Photo-atomic effect: Temperature dependence of the photodesorption of Na and from polymer surfaces

Alkali metals adsorbed to surface films of the polymer poydimethylsiloxane (PDMS) have been shown to exhibit a unique photodesorption behavior, characterized by a frequency threshold and high efficiency. In this work, the temperature dependence of the photodesorption yields of Na and Na ₂ from PDMS surfaces were measured between room temperature and 183 K. Over most of the temperature range, the yields exhibited an Arrhenius behavior characterized by thermal activation energies of 0.36 eV and 0.34 eV for Na and Na ₂ , respectively. These values are suggestive of a surface diffusion as one of the elementary steps in the photodesorption mechanism. Moreover, the similarity of the two values indicates that the same elementary step applies to the desorption of both Na and Na ₂ . Received 23 April 1999 and Received in final form 15 July 1999     

Bond dissociations in hypervalent ammonium radicals prepared by collisional neutralization of protonated six-membered nitrogen heterocycles

Hypervalent organic ammonium radicals were generated by collisional neutralization with dimethyl disulfide of protonated 1,4-diazabicyclo[2.2.2]octane (1H⁺), N,N′-dimethylpiperazine (2H⁺) and N-methylpiperazine (3H⁺). The radicals dissociated completely on the 5.1 μs time-scale. Radical 1H^• underwent competitive N−H and N−C bond dissociations producing 1,4-diazabicyclo[2.2.2]octane and small ring fragments. Dissociations of radical 2H^• proceeded by N−H bond dissociation and ring cleavage, whereas N−CH₃ bond cleavage was less frequent. Radical 3H^• underwent N−H, N−CH₃ and N−C_ring bond cleavages followed by post-reionization dissociations of the formed cations. The pattern of bond dissociations in the hypervalent ammonium radicals derived from six-membered nitrogen heterocycles is similar to those of aliphatic ammonium radicals. © 1997 John Wiley & Sons, Ltd.     

The use of contact angle measurements to estimate the adhesion propensity of calcium carbonate to solid substrates in water

We have studied a series of solids using contact angle measurements; stainless steel, gold, aluminium, titanium nitride and PTFE that are frequently used in domestic water environments. It was found the influence of electron-donor (γ⁻) and electron-acceptor (γ⁺) free energies on material scaling rate was dominated by water wetting angles, providing materials exhibit an average roughness below 100 nm. The γ⁻ component had the greatest influence on theoretical adhesion, while γ^LW, (Lifshitz-van der Waals) γ⁺ and γ^AB (acid-base) had little effect. From the materials analysed, amorphous carbon coatings were least adhesive, while ‘kettle coating’ and highly roughened steel the most adhesive. The size and distribution of asperities also influenced the polar free energies and subsequent adhesion due to fluctuations in the wetting angle. The results obtained indicate works of adhesion can be used as a complementary technique with Lewis acid-base theory to deliver useful information about the propensity of scale to deposit on solids.     

Understanding charge transfer of Li~+ and Na~+ ions scattered from metal surfaces with high work function

For Li~+ and Na~+ ions scattered from high work function metal surfaces, efficient neutralization is observed, and it cannot be explained by the conventional free electron model. In order to explain these experimental data, we investigate the velocity-dependent neutral fraction with the modified Brako–Newns(BN) model. The calculated results are in agreement with the experimental data. We find that the parallel velocity effect plays an important role in neutralizing the Li~+ and Na~+ ions for large angle scattering. The nonmonotonic velocity behavior of neutral fraction is strongly related to the distance-dependent coupling strength between the atomic level and metal states.     

在线中和富集及标准加入离子色谱法测定大气吸收液中的痕量阴离子

建立了大体积进样后的在线中和富集及在线标准加入离子色谱法,实现了对大气碱性吸收液中痕量氯离子、亚硝酸根、硝酸根、硫酸根的直接测定。比较了不同阀切换时间窗及在线中和柱的选择,确定了最佳的实验条件。利用戴安公司“谱睿”在线中和技术,通过Inguard H在线中和柱和CRD 200在线二氧化碳去除装置的共同作用,有效地去除了碱性吸收液中的OH~和CO2~3,使测定干扰降低到最小;通过大体积进样和在线富集,改进了样品的检出限,Cl~, NO~2, NO~3和SO2~4的检出限分别为17.5、171、34.7和42.4 ng/L;在线标准加入解决了痕量阴离子标准溶液的配制难题及NO~2低回收率对检测结果的影响。本方法实现了自动化分析,结果准确,重复性好,检测效率高,可用于常规离子色谱条件下无法测定的强碱性基体样品中痕量阴离子的准确测定。     

Study on the pre-chopper in CSNS LEBT

Physical designing of the pre-chopper in CSNS LEBT is carried out,which includes the deflecting voltage,the length and the width of the deflecting plates,and the gap between the deflecting plates.The most outstanding feature of the design is that both the gap and the width vary with the beam envelope size.So both the requried deflecting voltage and the loaded capacitance are lowered.In order to avoid destruction of the space charge neutralization by the pre-chopper in the whole LEBT,an electron-trapping electrode is arranged to confine the electrostatic field of the pre-chopper to the local area.To examine the reliability of the pre-chopping design in CSNS LEBT,a similar pre-chopping design in ADS RFQ LEBT is set up and an experiment on the pre-chopper is prepared.3-dimensional simulations are carried out to determine the loaded capacitance and the applied voltage of the electron-trapping electrode.     

铈铁复合氧化物阴离子吸附剂的表面酸碱特性研究

研究了用于水体砷等有害阴离子去除的稀土铈铁复合氧化物吸附剂的表面酸碱特性。利用电位滴定实验求定了铈铁复合氧化物吸附剂、铁氧化物和铈氧化物的表面质子电荷密度s0、零电荷点pHzpc (分别为5.8,6.2和6.8),表明特性吸附在砷等的去除中起主要的作用,铈铁复合氧化物吸附剂的表面总吸附位NS为4.1×10-3mol/L,运用表面络合恒定容量模式求算此复合氧化物吸附剂的表面固有酸度常数pKa1和pKa2,为进一步研究有害阴离子与去除材料的表面络合作用机制提供了重要参数。     

Protonated silanoic acid HSi(OH)2+ and its neutral counterpart: a tandem mass spectrometric and CBS-QB3 computational study

Protonated silanoic acid, HSi(OH)₂⁺, 1a ⁺, is cleanly generated by the dissociative electron ionization of triethoxysilane, HSi(OC₂H₅)₃, and tetraethoxysilane, Si(OC₂H₅)₄. This follows from tandem mass spectrometric experiments and CBS-QB3 model chemistry calculations. The calculations predict that 1a ⁺ (ΔH_f(298 K) = 205 kJ mol⁻¹) is separated by high barriers from its isomers HOSiOH₂⁺, 1b ⁺ and HSi(O)OH₂⁺, 1c ⁺. Low-energy (metastable) ions 1a ⁺ dissociate by loss of H₂O via the pathway 1a ⁺ → 1b ⁺ → SiOH⁺ + H₂O. Analysis of the metastable peak for this process confirms that the isomerization step 1a ⁺ → 1b ⁺ is rate determining. The calculations further predict that the incipient ions 1b ⁺ communicate via a low barrier with the proton-bound dimer SiO···H···OH₂⁺, 1d ⁺. This dimer ion is much lower in energy than its counterpart OSi···H···OH₂⁺, 1e ⁺, which is calculated to be only marginally stable. A comparison of the potential energy diagram for the silicon-containing ions 1a ⁺– 1e ⁺ with that of their carbon analogues reveals that the dissociation chemistries of HSi(OH)₂⁺ and HC(OH)₂⁺ are only superficially similar. Neutralization–reionization experiments confirm the theoretical prediction that the HSi(OH)₂^• radical (ΔH_f(298 K) = −455 kJ mol⁻¹) is a stable species in the rarefied gas phase. However, owing to a mismatch of Franck–Condon factors a large fraction of the neutralized ions dissociates by loss of H^• yielding Si(OH)₂. Copyright © 2004 John Wiley & Sons, Ltd.