitsa [61] studied the factors exerting a significant influence on the termination of the combustion of natural materials (wood and peat) with the use of synthetic nitrogenand phosphorus-containing fire retardants with different efficiencies. With the use of a mathematical experimental design method, it was confirmed that the inhibition of gas-phase radical processes by volatile nitrogen-containing products is the predominant process of combustion suppression. ...
Polymer based materials are used as in industry as in households. They are rapidly developing. Due to their cost, they often replace the traditional materials. The disadvantage of its use, both natural and synthetic polymers, is their sensitivity to flame because of their main constitute element, i.e. carbon. In general, the flammability of polymer materials depends on their chemical composition. Their flammability can be reduced by interfering the combustion process at any stage. A common approach to improve the flame-retardant properties of polymers is to apply the flame retardants. Those are used to prevent, minimize, suppress or stop the combustion process of polymer materials. They act to break the self-sustaining polymer combustion cycle and consequently reduce the burning rate or extinguish the flame in several ways. This paper compiles current research findings and results related to wood and wood composites, fabrics and PU/PUR foams flammability reduction, applying the flame-retardant treatment.
... Studies on providing fire-retardancy to wood and plywood have been carried out for more than 70 years [8]. Processes include coating or impregnation with boric acids [11], borax [12], ammonium chloride [8], and ammonium polyphosphate [13,14] vacuum pressure treatment with diammonium hydrogen phosphate and ammonium sulphate [15], and many others. However, studies specific to plywood made of radiata pine veneers, as mentioned earlier, are limited. ...
Wood and wood-based products are abundantly used, especially in structural applications, due to the impetus for sustainable development. The present work helps highlight the fire performance of plywood, one of the most used wood-based laminated structural components, under three different heat fluxes of 35 kW/m2, 50 kW/m2, and 65 kW/m2. The effects on the various fire reaction properties, namely, time to ignition, heat release rate, peak heat release rate, time to peak heat release rate, time to flameout, total burn time, and mass loss, were observed and reported. The times to ignition (42.2% and 35.4%), peak heat release rate (27.7% and 18.9%), flameout (22.2% and 28.6%), burn time (10.6% and 16.1%), and residual mass (25% and 53.3%) were reduced with the increase in heat flux from 35 kW/m2 to 65 kW/m2, respectively, whereas the peak heat release (21.7% and 2.4%) and ignition temperature (6.5% and 6.6%) were observed to increase. The vertical burning test (UL-94) illustrated the plywood samples to have a V-1 rating, with self-extinguishing capabilities. A numerical predictive model has also been developed based on the Fire Dynamics Simulator to predict the time to ignition, time to flameout, and heat release rate trend along with the peak heat release rate—it is shown to have good agreement with the experimental results, with an average correlation coefficient of 0.87.
... The set of regulatory documents stipulating technical safety parameters for buildings, requirements, classification and quality of all wooden elements and structures necessary for wooden construction play an important role in the modern wooden house construction development in Russia. Providing fire, sanitary and environmental safety including using fire protection methods to wooden building structures and cladding materials is still relevant [1][2][3][4][5][6]. ...
... A P-N-B FRW fire retardant prepared by the Northeast Forestry University of China has good flame retardation, corrosion prevention and insect prevention, and it can increase the flame retardation of wood to B1 level [19]. Yang impregnated veneers with ammonium polyphosphate, boric acid and borax, finding that the total heat release and total smoke output of plywood were decreased significantly, thus proving the good synergistic effect of ammonium polyphosphate, boric acid and borax in flame retardation and smoke inhibition [20,21]. According to Winandy's studies, the bonding performance of flame-retardant treatment would be decreased. ...
(1) A compound protectant was prepared using manganese chloride, phosphoric acid, boric acid and ammonium chloride, and then a veneer was immersed in the prepared protectant to prepare plywood in this paper. Great attention was paid to discussing influences of such protectant on fire resistance, decay resistance, anti-mold property and bonding performance of plywood. Results demonstrated that after protectant treatment, the plywood showed not only good fire resistance and smoke inhibition, but also strong char-formation ability, slow flame spreading, long time to ignition, small fire risk and high safety level. (2) The mass loss rates of plywood with protectant treatment after infection and erosion in wood-destroying Coriolus versicolor and Gloeophyllum trabeum were 19.73% and 17.27%, reaching the II-level corrosion grade. (3) There is not a significant difference with Aspergillus niger V.; however, it was possible to observe a strong difference with Trichoderma viride Pers. ex Fr., indicating that the protectant acted as a good anti-mold product for plywood. (4) The protectant influenced the bonding interface of wood and bonding conditions of the adhesive. The bonding strength of plywood was weakened, but it still met the requirements on bonding strength of GB/T 9846-2015. (5) The protectant changed the thermal decomposition and thermal degradation of plywood, inhibiting the generation of inflammable goods, blocking transmission of heats and lowering the thermal decomposition temperature of plywood. These promoted dehydrations and charring of wood and the generated carbon had a high thermal stability. (6) Compared with untreated plywood, the prepared protectant treatment significantly enhanced the fire resistance of plywood, reduced its biodegradability by wood-decaying fungi and showed good mold resistance.
... Therefore, this type of flame retardant is basically harmless to humans and the environment. The flame-retardant mechanism of phosphorus-containing flame retardants is divided into a gas phase and a condensed phase (Fig. 5) [56]. In the gas phase, phosphorus-containing functional groups are decomposed by heat to form PO • and PO 2 • free radicals, which can capture the high-energy free radicals H • and OH • released during the combustion of the polymer and quench the flame. ...
Compared with traditional metal tanks, prototype linerless composite cryogenic propellant tanks can achieve weight reductions up to 20%–40%. This prototype has recently become the trend in developing lightweight space vehicles. Moreover, this prototype promotes the research and development of new generations of inexpensive, high-capacity and recoverable space vehicles. In this review, the progress in research on composite cryogenic storage tanks by various space agencies is systematically analysed. Several key issues, including liquid oxygen compatibility and cryogenic mechanical and antileakage properties, in the process of manufacturing composite cryogenic tanks are summarised. Various solutions to these technical difficulties are briefly discussed. Finally, the directions that the development of composite cryogenic propellant tanks may take are explored.
... ESCI 2018 methods and approaches to fire protection could be distinguished. Those methods could be applied separately or in multiple combinations [6][7][8]. Thus, fire protection of building structures could be defined as a combination of methods and approaches which allow maintaining bearing and other design properties when exposed to fire during certain period of time. There are many aspects to consider such as an access of oxygen, air draft, and projected fire intensity depending on the presence of flammable substances in the premises [9][10][11]. ...
Fire protection of timber is represented by the combination of methods and techniques that allow maintaining bearing and other design properties of building structural units when exposed to fire during certain period of time. The variety of factors, such as an access of oxygen, air draft, and projected fire intensity should be taken into account while choosing efficient methods and techniques of fire protection. Along with that, when applying various methods of fire protection, it’s crucial to preserve natural properties of timber determining comfortable indoor climate. Within this context, “soft” timber modification is preferable. Thus, finding methods lowering combustibility of timber, while preserving its unique natural properties, represents the goal of this study. The present paper studies fire-proof efficiency of compounds based on mono-and di-ethanolamine-(N→B)-phenyl borates by means of ‘ceramic pipe’ method. Durability of shielding effect of the designed compositions was assessed by the method of determining ageing resistance. It was established that “soft” surface modification by the compositions based on mono-and di-ethanolamine-(N→B)-phenyl borates allows upgrading timber to the class of flash-resistant materials and enables to increase fire resistance significantly (period of fire resistance accounts for 90 min), along with that, protective effect remains after accelerated ageing of timber.
... It could be attributed to the grafted DMP decomposing and producing phosphoric and polyphosphoric acid, which stimulated the cotton fabric to form a protective char layer and protected the cotton fabrics from further burning (Alongi et al. 2013a, b). On the other hand, the nitrogen element also acted as a flame retardant in the gas phase, and the phosphorus and nitrogen elements played a synergistic flame retardant effect (Bogdanova et al. 2016). As a result, the flame retardancy of the cotton fabric was enhanced. ...
Phosphorus- and nitrogen-containing compounds were grafted on a cotton fabric surface by three steps. Firstly, the cotton fabric was oxidized by sodium periodate to form aldehyde groups, and then the aldehyde groups were reacted with the organic amine to generate Schiff bases. Finally, the Schiff bases were reacted with dimethyl phosphate by the phosphine hydride addition reaction. The chemical structure of grafted cotton fabric was characterized and confirmed. The results demonstrated that the limiting oxygen index (LOI) value of the modified cotton fabric dramatically increased from 19.5% for pure cotton fabric to 28.1% due to the chemical grafted on the cotton surface. After washing, the LOI value slightly decreased to 27.4%, which indicated that the prepared cotton fabric possessed superior washing durability. Thermogravimetry and cone calorimetry results demonstrated that the grafted flame retardant stimulated the thermal degradation and charring of cotton fabric ahead of time and formed sufficient char residue at high temperature, which efficiently prevented the underlying cotton fabric from degradation and combustion. Consequently, the flame retardancy of the cotton fabric was enhanced.
In this article, a P‐N synergistic flame retardant AG601‐DOPO (abbreviated as A‐D) was prepared by the reaction of tetrafunctional glycidyl amine epoxy resin (AG601) with 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO). The chemical structure of the product was confirmed by Fourier transform infrared (FT‐IR) spectroscopy and mass spectrometry (MS). Then, A‐D and bisphenol A benzoxazine (BA‐a) were mixed in different proportions to form a binary mixed system BA‐a‐A‐D (abbreviated as BAD) to improve the flame retardant properties of BA‐a. The results showed that the addition of A‐D can greatly improve the flame retardancy of BA‐a. When the content of A‐D was greater than or equal to 10%, the UL‐94 of BAD cured resin can reach the V‐0 rating. With the increasing of A‐D content, the LOI of BAD cured resin was increased from 23.8% to 37.1%. The results of cone calorimetry (CONE) test indicated that the total heat release (THR) was decreased from 120.7 to 78.2 MJ/m², and the decrease was 35.2%. In addition, the effect of the introduction of A‐D on the thermal stability and heat resistance of BA‐a resin was analyzed. It was found that the temperature of the BAD‐cured resin at 5% thermal weight loss (Td5%) was above 300°C and the glass transition temperature (Tg) was above 186°C, still maintaining good thermal properties. Finally, the mechanical properties of BAD cured resin decreased slightly without affecting the use of materials.
Because the existing fire prevention and extinguishing materials for coal mining cannot adhere to coal for long periods of time, this study investigated their colloid components. A colloid recipe of sodium silicate as the base material, sodium bicarbonate as the coagulation accelerator and sodium polyacrylate as the polymer additive was determined. An optimum proportion was obtained by orthogonal tests, whereby the ratio of water to solid was 4:1, sodium silicate accounted for 4%, sodium bicarbonate accounted for 5% and sodium polyacrylate accounted for 0.75‰. Comparing the performance of four other typical materials of fire prevention and extinguishing through contrast experiments, we observed that the new material has advantages of dropping the temperature, lowering the concentration of oxygen and carbon monoxide and increasing the concentration of carbon dioxide. In addition, a field test was conducted with the new material. After injection, three zones of spontaneous combustion showed clear changes: the oxidation temperature rise zone was ahead by 8 m, its length was shortened by 20 m and the choking zone moved up by 28 m. These changes indicated the improvement of colloid could significantly increase the effect of fire prevention and extinguishing materials.
Data on the influence exerted by the synthesis conditions and by the nature and relative amounts of precursor reagents on the properties of metal-ammonium phosphates, promising as components of fire-retardant and fire-extinguishing additives, are summarized and analyzed. The manner in which the solution pH and nature and relative amounts of the reacting metal-, nitrogen-, and phosphorus-containing compounds affect the phase composition, solubility, aggregative state, and fundamental aspects of thermal transformations of products being synthesized on the basis of di- and trivalent metal-ammonium phosphates in a wide temperature range is determined.
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