The Effect of Flame-Retardant Additives DDM-DOPO and Graphene on Flame Propagation over Glass-Fiber-Reinforced Epoxy Resin under the Influence of External Thermal Radiation.

The flammability of various materials used in industry is an important issue in the modern world. This work is devoted to the study of the effect of flame retardants, graphene and DDM-DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-4,4'-diamino-diphenyl methane), on the flammability of glass-fiber-reinforced epoxy resin (GFRER). Samples were made without additives and with additives of fire retardants: graphene and DDM-DOPO in various proportions. To study the flammability of the samples, standard flammability tests were carried out, such as thermogravimetric analysis, the limiting oxygen index (LOI) test, and cone calorimetry. In addition, in order to test the effectiveness of fire retardants under real fire conditions, for the first time, the thermal structure of downward flame propagation over GFRER composites was measured using thin thermocouples. For the first time, the measured thermal structure of the flame was compared with the results of numerical simulations of flame propagation over GFRER.

Improving the Predictive Accuracy for Ketene in Diacetyl Laminar Premixed Flames: Experiment and Model Analysis.

Ketene is an important species in core mechanisms for the combustion of hydrocarbon and oxygenated fuels, but direct experiments with ketene are challenging to conduct due to its high reactivity. Diacetyl can be used as a precursor of ketene, and abundant ketene is present in premixed flames of diacetyl. However, predictions of ketene in diacetyl flames with previous models have significant uncertainties. The study of Sun et al. [Sun, W.; Wang, J.; Huang, C.; Hansen, N.; Yang, B. Combust. Flame, 2019, 205, 11-21, DOI: 10.1016/j.combustflame.2019.03.037] shows that the flame structure measurements should be performed under certain conditions to improve the predictive accuracy of ketene in diacetyl flames. In this work, the structures of three laminar premixed flames of diacetyl under atmospheric pressure in a range of equivalence ratios are examined with flame-sampling molecular-beam mass spectrometry (MBMS). With the new experimental data and the data available in literature, Bayesian analysis is performed to optimize the kinetic model. The obtained optimized model is compared with the original one, and the results show that the optimized model agrees better with the experimental data than the original one. The uncertainties of the rate coefficients of some key reactions are constrained with these experimental data, which eventually leads to smaller modeling uncertainties for ketene concentrations under studied conditions.

Flame-Retardant Glass Fiber-Reinforced Epoxy Resins with Phosphorus-Containing Bio-Based Benzoxazines and Graphene.

This paper presents a study of the flammability and thermal decomposition products of glass fiber-reinforced epoxy resin (GFRER) with the addition of cardanol-based phosphorus-containing benzoxazine monomer (CBz) and graphene and their combinations in different proportions (up to 20 wt.%). The addition of CBz alone or in combination with graphene resulted in an increase in the limiting oxygen index (LOI) and self-extinguishing in the UL-94 HB test. The flame-retardant samples had better tensile mechanical properties than the sample without additives. The differential mass-spectrometric thermal analysis (DMSTA) of the thermal decomposition products of GFRER without additives and with the addition of CBz and graphene was carried out. CBz addition promoted the thermal decomposition of high-molecular-weight products of epoxy resin decomposition in the condensed phase and at the same time decreased the time of release of low-molecular-weight thermal decomposition products into the gas phase. Graphene addition resulted in an increase in the relative intensities of high-molecular-mass peaks compared to GFRER without additives.

Cobalt-Imidazole Complexes: Effect of Anion Nature on Thermochemical Properties.

A solvent-free method was proposed for the synthesis of hexaimidazolecobalt(II) nitrate and perchlorate complexes-[Co(C3H4N2)6](NO3)2 and [Co(C3H4N2)6](ClO4)2-by adding cobalt salts to melted imidazole. The composition, charge state of the metal, and the structure of the resulting complexes were confirmed by elemental analysis, XPS, IR spectroscopy, and XRD. The study of the thermochemical properties of the synthesized complexes showed that [Co(C3H4N2)6](NO3)2 and [Co(C3H4N2)6](ClO4)2 are thermally stable up to 150 and 170 °C, respectively. When the critical temperature of thermal decomposition is reached, oxidative two-stage gasification is observed. In this case, the organic component of the [Co(C3H4N2)6](NO3)2 complex undergoes almost complete gasification to form Co3O4 with a slight admixture of CoO, which makes it attractive as a component of gas-generation compositions, like airbags.

CO2 Methanation: Solvent-Free Synthesis of Nickel-Containing Catalysts from Complexes with Ethylenediamine.

CO2 methanation was studied in the presence of nickel catalysts obtained by the solid-state combustion method. Complexes with a varying number of ethylenediamine molecules in the coordination sphere of nickel were chosen as the precursors of the active component of the catalysts. Their synthesis was carried out without the use of solvents, which made it possible to avoid the stages of their separation from the solution and the utilization of waste liquids. The composition and structure of the synthesized complexes were confirmed by elemental analysis, IR spectroscopy, powder XRD and XPS methods. It was determined that their thermal decomposition in the combustion wave proceeds in multiple stages with the formation of NiO and Ni(OH)2, which are reduced to Ni0. Higher ethylenediamine content in the complex leads to a higher content of metal in the solid products of combustion. However, different ratios of oxidized and reduced forms of nickel do not affect the initial activation temperature of nickel catalysts in the presence of CO2. It was noted that, after activation, the sample obtained from [Ni(C2H8N2)2](NO3)2 exhibited the highest activity in CO2 methanation. Thus, this complex is a promising precursor for CO2 methanation catalysts, and its synthesis requires only a small amount of ethylenediamine.

The Influence of Flame Retardants on Combustion of Glass Fiber-Reinforced Epoxy Resin.

For the first time, next to the flammability tests (LOI, UL-94 HB, VBB, TGA), experimental tests and computer simulation have been conducted on the flame spread and combustion of glass fiber-reinforced epoxy resins (GFRER) with 6% graphene and 6% DDM-DOPO flame-retardant additives. The downward rates of flame spread (ROS) in opposed flow with oxidizer and the upward ROS along GFRER composites have been first measured as well as the distribution of temperature over the combustion surface of the composites with flame-retardant additives and without them. The LOI and UL-94 HB tests showed a reduction in the flammability of GFRER when flame retardants were added and predicted a higher effectiveness of DDM-DOPO compared to graphene. Adding DDM-DOPO resulted in increasing the rate of formation of the volatile pyrolysis products and their yield, indicating, together with the other data obtained, the gas phase mechanism of the flame retardant's action. Adding graphene resulted in an increase in the soot release on the burning surface and an increase in the amount of non-volatile pyrolysis products on the burning surface, reducing the amount of fuel that participated in the oxidation reactions in the gas phase. The developed numerical combustion model for GFRER with a DDM-DOPO additive, based on the action of DDM-DOPO as a flame retardant acting in the gas phase, satisfactorily predicts the effect of this flame retardant on the reduction in downward ROS over GFRER for 45-50% oxygen concentrations. The developed model for GFRER with graphene additive, based on a reduction in the amount of fuel and increase in the amount of incombustible volatile pyrolysis products when graphene is added, predicts with good accuracy downward ROS over GFRER depending on oxygen concentration.

Propylene Oxide Addition Effect on the Chemical Speciation of a Fuel-Rich Premixed n-Heptane/Toluene Flame.

1,2-Propylene oxide (PO, C3H6O) is considered as a promising agent for improving fuel. In this work, the effect of PO additives on the species pool in a premixed burner-stabilized fuel-rich (ϕ = 1.6) flame fueled by n-heptane/toluene mixture (7/3 by volume of liquids) at atmospheric pressure is studied by the flame-sampling molecular beam mass spectrometry and numerical modeling in order to get insight into the chemical aspects of the influence of oxygenates with an epoxy group on the formation of abundant intermediates (including PAH precursors) during combustion of fossil fuels. The flames with various loadings of PO in the fuel blend (from 0 to 16.3% in mole basis) are examined, and detailed kinetic mechanisms available in the literature are validated against the measurements of mole fraction profiles of reactants, major products, and many intermediate species. A higher reactivity of the fresh mixture and a reduction in the peak mole fractions of intermediates playing an important role in PAH formation (benzene, styrene, ethylbenzene, phenol, acetylene, diacetylene, etc.) are observed when PO is added. This was found to be due to simultaneously two factors: the partial replacement of "sooting" fuel (toluene, which is the main precursor of these species) with oxygenated additive, and the changes in the flame radical pool caused by PO addition. Propylene oxide additive was found to change the ratio between H, OH, O, and CH3 toward an increase in the proportion of O and CH3. The detailed kinetic mechanisms considered in the work are found to overpredict the peak mole fraction of acetylene, a key species playing a crucial role in PAH growth. Its chemistry is revisited in order to provide a better prediction of C2H2 and, as a result, PAHs.

Mechanisms of the Action of Fire-Retardants on Reducing the Flammability of Certain Classes of Polymers and Glass-Reinforced Plastics Based on the Study of Their Combustion.

In the present review, using an integrated approach based on the experimental and theoretical study of the processes of thermal decomposition and combustion of practically important polymers, such as polymethyl methacrylate, polyethylene, and glass-fiber-reinforced epoxy resin, the features of the mechanism for reducing the combustibility of these materials with phosphorus-containing flame-retardants (FR), as well as graphene, are identified. A set of original experimental methods was developed and applied that make it possible to study the kinetics of thermal decomposition and the thermal and chemical structure of the flames of the studied materials, including those with FR additives, as well as to measure the flame propagation velocity, the mass burning rate, and the heat fluxes from the flame on the surface of a material. Numerical models were developed and tested to describe the key parameters of the flames of the studied polymeric materials. An analysis of the experimental and numerical simulation data presented showed that the main effect of phosphorus-containing fire-retardants on reducing the combustibility of these materials is associated with the inhibition of combustion processes in the gas phase, and the effect of adding graphene manifests itself in both gas and condensed phases.

Experimental and Numerical Study of Downward Flame Spread over Glass-Fiber-Reinforced Epoxy Resin.

For the first time, a comprehensive study of downward flame spread over glass-fiber-reinforced epoxy resin (GFRER) slabs in oxidizer flow has been carried out experimentally and numerically. Microthermocouples were used to measure the temperature profiles on the solid fuel's surface and in the flame, and a video camera was used to measure the rate of flame spread (ROS). The ROS was found to be linearly dependent on the oxygen concentration, to be inversely proportional to the slab thickness and not to depend on the direction of the flame spread over the slab. The absence of the influence of the forced oxidizing flow velocity and the weak influence of the GFRER pyrolysis kinetics on the ROS were observed. For the first time, a numerical model of flame spread over reinforced material with thermal conductivity anisotropy was developed on the basis of a coupled 'gas-solid' heat and mass transfer model, using modifications of the OpenFOAM open-source code. The sensitivity analysis of the model showed that the thermal conductivity in the normal direction to the GFRER surface had a much greater effect on the ROS than the thermal conductivity along the direction of flame propagation. The numerical results show good agreement with the experimental data on the dependences of the ROS on oxygen concentration, slab thickness and the N2/O2 mixture flow velocity, as well as temperature distributions on the fuel surface, the maximum flame temperatures and the flame zone length.

The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C2H8N2)3](ClO4)2 with Overlapping Stages.

This work describes the mathematical modeling of the thermal decomposition of the complex compound [Ni(En)3](ClO4)2 (En = C2H8N2 = ethylenediamine) in an inert atmosphere under non-isothermal conditions. This process is characterized by several simultaneous and intense stages: elimination of ethylenediamine from the nickel coordination sphere, decomposition of perchlorate anions, and explosive-like oxidation of free or bound ethylenediamine. These stages overlap and merge into a one step on the differential thermogravimetric curve. Typically, this curve is modeled as a one-stage process during kinetic analysis. In this paper, for the first time, the data from the dynamic mass-spectral thermal analysis and thermogravimetric analysis were modeled using the hybrid genetic algorithm, and the results were compared. A two-stage scheme of [Ni(En)3](ClO4)2 thermolysis was proposed and the kinetic parameters for each stage were obtained. It was shown that the decomposition of [Ni(En)3](ClO4)2 begins with the elimination of one molecule of ethylenediamine (stage A), then the perchlorate anions quickly decompose with the evolution of oxygen (stage B). We believe that the resulting ClO4-x- (x = 1-3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B).