DETECTING THE REGULARITIES OF PROPAGATION OF AN UNSTABLE FLAME FRONT USING OPTICAL 4D SPECTROSCOPY AND COLOR HIGH-SPEED FILMING
Аннотация и ключевые слова
Аннотация (русский):
The main objective of this book is to acquaint the reader with the main modern problems of the multisensor data analysis and opportunities of the hyperspectral shooting being carried out in the wide range of wavelengths from ultraviolet to the infrared range, visualization of the fast combustion processes of flame propagation and flame acceleration, the limit phenomena at flame ignition and propagation. The book can be useful to students of the high courses and scientists dealing with problems of optical spectroscopy, vizualisation, digital recognizing images and gaseous combustion. The main goal of this book is to bring to the attention of the reader the main modern problems of multisensory data analysis and the possibilities of hyperspectral imaging, carried out in a broad wave-length range from ultraviolet to infrared by methods of visualizing fast combustion processes, propagation and flames acceleration, and limiting phenomena during ignition and flame propagation. The book can be useful for students of higher courses and experimental scientists dealing with problems of optical spectroscopy, visualization, pattern recognition and gas combustion.

Ключевые слова:
Remote measurements, optoelectronic methods, multisensor data analysis, hyper spectral shooting, ramjet engine, Catalytic Stabilization
Текст
It is shown that when the propagation of the FF flame front from spherical to propagation in a pipe occurs, phenomena caused by instability flat flame by the example of combustion of stoichiometric mixtures of n-pentane (C5H12) with air, diluted with carbon dioxide (CO2) and argon (Ar), at total atmospheric pressure. It is shown that, upon deceleration of the FF near the end wall of the reactor, a smooth FF acquires a cellular structure. It is shown that qualitative modeling of the results obtained is possible when analyzing the Navier-Stokes equations for a compressible medium in the approximation of a small Mach number. Using the methods of 4D optical spectroscopy and color high-speed filming, the features of combustion in flame cells caused by hydrodynamic instability have been experimentally observed for the first time. It is shown that any combustion cell is essentially a separate “chemical reactor”, in each of which the process of complete chemical transformation is carried out. Key words: flame front, hydrodynamic instability, flat flame, cellular structure, hyperspectrometer, color high-speed filming Let us recall that in real conditions, the processes of gas-phase combustion proceed under conditions of unsteady flows, fluctuations in density and pressure, i.e. are nonstationary [1]. As shown by L.D. Landau, from a hydrodynamic point of view, a flat flame should be unstable [2]. This Chapter is devoted to the consideration of combustion in unsteady and unstable modes. The main attention is paid to the use of the methods of color high-speed filming and 4D optical spectroscopy, which makes it possible to register the intensity of the optical spectrum simultaneously depending on the wavelength, time and coordinate to establish the features of these processes. Unstable modes manifest themselves in combustion processes in various forms and can be classified as thermal diffusion, hydrodynamic and thermoacoustic [3-9], see also Chapter 3. Determining the nature of the chemical transformation during unstable combustion is an urgent problem both from the point of view of theory and in practical applications related to both the intensification of combustion and the issues of explosion safety. Experimentally, this issue was solved for the case of thermal diffusion instability, for which it was necessary to carry out experiments under zero gravity on the ISS. In [10], it was experimentally shown for the first time that in the presence of instabilities of a thermodiffusion nature (lean mixtures of hydrogen with oxygen), in zero gravity, there is a mode of formation of separate isolated stationary combustion cells. In other words, there are separate "chemical reactors" in a combustible environment. In this regard, we note that more than 50 years ago Zeldovich [4] showed that stationary heating and mass conservation equations admit a solution corresponding to a stationary spherical flame, although the same governing equations in plane geometry admit a solution in the form of a combustion wave. In the simplest case of spherical geometry, the solutions of the stationary equations of free convection for temperature T and chemical particles C: 2T = 0 and 2С in polar coordinates have the form c1 + c2/r, where c1 and c2 – constants. This form satisfies the requirement that T and Y are bounded as r. For cylindrical and planar geometries, the corresponding solutions have the form c1 + c2 ln(r) and c1 + c2r, respectively, which are obviously not bounded as r. For this reason, the theory allows stable solutions for a ball of flame, but not, say, a "cylinder of flame". It is these stable balls of flame predicted by Ya. B. Zeldovich that were observed in [10]. Despite the fact that the internal hydrodynamic instability of a flat flame has been recognized for almost a century, and that the first attempts at an analytical description were made more than fifty years ago, data on experimental measurements of the growth rates of flat flame perturbations began to appear in the literature relatively recently. One of the reasons for this is the experimental difficulty of controlling the initially flat front of the flame of premixed mixtures in a regime in which the flat front is unstable. A direct experimental test of Landau's hypothesis was carried out in [11]. Note that the FF is not characterized by only one characteristic frequency, but by a set of frequencies, which leads to the existence of regions of flame instability, often manifested in the appearance of cellular structures during combustion [2-5]. An important feature is that the boundaries of the instability region shift with an increase in the acoustic amplitude, i.e. it is possible to stabilize a planar phase transition with respect to hydrodynamic instability using an external acoustic field. In [11], an experiment was described in which the growth rate of cellular structures at the boundary of a plane flame was directly measured. The flat shape of the unstable laminar flame front was maintained by imposing an acoustic field. The growth rate of two-dimensional disturbances in time was observed after the acoustic field was turned off. Thus, Landau's hypothesis was verified by imposing an external factor i.e. an acoustic field. This experiment also illustrates the relationship between the main factors causing the instability of hydrodynamic and acoustic flames [9]. In experiments with a spherical FF, conditions are possible under which an unperturbed regime can be realized at a certain stage of FF propagation, since perturbations of a spherical FF develop more slowly than a flat flame [12]. The instability of a spherical flame has a specific character associated with the fact that its front surface area is continuously growing. If the disturbances on the spherical FF increase more slowly than according to the linear law when the radius of the sphere as a whole grows, the FF smoothes out over time, despite the increase in the absolute value of the amplitude of the curvatures. The properties of the flame in this case approach the properties of an undisturbed spherical FF [12]. Thus, in a spherical flame, disturbances grow in time more slowly than in a flat flame [12]. However, after the phase transition loses its spherical shape, for example, during propagation in a cylindrical channel, the conditions for the rapid growth of the phase transition surface disappear and the instability predicted by L.D. Landau [2]. In such an experiment, no external flame stabilization is required, since the initial spherical FF is initially undisturbed until it touches the reactor walls. In this Chapter, using the example of the combustion of mixtures of n-pentane with air, the spatial propagation of a FF in a reactor of constant volume is investigated under conditions when the FF loses its spherical shape and the hydrodynamic instability of a plane flame front according to Landau is manifested. We assumed that the deceleration of the FF and the reaction products upon touching the FF wall would be accompanied by the onset of combustion instability. In this case, an additional reason for the instability of combustion under our conditions will be the splash of cold gas from the mains and its ignition, as well as the amplification of acoustic vibrations that repeatedly pass through the FF. In order to find out the features of the described unstable combustion regime in this Chapter, the spatial propagation of the FF of stoichiometric mixtures of n-pentane with air in the presence of inert gas additives, at 1 atm and an initial temperature of 298 K in a constant-pressure bomb was investigated by methods of high-speed color photography and optical 4D spectroscopy. It should be noted that in stoichiometric flames of mixtures diluted with an inert gas, one should not expect the appearance of instabilities of either a thermodiffusion (there is no large difference in the transfer coefficients) or a thermoacoustic nature (the normal flame propagation rate is low). Experimental part The experiments were carried out in a cylindrical reactor with a volume of 2826 cm3 made of stainless steel, 25 cm long and 12 cm in diameter, equipped with removable covers and an optical quartz window at the end. Here a photograph of a setup for studying combustion is shown in fig. 1a where: 1- stainless steel reactor, 2- optical quartz glass, 3- line along which the hyperspectral survey was carried out, the width of which is about 1 mm (see Chapter 2). Figure 1b shows a diagram of this installation where: 1- reactor, 2- electric heater, 3- thermal insulation, 4- valves, 5- mixer, 6- optical window, 7- digital film camera, 8- hyperspectrometer, 9- pressure sensor, 10 - information recording system based on ADC and computer, 11- digital millivoltmeter, 12- spark ignition system). In the center of the reactor, spark ignition electrodes were located, the distance between which was 0.5 mm. Fig. 1. a - photograph of the installation for studying combustion; b - block diagram of the experimental installation. The experiments were carried out in the following sequence. A combustible mixture of a given composition prepared in advance in a cylinder was admitted into the reactor to the required pressure, and then ignition was initiated with a spark (1.5 J). Registration of the FF ignition and propagation was carried out through the optical window with a hyperspectrometer and a color high-speed film camera (Fig. 2) Casio Exilim F1 Pro (frame rate - 60 - 1200 s-1). The data obtained were recorded into the computer memory and then processed. Chapter 2 details the experimental setup using a hyperspectrometer and high-speed video (see Figure 16 in Chapter 2). Let us briefly recall that spectroscopic measurements were carried out using a 4D spectrometer (hyperspectrometer), which allows simultaneous measurements of spectral and spatial coordinates [13, 14]. A hyperspectrometer (of the push broom type) registers a narrow band on the sensed object at the same time. Registration is carried out on a two-dimensional photodetector matrix, according to one coordinate of which the spatial coordinate is measured, and according to the other - the spectral one (wavelength). Two more (up to 4D dimensions) are signal intensity and time. Fig. 2. The location of the high-speed video camera for filming the combustion process. Since the data are taken from the photodetector matrix of the hyperspectrometer at a frame rate of up to 300 Hz, the time dependence of the emission spectra of the combustion process is thus recorded. In this work, both video recording of the combustion with a video camera and registration of the combustion process with a hyperspectrometer were carried out, and then the obtained data were compared. The measurements were performed using a VID-IK3 hyperspectrometer [14] (see Chapter 2). Before each experiment, the reactor was evacuated using a 2NVR-5D forevacuum pump. The pressure in the reactor was monitored with an exemplary pressure gauge and a vacuum gauge. Gases Н2, n-pentane (n-С5Н12), Аr, CO2, CCl4 were of the "okhch" grade. Carbon tetrachloride CCl4 was used as a combustion inhibitor for n-pentane. Experiments in a stainless steel reactor were carried out with pre-prepared mixtures of 40% H2 + air + (0 ÷ 1%) CCl4 and stoichiometric mixtures of n-pentane (n-C5H12) with air diluted with argon (Ar) or carbon dioxide (CO2) at total atmospheric pressure. Ar additions to the previously prepared stoichiometric mixture of 2.5% С5Н12 - 97.5% air were 15%, СО2 - 10%, CCl4 additions to a diluted stoichiometric mixture of n-pentane with air were up to 2%. Fig. 3. Location of the IR-VID3 hyperspectrometer (1) on the rotating device (2) Results and discussion of experiments It was found in preliminary experiments with mixtures of 40% H2 with air that, in accordance with [5], additions of CCl4 in an amount of up to 2% to this mixture do not noticeably affect either the flame front propagation velocity or the FF emission spectrum in the visible region. Therefore, for the presentation in this work, we have chosen the most illustrative pair “film - spectrum” for a hydrogen – air mixture. The results of video recording of the combustion of a mixture of 40% H2 with air and the addition of 1% CCl4 at a pressure of 1 atm in a stainless steel reactor with a frame rate of 600 s-1 is shown in fig. 4. The number on the frame corresponds to the frame number when shooting. Combustion was initiated by a spark in the geometric center of the reactor. The frames of high-speed filming with a frame rate of 600 s-1 of the propagation of FF of mixtures of n-pentane with air for various compositions of combustible mixtures is shown in fig. 5-7. In these frames, after the moment of initiation, stationary propagation of the FF is observed until the moment it touches the side surface of the reactor. The number on the frame corresponds to the number of the frame during filming. It can be seen that the FF is deformed near the openings of the gas supply lines (Fig. 4, frame 31; Fig. 7, frame 50).Further propagation of the FF continues in the cylindrical part of the reactor in the direction of the end. In this case, the injection of a cold combustible mixture from the volume of the mains into the combustion products in the reactor is observed (Fig. 6). Fig. 4. Result of frame-by-frame processing of filming of initiated ignition of a mixture of 40% H2 with air and 1% CCl4 addition. It can be seen that the FF is deformed near the openings of the gas supply lines (Fig. 5, frame 31; Fig. 7, frame 50). Fig. 5. The result of time-lapse processing of filming of the process of propagation of a spherical flame front of a stoichiometric mixture of pentane with air and 10% CO2. Further propagation of the FF continues in the cylindrical part of the reactor in the direction of the end. In this case, the injection of a cold combustible mixture from the volume of the mains into the combustion products in the reactor is observed (Fig. 6). When passing to the combustion regime in a cylinder in diluted by Ar or CO2 + CCl4 mixtures, disturbances in the form of cells appear on the FF surface. Fig. 6. Filming of the process of propagation of a spherical flame front for a mixture of 80% (C5H12 + O2) stoich. + 20% Ar. Indeed, the FF radius grows so rapidly that instability does not develop against this background at the stage of a spherical flame, and the FF is not disturbed [12]. At the stage of propagation along the reactor, a hydrodynamically unstable flat flame arises, as predicted by theory [2]. This instability, as can be seen from Fig. 6 and 7, is expressed in the formation of cellular structures at the flame front. The formation of cells is characteristic for a certain degree of dilution with an inert additive. In fast-burning (not diluted with an inert gas) mixtures, cells are not recorded. In flames of combustible mixtures diluted with argon, the cellular structures are located motionless in space, while the size of the cells grows slightly (Fig. 6). With an increase in the degree of dilution of the stoichiometric mixture and the use of carbon dioxide and CCl4 instead of argon as a diluent, the cellular structures shift in the direction of gravity, the cell size stabilizes. In other words, it can be verified that their size distribution remains practically constant until the end of combustion, while the combustible mixture burns out near the bottom of the reactor (Fig. 7). Fig. 7. Result of frame-by-frame processing of filming of the process of propagation of a spherical flame front of a stoichiometric mixture of pentane with air + 10% CO2 + 1% CCl4. Let us carry out a qualitative examination of the propagation of a flame in a two-dimensional channel using the example of a plane problem in the "side view" projection in order to compare the results of the qualitative calculation with the experimental ones and to establish further directions for modifying the calculation. In this case, both the interaction of the FF with the end wall of the reactor and the transition of the FF of a circular shape to propagation in a flat channel upon initiation by a point source will be considered. As indicated above and as is known from the literature [16], the relationship between the main factors causing the instability of hydrodynamic and acoustic flames can be taken into account when considering the Navier-Stokes equations for a compressible medium in the acoustic approximation (which corresponds to substantially subsonic flames). Let's make a few important notes. It is well known that theoretical calculations of combustion processes carried out on the basis of kinetic schemes containing hundreds of elementary reactions do not have predictive power. Indeed, the overwhelming majority of rate constants and their temperature coefficients are not accurate enough to make reliable conclusions based on calculations with such errors. Typically, the value of error in the experimental determination of rate constants is from 50% to two orders of magnitude, and this is in the case of experimental determination. On the other hand, the problem of the completeness of the used kinetic mechanism remains unresolved, i.e. whether any important reaction that affects the ignition and combustion parameters has been missed. Moreover, since there are no uniqueness theorems for the solutions of the Navier-Stokes equations in a compressible reacting medium, the correspondence of the calculated profiles, for example, of intermediate reagents to the experimental, is not an argument in favor of the agreement between the calculation and experiment. There may be several sets of governing parameters describing the same profiles (until proven otherwise). In this sense, the following consideration of the Navier-Stokes equations in a reacting medium is only of a qualitative nature. It is due to the lack of evidence of the uniqueness of solutions for this type of systems of equations that we do not consider a detailed kinetic mechanism, but restrict ourselves to one activated reaction or the simplest chain mechanism (see below). Thus, a comparison of the recorded picture of the movement of the glow front and the result of the calculation, carried out without the involvement of a detailed kinetic mechanism in the form available today, is possible only qualitatively according to the trend of change in the speed of the front, namely, the interface between the initial "fresh" and actively reacting medium, as well as the nature of this boundary - the degree of its "smoothness" and disturbances of its structure. The Navier-Stokes equations for a compressible reacting medium in the low Mach number approximation were proposed in [16-20]. The indices t, x, y, z denote differentiation with respect to t, x, y, z. T = P t + u)x + (v)y + (w)z = 0 (vt +u ux +vuy +wuz) + P x /M 2 = 1/Fr + Sc(2u + 1/3 Kx) (ut +u vx +vvy +wvz) + P y / M 2=1/Fr + Sc(2v + 1/3 Ky) (I) (wt +u wx +vwy +wwz) + P z/ M 2 =1/Fr + Sc(2w + 1/3 Kz) [Tt +u Tx+v Ty+w Tz] - (Pt -(-1)M 2[P t +u P x +v P y +w P z] = 2T +1W [Ct + v Cy + uCx+ w Сz] = 2C - W W = (1-C) exp(/T), where K = ux + vy + wz, - viscous dissipation term, 2 - three-dimensional Laplace operator. P(x,y,t) = P0(t) +M2p2(x,y,t) + O(M3), P0(t) – static pressure, which is calculated based on conservation laws [17] , p2(x,y,t) – dynamic pressure. Here, (u, v, w) – velocity components in directions (x, y, z) respectively;  -density; T –temperature. The chemical reaction is represented by a one-step first-order Arrhenius reaction; Р - pressure, C – concentration of the reactant, 1-С - degree of conversion,  - dimensionless coefficient which has meaning E/R, where Е - activation energy, R - gas constant. Dimensionless parameter is Schmidt criterion Sc = v/D , D – diffusion coefficient, kinematic viscosity,  - ratio of heat capacities at constant pressure and constant volume; 1 characterizes the release of heat per unit of concentration С,  - kinetic coefficient proportional to the second Damköhler number [19]. Density, temperature, pressure and concentration are made dimensionless using the initial values 0=0.001 g/cm3 [5], T0 =1, P0 = 0T0,=10.5, =1.4,  =0.2, 1 =0.3, CP =0.3 0.3 cal/g.degrees [5] and С0=0, respectively. The Lewis number is assumed to be Le =1, which implies the equality Sc = Pr, where Pr =0CP v/ ,  - thermal conductivity and Cp – heat capacity at constant pressure. The length and speed scales are defined as l2d = Dtd , and Ud = ld / td, respectively. Then the Reynolds number, taking into account the choice of ld and Ud has the form Re = ld Ud / v = 1 / Sc. The Froude number Fr = Ud2/gld, where g - the gravitational acceleration, was taken equal to 0.07. The Mach number is defined as М =Ud /с0 and is taken equal to 0.025, where с0 – speed of sound. Obviously, if М=0, there are no pressure fluctuations. At M →0 the initial value of the average pressure P0 becomes much higher than the average value of ρ0Ud2 for pressure fluctuations around the average pressure P0. The velocity field as a function of the pressure gradient is determined by these pressure fluctuations around its mean value. If the standard pressure representation is used, then the usual change of variables P = P0p leads to the appearance of the factor 1/M2 in the grad p term in the momentum equation [16, 17, 20]. We will consider a two-dimensional problem and exclude the z coordinate: T = P (a) t + (v)y + (pu)x = 0 (b) (ut +vvy +uvx) + P y/M 2 =1/Fr + Sc(2v + 1/3 Ky) (c) (vt +vuy +uux) + P x/M 2 =1/Fr + Sc(2u + 1/3 Kx) (d) (II) [Tt+v Ty +u Tx] - (P t -(-1)M 2[Pt +u Px+v Py] = 2T +1W (e) [Ct + v Cy + uCx] = 2C  W (f) W = (1-C) exp(/T) (g) Ptt – 1/M22P = q(CP -1) Wt (h) where 2 = ( )yy + ( )хх two-dimensional Laplacian, K = vy + ux, Ptt = D2P/Dt2 , D( )/Dt - substantial derivative. In the calculations, it was assumed that the pressure values satisfy the wave equation (the last equation of system (II)), which, under the assumption of small disturbances introduced by the wave, can be obtained from the equations of continuity and conservation of momentum, taking into account internal energy sources and neglecting terms of order 1 / M4 [16, 17, 21, 22]. In a number of calculations, the reaction rate was set not by the Arrhenius equation, but using the simplest chain mechanism: С  2n (w0) and n + C  2n + products, described by Arrhenius's law. In this case, equations (f) and (g) of system (II) were replaced by the following equations: [Ct + v Cy + u Cx] = 2C - n W [nt + v ny + u nx] = 2n + 2n W W = C exp( - /T) The initial condition for the concentration of the mother substance changes to С0 = 1, n0 = 0. Since the last equation (h) of system (II), which describes wave processes in a moving inhomogeneous medium with internal heat sources, is obtained using the continuity equation and the equation of conservation of momentum (q = ld2/(Ud40) – It is a parameter that arises when the system is reduced equations to dimensionless form and in the subsequent qualitative calculation set equal to one), then system (II) is redefined. In order for the number of equations to correspond to the number of unknowns, the first-order equation (b) was excluded from system (II) during further analysis. The use of equation (h) provided a significant acceleration of the calculations carried out in this section, within the framework of the software package used in this work. This problem was solved by the finite element method using the software package (FlexPDE 6.08, A Flexible Solution System for Partial Differential equations, 1996-2008 PDE Solutions inc. [23]). The system of equations (II) was solved in an area. On the left boundary, the initiation condition T = 10 (initial dimensionless temperature T = 1) was set by a step (Fig. 8). At the boundaries of the region, dC/dx =0, dC/dy =0, n=0 and the convective heat transfer condition dT/dt =(T-T0), u=0, v=0, d/dx =0, d/dy =0. The results of a qualitative calculation of the interaction of a phase transition in a flat channel with an end wall in order to establish the effect of gravity on the evolution of cellular structures and compare the obtained qualitative results with experiment are shown in fig. 8. In this figure, the time in seconds is given under each "frame", the top row of the image refers to the absence of gravity. In each "frame" of the bottom row, gravity is directed from top to bottom. The bottom row shows a scale of dimensionless temperatures. In this case, initiation by a section and not point initiation of the opposite end is specified for reducing the calculation time. After initiation, a stationary combustion wave propagates from left to right that is shown in fig. 8. When the combustion wave approaches the right end, a cellular structure appears, which at g = 0 moves uniformly from left to right. The size of the cells increases slightly over time. In the presence of gravity (the bottom row of images in Fig. 8), it can be seen that the FF first approaches the "upper" part of the right boundary of the computational domain and only then to its "lower" part. Accordingly, the cellular structure moves “from top to bottom,” in qualitative agreement with experiment (Fig. 7). It can also be concluded from fig. 8 (top row of images) that if the flame velocity is high enough (an increase in Re), then the gravity does not have time to influence the flame propagation (i.e., formally, g0 takes place), and an immobile cellular structure with a weakly growing cell size should be observed. This is also in qualitative agreement with experiment (Fig. 6). When analyzing the combustion kinetics set by the chain mechanism, the calculation results are the same as those shown in Fig. 8 for  = 7, i.e. in accordance with work [5], the effective activation energy of the process proceeding by the chain mechanism is lower than for the molecular reaction described by the Arrhenius law. Thus, the patterns of evolution of the experimentally observed cellular structure obviously depend on the form of the heat release function, which is determined by the kinetic mechanism of the reaction. It is obvious that in order to proceed to the description of the quantitative regularities of the formation of regular structures on the FF, it is necessary to analyze the three-dimensional model. At the same time, the results of two-dimensional modeling are in qualitative agreement with the above-noted interrelation of the main factors responsible for the instability of hydrodynamic and acoustic flames. Since the interpretation of the cellular structure observed in our experiments in the interaction of the FF with the wall requires taking into account both hydrodynamic and acoustic parameters of burning gas. Fig. 8. Calculated dependences of the two-dimensional thermal field on time during the propagation of the flame front to the channel wall. The data obtained, in agreement with the information presented in the Introduction, indicate the gas-dynamic nature of the cellular structure of the phase transition observed in our experiments at the end of combustion. Thus, the cellular combustion mode is caused by the gas-dynamic instability inherent in plane flames [2]. It should be noted that the dependence of the FF structure and the role of this structure in the evolution of the flame front in a reactive gaseous medium on the initial conditions, in particular on the size of the reaction volume, have not yet been sufficiently investigated and require further study under conditions of large volumes. We point out that the above numerical simulation only allowed to establish the hydrodynamic nature of the flame instability. However, it does not allow us to reveal the features of combustion in each individual cell, in particular, due to the conventionality of the reaction kinetics considered in the simulation. This issue was solved experimentally using 4D spectroscopy, which allows recording optical radiation spectra from a given point in space. It allowed to obtain a spectrum emitted both from the boundary between the cells and from the inner region of the flame cell under our conditions. Hyperspectral cubes of the investigated combustible mixtures: 40% hydrogen + air + 1% CCl4, stoichiometric mixture of pentane with air + 10% CO2, stoichiometric mixture of pentane with air + 10% CO2 + 1% CCl4 are shown in Fig. 9 a-c. In Fig. 9 a-c, the x-axis corresponds to the red line in Fig. 1, and the y-axis corresponds to the dependence of the combustion process on time. Each line y corresponds to one frame of information accumulation on the photodetector matrix of the hyperspectrometer (300 frames / s). The optical combustion spectra of a mixture 40% H2 + air + 1% CCl4, recorded along a vertical line along the diameter of the optical window (line 3, Fig. 1), are shown in Fig. 10. It should be noted that the hydrogen flame at low pressures is practically invisible, since its radiation is mainly due to the radiation of hydroxyl radicals ОН А2–X2 in the ultraviolet region at 306 nm [24]. Attention is drawn to the features of the flame spectrum in the visible region, namely, the system of radiative bands in the region of 570 - 650 nm. They “visualize” the hydrogen flame at elevated pressures along with the lines of sodium (581 nm) and potassium (755 nm) atoms inherent in all hot flames [24] and in this case emitted from the region filled with combustion products. It can be seen from fig. 10 that at the selected time instant one FF is recorded along the x axis, located between coordinates 234 and 140. While the intensities of all spectral lines from the spectrum with coordinate 234 to the spectrum with coordinate 1 change symbatically. There is no situation when the intensity of the bands in one region of the spectrum in space increases, and in the other region of the spectrum decreases. This is due to the fact that the observed spectral lines belong only to the reaction products or appear in the zone of the reaction products (Na, K). They indicates the stability of the hydrogen combustion flame front (the presence of only one phase transition), which can also be seen from the high-speed filming frames given in fig. 4. Bands in the region of 600 nm were also observed in a hydrogen flame in [25]. Below is table 4 from work [25], in which the assignment of the bands in Fig. 12 to water vapor, which is a product of the hydrogen oxidation reaction. Fig. 9. Hyperspectral cubes: a) combustion of 40% hydrogen in air, b) combustion of a stoichiometric mixture of n-pentane with air and 10% CO2, c) combustion of a stoichiometric mixture of n-pentane with air, 10% CO2 and 1% CCl4. Fig. 10. Combustion spectrum of a mixture of 40% hydrogen + air + 1% CCl4, pressure of 1 atm along the red line y = 15 (Fig. 1a). Table Comparison of the radiative bands of a hydrogen flame with sheets of water. I II III Quantum by R. Mecke Quantum numbers Radiant flame band Difference Water vapor absorption band No.  No. cm cm No. cm 1 17495.44 3, 2, 0 2 17492 + 3  2 16898.44 1, 4, 0 7 16878 + 21 2 16903 3 16821.62 1, 3, 2 8 16807 + 15 3 16821 4 15832.47 3, 1, 1 15 15815 + 17  5 15347/90 1, 3, 1 20 15340 + 8 4 15340 The combustion spectrum of a stoichiometric mixture of pentane with air + 10% CO2 is shown in fig. 11. This spectrum contains intense lines of atoms of alkali metals Na, K and bands of water vapor [26, 27]. All these particles appear in the zone of the reaction products. The absence of emission bands of intermediate products of the oxidation of hydrocarbons (С2, СН) is due to the fact that the intensity of the “hot” lines of atoms is high in comparison with the intensity of the emission bands of intermediate particles С2 and СН. A decrease in the reaction rate by introducing an active chemical additive (CCl4 in this work) should allow registration of the emission of C2 and CH particles, which will be demonstrated below. When analyzing the hyperspectral cube for the combustion spectrum of this combustible mixture (Fig. 9b), it was also found that only one FF is recorded at the selected time. The intensities of all spectral lines (Fig. 11) change in the same symbatic manner as in the case of a flame combustion of hydrogen, since all of them, as indicated above, belong to the reaction products. The result obtained indicates the stability of the flame front of a stoichiometric mixture of pentane with air + 10% CO2, which can also be seen from the high-speed filming frames shown in Fig. 5. It was shown above that the combustion of stoichiometric mixtures of pentane with air upon dilution with argon and CO2 becomes unstable and becomes cellular in the transition to combustion in a cylindrical tube. Fig. 11. Combustion spectrum of a mixture of pentane with air + 10% CO2, pressure 1 atm (point x = 105, y = 228). Let us consider the experimental results on the study of this cellular flame, caused, as established above, by gas-dynamic instability, by 4D spectroscopy. A typical frame characterizing the cellular combustion of a stoichiometric mixture of pentane with air with additions of 10% CO2 and 1% CCl4 at a total pressure of 1 atm is shown in figure 12a. A hyperspectral cube for this image along the vertical axis in the blue region C is demonstrated in fig. 12b. In Fig. 12c a fragment of this cube, on which the point of spectrum analysis is indicated. In fig. 12b and 12c clearly visible stripes associated with the boundaries of the cells, formed as a result of the movement in time of these boundaries. The spectrum of the flame recorded in the one indicated in Fig. 12 at a point on the border of one of the cells is demonstrated in fig. 13. Since the mixture contains the inhibiting additive CCl4, the combustion intensity is lower than in the absence of the additive. The release of heat is less, therefore, “hot” lines of Na and K atoms are not observed in the emission spectrum. This spectrum is consistent with the literature data [5] and contains СН (A1 Δ–X2 Π) bands in the 431 nm region, C2 (A3Pg –X3Pu) (1-0, 0-0, 0-1 transitions) in the 470 - 570 nm [28] and emission bands of water vapor (for example, (1, 2, 0), (3, 0, 0) [27]). Fig. 12. a) Video frame of cellular combustion of a stoichiometric mixture of pentane with air + 10% CO2 + 1% CCl4 pressure 1 atm, b) Hyperspectral image (hypercube) in pseudo color B c) highlighted fragment of Fig. 12b. It should be noted that the CH and C2 bands refer to the contribution of the zone of intense chemical transformation (FF zone) [5] to the total spectrum, and the emission bands of water vapor to the emission region of the combustion reaction products. This means that from the ratio of the intensities of the C2 and H2O bands in the spectrum, it is possible to make a qualitative conclusion about which combustion zone the spectrum characterizes i.e. the zone of the immediate flame front or the zone of reaction products. Namely, if the relative intensity of the C2 bands significantly exceeds the relative intensity of the water bands in the flame, then the radiation spectrum corresponds to the combustion zone. If the ratio of intensities is the opposite, then the spectrum refers to the reaction products. Drawing on the coordinate of the emission spectra of a stoichiometric mixture of pentane with air, diluted with 10% CO2 is shown in fig. 14 with the presence of 1% CCl4 along the window axis (along the vertical line in Fig. 12c) from top to bottom. Fig. 13. The spectrum of combustion of a mixture of pentane with air + 10% CO2 + 1% CCl4 pressure 1 atm (point x = 15, y = 46). As far as seen from fig. 14 along the window axis the intensities of the spectral bands do not change symbatically. While the relative intensity of the C2 bands has a maximum at x = 20 and x = 180 (where x is the coordinate shown in Fig. 9), the intensity of the H2O bands at those the same values of x has a minimum. This means, first, that combustion in space is heterogeneous, otherwise the intensities of the spectral lines would change smoothly in the direction of decreasing or increasing. In other words, using 4D spectroscopy, it is possible to register combustion cells, as was done by high-speed filming (Fig. 7, 12 a). Second, the fact that the intensity of the C2 bands has a maximum at the same values (x = 20, x = 180), at which the intensity of the H2O bands is minimal. It means that at these values of x, radiation occurs mainly from the flame front zone. At values of x at which the ratio of the intensities of the C2 and H2O bands is opposite, the radiation comes from the zone of the reaction products. Consequently, it was possible to determine that each combustion cell observed by using the 4D spectroscopy method in Fig. 12 a, is essentially a separate "chemical reactor", in each of which the process of complete chemical conversion is carried out. Fig. 14. Combustion spectra of a mixture of pentane with air + 10% CO2 + 1% CCl4 pressure 1 atm along the axis of the window (along the vertical line in Fig. 12c) y = 46 (t = 9 ms) Let us recall that it was experimentally shown in [10] for the first time that in the presence of instabilities of a thermodiffusion nature (lean mixtures of hydrogen with oxygen) under zero gravity, there is a mode of formation of separate isolated stationary combustion cells, i.e. separate "chemical reactors" in a combustible environment. In this work, the features of combustion in flame cells caused by hydrodynamic instability are experimentally established for the first time by using the methods of 4D optical spectroscopy and color high-speed filming. In addition, as a result of direct experimental test of Landau's hypothesis of the hydrodynamic instability of a plane flame front [11], the relationship was observed between the main factors responsible for the instability of hydrodynamic and acoustic flames [9]. This means that in the cell of the combustion front, caused by an instability of any nature (thermodiffusion, hydrodynamic, thermoacoustic), a complete cycle of transformations is carried out, which is characteristic of a given combustion process. Conclusions for Chapter 4 It is shown that when the FF propagation goes from spherical to propagation in a tube, phenomena caused by instability appear in the reactor flat flame by the example of combustion of stoichiometric mixtures of n-pentane (C5H12) with air, diluted with carbon dioxide (CO2) and argon (Ar), at total atmospheric pressure. It is shown that, upon deceleration of the FF near the end wall of the reactor, a smooth FF acquires a cellular structure. It is demonstrated that qualitative modeling of the results obtained is possible when analyzing the Navier-Stokes equations for a compressible medium in the approximation of a small Mach number. Using the methods of 4D optical spectroscopy and color high-speed filming, the features of combustion in flame cells caused by hydrodynamic instability have been experimentally established for the first time. It is shown that any combustion cell is essentially a separate “chemical reactor”, in each of which the process of complete chemical transformation is carried out. The results obtained on the spectral study and visualization of the propagation of fronts of unstable flames are important in solving the issues of explosion safety for volumes of complex geometry.
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