激光快速熔凝Al2O3/YAG共晶陶瓷的制备与组织

采用激光快速熔凝技术制备Al₂O₃/YAG共晶自生复合陶瓷, 研究Al₂O₃/YAG共晶陶瓷在高能激光束作用下,不同扫描速率(0.01~2.0mm/s)、超高温度梯度下的凝固组织特征及其生长机制,探索激光熔凝过程控制参数与凝固组织的关系.研究结果表明:激光熔凝Al₂O₃/YAG共晶陶瓷由无规则连续分布的Al₂O₃相和YAG相两相组成,没有晶界和其他相,Al₂O₃相的体积分数为(45.0±2.0)%,两相耦合生长,交错分布,是典型的快速凝固层片状非规则共晶组织;共晶层间距细密, 并随激光扫描速度的增大而减小,扫描速度为0.02mm/s 时,共晶间距约为1~2μm,扫描速度为2.0mm/s时,共晶间距仅为0.5μm左右;综合热分析表明,Al₂O₃/YAG共晶熔点为2096K,与相图吻合.     

Si对TiAl合金高温抗氧化性能的影响

利用X射线衍射、扫描电镜、能谱仪等手段研究了TiAl-Si(原子数分数为0~20%)合金在1 173 K大气中24 h的恒温氧化.结果表明:Si元素可以有效地提高TiAl合金的高温抗氧化性能;随着Si含量的增加,氧化膜厚度依次减薄,TiO₂的含量逐渐减少,Al₂O3的含量逐渐增加,添加到10%左右时就有连续致密的Al₂O₃保护膜形成;Si在0~20%的添加过程中并没发现Si的氧化物生成.分析表明:Si对抗氧化性能的贡献可归结于Si与Ti有很好的亲和力,可以有效地降低Ti离子的活度、阻碍Ti离子的向外扩散, 相对来说增强了Al离子的活度,促进连续致密的Al₂O₃保护膜生成.      

密闭空间内氢气和二氧化碳甲醇化系统的非均相模型及反应特性

在载人密闭空间内通过电解水方式为乘员供氧会产生副产物氢气（H₂）。此外,乘员还呼出二氧化碳（CO₂）。将H₂和CO₂催化合成甲醇（CH₃OH）是消除载人密闭空间内富余H₂和CO₂的最优方式之一。对其开展反应过程建模及反应特性研究有助于进行反应过程的控制,更好地维持载人密闭空间内的大气平衡。本文采用微元法建立了H₂和CO₂催化合成甲醇的物料计算模型和温度一维非均相模型,研究了不同反应压力、冷却介质温度以及入口反应气体中CO₂与CO比值等反应条件下的反应特性变化规律。结果显示,反应压力的增加、冷却介质的温升以及入口气体中CO₂与CO比值的减小均能促进各反应速率增加,进而使得H₂和CO₂消除量增加、甲醇合成率上升以及催化剂和反应气体最高温度上升。在保证反应速率增加且催化剂最高温度不超过合理反应温度区间的最大值573.15 K时需维持反应压力不大于8 MPa,冷却介质温度不高于538.15 K以及CO₂与CO比值不小于1。      

铝合金阳极化膜上铈转化膜沉积的电化学研究

阳极氧化膜在含1g/L CeCl₃和2.7 g/L H₂O₂的水溶液中阴极电解可以在其表面沉积富铈转化膜.用循环伏安、φ-t和j-t曲线等电化学测试方法对转化膜成膜反应进行了研究,以期获得对成膜机理的深入了解和证实根据其它工作提出的成膜机理.研究结果表明铈转化膜的生成包括阳极氧化膜的化学溶解和4价铈化合物的电化学还原两个过程;在阴极电位达到析氢电位之前,这两个过程主要是由H₂O₂在阴极的电还原改变了阴极表面附近溶液的局部pH值引起的,而O₂的还原通常不能引起这两个过程的发生.      

中国空间站燃烧科学实验系统PIV单元地面试验

中国空间站燃烧科学实验系统是用于开展微重力燃烧实验研究的综合性科学实验平台，可以实现燃烧流场测量。为了验证燃烧科学实验系统粒子图像测速(PIV)单元对燃烧流场测量的功能与可行性，本文基于与在轨状态一致的连续激光器和相机的空间布局，搭建了地面层流圆孔射流试验平台，选取Al₂O_3，TiO_2，ZrO₂三种示踪粒子进行冷态试验与热态试验。试验结果表明，自主研制Nd∶YVO₄泵浦连续激光器偏光角度合适，能照亮被测流场主流区域，燃烧科学实验系统PIV单元可用于低速燃烧流场测量；相同工况下，Al₂O₃粒子在冷态试验测量的速度值更接近于理论值，速度幅值比更接近1，更适用于低速流体测量。      

稀土元素对Al-Ni-Gd-Y合金晶化行为的影响

利用差示扫描量热仪(DSC)、X射线衍射(XRD)、透射电镜(TEM)研究了稀土元素(RE)对Al-Ni-Gd-Y非晶合金晶化行为的影响.Al-Ni-Gd-Y非晶合金的初始晶化温度随着稀土元素含量的增加而升高.在Al_(88-x)Ni₆Gd₆Y _x ( x =1,2,3,4)系中,随着Y含量的增加,初始晶化产物由面心立方Al(fcc-Al)变成为fcc-Al+Al₃Gd/Al₃Y+未知相.研究了热处理工艺对Al₈₆Ni₈Gd₃Y₃合金力学性能的影响,其中,当Al₈₆Ni₈Gd₃Y₃在568K下保温10min时,其显微硬度及韧性较高,析出尺寸为1~3nm的fcc-Al纳米晶颗粒.     

Nb离子注入γ-TiAl的高温循环氧化行为

研究了Nb离子注入的γ-TiAl合金在1123K和1173K空气中的高温循环氧化行为,用配有能谱仪的扫描电子显微镜对氧化层的形貌、显微结构进行了分析,用俄歇谱仪分析了注入元素和氧化层中各元素的分布.结果表明:Nb离子注入可以提高γ-TiAl合金的抗循环氧化性能.提高其抗氧化性能的主要原因归结于Nb离子在TiO₂中的掺杂作用.高价Nb的掺杂,降低了TiO₂的缺陷浓度,使TiO₂的生长受到抑制,在氧化初期形成了Al₂O₃保护层,从而推迟了氧化层的剥落时间.但Nb离子注入的γ-TiAl合金不具有长期的抗循环氧化性能.      

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研究了Nb离子注入的γ-TiAl合金在1123K和1173K空气中的高温循环氧化行为,用配有能谱仪的扫描电子显微镜对氧化层的形貌、显微结构进行了分析,用俄歇谱仪分析了注入元素和氧化层中各元素的分布.结果表明:Nb离子注入可以提高γ-TiAl合金的抗循环氧化性能.提高其抗氧化性能的主要原因归结于Nb离子在TiO₂中的掺杂作用.高价Nb的掺杂,降低了TiO₂的缺陷浓度,使TiO₂的生长受到抑制,在氧化初期形成了Al₂O₃保护层,从而推迟了氧化层的剥落时间.但Nb离子注入的γ-TiAl合金不具有长期的抗循环氧化性能.     

气相色谱法定量分析氧气中气体杂质方法研究

为寻找一种能够有效检测氧气中微量气体杂质的方法,采用配有氢火焰离子化检测器的气相色谱仪分析氧气中的微量气体杂质,研究了分析氧气中CO、CO₂及C₂H₂等气体杂质的操作参数,确定了氧气中微量气体杂质的分析方法,验证了该方法的可行性,该分析方法各组份分离效果良好,各种杂质组份定量精确度较高。     

Complex organics in laboratory simulations of interstellar/cometary ices.

We present the photochemical and thermal evolution of both non-polar and polar ices representative of interstellar and pre-cometary grains. Ultraviolet photolysis of the non-polar ices comprised of O2, N2, and CO produces CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. When polar ice analogs (comprised of H2O, CH3OH, CO, and NH3) are exposed to UV radiation, simple molecules are formed including: H2, H2CO, CO2, CO, CH4, and HCO (the formyl radical). Warming produces moderately complex species such as CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN and/or R-NC (nitriles and/or isonitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that after warming to room temperature what remains is an organic residue composed primarily of hexamethylenetetramine (HMT, C6H12N4) and other complex organics including the amides above and polyoxymethylene (POM) and its derivatives. The formation of these organic species from simple starting mixtures under conditions germane to astrochemistry may have important implications for the organic chemistry of interstellar ice grains, comets and the origins of life.     

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds.

The prebiotic synthesis of organic compounds using a spark discharge on various simulated prebiotic atmospheres at 25 degrees has been studied. Methane mixtures contained H2 + CH4 + H2O + N2 + NH3 with H2/CH4 molar ratios from 0 to 4 and pNH3 = 0.1 torr. A similar set of experiments without added NH3 was performed. The yields of amino acids (1.2 to 4.7% based on the carbon) are approximately independent of the H2/CH4 ratio and the presence of added NH3, and a wide variety of amino acids are obtained. Mixtures of H2 + CO + H2O + N2 and H2 + CO2 + H2O + N2, with and without added NH3, all give about 2% yields of amino acids at H2/CO and H2/CO2 ratios of 2 to 4. For the H2/CO and H2/CO2 ratios less than 1, the yields fall off drastically to as low as 10(-3)%. Glycine is almost the only amino acid produced from CO and CO2 atmospheres. These results show that the maximum yield is about the same for the three carbon sources at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. In addition, CH4 gives a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these results indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde parallel the amino acid results, with yields of HCN and H2CO as high as 13% based on the carbon. Ammonia is also produced from N2 in experiments with no added NH3 in yields as high as 4.9%. These results show that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges. The amount of ammonia formed by hydrolysis of HCN and various nitriles may have exceeded that formed directly in electric discharges.     

Organic solids produced from simple C/H/O/N ices by charged particles: applications to the outer solar system.

CH4, CO, and CO2 are all potential one-carbon molecular repositories in primitive icy objects. These molecules are all found in the Comet Halley coma, and are probable but, (except for CH4 detected on Triton and Pluto) undetected subsurface constituents in icy outer solar system objects. We have investigated the effects of charged particle irradiation by cold plasma discharge upon surfaces of H2O:CH4 clathrate having a 200:1 ratio, as well as upon ices composed of H2O plus C2H6 or C2H2 (sometimes plus NH3) which are also plausible constituents. These materials color and darken noticeably after a dose 10(9) - 10(10) erg cm-2, which is deposited rapidly (< or = 10(4) yr.) in solar system environments. The chromophore is a yellowish to tan organic material (a tholin) which we have studied by UV-VIS reflection and transmission, and IR transmission spectroscopy. Its yield, -1 C keV-1, implies substantial production of organic solids by the action of cosmic rays and radionuclides in cometary crusts and interiors, as well as rapid production in satellite surfaces. This material shows alkane bands which Chyba and Sagan have shown to well match the Halley infrared emission spectrum near 3.4 microns, and also bands due to aldehyde, alcohol and perhaps alkene/aromatic functional groups. We compare the IR spectral properties of these tholins with the spectra of others produced by irradiation of gases and ices containing simple hydrocarbons.     

Radiation-induced syntheses in cometary simulated models.

The behavior of an aqueous-dominant multicomponent cometary model is examined at high doses of ionizing radiation. The system is composed of a water mixture of HCN (0.2 mol dm-3), CH3CN (0.04 mol dm-3), C2H5CN (0.02 mol dm-3), CH3OH (0.12 mol dm-3) and HCO2H (0.01 mol dm-3. It was exposed to gamma rays at doses up to 18.5 MGy. The chemical kinetic database used in the computer treatment of experimental data consists of 79 reactions. A complex mixture of products has been synthesized: gases, amino acids, carboxylic acids and polymeric material. The results suggest that the pristine material in cometary nuclei may have been chemically altered by the action of cosmic rays and embedded radionuclides.     

Biogeochemical evidence of microbial activity on Mars.

We suggest a new interpretation of the data on so-called SNC meteorites and delta 13C values of the calcium carbonate minerals and organic matter discovered in them. The delta 13C value of calcite (up to 15 ppt) is accounted for by the microbial reaction CO2 + H2 ---> CH4 + H2O. Methane-forming bacteria also synthesize organic carbon (in the form of biomass) from CO2, and this process is accompanied by 12C fractionation. Therefore, the organic carbon of SNC meteorites is enriched with 12C (delta 13C as low as -35 ppt). The environmental conditions under which the calcite of SNC meteorites was formed were favorable for the activity of methanogens.     

利用WACCM-3模式对平流层动力、热力场及微量化学成分季节变化的数值模拟研究

利用美国NCAR最新的化学-气候耦合模式WACCM-3对平流层风场、温度场以及平流层臭氧等多种微量气体成分(O3, CH4, N2O, H2O, HCl, HNO3)的季节变化进行了数值模拟, 并使用ECMWF再分析资料与美国UARS卫星 搭载的HALOE, MLS, CLAES等探测器的观测资料, 对模式输出的动力、热力及化学成分浓度的气候平均值进行了验证. 结果表明, 在气候平均海表温度值驱动下, WACCM-3模式能够很好地再现ECMWF资料中平流层纬向平均风场与温度场的季节变化. 模拟结果中平流层化学成分的经向-垂直分布及其季节变化与卫星观测结果基本一致. 模式的动力、热力场在极地平流层以及热带对流层顶等区域存在一定的偏差. 这些偏差对于微量气体成分分布 的模拟具有一定影响, 特别是南半球冬(7月)、春(10月)季节南极平流层低层极夜 急流偏强, 造成极地地区附近的输送障碍增强, 从而导致CH4, N2O, H2O浓度比观测偏低. 此外, WACCM-3缺少热带平流层风场的准两年振荡(QBO) 机制, 这对于热带平流层东风急流以及低纬度平流层O3, CH4, N2O, H2O等成分经向输送的模拟结果也有一定影响.      

Neutral upper atmospheres of Venus and Mars

Numerous measurements of the neutral upper atmosphere above 100 km have been made from spacecraft over Venus and over Mars. The Venus exospheric temperatures are unexpectedly low (less than 300°K near noon and less than 130°K near midnight). These very low temperatures may be partially caused by collisional excitation of CO₂ vibrational states by atomic oxygen and partially by eddy cooling. The Venus atmosphere is unexpectedly insensitive to solar EUV variability. On the other hand, the Martian dayside exospheric temperature varies from 150°K to 400°K over the 11-year solar cycle, where CO₂ 15-μm cooling may be less effective because of lower atomic oxygen mixing ratios. On Venus, temperature increases with altitude on the dayside (thermosphere), but decreases with altitude from 100 to 150 km on the nightside (cryosphere). However, dayside Martian temperatures near solar minimum for maximum planet-sun distance and low solar activity are essentially isothermal from 40 km to 200 km. During high solar activity, the thermospheric temperatures of Mars sharply increase. The Venus neutral upper atmosphere contains CO₂, O, CO, C, N₂, N, He, H, D and hot nonthermal H, O, C, and N, while the dayside Mars neutral upper atmosphere contains CO₂, O, O₂, CO, C, N₂, He, H, and Ar. There is evidence on Venus for inhibited day-to-night transport as well as superrotation of the upper atmosphere. Both atmospheres have substantial wave activity. Various theoretical models used to interpret the planetary atmospheric data are discussed.     

Radiolysis of aqueous formaldehyde relevant to cometary environments.

The radiation chemistry of aqueous solutions of formaldehyde was studied in order to obtain an insight into the possible role of ionizing radiation on cometary environments. Aqueous solutions of 1.0 mol dm-3 formaldehyde were exposed to gamma-radiation in the dose range from 0.01 to 1200 kGy at 298 K. The radiation chemical yield of decomposition of formaldehyde was determined to be: G(-CH2(OH)2)-26.3 +/- 1.2. The high radiation chemical yield of decomposition was explained by a chain reaction initiated by the radical CH(OH)2 with formaldehyde. Computer fitting of the experimental data gives k(CH(OH)2 + CH2(OH)2)- 8.0xl0(1) dm3 mol-1 s-1. In the computer treatment of experimental findings we used 54 equations to consider the radiolysis of water and 11 reactions for the radiolysis of aqueous formaldehyde. Based on previous estimates of the total dose of ionizing radiation that comets have accumulated over 4.6 billion years, we predict a radiation damage-depth curve of formaldehyde in comet nuclei.     

Carbonaceous matter in cometary dust and coma.

The analysis of carbonaceous matter in p/Halley's dust and coma via mass spectrometry of positive ions is reviewed. Dust impact generated ions were analyzed by the PUMA instrument aboard VEGA I, and coma plasma ions by the PICCA instrument aboard GIOTTO. For the organic molecules results an overall C:H:O:N ratio of 1.:1.4:0.6:0.1. Most of this polymer material can formally be understood as an aggregation of monomers C2H2, CH2O, and HCN. Special emphasis is given to possible aromatic, especially heterocyclic, and other unsaturated ions, and their importance for abiotic chemical and prebiotic evolution. Aspects of the potential heterogeneous catalysis in liquid water at the inorganic grain backbone structure found by this analysis, too, are also treated.     

Radiation chemistry of the hippocampal brain slice.

The in vitro hippocampal brain slice is a 0.4 mm thick neural network that can be used to study brain responses to radiation and related injuries. This preparation is unique in that it responds to ionizing radiation within minutes after exposure without complications from changes in vascularity, blood flow, blood pressure, etc. Electrophysiological studies have shown that x- and gamma-rays alter synaptic transmission and spike generation, elements of normal brain activity. To evaluate the role of hydroxyl free radicals (OH) in these changes, slices were exposed to dilute H2O2 solutions. EPR spin trapping experiments verified that OH is produced. Neural responses, while similar, were not identical to those due to radiation, possibly because of a different distribution of OH. Although H2O2 is freely diffusible, it produces OH at specific sites where, e.g. iron reduces it. In contrast, x- and gamma-rays produce OH more uniformly throughout the tissue. H2O2 may provide a better model for high-LET radiation where yields of radical products of water radiolysis are decreased and peroxide reactions predominate.