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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.

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.

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. [ABSTRACT FROM AUTHOR]

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.

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.

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. [ABSTRACT FROM AUTHOR]

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).

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.

The solid-state combustion method was used to prepare nickel-based catalysts for CO2 hydrogenation from [Ni(C3H4N2)6](NO3)2 and [Ni(C3H4N2)6](ClO4)2. These complexes were synthesized by adding nickel nitrate and perchlorate to melted imidazole. The composition and structure of the obtained complexes was confirmed by ATR FTIR, powder XRD, and elemental analysis. The stages of thermal decomposition of the complexes and their kinetic parameters were established. It was found that incomplete gasification of more thermostable Ni(C3H4N2)6](ClO4)2 led to the formation of carbon, nitrogen, and chlorine impurities. According to powder XRD and XPS, the solid products of gasification of both complexes consist of NiO and Ni0 covered with nickel hydroxide and/or a carbonate layer. In the case of the sample prepared from [Ni(C3H4N2)6](ClO4)2, this layer was pronounced. Therefore, it limits the nickel reduction in the reaction medium of CO2 hydrogenation, even at 450 °C. The surface of the sample prepared from [Ni(C3H4N2)6](NO3)2 contains nickel oxide, which is easily reduced. So, the catalyst active phase is already formed at 250 °C in the presence of CO2 and efficiently catalyzes CO2 hydrogenation as the temperature increases. Therefore, [Ni(C3H4N2)6](NO3)2 is a promising precursor for the CO2 hydrogenation catalyst, and its solvent-free synthesis follows Green Chemistry principles.

Three-dimensional simulations of laminar flame propagating downwards the vertical surface of a rigid polyurethane slab heated by a radiative panel are presented and compared with the measurement data. The gas-phase model (ANSYS Fluent) allows for finite-rate volatile oxidation, soot formation and oxidation, emission, transfer, and absorption of thermal radiation. The solid-phase model Pyropolis considers heat transfer across the material layer and generation of combustible volatiles in thermal decomposition of the material. Kinetic model of material decomposition is derived to obey the microscale combustion calorimetry data for different heating rates. Transient behavior of propagating flame and pyrolysis zone, as well as spatial distributions of heat flux components, temperature, and mass burning rates over the specimen surface are examined. Variation of the thermal properties of the material during its thermal decomposition, as well as the specimen surface emissivity and reradiation are shown to be the important issues strongly affecting model predictions. Two distinct modes of counterflow flame spread, thermal and kinetic, are identified. In the thermal mode corresponding to fast chemistry in the gaseous flame, the flame propagation velocity is governed by the heating rate of the combustible material ahead of the flame front. Alternatively, in the kinetic mode, it is limited by the burning velocity of the volatile-air mixture forming ahead of the flame front. Simulation results are favorably compared with the measured propagation velocity.

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.

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.

Systematic experiments and complementing numerical simulations have been reported for the first time to understand the spread of a ground fire over pine needle bed of the Siberian boreal forests (Pinus silvestris) in still air. Using equipment and instrumentations specifically developed for the purpose, careful experiments have been conducted to reveal the effects of the bed width, fuel moisture content, fuel load, and the packing ratio on flame spread rate, temperature distributions in both gas and condensed phases. Temperatures are measured using fine thermocouples fixed at various locations from the bed surface. The surface temperature of the bed during flame propagation has been measured using a micro-thermocouple inserted in a single pine needle in the bed as well as using an infrared (IR) camera. Further, for the first time, the total and radiant heat fluxes from the flame to the bed surface have been measured using compact cooled sensors placed inside the needle bed, over which the flame propagates. In order to understand more about the flow field and flame spread process, a 3D numerical model based on the Fire Dynamics Simulator (FDS) has been used to simulate few of the experiments. The processes governing pine needle pyrolysis, char oxidation, gas phase combustion and radiation have been modeled using simplified approaches reported in literature. The model is capable of predicting experimentally measured flame propagation velocities for most of the cases quite well. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 ClO 4 − x − (x = 1–3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B). [ABSTRACT FROM AUTHOR]