磺酸型Gemini表面活性剂的合成及表面活性

以壬基酚、1,4-二溴丁烷和氯磺酸为主要原料,通过三步反应合成了新型的磺酸型Gemini表面活性剂9BA-4-9BA,讨论了合成反应时间、温度以及催化剂对产物纯度和产率等因素的影响,优化了反应过程。利用核磁共振谱和红外光谱表征了产物结构,并通过DCTA21表面/界面张力仪测试其水溶液中的表面张力。和传统表面活性剂相比,合成的Gemini表面活性剂9BA-4-9BA具有更高的表面活性,其临界胶束浓度和C20分别为6.2×10-4mol/L和1.1×10-5mol/L。     

The permeation resistance of interface and the directional dependence of permeation in plasma-grafted composite membranes

Composite membranes were prepared by grafting plasma-polymerized films onto the surface of nonporous poly (dimethylsiloxane) films. Gas permeabilities of the composite membranes were measured at 35°C, 1 atm for N₂, 0₂, CO₂ and CH₄. The permeation properties of the composite membrane was analyzed using the series resistance model. There was a great interfacial resistance to CH₄ permeation through the composite membrane. The interfacial resistance was negligible for the other gases. The interfacial resistance seems to be a result of an interfacial layer caused by the interaction between the bulk two layers. For CH₄ gas, the permeation rate through the composite membrane was affected by the direction of flow. The directional dependence was negligible for the other gases.     

Predicting external sulphur requirement of alfalfa from sulphate sorption isotherm of Tanzanian soils

For Tanzanian soils dominant in hydrous oxides of iron and amorphous ferri-alumino silicate, a 48-hour (hr) mixing period with the sulphate (SO₄) solution was adequate for a near-equilibrium condition. Although differing in their SO₄ sorption capacity, all the soils sorbed SO₄ at or beyond 1µg ml^–1 sulphur (S) concentration in the supernatant. Hydroxyl (OH) ions were displaced during SO₄ sorption as indicated by a significant positive correlation between the amount of sorbed SO₄ and the difference in pH values determined in 0.1N K₂ SO₄ and 0.1N KCl, i.e. the dpH values.In a greenhouse experiment, alfalfa was grown on eight soils at six adjusted S concentrations. Sulphur deficiency symptoms appeared in the control pots of those soils which were low in native sorbed SO₄, SO₄ sorption capacity and initial soil solution S concentration. Sulphur fertilization increased dry matter (DM) yield as well as response to applied S. The external S concentration, i.e. adjusted S concentration required for 95% of the maximum DM yield, ranged from 0.8 to 8.2µg S ml^–1 with values less than 2.0 on most of the soils. The external S concentration decreased hyperbolically as the SO₄ sorption capacity of the soils increased. The total amount of fertilizer S required to obtain the external S concentration in solution, and at the same time satisfy the SO₄ sorption capacity of the soil at the external S concentration (determined from the sorption isotherm) was defined as the external S requirement for the specified yield level of alfalfa. The external S requirement for 95% of the maximum yield of alfalfa varied from soil to soil due to differences in their capacity and intensity for S nutrition.Part of a thesis by the senior author for the MSc (Agric) degree of the University of Dar es Salaam     

阳离子型双子表面活性剂的合成及表面活性

合成了一种季铵盐型双子表面活性剂Gem in i 12-3-12,采用红外光谱、元素分析和两相滴定法对其结构和纯度进行了分析,测定了不同浓度表面活性剂水溶液的表面张力,并得到临界胶束浓度(CMC)、饱和吸附量(Γm ax)、单分子饱和吸附面积(Am in)。结果表明,Gem in i 12-3-12的收率为77.2%,纯度为98.4%,它与相应的单尾基十二烷基三甲基溴化铵(DTAB)的表面活性相当,但CMC比DTAB低14倍左右。     

温度和氧浓度对PX氧化的影响

根据不同温度、氧浓度下实测的PX液相催化氧化各中间组分浓度 时间关系,采用双曲型的动力学模型拟合实验数据,得到了各步反应活化能数据和速率常数与氧浓度的关系式。结果说明,PT酸氧化为4 CBA这一步的活化能最大,是整个连串反应过程的速率控制步骤;反应有一个氧浓度门槛值,在此值以上,反应速率不再明显增大,在此值以下,反应速率随氧浓度增大而增大。工业尾氧体积分数一般在4%～5%,相应的反应速率在最大速率的90%左右。     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

吸收过程的界面传质机理

以分子热力学为基础 ,对气体吸收过程进行了理论分析 ,导出了传质通量的数学表达式。根据该文分析 ,气液界面传质的源动力来自界面处气液两相的不平衡 ,即只要有传质发生 ,液相界面处的浓度就不会达到与气相呈平衡的浓度。对于气相阻力可以忽略的吸收过程 ,两相传质速率的大小主要取决于液相的溶质界面浓度和液膜厚度 ,影响溶质界面浓度和液膜厚度的主要因素是近界面液相侧的流场分布。利用近界面浓度与液膜厚度的激光测定结果 ,计算了甲醇、乙醇及正丙醇吸收CO2 气泡的传质通量 ,计算结果与实验值吻合良好     

Molar volume and ultrasonic studies of europium soaps in mixed organic solvents

The ultrasonic velocity and density measurements of europium soaps in a mixture of benzene and methanol (3:2, vol/vol) were used to evaluate various acoustic parameters and molar volume and to determine the critical micelle concentration. The results showed that the ultrasonic velocity, specific acoustic impedance, molar sound velocity, and molar compressibility increase, and intermolecular free length, adiabatic Compressibility, and relative association decrease with increasing concentration and chainlength of the soap. The results were interpreted in terms of soap-solvent interaction.     

某抽水蓄能电站下库进出水口水沙运动特性试验研究

利用河工模型对某抽水蓄能电站下库区进行了特征洪水过程及电站运行的联合模拟试验。试验表明在输沙槽与拦沙潜堰共同作用下,电站进出水口的含沙量得到有效控制。在来水含沙量低于3kg/m3时,进出水口含沙量都满足电站运行要求,但是在含沙量较高的洪水期,底部浑水会逆行至电站进出水口附近,导致过机含沙量较高,因此提出了增设非封闭式拦沙潜坝的修改方案。修改方案改善了进出水口前的水流结构,起到了良好的拦沙截淤作用,进出水口前含沙量及泥沙淤积大幅减少,蓄能期过机含沙量降低13%~22%。在含沙量较大的洪水期,电站不宜抽水运用,但适时采用发电运行有助于减轻下库进出水口前的泥沙淤积。