端羟基聚丁二烯(HTPB)的热分解研究

用TG-DTA考察了HTPB的热分解行为,表明HTPB热分解经历两个阶段.第一阶段主要产物为4-乙烯基-1-环己烯、丁二烯等,第二阶段主要产物为丁二烯、环戊烯、1,3环己二烯.说明HTPB在热分解初期主要是解聚反应并伴有环化、交联作用;第二阶段主要是环化、交联物的裂解.文中还对HTPB热分解的可能机制进行了讨论.     

酚醛浸渍碳烧蚀体(PICA)的制备、结构及性能

采用热塑性酚醛树脂溶液浸渍碳毡,经过溶胶-凝胶反应和常压干燥后,制备出一系列不同密度的酚醛浸渍烧蚀体(PICA)(0.27~0.47 g/cm3)材料,并系统研究了不同密度的PICA碳化前后微观形貌、力学性能及隔热性能的变化规律。结果表明:PICA具有典型的碳纤维增强酚醛气凝胶复合结构。不同密度的PICA均具有优异的力学性能和隔热性能,且弯曲强度为2.2~16.5 MPa,热导率为56~62 m W/(m·K)。在密度为0.40 g/cm3时,PICA弯曲强度最大,热导率最低。进一步通过1 000℃高温处理之后,相应的C-PICA材料仍然表现出轻质、高强、低热导率的特征。     

高氯酸铵粒度对AP-CMDB推进剂热分解特性的影响

利用热分析—质谱和红外联用法、高压差示扫描量热法研究了高氯酸铵(AP)粒度对AP-CMDB推进剂在0.1 MPa(常压)和1.0MPa压强下的热分解过程。结果表明,含不同粒度AP的AP-CMDB推进剂的热分解过程存在明显的差异,含大粒度AP(d50=96.8μm)的推进剂在常压和1.0 MPa下的热分解过程均出现了AP单体的高温分解阶段,含小粒度AP(d50=12.4,8.5和1.0μm)的推进剂在高压下均仅表现出一个快速分解阶段;AP-CMDB推进剂分解过程中的气体产物主要包括NO2,NO,N2O,CO2,CO,O2,N2,H2O,HCHO和HCl。     

刚性短切碳纤维预制体和酚醛浸渍碳烧蚀体的制备及性能

以短切碳纤维、热固性酚醛树脂为原料,经真空成型得到短切碳纤维预制体(Fiberform),再以Fiberform为骨架、酚醛树脂溶液为浸渍液,经反应干燥得到酚醛浸渍碳烧蚀体(PICA)。结果表明:Fiberform具有明显的各向异性,当Fiberform的密度由0.13 g/cm~3增大到0.18 g/m~3时,其纵向压缩强度由0.10 MPa增大到0.39 MPa,横向压缩强度由0.33 MPa增大到0.79 MPa。PICA具有酚醛气凝胶/碳纤维复合型结构,其密度可以通过控制酚醛树脂溶液浓度来调节。当PICA的密度由0.27 g/cm~3增大到0.43 g/cm~3,其纵向压缩强度由0.45 MPa增大到2.42 MPa,横向压缩强度由1.36 MPa增大到3.12 MPa。PICA的隔热性能与Fiberform相近,其纵向和横向热导率分别为0.08和0.11 W/(m·K)。     

Resol型酚醛树脂热解特征的TG-MS 研究

合成了一种低醛 /酚摩尔比 (1.3∶1)的Resol型酚醛预聚物。利用TG -MS详细研究了热交联固化后树脂的热分解特征。低于 35 0℃时 ,主要表现为分子内醚键断裂和脱端羟甲基 ,并逸出H2 O、CO2 和CH3 OH等产物及它们的碎片。在 35 0℃～ 75 0℃范围内 ,大分子主链在不同位置发生主链断裂而形成一甲基苯酚、二甲基苯酚和三甲基苯酚等产物及它们的碎片。说明了大分子主链热稳定性的提高是减少和防止Resol型酚醛树脂前驱体C/C复合材料缺陷的重要组成部分     

空间探测烧蚀防热材料应用及趋势

综述了国内外空间探测器烧蚀防热材料的种类及其应用情况,美国主要包括高密度酚醛/玻璃钢、蜂窝增强烧蚀防热材料、PICA及PICA-X以及高密度碳酚醛材料等,国内则主要包括酚醛/尼龙、蜂窝增强烧蚀防热材料和NF材料,介绍了这些材料所应用的探测器、气动加热环境、防热材料性能和防热结构成型技术。总结了美国空间探测防热材料研制中出现的两次烧蚀异常及导致的探测器选材变化,可见防热材料与热环境耦合关系复杂。同时介绍了我国针对防热材料抵御异常损伤开展的部分工作。最后对空间探测防热材料的应用与发展做出了展望。     

Reso1型酚醛树脂热解特征的TG—MS研究

合成了一种低醛/酚摩尔比(1.3：1)的Resol型酚醛预聚物。利用TG-MS详细研究了热交联固化后树脂的热分解特征。低于350℃时，主要表现为分子内醚键断裂和脱端羟甲基，并逸出H20、CO2和CH30H等产物及它们的碎片。在350℃—750℃范围内，大分子主链在不同位置发生主链断裂而形成一甲基苯酚、二甲基苯酚和三甲基苯酚等产物及它们的碎片。说明了大分子主链热稳定性的提高是减少和防止Resol型酚醛树脂前驱体C／C复合材料缺陷的重要组成部分。     

刚性短切碳纤维预制体和酚醛浸渍碳烧蚀体的制备及性能杨

以短切碳纤维、热固性酚醛树脂为原料,经真空成型得到短切碳纤维预制体(Fiberform),再以Fi鄄

berform 为骨架、酚醛树脂溶液为浸渍液,经反应干燥得到酚醛浸渍碳烧蚀体( PICA)。结果表明:Fiberform 具

有明显的各向异性,当Fiberform 的密度由0. 13 g/ cm3增大到0. 18 g/ m3 时,其纵向压缩强度由0. 10 MPa 增大

到0. 39 MPa,横向压缩强度由0. 33 MPa 增大到0. 79 MPa。PICA 具有酚醛气凝胶/ 碳纤维复合型结构,其密度

可以通过控制酚醛树脂溶液浓度来调节。当PICA 的密度由0. 27 g/ cm3增大到0. 43 g/ cm3,其纵向压缩强度由

0. 45 MPa 增大到2. 42 MPa,横向压缩强度由1. 36 MPa 增大到3. 12 MPa。PICA 的隔热性能与Fiberform 相近,

其纵向和横向热导率分别为0. 08 和0. 11 W/ (m·K)。

     

碳化锆液相陶瓷前驱体的制备及陶瓷化

以聚锆氧烷PNZ 为锆源、炔丙基酚醛PN 为碳源制备了一种ZrC 液相陶瓷前驱体PNZ-PN,该前
驱体经1 600℃热解能够转化为高度结晶的ZrC 陶瓷。通过FT-IR、DSC、TGA 对前驱体的固化过程及固化样
的热失重行为进行了分析;通过XRD、元素分析和SEM 对热解产物的晶相组成及微观形貌进行了分析。结果
表明:1 200℃以下,热解产物主要是ZrO2,1 400℃时开始发生碳热还原反应出现结晶度较小的ZrC,经1 600℃
热解后可完全转化为ZrC;PN 的加入量会影响热解过程中陶瓷样品的ZrO2 晶相及1 600℃热解产物的碳含量,
通过调整PN 的加入量最终可得到自由碳含量1. 66%、近似纯相的ZrC 陶瓷;得到的陶瓷粒子Zr、C 元素分布
均匀、粒径主要分布为100 ~200 nm。     

镁基水反应金属燃料的热分解性能

采用热重-差热分析联用(TG-DTA)、差示扫描量热(DSC)、加压热重(PTG)等热分析方法,研究了镁基水反应金属燃料热分解反应的基本特性及其变化规律。研究发现,燃料热分解过程中先后发生AP分解反应、HTPB分解反应,氩气中不发生Mg的氧化反应;添加催化剂、减小AP粒度、增大氧化剂与粘合剂比例、增大细Mg粉含量等,可以降低燃料中AP的分解温度T,减小表观活化能Ea,增大反应速率常数k;减小AP粒度、增大氧化剂与粘合剂比例可以降低燃料中HTPB的分解温度,减小表观活化能Ea,增大反应速率常数k;随着压强增大,AP与HTPB分解失重速率增大、AP失重百分数增大、燃料热分解凝聚相产物质量百分数减少,压强对AP分解影响较大,对HTPB分解影响较小。     

On the Flux of Water and Minor Volatiles from the Surface of Comet Nuclei

Surface temperature and the available effective energy strongly influence the mass flux of H₂O and minor volatiles from the nucleus. We perform computer simulations to model the gas flux from volatile, icy components in porous ice-dust surfaces, in order to better understand results from observations of comets. Our model assumes a porous body containing dust, one major ice component (H₂O) and up to eight minor components of higher volatility (e.g. CO, CH₄, CH₃OH, HCN, C₂H₂, H₂S), The body's porous structure is modeled as a bundle of tubes with a given tortuosity and an initially constant pore diameter. Heat is conducted by the matrix and carried by the vapors. The model includes radially inward and outward flowing vapor within the body, escape of outward flowing gas from the body, complete depletion of less volatile ices in outer layers, and recondensation of vapor in deeper, cooler layers. From the calculations we obtain temperature profiles and changes in relative chemical abundances, porosity and pore size distribution as a function of depth, and the gas flux into the interior and into the atmosphere for each of the volatiles at various positions of the body in its orbit. In this paper we relate the observed relative molecular abundances in the coma of Comet C/1995 O1 (Hale-Bopp) and of Comet 46P/Wirtanen to molecular fluxes at the surface calculated from our model. This revised version was published online in June 2006 with corrections to the Cover Date.     

Comet Halley's Gas Composition and Extended Sources: Results from the Neutral Mass Spectrometer on Giotto

The Neutral Mass Spectrometer on the Giotto spacecraft established that H₂O is the dominant species in Comet Halley's volatiles and determined the abundance of more than 10 parent species. The instrument discovered strong extended H₂CO and CO sources in the coma of Comet Halley. Polymerized H₂CO associated with the cometary dust and evaporating slowly as the monomer is most likely the extended H₂CO source. Photodissociation of the H₂CO into CO fully accounts for the extended CO source. This revised version was published online in June 2006 with corrections to the Cover Date.     

Outgassing History and Escape of the Martian Atmosphere and Water Inventory

The evolution and escape of the martian atmosphere and the planet’s water inventory can be separated into an early and late evolutionary epoch. The first epoch started from the planet’s origin and lasted ～500 Myr. Because of the high EUV flux of the young Sun and Mars’ low gravity it was accompanied by hydrodynamic blow-off of hydrogen and strong thermal escape rates of dragged heavier species such as O and C atoms. After the main part of the protoatmosphere was lost, impact-related volatiles and mantle outgassing may have resulted in accumulation of a secondary CO₂ atmosphere of a few tens to a few hundred mbar around ～4–4.3 Gyr ago. The evolution of the atmospheric surface pressure and water inventory of such a secondary atmosphere during the second epoch which lasted from the end of the Noachian until today was most likely determined by a complex interplay of various nonthermal atmospheric escape processes, impacts, carbonate precipitation, and serpentinization during the Hesperian and Amazonian epochs which led to the present day surface pressure.     

Transient simulation of regression rate on thrust regulation process in hybrid rocket motor

The main goal of this paper is to study the characteristics of regression rate of solid grain during thrust regulation process. For this purpose, an unsteady numerical model of regression rate is established. Gas–solid coupling is considered between the solid grain surface and combustion gas.Dynamic mesh is used to simulate the regression process of the solid fuel surface. Based on this model, numerical simulations on a H2O2/HTPB(hydroxyl-terminated polybutadiene) hybrid motor have been performed in the flow control process. The simulation results show that under the step change of the oxidizer mass flow rate condition, the regression rate cannot reach a stable value instantly because the flow field requires a short time period to adjust. The regression rate increases with the linear gain of oxidizer mass flow rate, and has a higher slope than the relative inlet function of oxidizer flow rate. A shorter regulation time can cause a higher regression rate during regulation process. The results also show that transient calculation can better simulate the instantaneous regression rate in the operation process.     

HAN基电控固体推进剂电热耦合特性及燃烧特性实验研究

为了探究HAN基电控固体推进剂(ECSP)的电热耦合特性和燃烧性能,通过改变施加电压和环境压力对ECSP进行燃烧性能测试。在ECSP燃烧性能测试装置中采用电压、电流探头记录燃烧过程中通过推进剂的电压和电流,利用高速摄影仪记录推进剂的燃烧过程,借助法拉第电化学分解定律计算推进剂理论电化学分解质量在总燃烧消耗质量中的占比,分析电压和压力对推进剂燃速和质量损失的影响,同时拟合出ECSP燃速(r)与功率(P₁)和压力(P₂)的经验公式。结果表明：随着电压和压力的增加,ECSP理论电化学分解质量和实际燃烧质量增加,理论/总燃烧质量比值降低,燃速和质量损失增加。在ECSP的可控燃烧范围内,其燃速与功率和压力满足r = 0.0105P_1^0.705P_2^0.251。本文得到了热分解反应在ECSP的燃烧过程中占主导地位,是高压力下造成推进剂不可控燃烧的主要原因,为揭示ECSP的燃烧可控机理提供理论基础。     

石英纤维增强聚酰亚胺复合材料超低温铣削实验

石英纤维增强聚酰亚胺复合材料是一种非均匀的各向异性材料,采用传统铣削方法对其进行加工时存在刀具磨损严重、切削力较大、加工效率低等问题。为此本文采用超低温冷却铣削方法对石英纤维增强聚酰亚胺复合材料进行铣削实验,并与传统干铣削方式进行了对比,分析了包括加工表面形貌、粗糙度、切削力和刀具磨损等切削性能。结果表明:两种工况下,表面粗糙度随主轴转速的提高而降低,随切深的增加呈先降低后增大趋势;相对于干铣削,不同切削速度下超低温冷却铣削有效抑制了低速干铣削纤维起毛、高速干铣削黏结剂烧蚀缺陷,表面质量都得到改善,刀具耐用度得到提高。超低温冷却引起的复合材料切削力增大,纤维断屑方式的改变以及切削热的有效降低是提高加工质量的主要原因。     

Martian Volatiles: Isotopic Composition, Origin, and Evolution

Information about the composition of volatiles in the Martian atmosphere and interior derives from Viking spacecraft and ground-based measurements, and especially from measurements of volatiles trapped in Martian meteorites, which contain several distinct components. One volatile component, found in impact glass in some shergottites, gives the most precise measurement to date of the composition of Martian atmospheric Ar, Kr, and Xe, and also contains significant amounts of atmospheric nitrogen showing elevated ¹⁵N/¹⁴N. Compared to Viking analyses, the ³⁶Ar/¹³²Xe and ⁸⁴Kr/¹³²Xe elemental ratios are larger in shergottites, the ¹²⁹Xe/¹³²Xe ratio is similar, and the ⁴⁰Ar/³⁶Ar and ³⁶Ar/³⁸Ar ratios are smaller. The isotopic composition of atmospheric Kr is very similar to solar Kr, whereas the isotopes of atmospheric Xe have been strongly mass fractionated in favor of heavier isotopes. The nakhlites and ALH84001 contain an atmospheric component elementally fractionated relative to the recent atmospheric component observed in shergottites. Several Martian meteorites also contain one or more Martian interior components that do not show the mass fractionation observed in atmospheric noble gases and nitrogen. The D/H ratio in the atmosphere is strongly mass fractionated, but meteorites contain a distinct Martian interior hydrogen component. The isotopic composition of Martian atmospheric carbon and oxygen have not been precisely measured, but these elements in meteorites appear to show much less variation in isotopic composition, presumably in part because of buffering of the atmospheric component by larger condensed reservoirs. However, differences in the oxygen isotopic composition between meteorite silicate minerals (on the one hand) and water and carbonates indicate a lack of recycling of these volatiles through the interior. Many models have been presented to explain the observed isotopic fractionation in Martian atmospheric N, H, and noble gases in terms of partial loss of the planetary atmosphere, either very early in Martian history, or over extended geological time. The number of variables in these models is large, and we cannot be certain of their detailed applicability. Evolutionary data based on the radiogenic isotopes (i.e., ⁴⁰Ar/³⁶Ar, ¹²⁹Xe/¹³²Xe, and ¹³⁶Xe/¹³²Xe ratios) are potentially important, but meteorite data do not yet permit their use in detailed chronologies. The sources of Mars' original volatiles are not well defined. Some Martian components require a solar-like isotopic composition, whereas volatiles other than the noble gases (C, N, and H₂O) may have been largely contributed by a carbonaceous (or cometary) veneer late in planet formation. Also, carbonaceous material may have been the source of moderate amounts of water early in Martian history.     

Ignition enhancement of ethylene/air by NOx addition

Recently, non-equilibrium plasma assisted combustion (PAC) has been found to be promising in reducing the ignition delay time in hypersonic propulsion system. NO x produced by non-equilibrium plasma can react with intermediates during the fuel oxidation process and thereby has influence on the combustion process. In this study, the effects of NO x addition on the ignition process of both the homogeneous ethylene/air mixtures and the non-premixed diffusion layer are examined numerically. The detailed chemistry for ethylene oxidization together with the NO x sub-mechanism is included in the simulation. Reaction path analysis and sensitivity analysis are conducted to give a mechanistic interpretation for the ignition enhancement by NO x addition. It is found that for both the homogenous and non-premixed ignition processes at normal and elevated pressures, NO 2 addition has little influence on the ignition delay time while NO addition can significantly promote the ignition process. The ignition enhancement is found to be caused by the promotion in hydroxyl radical production which quickly oxidizes ethylene. The promotion in hydroxyl radical production by NO addition is achieved in two ways:one is the direct production of OH through the reaction HO2+NO = NO2+OH, and the other is the indirect production of OH through the reactions NO+O2=NO2+O and C2H4+O = C2H3+OH. Moreover, it is found that similar to the homogeneous ignition process, the acceleration of the diffusion layer ignition is also controlled by the reaction HO2+NO = NO2+OH.     

丙二醇改性水溶液的发汗冷却实验研究

针对液态水相变发汗冷却实验中的振荡、表面温度分布不均及结冰现象,对液体冷却剂进行调研,选取丙二醇添加剂对液态水改性,在主流温度573K,雷诺数1.2×10⁴的亚声速高温风洞中实验研究了不同丙二醇改性水溶液浓度和注入率下多孔平板的相变发汗冷却特性。结果表明：随丙二醇浓度增大,多孔平板对改性水溶液的渗透率增大,多孔平板表面温度的振荡幅度减小,同时振荡周期内温度波峰降低。因此,使用丙二醇改性水溶液作为冷却剂,发汗冷却结构表面温度分布更加均匀,热疲劳损伤减小,承温极限升高,进而烧蚀风险降低,这对有效且高效的热防护系统设计具有重要意义。另外,注入率越大平板表面冷却效果越好,表面温度的振荡幅度越小,因此增大注入率也是改善多孔板表面温度波动的有效方式。