双电离源(辉光放电/激光溅射电离)四极杆质谱仪的研制

本研究将辉光电离源与激光溅射电离源巧妙地结合在同一台仪器中,使固体样品在离子源腔体中既能辉光电离,也能激光电离;并且使用同一质量分析器,两种离子源的结果可以相互比对,进而得到更为准确的分析结果.此仪器主要由真空系统、离子源、离子传输系统、四极杆质量分析器及检测与数据采集系统等组成.实验中分别用两种离子源测试了标准样品SRM 1262b,并获得了半定量结果.结果表明,仪器具有定性能力强,分析速度快,检测灵敏度高等优点,对固体样品元素分析的检出限可达μg/g量级.实验表明,激光溅射电离质谱的性能优于辉光放电质谱.     

一种新型二次离子质谱的一次离子源及其离子光学系统

本研究设计了一种新型用于二次离子质谱的一次离子源及其离子光学系统.通过此一次离子源,大气压下产生的一次离子可以被加速、聚焦并传输到位于真空条件下的样品表面并电离样品得到可供质谱仪分析的二次离子.通过理论模拟结合实验系统研究了此一次离子源的主要组成部分——离子光学系统的原理、结构和性能.以电喷雾电离源为例,成功地将大气压...     

非平衡等离子体放电模式及反应器结构对氨气分解制氢的影响

在常压下研究了不同等离子体放电模式及反应器结构对氨分解制氢反应的影响.实验中调节反应器结构分别产生了介质阻挡放电和交流弧放电两种放电模式.通过对两种放电模式的放电图像、电压-电流波形和氨分解过程中等离子体区活性物种的发射光谱(OES)研究发现,与介质阻挡放电相比,交流弧放电为局部强放电,具有更高的电源效率和电子密度.因此,在介质阻挡放电中氨气分子大部分通过生成电子激发态物种NH3*,再与载能电子碰撞断裂N―H键进行氨分解反应;而在交流弧放电中载能电子具有更高的平均电子能量,可直接断裂氨气分子的N―H键生成NH2和NH等高活性物种,促进氨分解反应的进行.结果表明,交流弧放电的氨分解效果要明显优于介质阻挡放电.在交流弧放电模式下不同类型反应器对氨气分解转化率由高到低的顺序为:管-管管-板针-板板-板.在输入功率为30 W,气隙间距为6 mm时,管-管交流弧放电的氨气转化率达到60%左右,而板-板介质阻挡放电的氨气转化率仅为4%.     

掺硼p型非晶硅薄膜的制备及光学性能的表征

以高氢稀释的硅烷(SiH₄ )为反应气体,硼烷(B₂H₆)为掺杂气体,利用RF-PECVD方法,在玻璃衬底上制备出掺硼的氢化非晶硅(a-Si:H)薄膜,研究了硼掺杂量对氢化非晶硅(a-Si:H)薄膜的光学性能的影响.利用NKD-7000 W光学薄膜分析系统测试薄膜的透射谱和反射谱,并利用该系统的软件拟合得出薄膜的折射率、消光系数、吸收系数等光学性能参数,利用Tauc法计算掺硼的非晶硅薄膜的光学带隙.实验结果表明,随着硼掺杂量的增加,掺杂非晶硅薄膜样品在同一波长处的折射率先增大后减小,而且每一样品均随着入射光波长的增加而减小,在波长500 nm处的折射率均达到4.3以上;薄膜的消光系数和吸收系数随着硼掺杂量的增大而增大,在500 nm处的吸收系数可高达1.5×10⁵cm^-1.在实验的硼掺杂范围内,光学带隙从1.81 eV变化到1.71 eV.     

改善液体辅助表面解吸常压化学电离质谱成像空间分辨率的研究

液体辅助表面解吸常压化学电离源(LA-DAPCI)通过电晕放电产生的初级离子和高密度带电液滴,能够对样品表面的中性待测物进行解吸电离,该离子源具有较高的离子化效率,适合复杂基体样品的质谱成像研究.为了满足质谱成像对空间分辨率的要求,本实验通过优化离子源结构、萃取剂组成、萃取剂流量、载气流速、离子源的几何位置参数等实验条件,有效提高了LA-DAPCI源的空间分辨率(从(441±14) μm提高到(58±7)μm).应用LA-DAPCI-MS/MS方法对罗丹明6G进行测定,检测限为0.01 ng/cm2,实验结果令人满意,为其应用于复杂基体样品的质谱成像研究提供科学依据.     

三步离子交换方法用于粘土沉积物酸溶相中硼同位素测定

在采用酸溶法进行粘土沉积物中硼同位素组成测定时,大量存在的Al、Fe、稀土等元素在较高pH溶液中会形成能强烈吸附硼的氢氧化物沉淀,对硼的提取和硼同位素的测定产生较大影响.有效去除这些干扰元素一直是测定粘土沉积物酸溶相中硼同位素组成的瓶颈.本实验采用三步离子交换法萃取和纯化粘土沉积物中的硼,以AG 50W×8阳离子树脂柱去除所有能生成水不溶性氢氧化物的Al、Fe、稀土等元素,再采用Amberlite IRA 743硼特效树脂柱提取硼,最后采用Ion-exchangerⅡ与AG 50W×8组成的阴阳离子混合树脂柱进一步纯化硼提取液.结果表明,采用以上三步离子交换法提取粘土沉积物中硼的回收率高于90％,未观察到明显的硼同位素分馏,可满足粘土沉积物酸溶相中硼同位素组成高精度测定的需要.     

便携式气相色谱-质谱联用仪的研制及应用

将双曲面三维离子阱质谱技术与低热容气相色谱技术相结合,研制了便携式气相色谱-质谱联用仪(GC-MS).此仪器主要由进样系统、低热容气相色谱模块、气质接口以及小型化离子阱质谱模块等构成,其主机重量小于14 kg,体积为44 cm×36 cm×22 cm,功耗小于100W.该仪器中的离子阱质谱仪系统具有15～550 amu...     

W-SBA-15介孔分子筛的直接合成及其对环己烯环氧化反应的催化性能

 分别以Na2WO4和H2WO4为钨源,以正硅酸四乙酯为硅源直接合成了W-SBA-15介孔分子筛样品,并用小角XRD,N2吸附,FT-IR,UV-Vis,SEM和XRF等手段对合成的分子筛进行了表征. 结果表明,只用P123(EO20PO70EO20)为模板剂时,分子筛中钨的含量只是投料量的一半; 而以P123和十六烷基三甲基溴化铵为混合模板剂时,钨能有效地掺杂到SBA-15分子筛中. 当原料中的Si/W摩尔比为40时,W-SBA-15分子筛中的钨物种以高度分散状态存在,且以H2WO4为钨源比以Na2WO4为钨源更易将钨掺杂到SBA-15介孔分子筛中. W-SBA-15分子筛催化剂对环己烯环氧化反应具有较高的催化活性.     

细胞色素c在微-液/液界面上电化学行为的研究

本文采用电化学技术,研究了细胞色素c（Cyt c）在玻璃微米管尖端处形成的微-水/1,2-二氯乙烷（W/DCE）界面上的电化学行为.选用四丁基铵四苯硼（TBAT-PB）、四丁基铵四氯代苯硼（TBATPBCl）以及四丁基铵四氟代苯硼（TBATPBF）三种不同的有机相支持电解质来研究Cyt c在W/DCE界面上的反应.在电势窗较窄的含TBATPB体系中只能够观察到吸附过程;在电势窗较宽的含TBATPBCl和TBATPBF的体系中,可以同时观察到吸附与离子转移过程.当Cyt c浓度较低时,两种过程都可以观察到;当Cyt c浓度较高时,主要是吸附.文中对这些过程的机理进行了探讨.     

碳化钨纳米晶合成及其电化学性能

用Mg作还原剂,无水乙醇和WO3分别作为C源和W源,采用简单的溶剂热法合成了碳化钨(WC)纳米晶,并讨论了温度和时间对合成WC的影响,以及其形成的机理.通过X射线衍射、透射电子显微镜、能量色散谱和电化学方法表征了WC的物相结构、表面形貌、化学组成和电化学性能.结果表明,合成温度低至500℃时也能合成六方WC相.生成C的量超过W的量,说明纯化后的产物由C和WC组成.WC的粒径大约在40~70nm,分布于膜状碳上.将溶剂热法制备出的WC加入Pt/C中,其协同催化氧还原效果非常明显,起峰电势比Pt/C催化剂正移了173mV.     

Infrared Femtosecond Laser Preionization in Secondary Ion Mass Spectrometry of Silver Surface

An alternative secondary ion mass spectrometry utilizing laser preionization is introduced. The native Ag sample surface is first irradiated with laser pulse (100 fs duration, 10(10)-10(11) W/cm(2) intensity, 1240 nm wavelength) and subsequently bombarded with primary ions (Bi(3)(+), 10 ns duration, 25 keV energy). Multiple correlation patterns are observed in the mass spectra, confirming the mutual laser-secondary ion mass spectrometry (SIMS) interplay in the preionization mechanism. The Ag(+), C(3)H(5)(+), C(3)H(5)O(3)(+), and AgOH(+), C(4)H(5)O(4)(+) are observed with the shallow and steep increasing of intensities at 1.3?×?10(11) W/cm(2) and 1.5?×?10(11) W/cm(2), respectively. Two ionization mechanisms are identified, the ion sputtering regime for intensities of less than 1.4?×?10(11) W/cm(2) and the multiphoton ionization at higher intensities. The Ag saturation intensity obtained from fitting is 2.4?×?10(13) W/cm(2), close to the one reported for postionization. The proposed preionization approach might eliminate the need for high peak power/high intensity laser source and, moreover, the experiment geometry ensures that large areas of the sample are affected by the laser beam.     

Recent progress of high-power negative ion beam development for fusion plasma heating

A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D⁻ ion beam. In the preliminary experiment using one ion source, a D⁻ ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D⁻ beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/I_D⁻ < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H⁻ ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator.     

发光二极管诱导荧光用于毛细管电泳检测

利用发光二极管作为激发光源，组装了用于毛细管电泳的荧光检测器。光纤用于传输荧光信号；光纤端面修饰成球形使耦合效率比平面端光纤提高了50．8％；光阑、光纤及毛细管检测池之间的光学校准简单、便捷。荧光素染料用于评价该体系性能，得到了fmol的质量检出限。     

Innovative energy efficient low-voltage electron beam emitters

Advanced electron beams (AEB) has developed a modular, low voltage (80–125 keV), high beam current (up to 40 ma), electron emitter with typically 25 cm of beam width, that is housed in an evacuated, returnable chamber that is easy to plug in and connect. The latest in nanofabrication enables AEB to use an ultra-thin beam window. The power supply for AEB's emitter is based on solid-state electronics. This combination of features results in a remarkable electrical efficiency. AEB's electron emitter relies on a touch screen, computer control system. With 80 μm of unit density beam penetration, AEB's electron emitter has gained market acceptance in the curing of opaque, pigmented inks and coatings used on flexible substrates, metals and fiber composites and in the curing of adhesives in foil based laminates.     

A wide-angle secondary ion probe for organic ion imaging

A secondary ion source has been developed for an organic ion microprobe capable of imaging samples up to 2 em in diameter. The source uses a focused 5 keY Cs⁺ ion beam which is rastered across the sample surface, and secondary ions from each point on the sample are collected and formed into a low energy beam to be analyzed by a quadrupole mass filter. Dynamic emittance matching is employed to deflect ions from off-axis points on the sample back onto the mass analyzer axis. Rastering and dynamic emittance matching are rapidly controlled by assembly language programs using an IBM/AT (80286) type computer. A low energy ion monitor was used to tune and evaluate the secondary ion source by providing a magnified cross-sectional image of the ion beam at the source exit aperture. A well-focused and centered secondary ion beam was obtained from each point on the sample, indicating that large-scale dynamic emittance matching with high collection efficiency is possible. Mass resolved images of grids and glycerol samples are shown to demonstrate the performance of the integrated secondary ion source mass analyzer and control system.     

Determination of ultratrace nitrogen in pure argon gas by dielectric barrier discharge-molecular emission spectrometry

A dielectric barrier discharge (DBD) was used as a new atmospheric optical emission detector for the determination of trace nitrogen in pure argon gas in this work. The whole system was composed of an ac ozone generation device for power supply, a six-way valve, a laboratory-built DBD device and a USB2000 charge coupled device (CCD). Trace nitrogen in argon was detected at nitrogen molecular emission line of 337 nm. This method features with several advantages: atmospheric working condition, low power consumption (≤ 12 W), simple and cheap instrumentation, fast response and high sensitivity and accuracy. Under the optimized conditions, the limits of detection can be down to 34 ppb.     

Ga‐focused ion beam time‐of‐flight secondary ion mass spectrometer analysis of the grain boundary segregation/precipitation of boron in steel

Ga‐focused ion beam time‐of‐flight secondary ion mass spectrometry (FIB‐TOF‐SIMS) analysis was performed to investigate the grain boundary segregation/precipitation of boron in steel. To overcome the low secondary ion yield from the primary Ga⁺ source and the sensitivity using a high‐resolution Ga‐FIB source, a low energy oxygen ion beam was used prior to the Ga‐FIB‐TOF‐SIMS analysis. As a result, it was found that Ga‐FIB‐TOF‐SIMS is a very powerful tool for mapping boron segregation and/or precipitation in steel with a spatial resolution of ~200 nm. In addition, the results were strongly dependent on the surface composition. Copyright © 2014 John Wiley & Sons, Ltd.     

Ion implantation doping and electrical properties of high-temperature ladder polymers

We report the first ion implantation doping studies on high-temperature ladder polymers and show that insulting films of the benzimidazobenzophenanthroline-type ladder polymer (BBL) can be doped by boron, argon, and krypton implantation to conductivities as high as 224 S/cm at a dose of 4.0 × 10¹⁶/cm² while retaining the excellent mechanical properties of the pristine films. Effects of dose (ions/cm²) and beam current density (microamps/cm²) on electrical conductivity at fixed ion energies are reported. The temperature dependence of the conductivity indicates that the implanted ladder polymer films are semiconductors. Spatially selective implantation, creating regions of conducting lines in an insulating matrix, which suggests microelectronic device applications of the ladder polymers, is demonstrated.     

Development of an ion mobility spectrometer for use in an atmospheric pressure ionization ion mobility spectrometer/mass spectrometer instrument for fast screening analysis

An ion mobility spectrometer that can easily be installed as an intermediate component between a commercial triple-quadrupole mass spectrometer and its original atmospheric pressure ionization (API) sources was developed. The curtain gas from the mass spectrometer is also used as the ion mobility spectrometer drift gas. The design of the ion mobility spectrometer allows reasonably fast installation (about 1 h), and thus the ion mobility spectrometer can be considered as an accessory of the mass spectrometer. The ion mobility spectrometer module can also be used as an independently operated device when equipped with a Faraday cup detector. The drift tube of the ion mobility spectrometer module consists of inlet, desolvation, drift, and extraction regions. The desolvation, drift and extraction regions are separated by ion gates. The inlet region has the shape of a stainless steel cup equipped with a small orifice. Ion mobility spectrometer drift gas is introduced through a curtain gas line from an original flange of the mass spectrometer. After passing through the drift tube, the drift gas serves as a curtain gas for the ion-sampling orifice of the ion mobility spectrometer before entering the ion source. Counterflow of the drift gas improves evaporation of the solvent from the electrosprayed sample. Drift gas is pumped away from the ion source through the original exhaust orifice of the ion source. Initial characterization of the ion mobility spectrometer device includes determination of resolving power values for a selected set of test compounds, separation of a simple mixture, and comparison of the sensitivity of the electrospray ionization ion mobility spectrometry/mass spectrometry (ESI-IMS/MS) mode with that of the ESI-MS mode. A resolving power of 80 was measured for 2,6-di-tert-butylpyridine in a 333 V/cm drift field at room temperature and with a 0.2 ms ion gate opening time. The resolving power was shown to be dependent on drift gas flow rate for all studied ion gate opening times. Resolving power improved as the drift gas flow increased, e.g. at a 0.5 ms gate opening time, a resolving power of 31 was obtained with a 0.65 L/min flow rate and 47 with a 1.3 L/min flow rate for tetrabutylammonium iodide. The measured limits of detection with ESI-MS and with ESI-IMS/MS modes were similar, demonstrating that signal losses in the IMS device are minimal when it is operated in a continuous flow mode. Based on these preliminary results, the IMS/MS instrument is anticipated to have potential for fast screening analysis that can be applied, for example, in environmental and drug analysis.     

Compact polytetrafluoroethylene assembly-type capillary electrophoresis with chemiluminescence detection

We have developed a compact polytetrafluoroethylene (PTFE) assembly-type capillary electrophoresis with chemiluminescence (CL) detection system. Luminol-microperoxidase-hydrogen peroxide chemiluminescence reaction was adopted. The device is rectangular in shape (60 mm x 40 mm x 30 mm) and includes three reservoirs (sample, migration buffer, and detection reservoirs) with electrodes. The detection reservoir includes an optical fiber to transport light at the capillary tip to a photomultiplier tube. Isoluminol isothiocyanate (ILITC) was analyzed as a model using this device with fused-silica or polytetrafluoroethylene capillary tubes 10 cm in length. We also used the sample reservoir as a reactor for an immune reaction between anti-human serum albumin immobilized on glass beads and isoluminol isothiocyanate-labeled human serum albumin. The present polytetrafluoroethylene assembly with the capillary tube was useful as a palm-sized analysis device for separation and detection, as well as a reactor.