航空发动机燃烧室燃烧过程与排放物生成的反应动力学数值模拟

选用正癸烷作为航空煤油的替代燃料,建立了正癸烷的化学反应详细机理与简化机理(包括50种组分,118个基元反应).分别采用详细机理与简化机理对正癸烷在激波管中的着火延迟时间、在预混燃烧炉内的燃烧过程进行了数值计算,并与实验结果进行了对比分析.同时,耦合该简化机理与CFD计算软件Fluent,对某型航空发动机环管形燃烧室中单个火焰筒内流动特性与燃烧过程、排放物及活性中间组分生成的反应动力学特性进行了详细分析,并与采用C₁₂H₂₃为燃料的单步反应机理的计算结果进行了对比分析.结果表明:采用简化机理计算得到的着火延迟时间、反应物与各主要生成物摩尔分数的整体变化趋势与实验数据吻合较好;与采用C₁₂H₂₃为燃料的单步反应机理相比,采用正癸烷为替代燃料的简化反应机理计算得到的温度场分布更符合实际,其出口平均温度亦更为接近燃烧室出口设计温度;同时,能更为详细了解燃料低温裂解过程及裂解产物、中间产物及主要排放物的生成规律.      

Methane pyrolysis in preparation of pyrolytic carbon: Thermodynamic and kinetic analysis by density functional theory

The density functional theory has been successfully applied in analyzing pyrolytic carbon deposition by methane pyrolysis from the view of thermodynamics and kinetics based on a total number of 39 elementary reactions. M06-2X/def2-TZVP level was employed to optimize species structures and locate the transition states. The enthalpy changes and Gibbs free energy changes of all the reactions in the temperature range of 298.15–1800 K were derived with optimized species. Results show that the reacting temperature should be above 1200 K based on the equilibrium constant analysis, which is consistent with the typical reaction temperature adopted in experiments. Potential energy surface profiles report that radical attacking reactions have lower energy barriers than those direct decomposition reactions, especially hydrogen radical attacking reactions. The energy barriers of the first steps, dehydrogenations of methane and ethylene, are 272.4 kJ·mol⁻¹ and 288.9 kJ·mol⁻¹ at 1200 K, which are very close to the experimental activation energy for methane pyrolysis. The most favorable decomposition reaction path is the path of hydrogen radical attacking reactions. The highest energy barrier of the path at 1200 K is 185.7 kJ·mol⁻¹ presented by the C–H bond breaking in ethynyl attacked by hydrogen radical.     

一种酚醛树脂模型化合物热解反应的密度泛函理论研究及实验验证

邻-邻位亚甲基桥是酚醛树脂主体结构单元之间的主要链接方式之一。采用Gaussian 09中的密度泛函理论B3LYP/6-311G(d,p)方法,对邻-邻位亚甲基桥型模型化合物邻位双羟苯基甲烷(2BHM)的热解反应机理进行了量子化学理论研究。设计了5种热解反应途径,对每种反应途径的反应物、产物和过渡态的结构进行了能量梯度全优化,并对过渡态进行了IRC验证。计算了各反应途径的标准动力学参数,最后进行了相关实验验证。计算结果表明Path3为2BHM的最优热解路径,对应的产物为苯酚和邻甲酚,所有路径的终产物中均有苯酚,且CO_2要比CO更容易生成。热解实验结果显示热解产物中苯酚含量最高,而CO并未出现。这说明计算结果与实验结果基本一致,同时也表明应用量子化学计算理论研究酚醛树脂的热解机理是一种有效的研究方法。     

一种航空煤油数值模拟替代燃料的化学反应简化机理

通过对一种航空煤油数值模拟替代燃料(正癸烷)着火与燃烧的化学反应详细机理(包括67种组分,344个反应)进行反应流与敏感性分析,建立了该替代燃料的化学反应简化机理(包括50种组分,118个反应).分别采用详细机理与简化机理对正癸烷在激波管中的着火延迟时间、在预混燃烧炉内的燃烧过程进行了数值计算,并与实验结果进行了对比分析.结果表明:与实验数据相比,采用详细机理与简化机理计算得到的着火延迟时间、反应物与主要生成物的摩尔分数与炉壁距离的整体变化趋势吻合较好.正癸烷可以作为航空煤油的一种数值模拟替代燃料,同时,所建立的化学反应简化机理能很好的描述正癸烷着火与燃烧的动力学特性.      

热重质谱联用技术对酚醛树脂热解行为及动力学研究

采用热重分析法和热重质谱联用技术考察了氨酚醛树脂的热解反应行为,以Coats-Redfern积分法对实验数据进行动力学解析,得到了氨酚醛树脂热解反应的动力学参数。结果表明,氨酚醛树脂的热解反应分为两种:在600℃以下的低温区,以链断裂反应为主;在600～800℃的高温区,以脱氢反应为主。氨酚醛树脂热解反应可以用两个分段一级动力学方程来描述,升温速率对两种热解反应的表观活化能影响都不大。     

正癸烷预混燃烧的详细反应动力学数值模拟

提出了正癸烷预混燃烧的详细化学反应机理,并对正癸烷预混燃烧过程进行了数值计算.同时,详细分析了反应物、主要生成物及多种中间组分摩尔分数的变化趋势,并分别与采用正癸烷与航空煤油为燃料的燃烧火焰的实验结果进行了对比分析.结果表明,正癸烷与航空煤油预混燃烧火焰中反应物与生成物摩尔分数的变化趋势基本一致;通过数值计算所得到的主要反应物与生成物摩尔分数的变化趋势与两种燃料(正癸烷与航空煤油)燃烧火焰的实验值基本吻合,说明该详细反应机理能很好地反映正癸烷预混燃烧过程的详细动力学特性.同时,通过反应流分析发现,正癸烷的消耗主要通过热裂解反应以及H,OH自由基的提取反应来实现.      

石墨烯/二氧化硅三维杂化材料的制备及其在改性酚醛泡沫中的应用

为了得到结构和力学性能良好的酚醛泡沫,利用原位生成的方法制备了石墨烯/二氧化硅(GNPs/SiO_2)杂化材料,并将其用于酚醛泡沫的制备当中。对杂化材料进行了红外光谱分析,透射电镜以及X射线衍射分析,验证了石墨烯表面SiO_2球体(粒径在150~180 nm)的存在。对泡沫的结构和压缩性能进行对比分析,发现三维杂化材料相比二维石墨烯能够更好的改善酚醛泡沫的泡孔结构,杂化材料为0.5wt%时,GNPs/SiO_2改性酚醛泡沫的泡孔尺寸更小,结构更均匀;同时杂化材料改性酚醛泡沫表现出更优异的力学性能,其压缩强度和弹性模量分别达到0.22和4.1 MPa,比纯酚醛泡沫分别提高了91%和86%。     

石墨烯/聚合物纳米复合材料研究进展

介绍了近年来石墨烯改性聚合物和功能化石墨烯改性聚合物纳米复合材料的研究现状。其中,在石墨烯改性聚合物方面,主要论述了石墨烯改性聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)以及聚苯胺(PANI)纳米复合材料的制备方法和性能改善;在功能化石墨烯改性聚合物方面,主要论述了二苯基甲烷二异氰酸酯(MDI)、十八烷基胺(ODA)、氯化铝(Al Cl3)等对石墨烯的修饰以及改性后的石墨烯对聚合物的影响。最后,对石墨烯/聚合物纳米复合材料的潜在应用和发展前景做出了展望。     

RANS simulations on combustion and emission characteristics of a premixed NH3/H2 swirling flame with reduced chemical kinetic model

Ammonia (NH₃) is considered as a potential alternative carbon free fuel to reduce greenhouse gas emission to meet the increasingly stringent emission requirements. Co-burning NH₃ and H₂ is an effective way to overcome ammonia’s relative low burning velocity. In this work, 3D Reynolds Averaged Navier-Stokes (RANS) numerical simulations are conducted on a premixed NH₃/H₂ swirling flame with reduced chemical kinetic mechanism. The effects of (A) overall equivalence ratio Φ and (B) hydrogen blended molar fraction X_H2 on combustion and emission characteristics are examined. The present results show that when 100%NH₃-0%H₂-air are burnt, the NO emission and unburned NH₃ of at the swirling combustor outlet has the opposite varying trends. With the increase of Φ, NO emission is found to be decreased, while the unburnt ammonia emission is increased. NH₂ → HNO, NH → HNO and HNO → NO sub-paths are found to play a critical role in NO formation. Normalized reaction rate of all these three sub-paths is shown to be decreased with increased Φ. Hydrogen addition is shown to significantly increase the laminar burning velocity of the mixed fuel. However, adding H₂ does not affect the critical equivalence ratio corresponding to the maximum burning velocity. The emission trend of NO and unburnt NH₃ with increased Φ is unchanged by blending H₂. NO emission with increased X_H2 is increased slightly less at a larger Φ than that at a smaller Φ. In addition, reaction rates of NH₂ → HNO and HNO → NO sub-paths are decreased with increased X_H2, when Φ is larger. Under all tested cases, blending H₂ with NH₃ reduces the unburned NH₃ emission, especially for rich combustion conditions. In summary, the present work provides research finding on supporting applying ammonia with hydrogen blended in low-emission gas turbine engines.     

Competing effects of surface catalysis and ablation in hypersonic reentry aerothermodynamic environment

Under hypersonic flow conditions, the complicated gas-graphene interactions including surface catalysis and surface ablation would occur concurrently and intervene together with the thermodynamic response induced by spacecraft reentry. In this work, the competing effects of surface heterogeneous catalytic recombination and ablation characteristics at elevated temperatures are investigated using the Reactive Molecular Dynamics(RMD) simulation method. A GasSurface Interaction(GSI) model is establi...     

Photochemistry in Outer Solar System Atmospheres

The photochemistries of the H₂-He atmospheres of the gas giants Jupiter, Saturn and ice giants Uranus and Neptune and Titan’s mildly reducing N₂ atmosphere are reviewed in terms of general chemical and physical principles. The thermochemical furnace regions in the deep atmospheres and the photochemical regions of the giant planets are coupled by vertical mixing to ensure efficient recyling of photochemical products. On Titan,mass loss of hydrogen ensures photochemical evolution of methane into less saturated hydrocarbons. A summary discussion of major dissociation paths and essential chemical reactions is given. The chapter ends with a overview of vertical transport processes in planetary atmospheres.     

Effect of nickel introduced by electroplating on pyrocarbon deposition of carbon-fiber preforms

In order to improve the deposition rate and microstructure of pyrocarbon, nickel was introduced by electroplating on carbon fibers and used as a catalyst during the deposition of pyrocarbon at 1000 C using methane as a precursor gas. The distribution of nickel catalyst and the microstructure of pyrocarbon were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS）, X-ray diffraction（XRD）, and Raman micro-spectrometry. Results show that nano-sized nickel particles could be well distributed on carbon fibers and the pyrocarbon deposited catalytically had a smaller d002 value and a higher graphitization degree compared with that without catalyst. In addition, the deposition rate of pyrocarbon in each hour was measured.The deposition rate of pyrocarbon in the first hour was more than 10 times when carbon cloth substrates were doped with nickel catalysts as compared to the pure carbon cloths. The pyrocarbon gained by rapid deposition may include two parts, which are generation directly on the nickel catalyst and formation with the carbon nanofibers as crystal nucleus.     

高温处理对液相气化沉积碳/碳复合材料微观组织结构及力学性能的影响

 对用快速液相气化法制备的碳 /碳复合材料进行了石墨化处理;用 X-ray衍射技术和扫描电子显微镜对高温处理前后材料的微观组织结构及断口形貌进行了研究观察;分析了影响石墨化前后微观结构、力学性能变化及断裂失效模式的因素及机理。结果表明 :经石墨化处理后,d₀₀₂ 值降低,L_c 值升高,弯曲强度σ_f大幅度降低,层间剪切强度 ILSS升高,但随热处理温度提高,ILSS值有降低趋势。     

The Hydrogen Exospheric Density Profile Measured with ASPERA-3/NPD

We have evaluated the Lyman-α limb emission from the exospheric hydrogen of Mars measured by the neutral particle detector of the ASPERA-3 instrument on Mars Express in 2004 at low solar activity (solar activity index = 42, F_10.7=100). We derive estimates for the hydrogen exobase density, n _H = 10¹⁰ m^?3, and for the apparent temperature, T > 600 K. We conclude that the limb emission measurement is dominated by a hydrogen component that is considerably hotter than the bulk temperature at the exobase. The derived values for the exosphere density and temperature are compared with similar measurements done by the Mariner space probes in the 1969. The values found with Mars Express and Mariner data are brought in a broader context of exosphere models including the possibility of having two hydrogen components in the Martian exosphere. The present observation of the Martian hydrogen exosphere is the first one at high altitudes during low solar activity, and shows that for low solar activity exospheric densities are not higher than for high solar activity.     

纳秒脉冲滑动弧放电等离子体裂解煤油实验研究

为改善极端条件下航空煤油的点火和燃烧性能,提高煤油活性,本文在大气压氮气环境下利用纳秒脉冲电源产生的滑动弧等离子体进行煤油裂解实验研究,得到了包含活性更高的气态轻质烃和氢气等小分子物质的裂解气。通过改变电源输出脉冲电压的上升沿时间和下降沿时间,得到了裂解气产量、碳氢比以及裂解气中各组分选择性的变化规律,并总结了相关的部分反应路径。实验结果如下：裂解气产量随着上升沿时间的增加而减小,随着下降沿时间的增加而上升,裂解气碳氢比则呈现相反的变化规律；裂解气主要组分中,乙烷选择性最高,在各实验工况下均超过30%；随着上升沿时间和下降沿时间的增加,裂解气中丙烷和丙烯的选择性均降低,氢气的选择性上升；上升沿时间和下降沿时间的变化对裂解效果产生影响的主要原因是改变了反应的路径。实验结果表明,纳秒脉冲滑动弧放电等离子体可以将煤油中的部分大分子烃类转化为气态轻烃和氢气等高活性组分。同时,增加纳秒脉冲电压下降沿时间能够改善滑动弧等离子体的裂解效果,获得更多活性更高的小分子物质。     

石墨烯基吸波材料研究新进展

吸波材料的性能是影响雷达隐身的关键因素,其研究对军用和民用都具有非常重要的意义。石墨烯由于其独特的吸波性能,成为吸波材料研究的一大热点。本文综述了石墨烯/铁氧体、石墨烯/金属微粉、石墨烯/磁性金属、石墨烯/导电聚合物和石墨烯/磁性材料/导电聚合物等复合吸波材料在吸波领域的最新研究应用现状,并展望了吸波材料未来发展趋势。     

Kinetics of gas-Grain Reactions in the Solar Nebula

Thermochemical equilibrium calculations predict gas phase, gas-grain, and solid phase reactions as a function of pressure and temperature in the solar nebula. However, chemical reactions proceed at different rates, which generally decrease exponentially with decreasing temperature. At sufficiently low temperatures (which vary depending on the specific reaction) there may not have been enough time for the predicted equilibrium chemistry to have taken place before the local environment cooled significantly or before the gaseous solar nebula was dispersed. As a consequence, some of the high temperature chemistry established in sufficiently hot regions of the solar nebula may be quenched or frozen in without the production of predicted low temperature phases. Experimental studies and theoretical models of three exemplary low temperature reactions, the formation of troilite (FeS), magnetite (Fe₃O₄), and hydrous silicates, have been done to quantify these ideas. A comparison of the chemical reaction rates with the estimated nebular lifetime of 0.1-10 million years indicates that troilite formation proceeded to completion in the solar nebula. Magnetite formation was much slower and only thin magnetite rims could have formed on metal grains. Hydrous silicate formation is predicted to be even slower, and hydrous silicates in meteorites and interplanetary dust particles probably formed later on the parent bodies of these objects, instead of in the solar nebula. This revised version was published online in June 2006 with corrections to the Cover Date.     

C/C复合材料在再入模拟环境中烧蚀性能研究

为了研究轴棒法编织的高密度碳/碳(C/C复合材料在再入飞行时的烧蚀性能,采用热等离子体地面模拟再入烧蚀系统对C/C复合材料进行烧蚀试验。试验中分别采用氮气(N、氧气(O和空气作为工作气体,对比研究C/C复合材料在不同环境中的烧蚀率和烧蚀性能。结果表明,三种情况下试样的烧蚀率和微观形貌有很大差异;纯氧气时氧化反应的线烧蚀率和质量烧蚀率分别为0.0423mm/s和0.0451g/s大于纯氮气时氮化反应的0.0314mm/s和0.0338g/s也大于空气成分时复合反应的0.0215mm/s和0.0208g/s在试样烧蚀的热影响区发生轻微开裂;三种工况下的烧蚀机理不同,分别是碳的升华、碳的氧化和碳氮反应的某种组合。     

Who is who in Algol-land ?- Part I -

We computed the evolution through case A mass transfer for 8 systems with mass of the primary equal to 3 and 5 M₀, mass ratios 0.7 and 0.9, and different periods. To this we added similar results from Packet (1988) for M_i = 9 M₀, q_i = 0.6, P_i = 1.62 d.During the mass transfer two competing mechanisms in the gainer decide on the evolution of the system: the rejuvenation of this star as the increasing convective core mixes fresh hydrogen into the inner regions, and the acceleration of nuclear burning, responding to the increasing mass.In all the cases the net result is a faster decrease of the central hydrogen content compared to the mass losing star. The secondary fills its own critical Roche lobe and reversed mass transfer starts.From our results and those of Nakamura and Nakamura (1984), we find that reversed mass transfer occurs after core hydrogen burning of the secondary (case A₁B₂) approximately for periods larger than 1 d (M_1i = 3 M₀) to 2 d (M_1i = 13.4 M₀). For smaller periods this happens before the gainer ends its core hydrogen burning (case A₁A₂).     

RP-3航空煤油/正丁醇混合燃料燃烧机理构建及动力学分析

为探究大分子碳氢/小分子醇类燃料氧化机理,明晰航空煤油/生物质替代燃料的燃烧本质,构建并验证了包含173种组份、720步反应的RP-3航空煤油/正丁醇混合燃料反应机理,并对其在压力为0.1MPa、当量比为1.0、温度为1100,1300,1500K条件下进行了化学动力学模拟分析。结果表明：在低温条件下,正丁醇会延长混合燃料着火延迟期,30%的掺醇比使混合燃料着火延迟期延长了101.3μs;烷烃脱氢后的异构体以及裂解后的小分子基元团都随温度的升高而增多,正丁醇的添加对大分子异构化及裂解过程影响较小;温度的升高使除R1（H+O₂=O+OH）外的大部分反应的敏感性系数显著降低并保持在30%以内。而正丁醇的添加使消耗OH,HO₂等物质的反应的敏感性系数提高,也会影响小分子基元团的摩尔分数。