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.     

壳聚糖季铵盐的合成及其对鞣酸的絮凝性能

通过引入季铵盐基团的方法对壳聚糖进行改性得到完全溶于水的壳聚糖季铵盐,IR谱图表明取代反应主要发生在壳聚糖的氨基上。以中药药液中的主要杂质之一鞣酸为对象进行了絮凝试验,结果显示其鞣酸去除率,明显高于壳聚糖。同时壳聚糖季铵盐絮凝剂投加量适用范围更宽,有利于实际使用。     

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.     

Polymer electrolytes from PEO and novel quaternary ammonium iodides for dye-sensitized solar cells

Polymer electrolytes were prepared by blending high molecular weight poly(ethylene oxide) (PEO) and a series of novel quaternary ammonium iodides, the polysiloxanes with oligo(oxyethylene) side chains and quaternary ammonium groups. X-ray diffraction (XRD) measurements ensured relatively low crystallinity when the quaternary ammonium iodides were incorporated into the PEO host. The ionic conductivity of these complexes was improved with the addition of plasticizers. The improvement in the ionic conductivity was determined by the polarity, viscosity and amounts of plasticizers. A plasticized electrolyte containing the novel quaternary ammonium iodide was successfully used in fabricating a quasi-solid-state dye-sensitized solar cell for the first time. The fill factor and energy conversion efficiency of the cell were calculated to be 0.68 and 1.39%, respectively.     

Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants

The thermal stability of seven organically modified montmorillonites (‘organoclays’) has been investigated using differential thermal analysis, differential scanning calorimetry, and thermogravimetry in conjunction with X-ray diffractometry. Six organoclays were synthesised by replacing the interlayer inorganic cations, initially present, with quaternary phosphonium and ammonium surfactant cations. The samples modified with tetrabutylphosphonium (TBP), and butyltriphenylphosphonium (BTPP) ions have an appreciably higher thermal stability than the octadecyltrimethylammonium (ODTMA)-modified clays. Thus, in the case of TBP- and BTPP-modified montmorillonites, the onset temperature of decomposition is close to 300 °C. Samples modified with hexadecyltributylphosphonium (HDTBP) ions have a lower onset temperature of decomposition of 225 °C. In comparison, the onset temperature for ODTMA-montmorillonites (obtained at different concentrations of ODTMA-bromide) ranges from 158 to 222 °C, being highest where the concentration of intercalated surfactant is lowest. The onset temperature for a commercial alkylsilane-treated quaternary ammonium-modified organoclay (S-BEN N-400FP) is 207 °C. The basal spacing of the TBP- and BTPP-modified clays is 1.7–1.8 nm, indicating a monolayer arrangement of quaternary phosphonium ions in the interlayer space, while the value of 2.5 nm for HDTBP-montmorillonite indicates a more open structure. The ODTMA-modified samples have basal spacings ranging from 1.9 to 2.1 nm, indicative of a bilayer to pseudo-trilayer arrangement. The exceptionally high basal spacing of 3.4 nm for the S-BEN N-400FP organoclay might be due to interlayer penetration of organosilane hydrolysis products during synthesis. The thermal properties of organoclays are apparently related to the nature of the surfactants and their arrangement in the interlayer space of montmorillonite.     

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.     

柴达木盆地涩北地区第四系泥岩型生物气储层孔隙有效性评价

通过低场核磁共振实验分析了柴达木盆地涩北地区第四系泥岩型生物气储层在饱和水状态及渐变烘干温度状态下的T₂谱,明确了孔隙流体的核磁响应特征,以评价孔隙的有效性。研究结果表明： ①核磁共振实验是以饱和水状态T₂谱为基础,采用正态分布函数拟合构建了离心束缚水T₂谱,确定了可动流体和毛管束缚流体T₂截止值,用于划分出流体类型并开展了孔隙有效性评价。②研究区岩样饱和水状态T₂谱谱峰呈左小右大的形态,右峰幅度值远大于左峰,占T₂谱幅度值90%以上;随着烘干温度的升高,T₂谱幅度减小且左移趋势明显;束缚水T₂谱形态近似于正态分布,起始位置与饱和水状态的T₂谱基本重合。③研究区可动流体T₂截止值T_{2 C1}平均为3.3 ms,毛管束缚流体T₂截止值T_{2 C2}平均为1.8 ms;孔隙流体包括可动水、毛管束缚水和黏土束缚水,黏土束缚水T₂小于T_{2 C2},毛管束缚水T₂大于T_{2 C2}且小于T_{2 C1},可动流体T₂大于T_{2 C1};毛管束缚水含量最高,黏土束缚水其次,两者占总孔隙流体的84.43%～95.06%,可动水含量低。④研究区储层有效孔隙占总孔隙的54.99%,主要为毛管束缚孔,黏土束缚孔为无效孔隙;黏土含量越高,有效孔隙度越小。