酚醛树脂激波管试验的高温热解研究

使用激波管作为加热手段研究酚醛树脂在1200~1800K温度范围内的热解特征。气相产物中主要碳氢产物是甲烷、乙烯、乙炔、苯和甲苯。获得试验温度范围内主要碳氢产物分布随热解温度的变化关系。结果表明,在试验温度范围内随着热解温度的升高酚醛树脂的热解机理发生重大变化。1400K以下热解断键过程主要发生在亚甲基桥链结构上;1400K以上芳环开环成为主要的热解通道,生成大量的乙炔。     

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。     

Radical recombination in a hydrocarbon-fueled scramjet nozzle

To reveal the radical recombination process in the scramjet nozzle flow and study the effects of various factors of the recombination, weighted essentially non-oscillatory(WENO)schemes are applied to solve the decoupled two-dimensional Euler equations with chemical reactions to simulate the hydrocarbon-fueled scramjet nozzle flow. The accuracy of the numerical method is verified with the measurements obtained by a shock tunnel experiment. The overall model length is nearly 0.5 m, with inlet static temperatures ranging from 2000 K to 3000 K, inlet static pressures ranging from 75 k Pa to 175 k Pa, and inlet Mach numbers of 2.0 ± 0.4 are involved.The fraction Damkohler number is defined as functions of static temperature and pressure to analyze the radical recombination progresses. Preliminary results indicate that the energy releasing process depends on different chemical reaction processes and species group contributions. In hydrocarbon-fueled scramjet nozzle flow, reactions with H have the greatest contribution during the chemical equilibrium shift. The contrast and analysis of the simulation results show that the radical recombination processes influenced by inflow conditions and nozzle scales are consistent with Damkohler numbers and potential dissociation energy release. The increase of inlet static temperature improves both of them, thus making the chemical non-equilibrium effects on the nozzle performance more significant. While the increase of inlet static pressure improves the former one and reduces the latter, it exerts little influence on the chemical non-equilibrium effects.     

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。     

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.      

基于激波管的等离子体辅助甲烷点火

在激波管实验系统的基础上,设计了等离子体放电单元,开展了等离子体对甲烷点火延迟时间影响的研究。测量了等离子体放电时的伏安特性曲线。测量了甲烷自点火延迟时间、持续放电条件下的点火延迟时间以及放电后断电下的点火延迟时间。对甲烷点火过程中的化学反应路径进行了分析。结果表明:等离子体放电电压与电流并不呈现相同的变化趋势,放电过程中气体电阻不断发生变化。很少的放电能量(小于4J)即可有效减少甲烷的点火延迟时间,在关闭电源后,放电产生的粒子依然可以在一定程度降低甲烷点火延迟时间。在低温或高温点火条件下等离子体对甲烷点火延迟时间的影响机理基本相同。点火温度较低(小于1000K),或者较高(大于1600K)时,持续放电对甲烷点火延迟的缩短效果更加明显,可以将甲烷的点火延迟时间缩短1个数量级或1个数量级以上。等离子体对甲烷点火延迟的作用效果是点火温度与等离子体质量摩尔浓度耦合影响的结果。      

反应机理对air/H2燃烧系统多场耦合仿真的适用性

针对某air/H2燃烧系统,建立起流动、传热、燃烧多场耦合有限体积动态数值模型,构建了通用化的反应机理库和配套的物性参数库,分别采用热力计算方法和3套氢氧反应机理方法进行仿真;基于反应机理的仿真描述了点火与熄火过程,揭示了各基元反应和组分变化对燃烧流动瞬态过程的影响。与已经过试验验证的热力计算方法对比,结果表明:Williams机理符合最好,Conaire机理次之,Evans机理符合相对较差。相比Conaire机理,采用Williams反应机理使反应熄火温度由1200K降低至1155.3K,在1222.3K的低温工况下,计算结果误差由Conaire机理的4.7%降低至2.74%,使多场耦合数值系统的应用范围更广、计算结果更佳;低温工况下,H2O2及其相关反应对氢氧机理的描述精度会产生较大影响。      

基于HyChem方法的正丙基环己烷反应动力学模型

采用Hybrid Chemistry （HyChem）建模方法对正丙基环己烷开展模型研究,以七步集总反应对大分子燃料热解形成小分子产物这一过程进行建模,小分子产物氧化过程则以小分子详细机理USC Mech Ⅱ进行描述。将两个子机理结合构建了正丙基环己烷的HyChem反应动力学模型（包括112个组分和791个基元反应）,并通过流动管热解、点火延迟时间以及层流火焰速度的实验数据进行了模型验证。验证结果表明,正丙基环己烷HyChem反应动力学模型可以很好的预测正丙基环己烷热解过程中主要组分分布情况,在宏观燃烧参数的预测方面也有很好的表现,对点火延迟时间的计算相对误差为29.7%,对火焰传播速度的计算相对误差为11.1%。      

高硅氧纤维/酚醛泡沫复合材料的结构与性能

以高硅氧短切纤维毡为增强体,分别以酚醛树脂和酚醛泡沫为基体,制备了高硅氧/酚醛与高硅氧/酚醛泡沫两种复合材料,采用红外光谱分析、扫描电镜分析、热失重分析等方法对其结构和性能进行了表征。结果表明,两种材料具有相似的基体化学结构和相近的固化反应温度,均具有良好的耐热性能,性能测试结果表明,复合材料中基体由酚醛树脂变成酚醛泡沫后,力学性能明显降低,同时,密度由1.65 g/cm3降低至0.5 g/cm3,热导率由0.5 W/(m·K)降低至0.09 W/(m·K)。     

SCC investigation of low alloy ultra-high strength steel 30CrMnSiNi2A in 3.5wt%NaCl solution by slow strain rate technique

To evaluate stress corrosion cracking(SCC) mechanism of low alloy ultra-high strength steel 30CrMnSiNi2 A in environment containing NaCl, SCC behavior of the steel in 3.5wt% NaCl solution is investigated by slow strain rate technique(SSRT) with various strain rates and applied potentials, surface analysis technique, and electrochemical measurements. SCC susceptibility of the steel increases rapidly with strain rate decreasing from 1 · 10 5s 1to 5 · 10 7s 1, and becomes stable when strain rate is lower than 5 · 10 7s 1. SCC propagation of the steel in the solution at open circuit potential(OCP) needs sufficient hydrogen which is supplied at a certain strain rate.Fracture surface at OCP has similar characteristics with that at cathodic polarization 1000 mVSCE, which presents characteristic fractography of hydrogen induced cracking(HIC).All of these indicate that SCC behavior of the steel in the solution at OCP is mainly controlled by HIC rather than anodic dissolution(AD).     

Role of hydrogen in the dissociation of CH4 on different graphene by DFT study

The effect of hydrogen on the growth mechanism of pyrocarbon has attracted much attention. The influence of hydrogen on the dissociation from CH4to C2H2on pristine graphene,N-doped graphene and vacancy graphene have been investigated by using density functional theory.There are two kinds of heterogeneous reaction pathways when the hydrogen is involved, i.e., dehydrogenation reactions and H-abstraction reactions. The transition state calculations were performed to acquire the reaction pathways on...     

A visco-elastoplastic constitutive model of aircraft polymethylmethacrylate related to strain rate and temperature

The visco-elastoplastic mechanical behavior related to the applied strain rate and temperature around the glass transition temperature of Polymethylmethacrylate (PMMA) has been systematically investigated. The uniaxial tensile test was performed at strain rate and temperature rangs 1.0 × 10⁻⁴–1.0 × 10⁻² s⁻¹ and 363–393 K, respectively, and the Dynamic Mechanical Analysis (DMA) test was carried out between 363 K and 413 K at various frequencies. Moreover, the robust complex constitutive model considering the temperature and strain rate effect is proposed. A nonlinear viscoelastic model is established to describe the viscoelastic response on the basis of the Zhu-Wang-Tang (ZWT) model and the time temperature equivalence principle, including the dependence of strain rate and temperature. Considering the yield stress, the cooperative model is adopted. The viscoplastic mechanical response is manifested as the competition performance of the softening deformation and hardening behavior. The predicted mechanical responses maintain good consistency with the experimental results, indicating that the visco-elastoplastic constitutive model proposed can accurately predict the mechanical behavior of PMMA materials within the imposed strain rate and near the glass transition temperature range.     

Energetic Hydrogen and Oxygen Atoms Observed on the Nightside of Mars

We present measurements of energetic hydrogen and oxygen atoms (ENAs) on the nightside of Mars detected by the neutral particle detector (NPD) of ASPERA-3 on Mars Express. We focus on the observations for which the field-of-view of NPD was directed at the nightside of Mars or at the region around the limb, thus monitoring the flow of ENAs towards the nightside of the planet. We derive energy spectra and total fluxes, and have compiled maps of hydrogen ENA outflow. The hydrogen ENA intensities reach 10⁵ cm⁻² sr⁻¹ s⁻¹, but no oxygen ENA signals above the detection threshold of 10⁴ cm⁻² sr⁻¹ s⁻¹ are observed. These intensities are considerably lower than most theoretical predictions. We explain the discrepancy as due to an overestimation of the charge-exchange processes in the models for which too high an exospheric density was assumed. Recent UV limb emission measurements (Galli et al., this issue) point to a hydrogen exobase density of 10¹⁰ m⁻³ and a very hot hydrogen component, whereas the models were based on a hydrogen exobase density of 10¹² m⁻³ and a temperature of 200 K predicted by Krasnopolsky and Gladstone (1996). Finally, we estimate the global atmospheric loss rate of hydrogen and oxygen due to the production of ENAs.     

含锆沥青热解缩聚行为研究

利用TG/ DTG 方法对含锆沥青热解缩聚行为进行研究,并与基础沥青进行对比。结果表明:含

锆沥青与基础沥青热解反应特征相似,但比基础沥青热分解起始温度高,黏度大;随着升温速率的提高,含锆沥

青起始和终止的分解温度升高,DTG 峰形变尖锐,峰位向高温方向移动;含锆沥青与基础沥青表观活化能相

当,表明在现有锆含量下,含锆沥青的反应活性与基础沥青相比没有明显变化。

     

酚醛树脂热解高斯分峰法

为了准确描述酚醛树脂热解时相互重叠的反应过程,进行了5种线性升温速率下的酚醛树脂热分析试验,提出一种高斯分峰方法。该方法通过分析酚醛树脂的微分热重(DTG)曲线以及不同温度下热分解产物的种类和含量,将酚醛树脂热解划分为四个反应过程。分峰结果与试验结果吻合较好,对后续准确求解酚醛树脂各个反应过程热分解动力学参数有重要意义。     

微环形腔内有氧条件下CH4/H2O/CO2催化重整反应特性数值研究

基于表面反应详细机理,数值研究了微环形腔内有氧条件下,组分、温度、质量流量对甲烷/水/二氧化碳催化重整反应特性的影响.结果表明:低温下,增大水的含量可提高产氢量,而增大二氧化碳含量对产氢量无明显影响.增大二氧化碳或水的含量,可提高甲烷转化率.低温下二氧化碳、水等组分的改变对甲烷重整反应的影响较小,高温下组分的影响增强.质量流量增大,出口氢气、一氧化碳质量分数和甲烷转化率明显降低.高流量下加入水或二氧化碳对甲烷转化率的影响已不再明显.当水(二氧化碳)作为产物时,质量流量的增大对其影响并不大;而做为反应物时,质量流量增大,使出口处水(二氧化碳)的质量分数升高.      

Microstructure,porosity and mechanical properties of selective laser melted AlSi10Mg

Finite element modeling (FEM), microscopy, X-ray computed tomography (CT) and mechanical property tests were used to study the microstructure, porosity and mechanical properties of an AlSi10Mg alloy produced by selective laser melting (SLM). The simulation of the melt pool and thermal history under different energy densities produced an optimized result with an energy density of 44.5 J·mm⁻³. The high cooling rate during the SLM process significantly refined the previous α-Al dendrites. The growth direction of the network-like Al-Si eutectic structure at different orientations confirmed the anisotropic nature of the microstructure. Furthermore, the microhardness, tensile testing and fracture analysis results proved that there were no obvious distinctions in the strength between the transverse and longitudinal directions, and that the ductility was anisotropic, possibly due to the shape and distribution of the pores. The pores measured by X-ray CT at different energy densities confirmed that the sphericity of the pores was inversely related to pores volumes. With optimized processing conditions, the porosity of the selective laser melted sample decreased leading to the improved fabricated fuel system component via SLM.     

一种多代路径通量分析化学机理简化方法

基于路径通量分析,在考虑组分间直接和间接多代相关反应的基础上,建立了一种新型化学机理简化方法。以预选组分为基础,通过计算预选组分直接参与,以及第二代、第三代和第四代间接参与的所有生成反应与消耗反应中其它组分相对于预选组分的路径通量之和,以此决定相关组分及其所参与反应的取舍。用该多代路径通量分析简化法对甲烷及正庚烷反应机理进行了简化,计算结果与详细化学机理、直接关系图简化法简化结果、二代路径通量分析简化法简化结果进行了对比,结果证明了该多代路径通量分析简化法具有更高的简化精度。多代路径通量分析简化法为反应流模拟中大型化学机理的精确简化提供了一种新的解决思路。     

化学反应动力学对超声速燃烧的影响

非平衡化学反应是超声速燃烧中非常重要的过程,其反应动力学模拟直接影响其内部温度分布。针对某支板氢燃料超声速燃烧室,分别采用了单步化学反应动力学、7组分8步反应和9组分19步反应动力学模型,对比了燃烧反应速率、内部温度场和速度场的分布。结果表明,采用详细化学反应动力学,燃烧热释放缓慢,在流场中下游自由基参与反应,其温度场与试验值吻合更好。