WO2022062118A1 - 一种液体样品元素在线检测的装置与方法 - Google Patents

一种液体样品元素在线检测的装置与方法 Download PDF

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WO2022062118A1
WO2022062118A1 PCT/CN2020/128386 CN2020128386W WO2022062118A1 WO 2022062118 A1 WO2022062118 A1 WO 2022062118A1 CN 2020128386 W CN2020128386 W CN 2020128386W WO 2022062118 A1 WO2022062118 A1 WO 2022062118A1
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sample
chamber
mist
fog
water pump
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PCT/CN2020/128386
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French (fr)
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钟石磊
隋明达
蒋丽丽
范延胜
薛媛媛
周洁
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青岛大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited

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  • the invention relates to a device and method for on-line detection of liquid samples.
  • the technology realizes continuous on-line sample injection through an ultrasonic atomization assisted sampling device, and utilizes laser-induced breakdown spectroscopy technology to realize online, real-time and accurate detection of elemental components in water bodies.
  • Qualitative detection belongs to the field of optical analysis instruments, and is expected to be applied in the fields of water environment monitoring and natural water scientific investigation.
  • LIBS Laser-induced breakdown spectroscopy
  • a focused laser pulse to break down a sample to generate a transient plasma.
  • the qualitative determination of the elemental composition in the sample is realized.
  • techniques for quantitative analysis This technology has received extensive attention due to its ability to perform rapid, real-time analysis.
  • LIBS technology has been deeply applied.
  • the application of this technology to the field of elemental composition analysis of liquid samples also has good prospects. It is foreseeable that this technology can play a role in the fields of heavy metal pollution of water resources, detection of marine metal elements, and monitoring of industrial and domestic sewage.
  • the sensitivity and stability of LIBS water body detection are affected due to the influence of matrix effects. Therefore, the LIBS technology for on-line and on-site detection of metal elements in water has encountered difficulties.
  • the invention utilizes the proposed ultrasonic continuous sampling device to change the sample shape continuously and rapidly, and combines with the LIBS detection method to realize on-site, rapid, online and highly sensitive LIBS detection of metal elements in water, and is expected to be applied in related fields.
  • the invention provides a liquid sample ultrasonic atomization auxiliary breakdown spectroscopy device, including an ultrasonic atomization auxiliary sampling device, a laser induced breakdown device and a spectral detection device.
  • the ultrasonic atomization auxiliary sampling device includes a filter system 1, a sample water pump 2 to be tested, a standard sample water pump 3, a cleaning water pump 4, an atomization drive main board 5, a slope base 6, a drainage pipe 7, a fog chamber bottom plate 8, and a spray chamber.
  • Sheet 9 fog chamber rear panel 10, fog chamber middle partition 11, fog chamber top panel 12, fog chamber front panel 13, air intake fan 14, secondary buffer fog chamber 15, duct 16 and exhaust fan 17,
  • the filtration system 1 is communicated with the sample water pump 2 to be tested;
  • the sample water pump 2 to be tested, the standard sample water pump 3 and the cleaning water pump 4 are connected in parallel with the front panel 13 of the fog chamber;
  • the fog chamber bottom plate 8, the atomizing sheet 9, the fog chamber rear panel 10, the fog chamber middle partition 11 and the fog chamber front panel 13 constitute a sample chamber; the sample chamber is fixed on the upper surface of the slope base 6, so The atomization drive main board 5 is communicated with the atomization sheet 9, and the bottom of the rear panel 10 of the mist chamber is provided with a drainage pipe 7;
  • the front panel 13 forms a primary buffer fog chamber; the front panel 13 of the fog chamber communicates with the intake fan 14 ; the front panel 13 of the fog chamber is provided with an outlet to communicate with the secondary buffer fog chamber 15 , and the secondary buffer
  • the mist chamber 15 is communicated with the guide pipe 16 and the exhaust fan 17 in sequence;
  • the laser-induced breakdown device includes a pulsed laser 18 and a focusing lens group 19, and the focusing lens group 19 is located at the end of the pulsed laser 18;
  • the spectral detection device includes a collection lens group 20, an optical fiber 21 and a spectrometer 22 connected in sequence;
  • the spectrometer 22 is connected to a computer 23 .
  • the present invention also provides a method for performing ultrasonic atomization-assisted breakdown spectroscopy of liquid samples using the device described in the above technical solution, comprising the following steps:
  • the liquid sample to be tested is filtered by the filtration system 1, it is continuously introduced into the sample chamber by the cleaning water pump 4; when the liquid sample entering the sample chamber flows through the atomizing sheet 9, the ultrasonic waves generated by the atomizing sheet 9 will continue to strongly affect the sample.
  • the gas is injected into the sample chamber by the intake fan 14, and the formed air pressure pushes the atomized liquid sample in the atomization chamber to continuously flow into the first-level buffer mist chamber, and then flows
  • the atomized sample is continuously sent into the guide tube 16 through the secondary buffer fog chamber 15, and is continuously sprayed at the rear end of the guide tube 16 to form a continuous flow and uniform droplet mist column, and the rear end is collected by the exhaust fan 17.
  • the laser pulses emitted by the pulsed laser 18 are focused on the sample fog column by the focusing lens group 19, break down the sample, and generate plasma; the optical radiation generated when the plasma is cooled is focused and coupled into the optical fiber 21 by the collection lens group 20 , and spectroscopically detected by the spectrometer 22, and the spectral signal is displayed and stored by the computer 23;
  • the standard sample water pump 3 is used for data correction.
  • the invention also provides a method for ultrasonic atomization-assisted breakdown spectroscopy of liquid samples.
  • the ultrasonic atomization auxiliary sampling device is used to carry out continuous and rapid sample injection and sample atomization, and the laser-induced breakdown device is used to break down the sample mist column. , real-time, online and accurate detection of the target element in the sample through the spectral detection device.
  • the water pump is continuously introduced into the sample chamber; when the liquid sample entering the sample chamber flows through the atomizing sheet, the ultrasonic wave generated by the atomizing sheet will continuously and strongly oscillate the sample, thereby It is converted into a uniform mist liquid sample; then the gas is injected into the sample chamber by the air intake fan, and the formed air pressure pushes the atomized liquid sample in the atomization chamber to continuously flow into the first-level buffer spray chamber, and then flows through the second-level buffer spray chamber
  • the buffer mist chamber continuously sends the atomized sample into the guide tube, and sprays continuously at the back end of the guide tube to form a continuous flow and uniform droplet mist column.
  • the rear end is collected by the exhaust fan; the pulse laser emits The laser pulses are focused on the sample fog column by the focusing lens group, break down the sample, and generate plasma; the optical radiation generated when the plasma is cooled is focused and coupled into the optical fiber by the collecting lens group, and detected by the spectrometer, and the spectral signal is detected by the computer. display and storage.
  • three water pumps are used to inject the sample to be tested, the standard sample and deionized water, and the liquid flow and the ultrasonic vibration of the atomizing sheet are used to generate continuous atomized samples, and the air intake fan generates The air pressure pushes along a fixed path to form a continuously flowing sample mist column.
  • the gas injected into the sample chamber by the intake fan is air, argon, helium, and nitrogen.
  • the pulse width of the pulse of the pulsed laser is in the order of nanoseconds or in the order of femtoseconds, and the laser wavelength of the pulsed laser is selected between 266 nm, 355 nm, 532 nm and 1064 nm.
  • the working spectral range of the spectrometer is between 200 nm and 1000 nm, and the spectral resolution is 0.1 nm.
  • the acquisition gate delay time of the detector of the spectrometer is selected from 200ns to 1500ns, and the integration gate width is selected from 900ns to 30000ns.
  • the inner diameter of the guide tube is selected between 0.125mm-3mm.
  • the standard sample is pre-configured, and the element types and concentrations are known, which are used for data correction to improve the system accuracy.
  • the present invention can be divided into an ultrasonic atomization auxiliary sampling device, a laser pulse emission device (laser induced breakdown device) and a spectral analysis device (spectral detection device). ) in three parts.
  • the ultrasonic atomization auxiliary sampling device is mainly composed of a filter device 1, a sample water pump 2, a standard sample water pump 3, and a cleaning water pump 4.
  • the liquid is introduced into the fog chamber bottom plate 8, the atomizing sheet 9, the fog chamber rear panel 10, and the fog chamber.
  • the first-level buffer mist chamber composed of the middle partition plate 11, the rear panel of the mist chamber 10, the top plate of the mist chamber 12, and the front panel of the mist chamber 13, and then flows through the second-level buffer mist chamber 15)
  • the atomized sample is continuously sent into the guide tube 16 , a flowing mist column is formed at the nozzle for online real-time detection, and the remaining liquid sample is discharged from the drain nozzle 7, of which the sample water pump 2, standard sample water pump 3, and cleaning water pump 4 can be individually controlled in time-sharing;
  • laser pulse emission device which mainly includes a pulsed laser 18 and a focusing lens group 19, which are used to generate laser pulses required for breakdown of the sample;
  • the spectral analysis device mainly includes a collection lens group 20 and a spectrometer 22, which are used to collect the spectral radiation generated by the breakdown.
  • the invention utilizes a specially designed ultrasonic atomization auxiliary sampling device to realize continuous and rapid sampling, which reflects the characteristics of real-time and online analysis of the device, and the existence of standard samples makes the invention have higher accuracy; Break down the sample, and use the spectral analysis equipment and time-resolved image sensor to analyze the ablation process and plasma characteristics to achieve online real-time detection of the sample.
  • Fig. 1 is the structural representation of the device (ultrasonic atomization assisted sample introduction device) of liquid sample ultrasonic atomization-assisted breakdown spectroscopy, wherein 1 is a filter system, 2 is a water pump for the sample to be tested, 3 is a standard sample water pump, and 4 is a cleaning water pump , 5 is the main board of the atomization drive, 6 is the slope base, 7 is the drainage pipe, 8 is the bottom plate of the fog chamber, 9 is the atomizing sheet, 10 is the rear panel of the fog chamber, 11 is the partition plate of the fog chamber, and 12 is the top plate of the fog chamber , 13 is the front panel of the fog chamber, 14 is the intake fan, 15 is the secondary buffer fog chamber, 16 is the guide tube, 17 is the exhaust fan, the above components constitute the ultrasonic atomization auxiliary sampling device; 18 is the pulse laser, 19 is a focusing lens group, both of which form a laser pulse emitting device; 20 is a collecting lens group, 21 is an optical fiber, 22 is
  • the present invention is implemented as follows.
  • This device has three water pumps, namely the sample water pump 2 to be tested, the standard sample water pump 3, and the cleaning water pump 4, which are respectively used for actual detection, data correction, and cleaning.
  • the sample chamber consisting of the fog chamber bottom plate 8, the atomizing sheet 9, the fog chamber rear panel 10, the fog chamber middle partition plate 11, and the fog chamber front panel 13 is continuously introduced.
  • the entire fog chamber is fixed above the inclined base 6, so that the bottom plate 8 of the fog chamber forms a certain angle with the horizontal plane.
  • After the liquid sample enters the sample chamber it flows through the upper side of the atomizing sheet 9 fixed on the bottom plate 8 under the action of gravity. A uniform mist of droplets suspended in the air.
  • the formed air pressure pushes the atomized liquid sample in the atomization chamber to continuously flow into the partition plate 11 in the atomization chamber, the rear panel 10 of the atomization chamber, the top plate 12 of the atomization chamber, and the mist chamber.
  • the first-level buffer mist chamber composed of the front panel 13 of the chamber, and then flows through the second-level buffer mist chamber 15 to continuously send the atomized sample into the guide pipe 16, and continuously sprays out at the rear end of the guide pipe 16 to form continuous flow and droplets.
  • the uniform sample mist column is collected by the exhaust fan 17 at the rear end.
  • the laser pulses emitted by the pulsed laser 18 are focused on the sample mist column at the rear end of the guide tube 16 through the focusing lens group 19 to break down the sample and generate plasma.
  • the optical radiation generated when the plasma is cooled is focused and coupled into the optical fiber 21 by the collection lens group 20 , and spectrally detected by the spectrometer 22 , and the spectral signal is displayed and stored by the computer 23 .
  • the function of the slope base 6 is to fix the ultrasonic atomization auxiliary sampling device to keep it at a certain inclination angle, so that the liquid sample flows through the atomization sheet 9 in one direction, realizes the atomization of the sample, and makes the unatomized liquid sample flow in the direction Drain port for easy drainage.
  • the length of the middle partition plate 11 exceeds that of the atomizing sheet 9, and the inclination angle enables the droplets condensed on the surface to drip down near the water outlet 7 and discharge directly from the water outlet 7, thereby reducing the residue of the atomized sample and reducing the memory effect.
  • the function of the exhaust fan 17 is to condense the atomized sample so as to form a mist column to facilitate the experiment and to discharge the sample after the experiment.
  • the wavelength of the pulse output by the pulsed laser 18 can be arbitrarily selected in the infrared to ultraviolet band according to the research purpose; the pulse width of the pulse can be in the order of nanoseconds or femtoseconds; in order to cover the wavelength from ultraviolet to infrared, the laser wavelength can be Choose between 266nm, 355nm, 532nm and 1064nm; the energy of the pulse can also be selected as required.
  • the spectrometer 22 adopts a grating spectrometer, an echelle grating spectrometer or a folded grating spectrometer, and the detection range is 200nm-1000nm.
  • the spectrometer resolution should be at least 0.1 nm.
  • the spectrum acquisition delay time is selected between 200ns and 1500ns.
  • the optimal integration gate width is selected between 900ns-30000ns.
  • the computer 23 is used to display and store the spectral signals recorded by the spectrometer 22, and to process the signals. Under the same experimental conditions, the concentration of the target element in the droplet sample can be inverted according to the intensity of the characteristic spectral peak of the target element.
  • the method can perform experiments on liquid samples in various environments, thereby realizing on-line detection.
  • the method can realize continuous and rapid sample injection and atomization, so as to carry out on-line and real-time detection. This method improves the detection accuracy due to the existence of standard samples.

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Abstract

一种液体样品在线检测的装置与方法，属于光学分析仪器领域，利用特殊设计的超声波雾化辅助进样装置实现了连续、快速进样，体现出本装置实时、在线分析的特点，标准样的存在使得检测具有更高的精确度；并利用激光脉冲击穿样品，利用光谱分析设备和时间分辨图像传感器分析烧蚀过程和等离子体特性实现样品在线实时检测。检测系统可以用于海洋及淡水环境中重金属元素及其它重要金属元素的现场快速检测领域，以及在工业污水排放中的金属元素实时在线检测等领域展开应用，也可以应用于科研领域中的基础研究。

Description

一种液体样品元素在线检测的装置与方法
本申请要求于2020年09月22日提交中国专利局、申请号为CN202010999441.2、发明名称为“一种液体样品元素在线检测的装置与方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种液体样品在线检测的装置与方法，该技术通过超声波雾化辅助进样装置实现连续在线进样，利用激光诱导击穿光谱技术在线、实时、精确的实现水体中的元素成分的定性检测，属于光学分析仪器领域，有望在水体环境监测和自然水体科学调查等领域应用。
背景技术
激光诱导击穿光谱技术(Laser induced breakdown spectroscopy，LIBS)是利用聚焦的激光脉冲击穿样品产生瞬态等离子体，通过检测样品等离子体中元素所发射的特征光谱，实现对于样品中元素成分的定性定量分析的技术。该技术具有快速、实时分析的能力，因此受到了广泛的重视。在诸如冶炼产品元素成分分析等领域，LIBS技术已经得到较为深入应用。将这种技术应用到液体样品的元素成分分析领域中也具有较好前景，可预见该技术能够在水资源的重金属污染，海洋金属元素探测和工业、生活排放污水监测等领域中发挥作用。然而，当应用于水体成分检测时，由于受到基质效应的影响，LIBS水体检测的灵敏度和稳定性都受到了影响。因此，水体金属元素在线、现场检测LIBS技术遇到了困难。
发明内容
本发明利用所提出的利用超声波连续进样装置连续快速的改变样品形态，并结合LIBS检测方法，实现水体金属元素现场、快速、在线、高灵敏LIBS检测，有望在相关领域得到应用。
本发明提供了一种液体样品超声波雾化辅助击穿光谱的装置，包括超声波雾化辅助进样装置、激光诱导击穿装置和光谱检测装置，
所述超声波雾化辅助进样装置包括过滤系统1、待测样品水泵2、标 准样水泵3、清洗水泵4、雾化驱动主板5、斜坡底座6、排水管道7、雾室底板8、雾化片9、雾室后面板10、雾室中隔板11、雾室顶板12、雾室前面板13、进气风扇14、二级缓冲雾室15、导流管16和排气风扇17，
所述过滤系统1与待测样品水泵2连通；
所述待测样品水泵2、标准样水泵3和清洗水泵4并联后与所述雾室前面板13连通；
所述雾室底板8、雾化片9、雾室后面板10、雾室中隔板11和雾室前面板13组成样品舱；所述样品舱固定于所述斜坡底座6的上表面，所述雾化驱动主板5与雾化片9连通，所述雾室后面板10的底部设有排水管道7；所述雾室中隔板11、雾室后面板10、雾室顶板12和雾室前面板13组成一级缓冲雾室；所述雾室前面板13与进气风扇14连通；所述雾室前面板13设有出口与所述二级缓冲雾室15连通，所述二级缓冲雾室15与导流管16和排气风扇17顺次连通；
所述激光诱导击穿装置包括脉冲激光器18和聚焦透镜组19，所述聚焦透镜组19位于所述脉冲激光器18的端部；
所述光谱检测装置包括依次连接的收集透镜组20、光纤21和光谱仪22；
所述光谱仪22与计算机23连接。
本发明还提供了一种利用上述技术方案所述的装置进行液体样品超声波雾化辅助击穿光谱的方法，包括以下步骤：
待测液体样品经过滤系统1过滤后，由清洗水泵4持续不断的导入样品舱；进入样品舱的液体样品流经雾化片9时，雾化片9产生的超声波会不断的对样品进行强烈震荡从而使其转化为均匀雾状液体样品；然后由进气风扇14将气体注入样品舱，所形成的气压推动雾化室中雾化后的液体样品持续的流入一级缓冲雾室，然后流经二级缓冲雾室15将雾化样品持续送入导流管16，在导流管16后端持续喷出从而形成不断流动、液滴均匀的样品雾柱，后端由排气风扇17收束收集；脉冲激光器18发射出的激光脉冲经聚焦透镜组19聚焦在样品雾柱，击穿样品，产生等离子体；等离子体冷却时产生的光辐射都由收集透镜组20聚焦耦合到光纤21中，并由光谱仪22分光检测，光谱信号由计算机23显示和存储；
所述标准样水泵3用于数据校正。
本发明还提供了一种液体样品超声波雾化辅助击穿光谱的方法，通过超声波雾化辅助进样装置进行连续、快速进样和样品雾化，使用激光诱导击穿装置，击穿样品雾柱，通过光谱检测装置对样品中目标元素进行实时、在线、精确检测。
优选地，待测液体样品经过滤系统过滤后，由水泵持续不断的导入样品舱；进入样品舱的液体样品流经雾化片时，雾化片产生的超声波会不断的对样品进行强烈震荡从而使其转化为均匀雾状液体样品；然后由进气风扇将气体注入样品舱，所形成的气压推动雾化室中雾化后的液体样品持续的流入一级缓冲雾室，然后流经二级缓冲雾室将雾化样品持续送入导流管，在导流管后端持续喷出从而形成不断流动、液滴均匀的样品雾柱，后端由排气风扇收束收集；脉冲激光器发射出的激光脉冲经聚焦透镜组聚焦在样品雾柱，击穿样品，产生等离子体；等离子体冷却时产生的光辐射都由收集透镜组聚焦耦合到光纤中，并由光谱仪分光检测，光谱信号由计算机显示和存储。
优选地，在继电器的控制下分别利用三个水泵注入待测样品、标准样和去离子水，利用液体流动和雾化片的超声波震荡，产生连续不断的雾化样品，并在进气风扇产生的气压推动下沿固定路线行进形成不断流动的样品雾柱。
优选地，所述进气风扇注入样品舱的气体为空气、氩气、氦气、氮气多种气体。
优选地，所述脉冲激光器的脉冲的脉宽为纳秒量级或飞秒量级，所述脉冲激光器的激光波长在266nm、355nm、532nm和1064nm之间选择。
优选地，所述光谱仪的工作光谱范围为200nm到1000nm之间，光谱分辨率为0.1nm。
优选地，所述光谱仪的探测器的采集门延时时间在200ns-1500ns之间选择，积分门宽为在900ns-30000ns之间选择。
优选地，所述导流管的内径尺寸在0.125mm-3mm之间选择。
优选地，所述标准样预先配置，元素种类与浓度已知，用于数据校正，提高系统精确度。
下面结合附图对本发明提供的液体样品元素在线检测的装置进行说明，本发明可以分为超声波雾化辅助进样装置、激光脉冲发射装置(激光诱导击穿装置)和光谱分析装置(光谱检测装置)三个部分。其中超声波雾化辅助进样装置主要由过滤装置1、待测样品水泵2、标准样水泵3、清洗水泵4将液体导入由雾室底板8、雾化片9、雾室后面板10、雾室中隔板11、雾室前面板13组成的样品舱，然后通过超声波震动将进入雾化室的液体样品部分转化为均匀雾状液体样品，并在进气风扇14气流的推动下流入由雾室中隔板11、雾室后面板10、雾室顶板12、雾室前面板13组成的一级缓冲雾室，然后流经二级缓冲雾室15)将雾化样品持续送入导流管16，在管口形成流动的雾柱以便进行在线实时检测，剩余液体样品由排水管口7排出，其中待测样品水泵2、标准样水泵3、清洗水泵4可以分时单独控制；激光脉冲发射装置，主要包括脉冲激光器18和聚焦透镜组19，用来产生击穿样品所需的激光脉冲；光谱分析装置主要包括收集透镜组20、光谱仪22，用来对击穿产生的光谱辐射进行采集。
本发明利用特殊设计的超声波雾化辅助进样装置实现了连续、快速进样，体现出本装置实时、在线分析的特点，标准样的存在使得本发明具有更高的精确度；并利用激光脉冲击穿样品，利用光谱分析设备和时间分辨图像传感器分析烧蚀过程和等离子体特性实现样品在线实时检测。
说明书附图
图1为液体样品超声波雾化辅助击穿光谱的装置(超声波雾化辅助进样装置)的结构示意图，其中1为过滤系统，2为待测样品水泵，3为标准样水泵，4为清洗水泵，5为雾化驱动主板，6为斜坡底座，7为排水管道，8为雾室底板，9为雾化片，10为雾室后面板，11为雾室中隔板，12为雾室顶板，13为雾室前面板，14为进气风扇，15为二级缓冲雾室，16为导流管，17为排气风扇，上述部件组成超声波雾化辅助进样装置；18为脉冲激光器，19为聚焦透镜组，两者组成激光脉冲发射装置；20为收集透镜组，21为光纤，22为光谱仪，组成光谱分析装置；23为计算机。
具体实施方式
本发明按照如下方式进行实施。此装置有三个水泵分别为待测样品水泵2、标准样水泵3、清洗水泵4，分别用于实际检测、数据校正、清洗， 实际检测时将待测液体样品用过滤系统1过滤后，由水泵持续不断的导入由雾室底板8、雾化片9、雾室后面板10、雾室中隔板11、雾室前面板13组成的样品舱。整个雾室固定于倾斜底座6上方，使雾室底板8与水平面成一定角度。液体样品进入样品舱后，在重力的作用下流经固定于底板8上的雾化片9上侧，在雾化驱动主板5的驱动下雾化片9产生的高频震荡，使液体样品转化为悬浮于空中的均匀雾状液滴。在进气风扇14注入的气体的带动下，所形成的气压推动雾化室中雾化后的液体样品持续的流入由雾室中隔板11、雾室后面板10、雾室顶板12、雾室前面板13组成的一级缓冲雾室，然后流经二级缓冲雾室15将雾化样品持续送入导流管16，在导流管16后端持续喷出从而形成不断流动、液滴均匀的样品雾柱，后端由排气风扇17收束收集。脉冲激光器18发射出的激光脉冲经聚焦透镜组19聚焦在导流管16后端的样品雾柱上，击穿样品，产生等离子体。等离子体冷却时产生的光辐射都由收集透镜组20聚焦耦合到光纤21中，并由光谱仪22分光检测，光谱信号由计算机23显示和存储。
斜坡底座6的作用是固定超声波雾化辅助进样装置，使其保持一定的倾斜角度，使液体样品单向流经雾化片9，实现样品的雾化，并使未雾化的液体样品流向排水口以便于排出。
中隔板11的长度超过雾化片9，倾斜角度使凝结于表面的液滴能够在排水口7附近滴下，直接从排水口7排出，进而减少雾化样品的残留，降低记忆效应。
排气风扇17的作用是收束雾化样品以便形成雾柱方便实验并将实验后样品排出样品。
脉冲激光器18输出的脉冲的波长可以根据研究目的在红外到紫外波段任意选择；脉冲的脉宽可以为纳秒量级，也可为飞秒量级；为了覆盖从紫外到红外波段，激光波长可以在266nm、355nm、532nm和1064nm之间选择；脉冲的能量也可以根据需要进行选择。
光谱仪22采用光栅光谱仪，也可以采用中阶梯光栅光谱仪或折叠光栅光谱仪，检测范围为200nm-1000nm。光谱仪分辨率至少应达到0.1nm。在进行成分检测分析时，为了避开初始时刻的连续背景辐射，光谱采集延时时间在200ns-1500ns之间选择。最佳积分门宽在900ns-30000ns之间选 择。
计算机23用来显示和存储光谱仪22记录的光谱信号，并对信号进行处理。在实验条件相同的情况下，根据目标元素特征谱峰的强度，可以反演液滴样品中目标元素的浓度。
本方法可以在各种环境中对液体样品进行实验，从而实现在线检测。本方法能够实现连续、快速进样和雾化，从而进行在线、实时检测。本方法由于标准样的存在，提高检测精确度。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种液体样品超声波雾化辅助击穿光谱的装置，其特征在于，包括超声波雾化辅助进样装置、激光诱导击穿装置和光谱检测装置，
    所述超声波雾化辅助进样装置包括过滤系统(1)、待测样品水泵(2)、标准样水泵(3)、清洗水泵(4)、雾化驱动主板(5)、斜坡底座(6)、排水管道(7)、雾室底板(8)、雾化片(9)、雾室后面板(10)、雾室中隔板(11)、雾室顶板(12)、雾室前面板(13)、进气风扇(14)、二级缓冲雾室(15)、导流管(16)和排气风扇(17)，
    所述过滤系统(1)与待测样品水泵(2)连通；
    所述待测样品水泵(2)、标准样水泵(3)和清洗水泵(4)并联后与所述雾室前面板(13)连通；
    所述雾室底板(8)、雾化片(9)、雾室后面板(10)、雾室中隔板(11)和雾室前面板(13)组成样品舱；所述样品舱固定于所述斜坡底座(6)的上表面，所述雾化驱动主板(5)与雾化片(9)连通，所述雾室后面板(10)的底部设有排水管道(7)；所述雾室中隔板(11)、雾室后面板(10)、雾室顶板(12)和雾室前面板(13)组成一级缓冲雾室；所述雾室前面板(13)与进气风扇(14)连通；所述雾室前面板(13)设有出口与所述二级缓冲雾室(15)连通，所述二级缓冲雾室(15)与导流管(16)和排气风扇(17)顺次连通；
    所述激光诱导击穿装置包括脉冲激光器(18)和聚焦透镜组(19)，所述聚焦透镜组(19)位于所述脉冲激光器(18)的端部；
    所述光谱检测装置包括依次连接的收集透镜组(20)、光纤(21)和光谱仪(22)；
    所述光谱仪(22)与计算机(23)连接。
  2. 一种利用权利要求1所述的装置进行液体样品超声波雾化辅助击穿光谱的方法，其特征在于，包括以下步骤：
    置于待测样品水泵(2)中的待测液体样品经过滤系统(1)过滤后，由清洗水泵(4)持续不断的导入样品舱；进入样品舱的液体样品流经雾化片(9)时，雾化片(9)产生的超声波会不断的对样品进行强烈震荡从 而使其转化为均匀雾状液体样品；然后由进气风扇(14)将气体注入样品舱，所形成的气压推动雾化室中雾化后的液体样品持续的流入一级缓冲雾室，然后流经二级缓冲雾室(15)将雾化样品持续送入导流管(16)，在导流管(16)后端持续喷出从而形成不断流动、液滴均匀的样品雾柱，后端由排气风扇(17)收束收集；脉冲激光器(18)发射出的激光脉冲经聚焦透镜组(19)聚焦在样品雾柱，击穿样品，产生等离子体；等离子体冷却时产生的光辐射都由收集透镜组(20)聚焦耦合到光纤(21)中，并由光谱仪(22)分光检测，光谱信号由计算机(23)显示和存储；
    所述标准样水泵(3)用于数据校正。
  3. 一种液体样品超声波雾化辅助击穿光谱的方法，其特征在于，通过超声波雾化辅助进样装置进行连续、快速进样和样品雾化，使用激光诱导击穿装置，击穿样品雾柱，通过光谱检测装置对样品中目标元素进行实时、在线、精确检测。
  4. 根据权利要求3所述的方法，其特征在于，待测液体样品经过滤系统过滤后，由水泵持续不断的导入样品舱；进入样品舱的液体样品流经雾化片时，雾化片产生的超声波会不断的对样品进行强烈震荡从而使其转化为均匀雾状液体样品；然后由进气风扇将气体注入样品舱，所形成的气压推动雾化室中雾化后的液体样品持续的流入一级缓冲雾室，然后流经二级缓冲雾室将雾化样品持续送入导流管，在导流管后端持续喷出从而形成不断流动、液滴均匀的样品雾柱，后端由排气风扇收束收集；脉冲激光器发射出的激光脉冲经聚焦透镜组聚焦在样品雾柱，击穿样品，产生等离子体；等离子体冷却时产生的光辐射都由收集透镜组聚焦耦合到光纤中，并由光谱仪分光检测，光谱信号由计算机显示和存储。
  5. 根据权利要求3或4所述的方法，其特征在于，在继电器的控制下分别利用三个水泵注入待测样品、标准样和去离子水，利用液体流动和雾化片的超声波震荡，产生连续不断的雾化样品，并在进气风扇产生的气压推动下沿固定路线行进形成不断流动的样品雾柱。
  6. 根据权利要求2或4所述的方法，其特征在于，所述进气风扇注入样品舱的气体为空气、氩气、氦气、氮气多种气体。
  7. 根据权利要求2或4所述的方法，其特征在于，所述脉冲激光器的 脉冲的脉宽为纳秒量级或飞秒量级，所述脉冲激光器的激光波长在266nm、355nm、532nm和1064nm之间选择。
  8. 根据权利要求2或4所述的方法，其特征在于，所述光谱仪的工作光谱范围为200nm到1000nm之间，光谱分辨率为0.1nm。
  9. 根据权利要求2或4所述的方法，其特征在于，所述光谱仪的探测器的采集门延时时间在200ns-1500ns之间选择，积分门宽为在900ns-30000ns之间选择。
  10. 根据权利要求5所述的方法，其特征在于，所述标准样预先配置，元素种类与浓度已知，用于数据校正，提高系统精确度。
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