激光烧蚀金属靶时气体电离分析

我们使用Ｎｄ：ＹＡＧ激光器烧蚀金属Ａｌ靶获得等离子体,利用光谱时－空分辨技术,关于环境气体分解及其对等离子体辐射特征的影响进行了研究。使用的气体是Ａｒ,Ａｉｒ,Ｎ２。结果发现,在等离子体形成初期,等离子体时－空分辨谱中有大量的环境气体离子谱线。基于Ａｌ等离子体不同激光能量下的时间－空间分辨谱。对激光烧蚀金属靶时气体电离现象进行了分析,对气体分解造成的影响进行了简单的讨论。     

Study on parameters influencing analytical performance of laser-induced breakdown spectroscopy

Lens-to-sample distances, delay time, atmospheric condition, laser pulse energy, etc. had obvious effects on the analytical performance of laser-induced breakdown spectroscopy. In this paper, these parameters are investigated in greater detail and we will explain how they have influences on the analytical performance. The results show that the focal plane under the sample surface can improve precision and detection limit, and the delay time should be decided according to sensitivity and accuracy. Spectral line intensity is stronger in argon than helium, nitrogen and air gas environment. Pulse energy should exceed energy threshold (about 50 mJ) which can generate plasma, and the energy should not exceed about 300 mJ to avoid plasma shielding. Under optimum parameters, concentration relative standard deviation of C, Si, Mn, P, S, Ni, and Cr for low-alloyed steel (sample number 11278) which were measured 11 times is 2.37%, 2.18%, 2.23%, 7.8%, 9.34%, 1.92%, and 2.13%, respectively. And the detection limit of C, Si, Mn, P, S, Ni, and Cr for pure steel is 0.0045%, 0.0072%, 0.0069%, 0.0027%, 0.0024%, 0.0047%, and 0.0024%, respectively.     

氩气含量对空气介质阻挡放电发射光谱的影响

利用介质阻挡放电实验系统测量了空气介质阻挡放电的发射光谱,研究了氩气含量对空气介质阻挡放电发射光谱的影响.在280～500 nm波长范嗣内,发现了氮分子第二正带系N2(C3∏u-B3∏g)的谱线和氮分子离子的第一负带系N2+(B3∑u+-X2∑g+)的谱线.在相同条件下加入10%氩气后,起始放电电压由26kV降低到23...     

发射光谱研究氩气/空气混合气体介质阻挡放电能量传递过程

使用水电极介质阻挡放电装置,对比氩气与氩气/少量空气的混合气体以及空气与空气/少量氩气的混合气体放电的发射光谱,研究了氩气与空气相混合时气体放电中的能量传递过程。实验发现, 当氩气中加入少量的空气时,氩原子谱线均变弱,说明空气中的氮分子对氩原子的各激发态具有猝灭作用。并且随着空气含量的增加,各谱线变弱的速率不同。越是与氮分子的激发电位接近的氩原子的激发态被猝灭的作用越明显。另一方面,当空气中加入少量氩气时,发现氮分子第二正带系和氮分子离子第一负带系的谱线均被增强。说明在空气/少量氩气放电中,氮分子的激发由于亚稳态氩原子的潘宁激发传能而增强。因此在氩气/空气混合气体放电中,气体成分及比例影响放电的发光特性和能量传输特性。     

Detection of explosives with laser-induced breakdown spectroscopy

Our recent work on the detection of explosives by laser-induced breakdown spectroscopy (LIBS) is reviewed in this paper. We have studied the physical mechanism of laser-induced plasma of an organic explosive, TNT. The LIBS spectra of TNT under single-photon excitation are simulated using MATLAB. The variations of the atomic emission lines intensities of carbon, hydrogen, oxygen, and nitrogen versus the plasma temperature are simulated too. We also investigate the time-resolved LIBS spectra of a common inorganic explosive, black powder, in two kinds of surrounding atmospheres, air and argon, and find that the maximum value of the O atomic emission line SBR of black powder occurs at a gate delay of 596 ns. Another focus of our work is on using chemometic methods such as principle component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) to distinguish the organic explosives from organic materials such as plastics. A PLS-DA model for classification is built. TNT and seven types of plastics are chosen as samples to test the model. The experimental results demonstrate that LIBS coupled with the chemometric techniques has the capacity to discriminate organic explosive from plastics.     

Validity of the two-term Boltzmann approximation employed in the fluid model for high-power microwave breakdown in gas

The electron energy distribution function （EEDF）, predicted by the Boltzmann equation solver BOLSIG＋ based on the two-term approximation, is introduced into the fluid model for simulating the high-power microwave （HPM） breakdown in argon, nitrogen, and air, and its validity is examined by comparing with the results of particle-in-cell Monte Carlo collision （PIC/MCC） simulations as well as the experimental data. Numerical results show that, the breakdown time of the fluid model with the Maxwellian EEDF matches that of the PIC/MCC simulations in nitrogen; however, in argon under high pressures, the results from the Maxwellian EEDF were poor. This is due to an overestimation of the energy tail of the Maxwellian EEDF in argon breakdown. The prediction of the fluid model with the BOLSIG＋ EEDF, however, agrees very well with the PIC/MCC prediction in nitrogen and argon over a wide range of pressures. The accuracy of the fluid model with the BOLSIG＋ EEDF is also verified by the experimental results of the air breakdown.     

激光诱导击穿光谱结合偏最小二乘法直接检测皮蛋壳中的Cu含量

运用激光诱导击穿光谱(LIBS)技术对皮蛋壳中Cu元素直接进行检测,获得样本中Cu元素的特征谱线信息,采用湿法消解结合原子吸收分光光度计(AAS)测量样品中Cu元素的真实含量。由于LIBS检测的精度和准确度受到样品基体复杂,环境噪声,系统噪声,激光能量稳定性等一系列因素的影响,采用传统的单变量赛伯-罗马金拟合方式对样品的LIBS相对强度和浓度进行线性拟合不能满足定性分析的要求,因此,采用一种多变量的分析-偏最小二乘(PLS)对LIBS光谱数据进行了处理,比较分析了不同点数平滑处理和五种预处理方法对PLS建模精度和准确度的影响。分析得出采用11点平滑结合多元散射校正(MSC)预处理能有效地提高PLS建立的模型的相关系数,降低均方根误差和平均相对误差,有效提高了模型的准确性。研究结果表明,激光诱导击穿光谱技术能够准确地直接检测皮蛋壳中重金属Cu的含量,下一步的工作将对皮蛋进行批量试验,寻找出蛋壳与蛋清、蛋黄中重金属Cu的数量关系,实现通过LIBS检测皮蛋壳便可知蛋清、蛋黄中重金属含量的目标,为农产品质量安全提供新的快速无损检测技术方法。     

Effect of ambient conditions on laser-induced breakdown spectra

The role of different ambient conditions on LIBS signal intensity was investigated for better understanding and performance of LIBS as a quantitative and qualitative analytical technique. For this purpose, the relative LIBS signal intensities were measured for a standard Cr line (520.8 nm) at different gas pressures of Ar, He, and air. The plasma was generated using a Q-switched pulsed Nd:YAG laser having wavelength of 1064 nm and pulse duration of 8 ns. The analysis revealed that the intensities of the spectral atomic Cr line (520.8 nm) were strongly enhanced under the argon environment in 10?C40 mbar range. The electron excitation temperature (T _e ) and number density (n _e ) were estimated by using a Boltzmann plot and a Stark broadening profile, respectively. For optimum dependence of LIBS, laser energy and pressure dependence was also studied. The electron temperature and number density showed an increase with increase in ambient gas pressure.     

氩气含量对空气介质阻挡放电发射光谱的影响

利用介质阻挡放电实验系统测量了空气介质阻挡放电的发射光谱,研究了氩气含量对空气介质阻挡放电发射光谱的影响。在280~500 nm波长范围内,发现了氮分子第二正带系Ｎ₂(Ｃ 3Π_ｕ-Ｂ 3Π_ｇ)的谱线和氮分子离子的第一负带系N+₂(B 3Σ＋_ｕ-Ｘ 2Σ＋_ｇ)的谱线。在相同条件下加入10%氩气后,起始放电电压由26 kV降低到23 kV,介质阻挡放电和发射光谱强度都增强,谱线的半宽明显加大。随氩气含量的增加,各个氮分子第二正带系谱线强度的变化趋势不同,而两条氮分子离子第一负带系谱线391.44和427.81 nm的光谱强度都是降低的。     

Shielding effect of laser-induced plasma in glass: pulse-to-pulse evolution of nitrogen and analyte emission lines

A characteristic of the plasma shielding effect was investigated through simultaneous measurement of time evolution of nitrogen emission in ambient air and analyte-specific emission in a glass matrix with varying lens-to-sample distance (LTSD), laser pulse energy, and repetition rate. Even under the threshold energy of air breakdown, strong nitrogen-emission lines could be measured by laser-induced breakdown spectroscopy (LIBS) for the glass samples in air at atmospheric pressure. The time evolution of the nitrogen emission was correlated reversely with a variation of various analyte emissions in the glass samples. Based on the reverse relation between the intensities of nitrogen and calcium emission intensities, the corrected values of the calcium emission line were calculated. This methodology shows consistent results independent of experimental conditions such as different LTSDs, laser energies, and repetition rates.     

TDLAS测量CO2的温度影响修正方法研究

可调谐二极管激光吸收光谱(TDLAS)技术测量CO₂浓度时,由于测量氛围温度变化的影响引起气体吸收谱线的线强和线型发生变化,最终导致浓度测量存在较大误差。为了克服温度变化对浓度测量的影响,选用中心波长在1 580 nm的DFB激光器,基于直接吸收法,模拟电厂尾部烟道内的高浓度二氧化碳气体环境,研究了在常温(298 K)和变温(298~338 K、间隔10 K)不同温度工况下CO₂浓度的测量。结果显示,常温浓度测量的最大相对误差为-5.26%,最小相对误差为1.25%,相对误差均方值为3.39%,验证了TDLAS测量系统在常温下有着良好的测量精度和稳定性,但其在变温测量时浓度测量结果误差较大,其最大相对误差已经超过25%。为了修正温度变化对浓度测量结果的影响,适应工业测量的需要,在变温测量基础上利用最小二乘法拟合出测量系统在不同温度下的浓度与气体吸收的修正关系式。经过修正后,CO₂浓度测量的相对误差降到5%以下,相对误差均方值降到3.5%以下。修正结果表明,所提出的修正方法可以有效抑制温度变化对浓度测量结果的影响,显著提高了测量系统在变温环境下的测量精度和稳定性,为TDLAS系统测量CO₂浓度的现场应用提供了理论支持和技术保障。     

Combination of RF-plasma jet and Laser-induced plasma for breakdown spectroscopy analysis of complex materials

Laser-induced breakdown spectroscopy method is modified using an external radiofrequency (RF) plasma jet that overlaps spatially with the laser-induced plasma. Short UV laser pulses (wavelength 193 nm) are employed to ablate iron oxide ceramics, zinc oxide ceramics and polyethylene pressed pellets in ambient air background. An RF generator (frequency 13.56 MHz, power ≤1 kW) and a gas nozzle system are employed to generate a continuous jet of argon and nitrogen plasma expanding into air. The optical emission of the overlapped plasma is analyzed using an Echelle spectrometer equipped with an intensified CCD camera. The time dependence of optical emission intensities and of plasma parameters is investigated by varying the spectrometer delay time with respect to the laser pulse. The emission intensities of major (Fe, Zn) and minor (Mn, Al) elements are moderately increased with the RF plasma jet (≤2×). The intensities of atomic lines and molecular bands from ablated polymer material are increased also.     

基于激光诱导击穿光谱的合金钢组分偏最小二乘法定量分析

在炼钢中合金浓度的检测和控制对产品质量影响很大,激光诱导击穿光谱(laser induced breakdown spectroscopy, LIBS)技术具有快速、非接触、无需制样等特点,非常适合应用于合金成分的在线分析。但是由于合金中的C, S, P元素的成分含量都很低,其原子发射谱线极易淹没在复杂的铁元素特征谱线之中,造成这些重要元素在线定量分析困难。以合金钢标准光谱样品为研究对象,获取激光诱导击穿光谱数据,采用定标曲线法(calibration curve, CC)和偏最小二乘法(partial least squares, PLS),对合金钢样品的主量和微量元素进行定量分析。比较两种方法的定标结果得出：对于主量元素,PLS方法的定量分析水平优于传统的CC法;更重要的是对于微量元素,由于特征谱线极弱,CC法无法得出定量结果,而PLS法仍然具有良好的定量分析能力。同时,将PLS法回归模型特征谱线处的回归系数与原始有背景干扰的光谱强度数据进行比较,阐述了LIBS数据定量分析中PLS方法的优势。结果表明,在激光诱导击穿光谱合金成分分析中,PLS方法适合用于C等微量元素的定量分析。     

介质阻挡放电点燃大气压直流均匀放电的光谱研究

由于大气压均匀放电等离子体在工业领域具有广泛的应用前景,为了获得大尺寸的大气压均匀等离子体,采用氩气作为工作气体,在大气压空气环境中利用同轴介质阻挡放电点燃了针-板电极间的大气隙(气隙宽度达到5 cm)直流均匀放电。研究发现,同轴介质阻挡放电能够有效降低针-板电极间的击穿电压。该均匀放电由等离子体柱、等离子体羽、阴极暗区和阴极辉区组成。其中等离子体柱和阴极辉区都是连续放电。而等离子体羽不同位置的放电是不同时的。事实上,等离子体羽放电是由从阴极向着等离子体柱移动的发光光层(即等离子体子弹)叠加而成。利用电学方法测量了放电的伏安特性曲线,发现其与低气压正常辉光放电类似,均具有负斜率。采集了放电的发射光谱,发现存在N₂第二正带系、氩原子和氧原子谱线。通过Boltzmann plot方法对放电等离子体电子激发温度进行了空间分辨测量,发现等离子体柱的电子激发温度比等离子体羽的电子激发温度低。通过分析放电机制,对以上现象进行了定性解释。这些研究结果对大气压均匀放电等离子体源的研制和工业应用具有重要意义。     

Application of Mn nano-flower sculptured thin films produced on interdigitated pattern as cathode and anode electrodes in field ionization gas sensor

The photolitography method was used for producing interdigitated configurations for cathode and anode electrodes of a field ionization gas sensor in which Mn helical nano-flowers with 3-fold symmetry were deposited using oblique angle deposition together with rotation of the substrate about its surface normal, with each rotation divided into six sections. These sections were alternately rotated at high and low speeds. Three different distances were chosen in the design between anode and cathode electrodes, namely 40, 100 and 200 μm. Physical structure and morphology of electrodes were studied by field emission scanning electron microscope and atomic force microscope analyses.The breakdown voltage of the system was studied for nitrogen, oxygen, argon, air and carbon mono-oxide gases. Investigations with these gases at different distances between anode and cathode and different gas pressures confirmed Paschen's Law. Results showed that at low pressures, decreasing the gap between electrodes increases the breakdown voltage. With fewer gas molecules between the electrodes the number of interactions between particles is reduced and higher energies are required for ionization of gas molecules. At high pressures, the breakdown voltage is decreased because of an increased number of molecular interactions. The sensor demonstrated good selectivity between the different gases and selectivity was enhanced with increasing gas pressure. A direct relationship was found at low pressures (e.g., 0.1 mbar) between the breakdown voltage and the gas ionization energy while at high pressures (e.g., 1000 mbar) this relationship was reversed.     

Pink afterglow in nitrogen-argon mixtures

The nitrogen pink afterglow was studied by optical emission spectroscopy in the DC flowing regime at a total gas pressure of 700 Pa and at the discharge current of 120 mA. The discharge was created in a Pyrex tube of 13 mm i.d. using nitrogen and argon of 99.999% purity with additional purification by Oxiclear columns and liquid nitrogen traps. The area ±3 cm around the observation point had to be cooled down to liquid nitrogen wall temperature in order to allow the study of the reactor wall temperature effect on the post-discharge. The maximum pink afterglow emission in pure nitrogen at ambient wall temperature was observed at a decay time of 6 ms. When the argon percentage in the gas mixture was increased the pink emission maximum was shifted to the later decay times. Simultaneously, the intensity of the pink afterglow decreased and at a 1:1 nitrogen-argon ratio the effect disappeared. Similar effects were also observed when the discharge tube wall around the observation point was cooled down to liquid nitrogen temperature. The argon atomic lines were only observed during the post-discharge at the highest argon concentration at a low wall temperature. The kinetic model showed that the pink afterglow quenching was connected to the decrease of the and pooling processes efficiency.     

空气—氩气冷却ICP：有机溶液分析的工作条件及检出限研究

研究了冷却气含50%空气的ICP中,MIBK溶液里金属元素不同性质谱线的信背比与入射功率、观察高度、冷却气流量及冷却气中空气含量等工作条件的关系。测定了8种元素12条谱线的检出限并与氩有机ICP中相同谱线的检出限进行比较。另外还测定了在引入MIBK溶液的情况下,空气-氩气ICP中心通道的激发温度。结果表明,具有中等激发能的谱线在含50%空气的空气-氩气有机ICP中的检出限优于氩气有机ICP中的检出限。     

分子发射光谱法测量微波等离子体气体温度

通过OH自由基A2Σ+→X2Π_r电子带系分子发射光谱测温法,实现了对氩气、氮气、空气三种大气压微波等离子体气体温度的测量。探究了不同微波功率、不同气体流量下气体温度的变化规律,测量了氮气、空气微波等离子体羽流的轴向温度分布。实验结果表明,不同工作条件下微波等离子体核心温度普遍超过2 000 K,空气微波等离子体可超过6 000 K;同样工作条件下三种微波等离子体气体温度满足：T_Ar<T_N2<T_Air;气体温度总体上随微波功率增加而小幅增加,随气体流量下降而小幅降低;氮气与空气等离子体羽流温度沿轴向迅速降低。为验证分子发射光谱测温法的准确性,以热电偶测温作为比对,对温度较低的介质阻挡放电氩气等离子体进行了温度测量,实验表明,分子发射光谱法与热电偶所测结果十分接近。     

可在线校准的大气CO_2浓度光声光谱监测系统研究

Fs光声光谱系统的谐振频率和池常数通常在实验室由标准气体标定得到,但在实际应用中,由于标准气体本身的不确定度以及与被测气体成分的不同、环境温湿度的变化,使得现场测量中谐振频率和池常数与实验室标定结果有偏差,从而导致测量结果不准确。为了解决以上问题,提出了基于大气中氧气的在线校准技术,并将该技术用于检测大气中二氧化碳浓度的光声光谱系统。大气中氧气浓度恒定为20.964%,通过探测氧气在763.73nm附近的扫频信号及峰值信号,实现共振频率和池常数的在线校准。该系统中光声池为直径6mm,长度100mm的一阶纵向共振模式结构。理论上分析了环境温湿度、气体成分对光声池性能的影响,同时给出了用标准气体、室内空气和室外空气标定的谐振频率和池常数,在标定结果的基础上,测量得到室内和室外的二氧化碳浓度值。实验结果显示,与校准过的气体分析仪的测量值相比,用被测大气中的氧气标定的谐振频率和池常数计算的二氧化碳浓度更准确,相对误差小于1%,远小于实验室标准气体标定计算的浓度相对误差。创新处在于,直接利用大气中的氧气对光声池的池常数和共振频率进行在线校准,有效的减小了标准气体标定带来的误差,以及环境变化带来系统漂移,提高光声系统在线监测的准确性和可靠性。     

基于近红外光谱法的沉积物间隙水化学组分快速测量

通过对巢湖柱状沉积物剖面间.隙水样品的近红外光谱(NIR)分析,采用OSC+WC和WC+OSC光谱预处理方法,结合偏最小二乘法(PLS)回归,建立了分层沉积物间隙水中TN,NH3-N,PO33-,TOC和SiO3的校正模型,该模型的TN,NH3-N,PO33-,TOC和SiO-3的预测值与实测值的校正相关系数分别为0....