Extraction of ions from polar solutions by high-strength electric field pulses

Extraction of ions from solutions of salts in ethylene glycol and water-glycerol mixture by high-strength electric field pulses is investigated. The conditions for stable extraction of ions from a polar liquid in the pulsed regime are ensured by using a track membrane with channels of a nanosize diameter as the interface between the liquid solution and vacuum. The possibility of barrier-free field evaporation of ions from polar liquids in electromembrane ion source for mass-spectrometric analysis of solutions is considered.     

Generation of an extraction electric field in an electromembrane ion source

A mechanism of generating an extraction field in an ion source in which a polymer track membrane with nanodimensional channels is used as an environment-vacuum interface is considered. A high electric field necessary for the effective extraction of ions from a liquid on the membrane surface into the gas phase is maintained by charging the vacuum surface of the membrane. Charging is provided by oppositely charged secondary ions resulting from the disintegration of primary cluster ions on the extraction electrode. A decrease in the source current observed when the vacuum surface discharges counts in favor of this mechanism. The extracted ion energy distribution in the neighborhood of the extraction zone is obtained by the retarding potential method. Various aspects of ion beam formation in the membrane ion source are discussed.     

Track-membrane-based interface for field evaporation of ions from polar solutions in the diffusion-drift regime

The possibility of realization of barrier-free field evaporation regime for ions from polar solutions in the conditions when the flux of ions from the liquid is limited by their diffusion and drift from the bulk to the surface is considered. The strength of the electric field extracting ions is estimated by simulating electric fields in an ion source with a track membrane as the interface with allowance for the sizes of channels in the membrane and their density. It is shown that when time-dependent electric fields are used, the regime of barrier-free field evaporation can be realized with an appropriate choice of geometrical parameters of the membrane.     

Polymer track membranes for atmospheric pressure field extraction of ions from liquid solutions

An approach to the generation of gas phase ions by field extraction from liquid solutions has been investigated. The method uses a polymer membrane with nano-size channels as an interface between the liquid and the atmospheric pressure gas. Ions are produced by dissociation in the polar solvent and secondary ion-molecular reactions in the solution, which fills the channels of the membrane. Field extraction of the ions from the channels is stimulated by pulses of the electric discharge between the membrane and an adjacent electrode in the gas. The gas-phase ions are removed from the extraction zone by air flow and are detected by mass spectrometry. Possibilities of the membrane interface for generation of gas phase ions have been demonstrated from mass spectral investigation curried out for angiotensin II, gramicidin S and cytochrome C solutions. The current kinetics of the membrane ion source has been investigated to elucidate the mechanism of the ion extraction.     

Generation of ions in a pulsed ion source with an interface based on a polymer track membrane

The time-of-flight spectra of ions generated during the extraction of negative ions from the KI solution in water–glycerin mixture by high-strength electric field pulses are studied using a source with an interface based on a polymer track membrane. It has been shown that the ions formed in secondary processes of bombardment of the membrane surface make a considerable contribution to the observed spectra. It has been found that the peaks of negative hydrogen ions have the highest intensity in the spectrum, indicating effective emission of these ions during the bombardment of polyethylene terephthalate by secondary ions with an energy of about 6 keV. The main trends in the modification of the membrane interface to reduce the fraction of secondary ions in the ion beam have been outlined.     

Ionization of solvent molecules by the field evaporation of ions from glycerol and ethylene glycol solutions

Using an electromembrane source, mass-spectrometric investigations into the field evaporation of ions from KI solutions in a water-glycerol mixture and in ethylene glycol are performed. The concentration of negatively charged solvent ions (deprotonated molecules) on the emitting surface of the liquid is determined. It is shown that, under the conditions of intense field evaporation of ions, the surface concentration of deprotonated glycerol and ethylene glycol molecules is several orders of magnitude higher than their equilibrium concentration in the absence of an electric field. The high concentration of solvent ions is associated with an increase in the autoprotolysis constant in a strong electric field.     

Field evaporation of impurity ions from a liquid gallium ion source

The charge states of ions emitted from a gallium liquid metal field ion (LMI) source contaminated with tin and copper have been measured. The results for tin show that the proportion of Sn²⁺ to Sn⁺ is much larger than is found for a LMI source of pure tin. A model in which Sn²⁺ is assumed to be produced by post-ionization of Sn⁺ is used to set an upper limit to the electric field at the point of emission. Its value is approximately equal to that predicted by field evaporation theory for a pure gallium source. Consequently the charge states of emitted impurity ions are determined by field strengths imposed by the main component.     

Isotopic ratio of evaporated ions,critical ionization distances,and ionization regions in the process of the field evaporation of molybdenum at high temperatures

A magnetic mass spectrometer with a field ion source has been used to study the steady-state field evaporation of molybdenum at a temperature of 1000–2000 K. Ions of all seven molybdenum isotopes have been observed in the process of evaporation; only low-charge ions Mo⁺² and Mo⁺ have been detected. The critical ionization distances and ionization regions for single- and double-charge Mo ions have been identified based on the measured ion energies and the experimentally determined intensity of the evaporation field. It has been demonstrated that ions are produced in the process of field evaporation of surface atoms at certain distances from the emitter surface in a very narrow spatial region.     

Field evaporation of doubly charged ions from a polar liquid

The effect of charge on field evaporation of ions from polar liquids is considered. Using the electromembrane ion source, we performed mass-spectral analysis of field evaporation of ions from the solution of sodium sulfate in a water-glycerol mixture. The composition of doubly charged cluster ions in the field evaporation from glycerol is determined. The rates of the field evaporation of doubly charged ions and singly charged ions are compared. It is shown that the ion charge as well as its localization considerably influences the efficiency of field evaporation of ions from polar liquids.     

Emission of positive ions from KCl and NaCl crystals exposed to high electric fields

It is demonstrated by means of combined optical microscopy and field desorption mass spectrometry that alkali ions and cluster ions are emitted from microcrystals of KCl and NaCl exposed to positive high electric fields. The ion emission is very strong at temperatures where the sublimation of the sample is optically observable, indicating that an enhanced sample sublimation is a key precondition for enhanced ion emission.     

Non-vacuum field desorption ion source implemented under super-atmospheric pressure

Standard field desorption (FD) ionization is implemented under high vacuum condition. In this paper, non-vacuum FD is performed under a super-atmospheric pressure environment using untreated tungsten wires as FD emitter, and the ion source was coupled to a commercial linear ion trap mass spectrometer. The operating pressure of the ion source was 6 bars which was high enough to provide sufficient dielectric strength to the working gas so that the high voltage that was required for FD could be applied to the emitter without occurrence of electrical discharge. Non-volatile sample deposited on the bare tungsten wire FD emitter was heated by flowing direct current through the emitter. Similar to vacuum FD, the formation of conical protrusion of the liquefied sample layer under the strong electric field was also observed. Using the present ion source, high pressure field-desorption of polar neutral compounds, organic salts and ionic liquids is demonstrated. Copyright ? 2012 John Wiley & Sons, Ltd.     

强电场中的脉冲束流强度测量方法

针对强电场中电场渗透的问题,采用特殊的法拉第筒法测量脉冲束流强度:在法拉第筒入口处用栅网屏蔽强电场,并用在收集板上加正压的方式抑制二次电子。采用解析计算和数值模拟方式对栅网的形状进行了选择,在同样的栅网丝宽和透过率的前提下,通过正六边形栅网的渗透电场最弱,因此选择正六边形栅网。将设计的法拉第筒用于一台真空弧离子源的束流强度测量,获得了该离子源的束流强度波形,其峰值流强约为550 mA;利用测量结果计算了混合离子束在Cu收集板上的二次电子发射系数,约为2.0。     

Electric-field-induced ion evaporation from dielectric liquid

A direct proof of ion field evaporation from dielectric liquids is presented. The flux of sodium ions ejected from the surface of an electrospray of formamide is measured using time-of-flight and retarding potential techniques. The electric field at the emitting surface is varied through the electrospraying parameters. We find that the evaporated ion current is a very steep function of the electric field.     

Charge state of ions in liquid metal field ion sources

The post-ionization model of field evaporation is shown to be consistent with observations of singly and doubly charged ions in liquid metal field ion sources. The model can be used to estimate the field strength at the apex of the Taylor cone which is found to be 1.9–2.0 V/Å for a Ga source. Experiments to test the post-ionization model and to determine the apex field strength more accurately are suggested. A possible method of obtaining ～μA currents of highly charged ions, e.g. Zr⁴⁺, Ta⁴⁺, Ga³⁺, As³⁺, is proposed.     

On the mechanism of liquid metal ion sources

We have developed a theoretical model of liquid metal ion source operation which consistently explains the shape and size of the ion emitting region, the mechanism of ion formation and properties of the ion beam. We find that field evaporation is the main current generating mechanism and that field evaporation and subsequent postionization produce the doubly and higher charged ions. Field ionization of thermally evaporated neutrals may make a significant, but not dominant, contribution to the current of singly charged ions. Our model is consistent with experimental results on energy spread, energy deficit and charge state ratios and we are able to explain the stability of the emitted ion current.     

Migration of chlorine in the X-ray fluorescence analysis of rocks

The intensity of the analytical ClKα-line continuously increases during the measurement of a rock sample. The main cause of this effect is the migration of chlorine into the irradiated (emitting) part of the sample. The hypothesis was credibly proved through the experiment in which a rock sample was measured first on one side, and then on the other. An increase in the intensity of the analytical line was observed in both measurements. The intensity in the second measurement registers an increase from the same or even the lower level than in the first part. The following chlorine migration model is proposed. Negative chlorine ions arise in the rock sample under the influence of primary X-ray radiation. X-ray photons knock out part of the ions from the sample; therefore, a positive electric field is formed in it at the sample–vacuum interface. It attracts chlorine ions from the depths of the sample, as well as chlorine ions flying outside. Thus, the number of chlorine atoms in the surface layer of the sample increases and consequently, the intensity of the analytical line of chlorine increases. Formation of chlorine ions, their migration, and concentration in the surface layer of the sample occur only under the influence of primary X-ray radiation.     

Ionization mechanism in a liquid-metal ion source. Source for high-melting metals

Investigations have been made of the ionization mechanism in a liquid-metal ion source. At the instant of ion current generation the surface of a liquid metal emitter frozen in a highvoltage field exhibits microprotrusions pulled from the liquid metal by the electric field. A double-focusing mass spectrometer identified two components in the ion beam extracted from the aperture in the extractor. One ion component forms at the tip of the emitter and has an energy spread not exceeding a few tens of electronvolts. The other ion component forms in the cathode plasma at the extractor. On the basis of these investigations, a mechanism is proposed for ion formation in a liquid metal ion source and this mechanism is used to produce a modified source design. The source can produce ion beams from high-melting metals and nonmetals, and beams of Ta, W, Mo, C, and Fe ions were obtained. Zh. Tekh. Fiz. 67, 82–87 (November 1997)     

真空中固液界面的离子束分析研究

原位实时地高精度测量固液界面的元素或离子(电荷)组成和动态变化对于界面反应和相互作用研究非常重要,但是传统的高分辨离子束分析实验在真空环境中不能直接测量液体样品。本文研制了一种固体-液体界面探针,该探针使用氮化硅-铝纳米复合膜作为真空密封窗和电化学电极,利用复旦大学核微探针成功开展了真空中固体-液体界面探针0.01 mol/L氯化钡和1 mol/L氯化镧溶液样品固体-液体界面的卢瑟福背散射(RBS)分析和粒子激发X射线(PIXE)分析。实验结果表明,真空环境下,固液界面探针纳米薄窗可承受2 MeV He+离子注量为1.0×1018 ions/cm2的辐照。微区PIXE分析成功获得了固液界面探针结构的元素分布。通过对卢瑟福背散射能谱进行分析,获取了20 nm分辨的电极界面微米深溶液中的La, Cl元素浓度。在1 mol/L的LaCl3固液界面电极表面,负电压(–2.3 V)时电解质离子在电极表面高浓度聚集,正电压(+2.3 V)时电解质在电极表面呈低浓度分布,在约1 250 nm深处电解质溶液趋向于体浓度。     

高压电场浓缩液体物料技术的研究及进展

高压电场干燥技术是一种全新的干燥技术 .文章对高压电场浓缩液体的机理进行了探讨 ,认为是内部离子注入、非均匀电场和外部离子风吹动三合一的结果 .通过以自来水、葡萄糖酸钠溶液等液体物料为样品 ,首次在高压电场下进行浓缩实验 ,表明高压电场能够加速水分子的脱出 .文章对当前的研究状况进行了介绍     

碳纳米管薄膜场蒸发效应

在超高真空系统中对基于丝网印刷方法制备的碳纳米管薄膜的场蒸发效应进行实验研究. 实验发现, 碳纳米管薄膜样品存在场蒸发现象, 蒸发阈值场在10.0-12.6 V/nm之间, 蒸发离子流可以达到百皮安量级; 扫描电子显微镜分析和场致电子发射测量结果表明, 场蒸发会使碳纳米管分布变得更加不均匀, 会导致薄膜的场致电子发射开启电压上升(240→300V)、场增强因子下降(8300→4200)、蒸发阈值场上升(10→12.6V/nm), 同时使得薄膜场致电子发射的可重复性明显变好. 场蒸发也是薄膜自身电场一致性修复的表现, 这种修复并非表现在形貌上, 而是不同区域场增强因子之间的差距会越来越小, 这样薄膜场致电子发射的可重复性和稳定性自然会得到改善.