Muliadi Ramli

New Technique for the Direct Analysis of Food Powders Confined in a Small Hole Using Transversely Excited Atmospheric CO2 Laser-Induced Gas Plasma

Taking advantage of the differences between the interactions of transversely excited atmospheric (TEA) CO2 lasers with metal and with organic powder, a new technique for the direct analysis of food powder samples has been developed. In this technique, the powder samples were placed into a small hole with a diameter of 2 mm and a depth of 3 mm and covered by a metal mesh. The TEA CO2 laser (1500 mJ, 200 ns) was focused on the powder sample surfaces, passing through the metal mesh, at atmospheric pressure in nitrogen gas. It is hypothesized that the small hole functions to confine the powder particles and suppresses the blowing-off of sample, while the metal mesh works as the source of electrons to initiate the strong gas breakdown plasma. The confined powder particles are then ablated by laser irradiation and the ablated particles move into the strong gas breakdown plasma region to be atomized and excited; this method cannot be applied for the case of Nd:YAG lasers because in such case the metal mesh itself was ablated by the laser irradiation. A quantitative analysis of a milk powder sample containing different concentrations of Ca was successfully demonstrated, resulting in a good linear calibration curve with high precision.

Quantitative hydrogen analysis of zircaloy-4 in laser-induced breakdown spectroscopy with ambient helium gas

This experiment was carried out to address the need for overcoming the difficulties encountered in hydrogen analysis by means of plasma emission spectroscopy in atmospheric ambient gas. The result of this study on zircaloy-4 samples from a nuclear power plant demonstrates the possibility of attaining a very sharp emission line from impure hydrogen with a very low background and practical elimination of spectral contamination of hydrogen emission arising from surface water and water vapor in atmospheric ambient gas. This was achieved by employing ultrapure ambient helium gas as well as the proper defocusing of the laser irradiation and a large number of repeated precleaning laser shots at the same spot of the sample surface. Further adjustment of the gating time has led to significant reduction of spectral width and improvement of detection sensitivity to ~50 ppm. Finally, a linear calibration curve was also obtained for the zircaloy-4 samples with zero intercept. These results demonstrate the feasibility of this technique for practical in situ and quantitative analysis of hydrogen impurity in zircaloy-4 tubes used in a light water nuclear power plant.

The role of He in enhancing the intensity and lifetime of H and D emissions from laser-induced atmospheric-pressure plasma

A series of measurements have been performed on the time dependences of the intensities of helium, hydrogen, and deuterium emission lines from the corresponding laser-induced helium plasma at atmospheric pressure for two different He flow rates. The prolonged Hα and Hβ emissions along with their constant intensity ratio over a relatively extended period indicate the need to provide an alternative excitation mechanism other than the well-known thermal excitation process in a hot plasma. This additional excitation mechanism is also related to the metastable excited state of a He atom as indicated by the similar characteristics of the observed time dependence of the emission intensities. The enhanced intensity and lifetime of He emission at a high He flow rate was explained in terms of the collision-induced increase in the number of He atoms excited to above the 2 S10 metastable state, which was also responsible for the delayed excitation of H and D atoms via an energy transfer mechanism involving a Penning-...

New Method of Laser Plasma Spectroscopy for Metal Samples Using Metastable He Atoms Induced by Transversely Excited Atmospheric-Pressure CO2 Laser in He Gas at 1 atm

A high-power transversely excited atmospheric-pressure (TEA) CO2 laser (600–1500 mJ) was focused on a metal target in surrounding He gas at 1 atm to produce strong He gas breakdown plasma, while leaving the metal surface undamaged, and a Q-switched Nd:YAG laser (60–90 mJ) was also simultaneously focused on the metal surface to be ablated at a slightly shifted spot position with various delay times (0–150 µs) relative to the TEA CO2 laser. It was concluded that the ablated atoms from the metal sample enter the He gas plasma region and are excited by metastable He atoms, which are produced in very large quantities in the He gas plasma region. Due to the fact that He gas plasma works as an exciting source with a very long lifetime (about 100 µs), the detected atomic emission lines are very narrow in spectral width with a very low background spectrum, and also the atomic emission spectrum profile does not follow the Boltzmann distribution during the long emission life. We call this new method LIPS-He*. This new method has high potential for realizing in situ high-sensitivity analysis.

Intensity distributions of enhanced H emission from laser-induced low-pressure He plasma and a suggested He-assisted excitation mechanism

An experimental study was conducted on the spatial distributions of hydrogen emission intensities from low-pressure plasmas generated by laser ablation of zircaloy-4 and black stone targets in nitrogen and helium ambient gases. In addition to confirming the previously observed intensity enhancement effect in ambient helium gas, the hydrogen and helium emission intensities measured along the plasma expansion direction revealed remarkable extended spatial distributions featuring unexpected maxima near the far end of the plasma where the available shock-wave generated thermal excitation energy should have been significantly reduced. This “anomalous” feature necessarily implied the presence of an additional excitation process beside the well known shock-wave excitation process which is responsible for the plasma emission of heavy atoms in low-pressure ambient gas. Further analysis of the data led to a suggested physical mechanism explaining the possible contribution of a helium metastable excited state to the...

Study of Hydrogen and Deuterium Emission Characteristics in Laser-Induced Low-Pressure Helium Plasma for the Suppression of Surface Water Contamination

An experimental study was conducted in search of the experimental condition required for the much needed suppression of spectral interference caused by surface water in hydrogen analysis using laser-induced low-pressure helium plasma spectroscopy. The problem arising from the difficulty in distinguishing hydrogen emission from hydrogen impurity inside the sample and that coming from the water molecules was overcome by taking advantage of similar emission characteristics shared by hydrogen and deuterium demonstrated in this experiment by the distinct time-dependent and pressure-dependent variations of the D and H emission intensities from the D-doped zircaloy-4 samples. This similarity allows the study of H impurity emission in terms of D emission from the D-doped samples and thereby separating it from the H emission originating from the water molecules. Employing this strategy has allowed us to achieve the large suppression of water induced spectral interference from the previous minimum of 400 microg/g to the current value of 30 microg/g when a laser beam of 34 mJ under tight focusing condition was employed. Along with this favorable result, this experimental condition has also provided a much better (about 6-fold higher) spatial resolution, although these results were achieved at the expense of reducing the linear calibration range from the previous 4 300 microg/g to the present 200 microg/g.

Spectral and Dynamic Characteristics of Helium Plasma Emission and its Effect on a Laser-Ablated Target Emission in a Double-Pulse Laser-Induced Breakdown Spectroscopy (LIBS) Experiment

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.

Direct evidence of mismatching effect on H emission in laser-induced atmospheric helium gas plasma

A time-resolved orthogonal double pulse laser-induced breakdown spectroscopy (LIBS) with helium surrounding gas is developed for the explicit demonstration of time mismatch between the passage of fast moving impurity hydrogen atoms and the formation of thermal shock wave plasma generated by the relatively slow moving major host atoms of much greater masses ablated from the same sample. Although this so-called “mismatching effect” has been consistently shown to be responsible for the gas pressure induced intensity diminution of hydrogen emission in a number of LIBS measurements using different ambient gases, its explicit demonstration has yet to be reported. The previously reported helium assisted excitation process has made possible the use of surrounding helium gas in our experimental set-up for showing that the ablated hydrogen atoms indeed move faster than the simultaneously ablated much heavier major host atoms as signaled by the earlier H emission in the helium plasma generated by a separate laser pr...

Deuterium analysis in zircaloy using ps laser-induced low pressure plasma

An experimental study on picosecond laser induced plasma spectroscopy of a zircaloy sample with low-pressure surrounding helium gas has been carried out to demonstrate its potential applicability to three-dimensional quantitative micro-analysis of deuterium impurities in zircaloy. This was achieved by adopting the optimal experimental condition ascertained in this study, which is specified as 7 mJ laser energy, 1.3 kPa helium pressure, and 50 μs measurement window, and which was found to result in consistent D emission enhancement. Employing these operational parameters, a linear calibration line exhibiting a zero intercept was obtained from zircaloy-4 samples doped with various concentrations of D impurity, regarded as surrogates for H impurity. An additional measurement also yielded a detection limit of about 10 μg/g for D impurity, well below the acceptable threshold of damaging H concentration in zircaloy. Each of these measurements was found to produce a crater size of only 25 μm in diameter, promisi...

Quantitative and sensitive analysis of CN molecules using laser induced low pressure He plasma

We report the results of experimental study on CN 388.3 nm and C I 247.8 nm emission characteristics using 40 mJ laser irradiation with He and N2 ambient gases. The results obtained with N2 ambient gas show undesirable interference effect between the native CN emission and the emission of CN molecules arising from the recombination of native C ablated from the sample with the N dissociated from the ambient gas. This problem is overcome by the use of He ambient gas at low pressure of 2 kPa, which also offers the additional advantages of cleaner and stronger emission lines. The result of applying this favorable experimental condition to emission spectrochemical measurement of milk sample having various protein concentrations is shown to yield a close to linear calibration curve with near zero extrapolated intercept. Additionally, a low detection limit of 5 μg/g is found in this experiment, making it potentially applicable for quantitative and sensitive CN analysis. The visibility of laser induced breakdown spectroscopy with low pressure He gas is also demonstrated by the result of its application to spectrochemical analysis of fossil samples. Furthermore, with the use of CO2 ambient gas at 600 Pa mimicking the Mars atmosphere, this technique also shows promising applications to exploration in Mars.