Ken-ichi Fukumoto

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.

Crater effects on H and D emission from laser induced low-pressure helium plasma

An experimental study has been performed on the effects of crater depth on the hydrogen and deuterium emission intensities measured from laser plasmas generated in low-pressure helium ambient gas from zircaloy-4 samples doped with different H and D impurity concentrations as well as a standard brass sample for comparison. The results show that aside from emission of the host atom, the emission intensities of other ablated atoms of significantly smaller masses as well as that of the He atom generally exhibit relatively rapid initial decline with increasing crater depth. This trend was found to have its origin in the decreasing laser power density arriving at the crater bottom and thereby weakened the shock wave generated in the crater. As the crater deepened, the declining trend of the intensity appeared to level off as a result of compensation of the decreasing laser power density by the enhanced plasma confinement at increasing crater depth. Meanwhile, the result also reveals the significant contribution...

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.

Development of Irradiation Capsules in Liquid Metal Environment in Joyo and Their Application to Irradiation Creep Measurement of Vanadium Alloys

In order to perform irradiation experiments in a liquid metal environment in a nuclear reactor, an irradiation technique with sodium bonding irradiation capsules was developed and a series of neutron irradiation experiments with sodium bonding irradiation capsules were performed in Joyo. The design and fabrication of sodium bonding capsules, sodium filling into capsules, capsule loading to Joyo, irradiation experiments, dismantling for irradiated capsules, removing the irradiated specimens from sodium-filled capsules, and sodium cleaning of the irradiated specimens were established through this study. Using the Joyo irradiation with the sodium bonding capsules where irradiation temperature was distributed uniformly, the irradiation creep experiment for highly purified V-4Cr-4Ti alloys, NIFS-Heat, was carried out and the knowledge about the irradiation creep behavior of the alloys was obtained.

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 Deuterium Analysis of Titanium Samples in Ultraviolet Laser-Induced Low-Pressure Helium Plasma

An experimental study of ultraviolet (UV) laser-induced plasma spectroscopy (LIPS) on Ti samples with low-pressure surrounding He gas has been carried out to demonstrate its applicability to quantitative micro-analysis of deuterium impurities in titanium without the spectral interference from the ubiquitous surface water. This was achieved by adopting the optimal experimental condition ascertained in this study, which is specified by 5 mJ laser energy, 10 Torr helium pressure, and 1–50 μs measurement window, which resulted in consistent D emission enhancement and effective elimination of spectral interference from surface water. As a result, a linear calibration line exhibiting a zero intercept was obtained from Ti samples doped with various D impurity concentrations. An additional measurement also yielded a detection limit of about 40 ppm for D impurity, well below the acceptable threshold of damaging H concentration in Ti and its alloys. Each of these measurements was found to produce a crater size of only 25 μm in diameter, and they may therefore qualify as nondestructive measurements. The result of this study has therefore paved the way for conducting further experiments with hydrogen-doped Ti samples and the technical implementation of quantitative micro-analysis of detrimental hydrogen impurity in Ti metal and its alloys, which is the ultimate goal of this study.

Excitation Mechanism of H, He, C, and F Atoms in Metal-Assisted Atmospheric Helium Gas Plasma Induced by Transversely Excited Atmospheric-Pressure CO2 Laser Bombardment

To clarify the excitation mechanism of hydrogen in transversely excited atmospheric-pressure (TEA) CO2 laser-induced helium gas plasma, atomic emission characteristics of H, C, F, and He were studied using a Teflon sheet (thickness of 2 mm) attached to a metal subtarget. The TEA CO2 laser (750 mJ, 200 ns) was focused on the Teflon sheet in the surrounding He gas at 1 atm. Atomic emissions of H, C, F, and He occurred with a long lifetime, a narrow spectrum width, and a low-background spectrum. The correlation emission intensity curves of H–He and F–He indicated a parabolic functions. To explain the emission characteristics, we offered a model in which helium metastable atoms (He*) play an important role in the excitation processes; namely, atoms collide with helium metastable atoms (He*) to be ionized by the Penning effect, and then recombine with electrons to produce excited states, from which atomic emissions occur.

Corrosion behavior of Hastelloy-N alloys in molten salt fluoride in Ar gas or in air

The effects of air on the corrosion of Hastelloy-N alloys in molten salt coolant containing fission product elements were investigated to determine the safety of structural materials in high-temperature reactors cooled with fluoride salt. Corrosion tests of Hastelloy-N in the molten fluoride salt FLiNaK in an alumina crucible and a graphite crucible under argon gas or air were performed at 773–923 K for 100 h. The depth of corrosive attack, as well as the extent of chromium and molybdenum depletion, increased with increasing temperature. The extent of Hastelloy-N corrosion in molten salt under air was significantly greater than under argon gas. The effect of adding the impurity cesium iodide to molten salt containing nuclear waste fuel on the corrosion behavior was negligible.