Search

An experimental study has been performed on the pressure-dependent plasma emission intensities in Ar, He, and N2 surrounding gases with the plasma induced by either nanosecond (ns) or picosecond (ps) yttrium aluminum garnet laser. The study focused on emission lines of light elements such as H, C, O, and a moderately heavy element of Ca from an agate target. The result shows widely different pressure effects among the different emission lines, which further vary with the surrounding gases used and also with the different ablation laser employed. It was found that most of the maximum emission intensities can be achieved in Ar gas plasma generated by ps laser at low gas pressure of around 5 Torr. This experimental condition is particularly useful for spectrochemical analysis of light elements such as H, C, and O, which are known to suffer from intensity diminution at higher gas pressures. Further measurements of the spatial distribution and time profiles of the emission intensities of H I 656.2 nm and Ca II 396.8 nm reveal the similar role of shock wave excitation for the emission in both ns and ps laser-induced plasmas, while an additional early spike is observed in the plasma generated by the ps laser. The suggested preference of Ar surrounding gas and ps laser was further demonstrated by outperforming the ns laser in their applications to depth profiling of the H emission intensity and offering the prospect for the development of three-dimensional analysis of a light element such as H and C.

Rapid quantitative analyses of powder samples available in tiny amounts have successfully been conducted by utilizing a transversely excited atmospheric (TEA) CO2 laser-induced He gas plasma. In this study, 4 mg of powder sample was homogeneously mixed with 4 mg of high-vacuum silicon grease and the silicon grease–mixed powder sample (SMP) was painted on a metal surface, which serves as a subtarget. The grease functions to strongly bind the powder and to suppress blow-off of the powder particles. When a TEA CO2 laser (750 mJ, 10.6 μm, 200 ns) was directly focused on the metal subtarget in He gas at 1 atmosphere, a hightemperature He gas plasma was induced, producing a profusion metastable He atoms. It is assumed that the powder particles together with the silicon grease were vaporized to be effectively atomized and excited through metastable He atoms. The result revealed that this technique can be widely employed in the rapid semi-quantitative analyses of powder samples present in minute amounts. A quantitative analysis of loam soil containing different concentrations of Cu was successfully demonstrated, resulting in a good linear calibration curve. The detection limits of Cr and Pb in loam soil were approximately 4 and 13 mg/kg, respectively. Also, we confirmed that this technique can be applied to check the quality of commercial products such as gold film (Au foil), mineral supplement tablets, and prestigious cosmetic powders.

Hydrogen emission has been studied in laser plasmas by focusing a TEA CO2 laser (10.6 μm, 500 mJ, 200 ns) on various types of samples, such as glass, quartz, black plastic sheet, and oil on copper plate sub-target. It was found that Hα emission with a narrow spectral width occurs with high efficiency when the laser plasma is produced in the low-pressure region. On the contrary, the conventional well-known laser-induced breakdown spectroscopy (LIBS), which is usually carried out at atmospheric air pressure, cannot be applied to the analysis of hydrogen as an impurity. By combining low-pressure laser-induced plasma spectroscopy with laser surface cleaning, a preliminary quantitative analysis was made on zircaloy pipe samples intentionally doped with hydrogen. As a result, a good linear relationship was obtained between Hα emission intensity and its concentration.

A special technique has been developed for the detection of the charge current in conjunction with emission measurement during laser plasma generation. The current detection was performed by placing a partially transmitting metal mesh electrode at a distance of 7 mm from the sample surface with the sample serving as the counter electrode. The electric field between the mesh and sample surface was set up and varied by applying a dc high voltage (0–400 V) between them. The laser plasma was generated by a Nd:YAG laser (64 mJ, 8 ns) tightly focused on a Cu sample through the mesh electrode in surrounding gas of various low pressures. Three Cu emission lines associated with different excited energy levels were detected, namely the Cu(I) 510.5 nm (3.8 eV), Cu(I) 521.8 nm (6.2 eV), and Cu(I) 427.5 nm (7.8 eV) spectral lines. The correlation between the time profile of plasma emission and that of the charge current was examined to elucidate the roles of electron recombination and electron collision processes in the excitation of Cu atoms in the plasma. The charge current time profiles obtained at various gas pressures were invariably found to exhibit spiky signal followed by a slowly decaying component, a lack of consistent correlation with the emission profile of the Cu(I) 521.8 and 510.5 nm lines, showing characteristics of the shock wave model. The result of this study has thus failed to turn up evidence for the significant roles of electron recombination and electron collision comparable to the role of the shock wave mechanism in the plasma emission process.

A systematic study has been performed on the spectral characteristics of the full spectrum of He emission lines and their time-dependent behaviors measured from the He gas plasmas generated by a nanosecond neodymium-doped yttrium aluminum garnet laser. It is shown that among the major emission lines observed, the triplet He(I) 587.6 nm emission line stands out as the most prominent and long-lasting line, associated with de-excitation of the metastable triplet (S = 1) excited state (1s 1 3d 1 ). The role of this metastable excited state is manifested in the intensity enhancement and prolonged life time of the Cu emission with narrow full width half-maximum, as demonstrated in an orthogonal double-pulse experiment using a picosecond laser for the target ablation and a nanosecond laser for the prior generation of the ambient He gas plasma. These desirable emission features are in dire contrast to the characteristics of emission spectra observed with N2 ambient gas having no metastable excited state, which exhibit an initial Stark broadening effect and rapid intensity diminution typical to thermal shock wave-induced emission. The aforementioned He metastable excited state is therefore responsible for the demonstrated favorable features. The advantage of using He ambient gas in the double-pulse setup is further confirmed by the emission spectra measured from a variety of samples. The results of this study have thus shown the potential of extending the existing laser-induced breakdown spectroscopy application to high-sensitivity and high-resolution spectrochemical analysis of wide-ranging samples with minimal destructive effect on the sample surface.

We have succeeded in applying laser-induced shockwave plasma spectroscopy (LISPS) to the problem of the detection and analysis of metal elements deposited from water samples by means of electrolysis. It is shown that metal elements are generally deposited in the form of a thin film on the electrode surface, while the electrode also conveniently serves as a subtarget for the relatively soft metal film, thereby providing the necessary conditions for the generation of shockwave plasma, which is favorable for highly sensitive spectrochemical analysis. It is shown that the detection sensitivity of this method reaches its highest value at low surrounding air pressure of around 1 torr. The lowest detection limit attained for various metal elements investigated in this experiment varies from around ten to a few tens of ppb. This limit can be readily improved upon by incorporating an optical multichannel analyzer into the detection system. We have thus presented a promising method for the realization of a compact mobile monitoring system for the accurate control of water and soil quality.

A special interferometric technique with high sensitivity has been devised on the basis of rainbow refractometry without the use of an additional and delicate amplitude-splitting setup. This new technique was used for the characterization of shock wave plasma induced by a Q-switched Nd:YAG laser on various metal samples under reduced surrounding gas pressures. An unmistakable signal of the density jump was detected simultaneously with the observation of the emission front signal. It proved that the emission front and the front of the blast wave coincided and moved together with time at the initial stage of the secondary plasma expansion. However, at a later stage, the emission front began to separate from and left behind the blast wave front propagating in the surrounding gas at low pressures. With the use of Cu and Zn samples, the experimental results showed that the separation of the emission front and blast wave front took place at about 5 mm above sample surface for laser energy of 140 mJ.

Excitation mechanisms for copper and zinc atoms as well as their ionic species in the Q-switched (Q-sw) Nd:YAG laser-induced shock wave plasma have been investigated with a time-gated optical multichannel analyzer (OMA) system for various experimental conditions. It is demonstrated that the shock excitation process is the main mechanism responsible for the emission spectra for laser energy ranging from 8 to 86 mJ and surrounding air pressure from 2 to 50 Torr. At air pressure below 2 Torr, collision-induced excitation appears to take over and becomes the operative mechanism. In all cases, the neutral emission dominates over the ionic emission, leading to a high signal-to-background ratio, which tends to decrease, however, at higher laser energy and air pressure.

An experimental study has been carried out on the dynamical process taking place in the secondary plasma generated by a Q-switched Nd:YAG laser (80 mJ, 8 ns) on a copper target at reduced pressure. Accurate dynamical characterization of the cross-sectional view of the plasma has been made possible by the unique combination of a plasma confinement configuration and the time-resolved measurement technique. In addition to reaffirming the role of the blast-wave mechanism in the generation of secondary plasma, an analysis of the time-resolved spatial distributions of emission intensities and the time-resolved spatial distributions of temperature was made. As a result, the occurrence of two-stage emission processes, the “shock excitation stage” and “cooling stage,” has been proved. For instance, at 2 Torr it is shown that the emission process is initiated by a brief shock excitation process (∼ 1 μs) and followed by a longer cooling process (∼ 3 μs). The experimental results concerning the characteristics of the plasma can be well understood by considering the two-stage processes.

A laser-induced shock wave plasma was generated by bombarding a brass target with a long-pulse YAG laser at reduced pressure. The characteristics of the laser plasma were studied by examining the reflection and diffraction of the laser plasma when an aluminum wedge block was placed in front of the plasma. A dramatic increase in the emission of the secondary plasma was observed, supporting the shock wave model. The collected data also confirm that the displacement length of the secondary plasma emission front is proportional time raised to the 0.6 power. The temperature of the secondary plasma was found to be 10,000 K at 5 mm above the target, decreasing to 6800 K at 10 mm above the target.

The characteristics of a laser-induced shock wave plasma which was induced by focusing a laser pulse on the surface of glass samples were examined by using radiation from a XeCl excimer laser and a TEA CO2 laser under reduced pressure of around 1 Torr. It was observed that shock wave plasma could not be generated by the TEA CO2 laser on low-melting-point glass because of the lack of expulsion from the sample surface. On the other hand, with the use of an excimer laser, shock wave plasma can be generated, even in low-melting-point glasses, thus making it amenable for spectrochemical analysis. Initial quantitative analysis was performed on a number of glass samples, and a linear calibration curve with a slope of near unity was obtained at a certain pressure. Furthermore, light elements such as Li and B, which are usually difficult to observe by the X-ray fluorescence method, were also successfully detected with a very low detection limit of less than 10 ppm. Other detection limits and background equivalent concentrations of almost all elements usually contained in glass, such as Na, Mg, Al, K, Ca, Ti, Zn, Zr, and Ba, were also presented. These results showed that the detection limit is much lower than those usually required for glass analysis.

A XeCl excimer laser (20 ns, 15–70 mJ) has been focused on a Zn plate in surrounding gas at low pressures (100–1500 Pa). The characteristics of the resultant plasma are examined with the use of a unique time-resolved spectroscopic method. A density jump in the distribution of Zn atoms is clearly observed, which indicates the generation of a shock wave. Furthermore, it is proved that the relationships among the displacement length of the front of the emission of the Zn neutral emission line, the pressure of the ambient gas, and the energy of the laser pulse are in good agreement with the theoretical result for a blast wave explosion. An application is also presented to show that the plasma induced by a blast wave is excellent as a light source for emission spectrochemical analysis because of its very low background emission intensity.

A TEA CO2 laser beam (500 mJ, 100 ns) has been focused on a Zn target at reduced ambient gas pressures. In order to confine the laser plasma into a limited space, a tube (7 × 7 × 20 mm) has been placed just in front of the target, and the laser beam has been focused through the tube on the target. The time-resolved spatial distributions of Zn emission lines show that emission intensity increases quickly with a distinct jump near the front of the plasma and that the emissions take place only in a limited thin layer. It is also shown that the displacement of the emission front is proportional to 0.6 power of time. These experimental results support the supposition that the plasma is excited by a plane shock wave induced by the laser bombardment. This laser plasma confinement technique shows the possibility of improving the sensitivity in laser microprobe spectrochemical analysis.

A unique technique for direct analysis of soil samples utilizing a special advantage of a transversely excited atmospheric (TEA) CO2 laser-induced plasma generated at atmospheric pressure on a metal target has been developed. In this technique, a metal subtarget, such as nickel plate, structured with intentional microholes on its surface, each with dimensions of around 100 μm in diameter and depth, was used to selectively trap small sized soil particles by immersing the metal plate subtarget into the polluted soil sample. The trapped small soil particles on the metal subtarget were irradiated by a TEA CO2 laser (10.6 μm, 1.5 J, 200 ns) at atmospheric pressure under defocused condition with a spot size of 3 mm × 3 mm. This trapping and confining scheme substantially suppresses the blowing off effect; thus, the trapped soil particles can effectively be dissociated and atomized in the microstructured holes. Using this method of a microstructured metal plate subtarget, quantitative analysis was carried out on loam soil samples polluted by Pb. A linear calibration curve was obtained with a detection limit of approximately 50 mg/kg. Preliminary quantitative studies were carried out for a quartz sand sample containing Cr and Hg, resulting in linear calibration curves with detection limits of approximately 25 mg/kg and 10 mg/kg, respectively, at this stage. This technique is promising as a potential field screening tool for soil analysis.

It has been demonstrated that a spectrochemical analysis of carbon using the laser plasma method can be successfully applied to inspect the carbonation of concrete by detecting carbon produced in aged concrete by a chemical reaction of Ca(OH)2 with CO2 gas in environmental air, turning into CaCO3, which induces degradation of the quality of building concrete. A comparative study has been made using a TEA CO2 laser (500–1000 mJ) and a Q-switched Nd– YAG laser (50–200 mJ) to search for the optimum conditions for carbon analysis, proving the advantage of the TEA CO2 laser for this purpose. Also, it was clarified that laser irradiation with suitable defocusing conditions is a crucial point for obtaining high sensitivity in the detection of carbon. Practical experiments on the inspection of carbonation were carried out using both a concrete sample that had been intentionally carbonated by exposure to high concentrations of CO2 gas and a naturally carbonated concrete sample. As a result, good coincidence was observed between the laser method and the ordinary method, which uses the chemical indicator phenolphthalein, implying that this laser technique is applicable as an in situ quantitative method of inspection for carbonation of concrete.

An experiment to investigate the potential of a laser-induced plasma method for determining concrete compressive strength was conducted by focusing a Nd:YAG laser on concrete samples with different degrees of compressive strength. This technique was developed in light of the role of the shock wave in the generation of a laser-induced plasma. It was found that the speed of the shock front depends on the hardness of the sample. It was also found that a positive relationship exists between the speed of the shock front and the ionization rate of the ablated atoms. Hence, the ratio of the intensity between the Ca(II) 396.8 nm and Ca(I) 422.6 nm emission lines detected from the laser-induced plasma can be used to examine the hardness of the material. In fact, it was observed that the ratio changes with respect to the change in the concrete compressive strength. The findings also show that the ratio increases with time after the cement is mixed with water.