Ignition,combustion, and agglomeration of encapsulated aluminum particles in a composite solid propellant. II. Experimental studies of agglomeration

The combustion characteristics of propellants containing AP, HMX, an energetic binder, and aluminum particles with various polymer coatings are studied at pressures of 0.15 and 4.6 MPa. It is found that the coatings influence the burning rate, the particle size distribution of condensed combustion products, and the completeness of aluminum combustion. It is shown that the agglomeration can be reduced by using aluminum with fluorine-containing coatings. The application of some coatings results in a reduction in the mass of the agglomerates with an insignificant increase in their size. The greatest effect was achieved when using aluminum coated with (CH₂=CH-CH₂-O)₂Si[OCH₂(CF₂-CF₂)₂H]₂ [bis(allyloxy)-bis(2,2,3,3,4,4,5,5-octafluoropentyloxy)silane]. For this coating, a size reduction is also observed for micron-size oxide particles. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 3, pp. 83–97, May–June, 2007.     

Reduction of agglomeration effect by aluminum trihydride in solid propellant combustion

Aluminum trihydride (AlH₃) has gained considerable attention as a substitute fuel for aluminum in solid propellants. In this study, we conducted a systematic investigation to evaluate the effects of AlH₃ content, ranging from 0 % to 18 %, on propellant ignition, combustion, and agglomeration. Experimental methods such as thermogravimetry−differential scanning calorimetry (TG-DSC), laser ignition, high-speed photography, and collecting condensed combustion products (CCPs) were employed. The results indicate that AlH₃ significantly promotes the high-temperature decomposition of ammonium perchlorate (AP). Meanwhile, the addition of cyclotetramethylene tetranitramine (HMX) in propellant does not affect the hydrogen release reaction of AlH₃. As the AlH₃ content increases from 0 % to 18 %, the spectral emission intensity of the propellants decreases, and the ignition delay time initially increases from 253 ms to 321 ms, and then decreases to 258 ms. Furthermore, the burning rate increases with increasing the AlH₃ content, while the pressure exponent is reduced from 0.551 to 0.460. The inclusion of AlH₃ in propellants significantly inhibits aluminum agglomeration near the burning surface. Additionally, as the AlH₃ content increases, the mean particle size D₄₃ of the CCPs decreases from 50.95 μm to 8.28 μm at 1 MPa. The agglomeration degree of aluminum is very weak at 7 MPa, especially when the AlH₃ content exceeds 9 %. The conclusions drawn from this study can serve as valuable guidance for optimizing propellant formulations.     

Effect of acceleration on agglomeration of aluminum particles during combustion of composite solid propellants

The effect of the normal acceleration (g-load) on formation of agglomerates and their distribution function is examined within the framework of the statistical model of aluminum agglomeration. A parametric study of aluminum agglomeration with different values of normal g-loads is performed. The theory developed predicts a new effect, namely, a nonmonotonic dependence of the mean-mass size of agglomerates leaving the burning surface on the magnitude of normal g-loads: with increasing g-load, the mean-mass size of agglomerates can increase if the g-loads are low or moderate and decrease if the g-loads are high; in the latter case, the size distribution of agglomerates becomes less spread and more stable. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 40–50, November–December, 2007.     

Experimental investigation of agglomeration during combustion of aluminized solid propellants in an acceleration field

Agglomeration during combustion of solid rocket propellants in an acceleration field up to 60 was studied experimental. In the experiments, the acceleration direction and magnitude were varied. The amount, chemical composition, and particle size of the agglomerates and the structure of the surface layer were determined as functions of the acceleration magnitude and direction. The most significant feature of the effect of tensile accelerations is an increase in the agglomerate mass to a certain limiting value, and that of compressive accelerations is the formation of a layer of condensed products on the burning-propellant surface. The data obtained provide a deeper understanding of the general physical picture of agglomerate formation and aluminized-propellant combustion and highlight the range of engine operation problems under flight conditions due to the presence of condensed combustion products. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 1, pp. 38–46, January–February, 2009.     

Effect of ultrafine aluminum on the combustion of composite solid propellants at subatmospheric pressures

This paper presents the results of an experimental study of the combustion of composite solid propellants with a double oxidizer (ammonium perchlorate/HMX) at pressures of 0.03–0.1 MPa. Systems containing a micron-sized aluminum powder (ASD-4) and the Alex ultrafine aluminum powder were investigated. It was shown that the replacement of ASD-4 by Alex in propellant systems led to an increase in the burning rate. The aluminum particle size and the oxidizer excess coefficient were found to affect the exponent in the power-law burning-rate dependence. The range of the oxidizer excess coefficient was determined that corresponded to the effective replacement of micron-sized aluminum by ultrafine aluminum for which the exponent in the power-law burning rate dependence decreases. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 1, pp. 47–55, January–February, 2009.     

Properties of the surface layer and combustion behavior of metallized solid propellants

The properties of the surface layer of burning metallized solid propellants are analyzed on the basis of available experimental data. A general physical concept of processes in the surface layer is developed. The structure called a skeleton layer is shown to play a key role in combustion. The factors influencing the properties of the skeleton layer are determined, and the effect of these of properties on the properties of condensed combustion products and the propellant burning-rate law is studied. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 4, pp. 156–165, July–August, 2009.     

RDX对含硼富燃料推进剂一次燃烧产物组分影响的计算研究

为了研究黑索今(RDX)对含硼富燃料推进剂一次燃烧产物组分的影响,用吉布斯最小自由能法计算了5种推进剂配方的一次燃烧产物组分,并通过测试燃烧产物中的总硼含量对热力学计算结果进行了验证。结果表明,采用最小自由能法计算含硼富燃料推进剂的一次燃烧产物组分,其结果准确、可靠;当含硼富燃料推进剂中RDX含量增加时,一次燃烧产物中B_4C和B_2O_3含量减少、C和BN含量增加,且一次燃烧温度也升高;提高一次燃烧压强可提高硼的氧化率、降低B_4C的生成量,有效提高一次燃烧温度,因此提高一次燃烧压强有助于提高含硼富燃料推进剂的二次燃烧效率。     

Ignition, combustion, and agglomeration of encapsulated aluminum particles in a composite solid propellant. I. Theoretical study of the ignition and combustion of aluminum with fluorine-containing coatings

This paper gives a brief review of methods for modifying metallic fuels for composite solid propellants, including the application of coatings onto aluminum particles (encapsulation). Requirements for the coating material are formulated. By means of thermodynamic calculations, it is shown that some fluorine-containing coatings reduce the content of the condensed phase in the propellant combustion products without decreasing the specific impulse. A mathematical model for the ignition of a single encapsulated particle is proposed. Calculations show a decrease in the ignition time of an aluminum particle with a fluorine-containing coating. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 5, pp. 46–55, September–October, 2006.     

高氯酸铵含量对高铝富燃料推进剂中重要组分高氯酸铵/铝 一次燃烧性能和铝粉团聚的影响

采用CO2激光点火装置联合高速摄影系统及扫描电子显微镜等凝聚相燃烧产物分析技术,研究了高氯酸铵(AP)含量对高Al富燃料推进剂中重要组分AP/Al一次燃烧过程中燃烧现象、引燃时间、燃烧扩散时间、燃尽时间、燃烧效率、颗粒团聚及凝聚相燃烧产物的表面形貌、粒径及其分布的影响。结果表明,各AP/Al混合粉体的燃烧过程均可分为表面引燃、燃烧扩散和火焰熄灭3个阶段,但各样品在不同燃烧阶段的燃烧现象存在明显差异。AP含量由10wt%增至30wt%,样品燃烧剧烈程度增强,燃烧过程中固相颗粒的溅射现象越加明显;在火焰熄灭阶段,各样品燃烧由以停留在样品燃面处的燃烧为主逐渐变为以溅射颗粒的燃烧为主,且随反应进行,燃面已燃固相颗粒最先熄灭,各样品表面引燃时间、燃烧扩散时间、燃烧持续时间均缩短,即燃烧反应速率逐渐加快。在AP/Al混合物中,铝粉的燃烧效率、凝聚相燃烧产物粒度及其团聚程度随AP含量增加而增加。     

Effect of the addition of ultrafine aluminum powders on the rheological properties and burning rate of energetic condensed systems

The effect of small additives (1.25–5.00%) of ultrafine aluminum powders (UFAP) on the rheology and combustion of model four-component energetic condensed systems is studied. It is found that the addition of UFAP decreases the temperature of HMX decomposition. Small additives of UFAP increase the burning rate of model energetic condensed systems and decrease the exponent ν in the burning rate law without deteriorating the rheological characteristics of the model propellants. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 1, pp. 54–59, January–February, 2007.     

KF对微米铝粉在水蒸气中着火燃烧特性的影响

为改善微米铝粉在水蒸气中的着火特性和燃烧效率,采用自行设计的管式炉实验平台研究了KF对30 ?m铝粉在1000℃水蒸气中着火燃烧特性的影响。用高速摄影系统记录了样品着火燃烧过程,并通过X射线衍射、扫描电镜技术和化学分析方法分析了产物组分、形貌和燃烧效率。结果表明,加入KF可显著降低30 ?m铝粉的点火延迟时间,与加入5wt% (0.003 g) KF相比,加入15wt% (0.009 g) KF后,样品的点火延迟时间减少了47.58 s;微米铝粉在1000℃水蒸气中不能着火,加入KF后能着火,这是因为KF与水蒸气反应生成KOH,KOH与Al2O3反应会破坏铝粉的氧化壳,加快铝与水蒸气的反应,促进铝粉着火。随KF加入量提高,样品的燃烧效率显著上升,最高为82.24%,比未添加KF样品的燃烧效率提升了38.75%。提高KF加入量,可产生更多的KOH,对氧化壳的破坏效果更显著,进一步促进铝与水蒸气反应,提高铝粉燃烧效率。     

Effect of a Sudden Change in Cross-Sectional Area of the Solid Rocket Motor Duct on Coagulation of Condensed Particles

Results of numerical simulations are reported for two-phase flows with allowance for coagulation and fragmentation of particles of polydisperse condensate in the combustor duct of the solid rocket motor (SRM) with a sudden change in cross-sectional area typical of solid-propellant charges of a complex shape. It is shown that a sudden change in cross-sectional area can lead to a significant (multiple) coagulation-induced increase in the mean particle size. The calculation results are validated by a test series on a model SRM with the use of a laser system for diagnosing particle dispersion.     

Method of reconstruction of the chemical composition and combustion efficiency of hydrogen-air mixtures from incomplete experimental data

A principal possibility of approximate reconstruction of the chemical composition in combustion of a hydrogen-air mixture at the end of the scramjet duct from incomplete experimental data (measured concentration of OH radicals and temperature) under the assumption of detailed chemical equilibrium of exchange reactions is analyzed. A closed algebraic system of equations including the concentration of OH radicals and the temperature as parameters is derived in this approximation. A code for solving this system numerically is developed for approximate determination of reaction completeness from the measured temperature and concentration of OH radicals. The model was tested by results of exact thermodynamic calculations of the Jouguet state and overdriven waves in a stoichiometric hydrogen-air mixture and various hydrogen-oxygen mixtures. In the range of pressures of 0.2 to 500 atm and temperatures of 2500 to 3500 K, this method allows the molecular weight and heat release to be reconstructed with accuracy sufficient for gas-dynamic calculations. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 4, pp. 13–20, July–August, 2008.     

铝/乙醇基纳米浆体燃料的着火燃烧特性研究

为了明确纳米铝粉从低浓度到高浓度变化对液体碳氢燃料着火燃烧特性的影响,采用液滴悬挂法研究了不同温度下(700~800℃)乙醇液滴和添加不同浓度(2.5wt%, 10wt%, 15wt%和20wt%)纳米铝粉的铝/乙醇基纳米浆体燃料液滴的着火燃烧特性。利用高速摄影系统捕捉了液滴整个燃烧过程,分析了其液滴寿命。通过热电偶对液滴附近气相温度的测量,获得了其着火性能参数。结果表明,添加纳米铝粉可以改善乙醇液滴的着火性能。不同铝粉浓度改善效果不同,低浓度时效果较好,着火延迟时间显著缩短,点火温度明显降低。随温度升高,乙醇及添加纳米铝粉的铝/乙醇基纳米浆体燃料液滴着火延迟时间及着火温度均明显降低。纳米铝粉(S2)对乙醇(S1)着火延迟时间和液滴寿命的降幅在750℃最大,其降幅分别达42.20%和18.43%。纳米铝粉(S3)着火温度降低,其最大降低幅度也出现在750℃,相对于乙醇(S1)降低幅度达28.57%。一定铝粉浓度范围内,液滴微爆炸程度和微爆炸时长随铝粉浓度升高而增大,但铝粉浓度超过10wt%后趋势变得平稳。     

The evolution of 100-µm aluminum agglomerates and initially continuous aluminum particles in the flame of a model solid propellant. II. Results

A quenching/sampling method was used to study the evolution of monodisperse 100-μm aluminum agglomerates and continuous particles in the flame of combustion products — composite propellant at a pressure of 0.7–8 MPa. The particle residence time in the flame was varied in the range 6–170 msec, whereas the calculated time of their combustion was ≈25 msec. The evolution of a burning particle is related to the consumption of metallic aluminum and the deposition of oxide in the form of a cap, which, after complete combustion of aluminum, is transformed to the final spherical oxide particle. The density of the final oxide particles was measured. The ratio of the diameters and masses of the initial metal particle and the final oxide particles was determined. Data on particle fragmentation during combustion were obtained by comparing the numbers of the initial metal particles and the final oxide particles. Considerable differences in the combustion behavior of the agglomerates and continuous particles of size 100 μm were not found. It was established that the smaller the size of the burning particle the less oxide is deposited on the particle and the more oxide is carried away in the form of oxide smoke. For 100-μm particles, the fraction of deposited oxide was found to be ≈0.1 of the total mass of oxide formed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 6, pp. 61–71, November–December, 2008.     

富氧燃烧中气体辐射模型对燃烧与换热数值模拟的影响

富氧燃烧过程中,由于使用再循环烟气代替空气中N₂作为稀释剂,烟气中存在大量CO₂和H₂O。CO₂和H₂O作为非极性三原子分子,具有N₂没有的辐射能力,导致富氧燃烧中气体辐射特性发生变化。在数值模拟过程中,气体辐射模型是一个重要的子模型。前人提出多种修改后适用于富氧燃烧的气体辐射模型,但不同气体辐射模型在不同富氧燃烧工况数值模拟中的影响尚未有统一研究。为了研究不同炉型下,气体燃烧和煤粉燃烧中气体辐射模型对燃烧换热模拟结果的影响,通过编程,将一种考虑CO影响的气体辐射模型以及文献中的6种典型气体辐射模型耦合入数值模拟计算。结果表明,在气体富氧燃烧中,气体辐射模型影响了火焰结构。同时,燃烧温度分布有所变化,不同模型结果之间差别最高可到500 K。气体与壁面之间的辐射换热受到影响。气体辐射模型对炉膛中心火焰区域影响较大,而对非火焰区域影响较小。在煤粉富氧燃烧过程中,当有效辐射层厚度在0.3 m左右时,如在100 kW下行炉中,气体辐射模型对煤粉燃烧数值模拟结果几乎没有影响。这可能是由于颗粒辐射在辐射换热计算中占主导地位。而当有效辐射层厚度在16 m左右时,如1000 MW塔式炉中,气体辐射模型对炉内切圆燃烧火焰温度以及组分浓度影响较大,温度差别可到100 K左右。而气体辐射模型对炉膛中心模拟结果没有影响。     

Effect of oxidation on the chemical nature and distribution of low-temperature pyrolysis products from bituminous coal

Two bituminous coals, a high volatile Eastern Canadian and a medium volatile Western Canadian, were used to investigate the effect of oxidation on yields and chemical composition of gases, liquids and chars produced during coal pyrolysis. Pyrolysis experiments were performed at 500 °C using the Fischer assay method. Mild oxidation of coals resulted in a decrease of liquid hydrocarbon yields. Further coal oxidation increased the proportion of aromatic carbon in liquid products as determined by n.m.r., and also increased the content of oxygen in liquid products. The content of oxygen in chars was markedly lower than in corresponding coals. An attempt is made to explain reactions occurring during oxidation and subsequent pyrolysis of coal on the basis of differences in chemical composition of gases, liquids and chars.     

Effect of macroscopic heterogeneity of the medium on the solid-state combustion wave characteristics in thermally and chemically heterogeneous media

A macroscopically heterogeneous medium is modeled by a set of cylinders (rods) pressed from a mixture of solid reagents, which have coaxial cylindrical cores made from an inert material. A three-dimensional mathematical model describing propagation of combustion waves over one cylinder is studied by numerical methods. The influence of the distance between the centerlines of the neighboring cylinders and transverse sizes of the cylinders on characteristics of combustion waves propagating over a heterogeneous medium is considered. It is demonstrated that there exists an optimal distance between the inert rods, which ensures a much higher velocity of the combustion wave along the specimen than the theoretically predicted velocity of the classical combustion wave propagating over a solid specimen. New types of spinning waves are described, whose motion makes the high-temperature spot move inside the charge mixture. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 3, pp. 39–49, May–June, 2008.     

A review of the literature on the gaseous products and toxicity generated from the pyrolysis and combustion of rigid polyurethane foams

The literature on rigid polyurethane foam has been reviewed with an emphasis on the gaseous products generated under various thermal decomposition conditions and the toxicity of those products. This review is limited to publications in English through 1984. Carbon monoxide (CO) and hydrogen cyanide (HCN) were the predominant toxicants found among more than a hundred other gaseous products. The generation of CO and HCN was found to increase with increasing combustion products from various rigid polyurethane foams. Lethality, incapacitation, physiological and biochemical parameters were employ as biological end points. In general, the combustion products generated from rigid polyurethane foam in the flaming mode appear from to be more toxic than those produced in the non-flaming mode. The LC₅₀ values for 30-min exposures ranged from 10 to 17 mg l^?1 in the flaming mode and were greater then 34 mg l^?1 in the non-flaming mode. With the exception of one case, in which a reactive type phosphorus containing fire retardant was used, the addition of fire retardants to rigid polyurethane foams does not appear to generate unusual toxic combustion products.     

Effect of heat release conditions on the phase composition of the combustion products of a Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript>/Al/C thermite mixture

An X-ray method was used to study the phase composition of the combustion products of a Fe₂O₃/TiO₂/Al/C thermite composite mixture, in particular, during combustion of samples under cooling by water. The data of the experiments are compared with the results of thermodynamic calculations. A probable explanation of the reasons of the angular displacement of the line of iron in the X-ray spectrum of the combustion products and a mechanism for the crystallization of an eutectic TiC + α-Fe mixture from the melt of the Ti/Fe/C ternary system. The composition of the combustion products was found to be different from the equilibrium one, which is manifested in the presence of defects in the carbon sublattice of titanium carbide. A probable explanation of the deficiency of carbon is proposed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 4, pp. 39–43, July–August, 2008.