ПОРІВНЯННЯ ПОЛІОЛІВ ЯК КАРБОНІЗУЮЧИХ АГЕНТІВ ВОГНЕЗАХИСНИХ КОМПОЗИЦІЙ ІНТУМЕСЦЕНТНОГО ТИПУ

Purpose. To study the influence of the carbonizing agent structure on the formation of thermal insulating char layer of intumescent system acid donor/polyol and on the fire protection efficiency of the system at high temperatures. Methodology. A fire retardant mixture of an acid donor (phosphates ammonium, urea, melamine)/ polyol was chosen as a model intumescent system. Dispersion of vinyl acetate copolymer with ethylene was used as a polymeric component. The study applied the characteristics of the char layer of the intumescent composition at a certain temperature. The volumetric intumescent coefficient (K, cm3/g), mass of char residue (m, %), structure and density of the char layer are proposed as the main estimated parameters of flame retardant effect. IR spectroscopy was used to identify products of thermolysis of intumescent systems. Determination of fire protection efficiency of intumescent coatings was carried out in a mini-oven under standard fire conditions. Findings. The influence of polyol structure on the formation of thermal insulating char layer of intumescent acid donor/polyol system and the prediction of fire protection efficiency of this system under high temperature conditions has been investigated. It has been shown that under conditions of thermal shock the fire protection efficiency is more dependent on the nucleophilic reactivity of the polyol towards the unsaturated phosphorus atom of the acid donor than on its thermal stability. It has been found that pentaerythritol, dipentaerythritol, starch, dextrin, xylitol and sorbitol are the most effective carbonizing agents, regardless of the structure of the acid donor. It has been proved by infrared spectroscopy that at high temperatures as a result of the decomposition of pentaerythritol one of the reaction products is the aldehydes interacting with pentaerythritol with the formation of oligomeric compounds with a simple ether bond C-O-C. At the same time, pentaerythritol can be considered as a universal source of carbon framework for intumescent flame retardants regardless of the phosphate structure used. Originality. It has been shown that an important factor to increase the fire protection efficiency of intumescent systems is the use of polyols with an increased nucleophilicity in the esterification between polyol and phosphoric acid.Practical value. The optimal polyols as carbonizing agents for formulation of intumescent coatings with enhanced fire protection properties have been determined.

ПОРІВНЯННЯ АМІНІВ ЯК ГАЗОУТВОРЮВАЧІВ ВОГНЕЗАХИСНИХ КОМПОЗИЦІЙ ІНТУМЕСЦЕНТНОГО ТИПУ

Purpose. Study of influence of blowing agents amines structure on the construction processes of thermal insulating char layer of intumescent system ammonium polyphosphate/pentaerythritol/amine and fire protection efficiency of this system at high temperatures. Methodology. A fire retardant mixture of ammonium polyphosphate/pentaerythritol/amine was chosen as a model intumescent system. Dispersion of vinyl acetate copolymer with vinyl ether of versatic acid was used as a polymeric component. A step-by-step study of the characteristics of the char layer of the intumescent composition was applied in the study, consisting in the analysis of the characteristics of the char formed after keeping the intumescent composition samples at a certain temperature between 100 and 800 °C, char residue mass (m, %), structure and density of the formed char layer. The method of infrared spectroscopy was used for identification of products of thermolysis of intumescent systems. Determination of fire protection efficiency of intumescent coatings was carried out in a mini-oven under standard fire conditions. Findings. The influence of the structure of amines blowing agents on the formation of char layer of intumescent system ammonium polyphosphate/pentaerythritol/amine was studied. Physico-chemical parameters of char layer formed during high temperature swelling of intumescent system components with varying amine: urea, melamine, dicyandiamide, guanidine, thiocarbamide, formylthiosemicarbazide, thiosemicarbazide, phenylethylcarbamide have been determined. In the temperature range 200–400 oC for systems with linear amines (urea, thiocarbamide, thiosemicarbazide), there is a rapid formation of insulating layer with intense outgassing (high intumescent coefficients K) and the same rapid its destruction with significant losses of char residue mass (Δm). The presence of melamine, dicyandiamide and guanidine in intumescent system provides constancy of intumescent coefficient at minimal mass loss. Chemical transformations of intumescent systems were studied by the method of infrared spectroscopy when the investigated amines were varied. It was found that linear diamines do not form stable spatially branched phosphamide compounds with phosphates as the basis of a thermostable heat-insulating frame. At the same time in IR spectra of char residue systems with melamine, dicyandiamide and guanidine the absorption bands of P-N-C bonds (1070–1050 cm-1) and P-N (980–950 cm-1) up to 600–700 oC are observed. Fire tests proved that melamine, dicyandiamide and guanidine are blowing agents providing maximum protection of metal against fire and can be used for composition of fire retardants for steel constructions.Originality. It has been proved that amines in intumescent polyphosphate system perform at least two functions: blowing agents by means of thermal destruction to incombustible gases and nucleophilic compound that takes part in char layer formation by aminolysis of electrophilic substrates.Practical value. The optimum amine blowing agents for developing formulations of intumescent coatings with enhanced flame retardant properties have been established.

Flameless combustion of wood: charring and heat release characteristics

Introduction. The article presents the results of a research on the two stages of thermal decomposition of timber. The first stage of thermal decomposition is flame combustion, which is followed by a transition to flameless combustion due to the formation of a char layer on the surface of wood. The flameless process is accompanied not only by heterogeneous combustion, but, at least, three reactions: pyrolysis, thermal oxidative destruction of wood and oxidation of resulting coke.Goals and objectives. The goal is to identify the criteria of charring and heat release under the influence of an external radiative heat flux on samples of coniferous and deciduous species of wood using a standard flowthrough calorimeter with a focus on flameless combustion. Methods. A standard OSU flow-through calorimeter, produced by Atlas (USA), was used to identify heat release characteristics under the influence of external radiative heat fluxes that had the density of 20, 35 and 52 kW/m2. The lower limit of heat, released in the complete combustion of samples, that had a char layer, was identified using bomb calorimeter C-5000.Results. The co-authors analyzed the charring process and characteristics of heat release using samples of wood species that were 10 and 25 cm thick. Wood samples were exposed to combustion under the influence of an external radiative heat flux that had the density of 20, 35 and 52 kW/m2 subsequent to the results of tests, conducted using the OSU calorimeter. The co-authors evaluated the charring velocity and the coke layer thickness for the cases of flame and flameless combustion; efficient combustion heat release and the combustion completeness coefficient, as well as the sample shrinkage. The co-authors demonstrated that a transition from flame combustion to heterogeneous combustion occurs upon completion of the quasi-neutral burning of wood samples, which corresponds to the final point of heat release velocity curves and marks a transition from the behaviour of a thermally thick material to that of a thermally thin material.Conclusion. The obtained experimental data allow to forecast a change in the physical and heat engineering properties, characteristics of heat release in the processes of flame and flameless combustion of different wood species with account taken of the char layer formed on its surface under the influence of various heat fluxes.

A Novel Self-Assembled Graphene-Based Flame Retardant: Synthesis and Flame Retardant Performance in PLA

In this study, a novel flame retardant (PMrG) was developed by self-assembling melamine and phytic acid (PA) onto rGO, and then applying it to the improvement of the flame resistance of PLA. PMrG simultaneously decreases the peak heat release rate (pHRR) and the total heat release (THR) of the composite during combustion, and enhances the LOI value and the time to ignition (TTI), thus significantly improving the flame retardancy of the composite. The flame retardant mechanism of the PMrG is also investigated. On one hand, the dehydration of PA and the decomposition of melamine in PMrG generate non-flammable volatiles, such as H2O and NH3, which dilute the oxygen concentration around the combustion front of the composite. On the other hand, the rGO, melamine, and PA components in PMrG create a synergistic effect in promoting the formation of a compact char layer during the combustion, which plays a barrier role and effectively suppresses the release of heat and smoke. In addition, the PMrGs in PLA exert a positive effect on the crystallization of the PLA matrix, thus playing the role of nucleation agent.

Effect of Bagasse Fiber As the Renewable Environmentally Friendly Material on the Properties of the Waterborne Intumescent Fireproof Coating

Bagasse was applied as fire-retardant filler to prepare the waterborne intumescent fireproof coating. The effect of bagasse on the properties of the fireproof coating was investigated by fire protection test, thermogravimetric (TG), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), water resistance test and mechanical properties test. The result demonstrated the coating contained 1.5wt.% bagasse performed best in fire protection, thermal stability, oxidation resistance. Moreover, the char layer was dense and continuous. However, the fireproof coating contained 2 wt.% bagasse had excellent performance in water resistance test and mechanical properties test due to its properties of fiber. In addition, the components and chemical structure of char layer were characterized to study the flame retardant mechanism of bagasse in the fireproof coating.

Peanut Shell Derived Carbon Combined with Nano Cobalt: An Effective Flame Retardant for Epoxy Resin

Biomass-derived carbon has been recognised as a green, economic and promising flame retardant (FR) for polymer matrix. In this paper, it is considered that the two-dimensional (2D) structure of carbonised peanut shells (PS) can lead to a physical barrier effect on polymers. The carbonised sample was prepared by the three facile methods, and firstly adopted as flame retardants for epoxy resin. The results of thermal gravimetric analysis (TGA) and cone calorimeter tests indicate that the carbon combined with nano Cobalt provides the most outstanding thermal stability in the current study. With 3 wt.% addition of the FR, both peak heat release rate (pHRR) and peak smoke production rate (PSPR) decrease by 37.9% and 33.3%, correspondingly. The flame retardancy mechanisms of the FR are further explored by XPS and TG-FTIR. The effectiveness of carbonised PS can be mainly attributed to the physical barrier effect derived by PS’s 2D structure and the catalysis effect from Cobalt, which contribute to form a dense char layer.

Synthesis and application of nano-MH/MPB as intumescent flame retardant (IFR)

Magnesium hydroxide/melamine phosphate borate (nano MH/MPB), a novel nano-composition intumescent flame retardant, was synthesized with the in-situ reaction method from MgCl2·6H2O sodium hydroxide (NaOH) and melamine phosphate borate (MPB) in the absence of H2O. The structure of the product was confirmed by EDAX IR and XRD. The effects of reaction temperature and time on the dimension of magnesium hydroxide were observed. The effects of mass ratio of magnesium hydroxide to MPB on the flame retardancy of nano-MH/MPB/EP were examined with the limiting oxygen test. The results show that the optimal condition of synthesis of MH/MPB is mMH/mMPB = 0.25, reacting under 75 ℃ for 30 minutes. Finally, the mechanism for flame retardancy of nano-MH/MPB/EP was pilot studied by means of IR of char layer and TG of MH/MPB.

ПІДВИЩЕННЯ ВОГНЕЗАХИСНОЇ ЕФЕКТИВНОСТІ ІНТУМЕСЦЕНТНИХ ЕПОКСИДНИХ ПОКРИТТІВ СПОЛУКАМИ ІНТЕРКАЛЬОВАНОГО ГРАФІТУ

Investigation of the effect of nitrate oxide graphite on the parameters of char layer, obtained from the system of ammonium polyphosphate / melamine / pentaerythritol / epoxy resin under the influence of temperatures of 200–800 °С. Methodology. A fire retardant mixture was chosen as a model intumescent system ammonium polyphosphate / melamine / pentaerythritol. As a polymer component was used bisphenols A / F epoxy resin together with a polyamidoamine hardener. Nitrate oxide graphite was obtained by oxidation of natural scaly graphite with fuming nitrogen acid. The effect of impurities of nitrate oxide graphite was determined by thermogravimetry on the intumescence coefficient of intumescent compositions and the mass of the char residue intumescent compositions in temperature range of 200–800 °С. Findings. The influence of nitrate oxide graphite on the characteristics was studied of char layer of epoxy intumescent system ammonium polyphosphate / melamine / pentaerythritol / epoxy resin. The study of thermal oxidative degradation was carried out intumescent compositions in the temperature range 200–800 °С. It was shown that intercalated graphite compounds increase the thermal stability of the formed char layer at temperatures > 600 °С. Determined intumescence coefficients and thermogravimetric analysis of modified intumescent systems was performed nitrate oxide graphite with different degrees of intercalation, in the conditions of 200–800 °С. It was established that the optimal parameters of the char layer are in terms of volume intumescence coefficient and mass of the char residue are provided by graphites, which contain 15–25% of intercalant in its composition. But the results obtained allow us to determine nitrate oxide graphite as a promising modifier of epoxy intumescent systems to increase its fire protection efficiency. Originality. The influence of degree of intercalation of nitrate oxide graphite was studied on the characteristics of char layer of epoxy intumescent system for the first time. Practical value. The optimal content of intercalant in nitrate oxide graphite was established for the development of formulations of intumescent epoxy coatings with increased fire retardant properties.