EXPERIMENTAL STUDIES OF NUCLEATION PHENOMENA WITHIN THERMAL BOUNDARY LAYERS—INFLUENCE ON CHEMICAL VAPOR DEPOSITION RATE PROCESSES

In carrying out partial vapor condensations using actively cooled surfaces it is known that 'mist' formation can occur within thermal boundary layers (Rosner and Epstein, 1968), dramatically modifying total deposition fluxes. Using a combination of flash-evaporation (Rosner and Liang, 1986) and laser probing techniques, we report new experimental results on binary alkali salt (K₂SO₄ + Na₂SO₄) deposition from combustion gases showing that the deposition rate of potassium sulfate first increases with the addition of sodium sulfate until the concentration of Na₂SO₄ reaches a (target surface temperature dependent) 'threshold' value. Further increases in the concentration of Na₂SO₄ dramatically decrease the total deposition rate of K₂SO₄, implying that potassium sulfate-containing microdroplets are formed within the thermal boundary layer, which, despite their thermophoretic drift toward the target, are not collected as effectively as the 'parent' K₂SO₄-vapor species. Laser light scattering measurements clearly reveal that suspended particles exist near the deposition surface under these conditions. Our experimental results on mass transfer rate and light scattering are consistent with those predicted using laminar boundary layer theory (Castillo and Rosner, 1989b) coupling both binary salt vapor deposition with particle vapor scavenging and deposition. Comparisons of our observed mist onset conditions (implying critical supersaturations near unity) with those expected using homogeneous nucleation theory suggest that the binary alkali sulfate mist nucleation mechanism is, instead, heterogeneous, even in our relatively 'clean' combustion products. Because of the; well-known vapor pressure reduction phenomenon associated here with the formation of non-ideal solutions, binary systems are shown to provide convenient 'vehicles' to investigate BL mist formation onset conditions and CVD-rate consequences without requiring the more extreme surface coolings characteristic of unary condensible vapor systems. An understanding of this dramatic phenomenon, obtained via such laboratory experiments and calculations, will allow its inclusion in future deposition rate calculations of engineering importance.     

5-氰基-4-氨基咪唑的合成与热性能

咪唑基含能化合物是目前高能化合物的重要研究方向，而5-氰基-4-氨基咪唑是设计、合成新型咪唑联四唑类高能高氮化合物的关键中间体。以5-甲酰胺基-4-氨基咪唑（AICON）为原料，经其与三氯氧磷（POCl3）的脱水反应获得了5-氰基-4-氨基咪唑（AICN），通过优化反应体系、反应温度、反应时间以及物料物质的量比，使得AICN的收率>65%，纯度（HPLC）>99.5%。此外，采用NMR、IR和元素分析对其进行了结构确征，利用热重分析法研究其热性能。结果表明：AICN的最佳反应条件为以POCl3为脱水剂，n(AICON)：n(POCl3)为1:10，反应升温模式为先快速升温至80~85 ℃，维持反应30 min，然后降温至70~75 ℃，维持反应1~1.5 h；AICN在40~1000 ℃温度区间存在两个失重过程，对应的热分解温度区间分别为40~400 ℃和400~1000 ℃、热失重分别为19.8%和60.7%、热分解峰温分别为256.5和698.4 ℃，表明其具有良好的热稳定性。     

多组分氯盐体系镁锂分离规律初探

以Na₂CO₃为沉淀剂,初步研究了多组分氯盐混合体系（0.6 mol MgCl₂+1.1 mol LiCl+3.2 mol NaCl）中选择性沉镁的工艺规律。结果表明：在25~80 ℃,总C与总Mg物质的量比[n（C_T）/n（Mg_T）]为 0.8~1.1时,25 ℃形成针状MgCO₃·3H₂O,40 ℃以上形成Mg₅（CO₃）₄（OH）₂·4H₂O不规则片状团聚微球,其中40~50 ℃形成的片状物较为分散且粒径较小,导致固液分离困难。40 ℃时沉镁率最低。温度越高,Li₂CO₃越易形成,沉锂率越大。n（C_T）/n（Mg_T）越大沉镁率和沉锂率越高。室温（25 ℃）、n（C_T）/n（Mg_T）=1.0时,沉镁率达98%以上,且沉锂率<0.1%,镁锂分离效果最好。     

湖泊富营养化过程中内源性营养盐释放规律的分析

通过采集3种典型营养级别湖泊沉积物,对其营养盐的释放规律进行研究.结果表明：在碱性条件下,富营养化湖泊沉积物中总磷、总氮释放量达到峰值;在中性条件下,富营养化湖泊沉积物中总有机碳释放量最大;在厌氧条件下,富营养化湖泊沉积物中氮、磷、COD的释放量最大.在平行实验条件下3个湖泊中的重度富营养化湖泊的氮、磷、COD的释放量最大.     

Organo-zincate molten salts as immobilising agents for organometallic catalysis

The combination of 1-n-butyl-3-methylimidazolium chloride with ZnCl₂ affords ionic mixtures with different melting point temperatures depending on the zinc molar fraction. RuCl₂(PPh₃)₃ immobilised in the low melting mixture (60°C) promotes the 1-hexene hydrogenation (turnover frequencies up to 44 min^–1) and the recovered solid catalyst phase can be reused several times.     

Water vapor adsorption in activated carbon modified with hydrophilic organic salts

Five different kinds of hydrophilic organic salts were used to modify commercial activated carbon in order to prepare hydrophilic carbon materials. Properties of the samples were analyzed by surface area analyzer and SEM-EDX. The hydrophilic organic salts with different properties were introduced into activated carbon and significantly affected the properties of the samples.During adsorption experiments, the water vapor adsorption amount in modified samples increases by 0.57-17.12 times in temperature range from 303 to 323 K and at relative pressure below 0.50. Water molecules combined with surface hydrophilic groups through H-bonding exhibit good thermo stability. The effects of temperature, oxygen content and properties of the hydrophilic organic salts on water vapor adsorption were studied. It is indicated that water vapor adsorption in modified samples is mainly affected by the surface oxygen content. The carboxylate radicals in the hydrophilic organic salts greatly affect the micropore structure of the modified samples, while the metal ions in them exhibit limited influence. Different adsorption capacity of modified samples can be explained with the electronegativity of elements presented by Pauling.     

含能材料锥形双螺杆安全混合径向间隙的研究

以锥形双螺杆挤出机挤出段、过渡体和挤出机头为研究对象,基于Polyflow非等温稳态和瞬态的有限元模拟,对不同径向间隙下流场中各场量分布情况和变化曲线进行分析,研究含能材料在挤出段、过渡体和挤出机头流道中的安全和混合问题。从安全和混合效果两方面考虑,建立了综合评价方法,优选径向间隙。结果表明,最大剪切速率、最高剪切应力和最高黏性耗散热均在挤出段流道入口附近,最高压力在挤出段流道出口处,最高温度在机头处;锥形双螺杆的混合效果随着间隙的增加而增加;在径向间隙为0.5 mm时,流道的安全性能最差,径向间隙为1 mm时,流道的安全性能最好。     

Electrochemical production of Sn-filled carbon nanotubes in molten salts

Sn-filled carbon nanotubes(CNTs) were prepared in situ by electrolysis of graphite in molten LiCl/SnCl2 mixtures. Transmission electron microscopy(TEM) investigation shows that the as-made products contain abun-dance of carbon nanotubes and most of them are filled with metal nanoparticles or nanorods. Some nanotubes are e-ven inserted with long continuous nanowires more than several micrometers in length. Selected area electron diffrac-tion(SAED) patterns and energy dispersive X-ray spectroscopy(EDS) of the filled nanotubes confirm the presence of Sn inside the nanotubes. The encapsulated Sn was further identified as β-Sn with tetragonal structure. Based on the experimental results, a possible growth mechanism of the Sn-filled nanotubes was also discussed.     

High temperature corrosion mechanisms and effect of alloying elements for materials used in waste incineration environment

Corrosion products on two typical materials, SA213-T12 steel and alloy 625 exposed to the actual combustion gas, were analyzed in addition to laboratory tests for penetration of corrosive matter. It has been clarified that corrosion products of oxides containing a little chlorides and sulphides show lamellar structures and that at the alloy-scale interface, chlorination, sulphidation, and oxidation occur under a low P_O2-high P_Cl2 condition. The formation of scale structures and the effect of corrosion-resistant alloying elements can be explained according to the stability tendencies of metals, chlorides, and oxides in the M-Cl-O equilibrium diagrams. The severity of corrosion environments at the interface is influenced by the penetration extent of corrosive matters through deposits and scales, and the protective effects of oxide films derived from alloying elements play an important role in preventing the corrosion. On the other hand, it has been shown that thermal fluctuation characterized in this kind of environment makes the lamellar scale structures and sometimes breaks and peels off the scale, and thus accelerates the corrosion. On the basis of the above mentioned knowledge, a new corrosion model is presented.