In situ Lithium Analysis In MgLi Alloys Using Laser Induced Breakdown Spectroscopy with a Compact Chamber.

This study explores the feasibility of in situ Lithium (Li) analysis in Magnesium-Lithium (MgLi) alloys using Laser-Induced Breakdown Spectroscopy (LIBS). It focuses on two Li emission lines: Li I 670.8 nm (resonance) and Li I 610.4 nm (non-resonance). Comparing charateristics at atmospheric and low pressures, self-reversal signature are observed in both emission lines at atmospheric pressure, complicating the analysis. Challenges in suppressing self-reversal effect using laser energy and detection window adjustments are noted. To address this, a compact chamber (80 mm × 50 mm × 50 mm) with adjustable pressure (using a portable vacuum pump) is developed. Lowering the pressure significantly reduces self-reversal effect, particularly for the Li I 610.4 nm line. This makes Li I 610.4 nm more suitable for analyzing high Lithium concentrations in MgLi alloys. Using standard samples, such as LA91 (8% Li) and LA141 (14% Li), the study successfully obtains Li I 610.4 nm spectra with proportional Li emission intensities. Even with a commercially affordable time-integrated charge-coupled device (CCD) detection system, the results indicate the efficacy of this approach for in situ Li analysis in MgLi alloys.

Optimization of Castor Oil-Based Ion Selective Electrode (ISE) with Active Agent 1,10-Phenanthroline for Aqueous Pb2+ Analysis.

This research has successfully fabricated ion selective electrode (ISE) for Pb2+ using castor oil (Ricinus communis L.)-based polyurethane (PU) membrane with 1,10-phenanthroline as the active agent. The sensitivity of the Pb2+ ISE obtained is 27.25 mV/decade with a linear range of [Pb(NO3)2] of 10−10−10−5 M and a coefficient of determination (R2) of 0.959. The system response reaches stability after 25 s of measurement. The Pb2+ has a detection limit of 10−10 M and gives a stable response at pH 7−8 with a 15-day lifetime. The investigation of the selectivity of the ISE was performed using the mixed solution method with log Kij values of <1. The selectivity order of Pb2+ ISE against the foreign ions is Ag2+ > Ca2+ > K+ > Mg2+ > Cu2+ > Fe3+ > Cr3+> Zn2+ > Cd2+. The Pb2+ ISE shows acceptable reproducibility and repeatability with standard deviation values of 0.065 and 0.0079, respectively. Fourier transform infrared (FT-IR) spectra confirmed that 1,10-phenanthroline was responsible for the formation of the Pb2+ ion entrapment via complexation. Other characterizations (crystallinity, micro-surface morphology, and mechanical strength) suggest the degradation of the membrane structure integrity after the application. The analysis results of Pb levels using the Pb2+ ISE in artificial and wastewater samples were not significantly different from the atomic absorption spectroscopy (AAS) measurement.

Simple defocus laser irradiation to suppress self-absorption in laser-induced breakdown spectroscopy (LIBS).

This study introduces a novel and simple way to suppress the self-absorption effect in laser-induced breakdown spectroscopy (LIBS) by utilizing a defocusing laser irradiation technique. For this purpose, a Nd:YAG laser with a wavelength of 1,064 nm and repetition rate of 10 Hz with energy in the range of 10 mJ-50 mJ was used. The laser irradiation was focused by using a 150-mm-focal-length plano-convex lens onto the sample surface under defocusing of approximately -6 mm. Potassium chloride (KCl) and sodium chloride (NaCl) pellet samples were used to demonstrate this achievement. When the defocus position is adjusted to -6 mm for KCl and NaCl samples, the self-reversal in the emission lines of K I 766.4 nm, K I 769.9 nm, Na I 588.9 nm, and Na I 589.5 nm vanish. Meanwhile, the FWHM values of K I 766.4 and K I 769.9 nm are 0.29 nm and 0.23 nm, respectively, during -6 mm defocus laser irradiation, as opposed to 1.24 nm and 0.86 nm under tight focus laser irradiation. Additionally, this work demonstrates that, when the laser energy is changed between 10 and 50 mJ, no self-reversal occurs in the emission lines when -6 mm defocus laser irradiation is applied. Finally, a linear calibration curve was generated using KCl at a high concentration ranging between K concentrations from 16.6% to 29%. It should be noted that, even at such high K concentrations, the calibration curve is still linear. This means that self-absorption is almost negligible. This simple change in defocus laser irradiation will undoubtedly contribute to the suppression of the self-absorption phenomenon, which disrupts LIBS analytical results.

Green Synthesis and Antimicrobial Activities of Silver Nanoparticles Using Calotropis gigantea from Ie Seu-Um Geothermal Area, Aceh Province, Indonesia.

Herein, we report our success synthesizing silver nanoparticles (AgNPs) using aqueous extracts from the leaves and flowers of Calotropis gigantea growing in the geothermal manifestation Ie Seu-Um, Aceh Besar, Indonesia. C. gigantea aqueous extract can be used as a bio-reductant for Ag+→Ag0 conversion, obtained by 48h incubation of Ag+, and the extract mixture in a dark condition. UV-Vis characterization showed that the surface plasmon resonance (SPR) peaks of AgNPs-leaf C. gigantea (AgNPs-LCg) and AgNPs-flower C. gigantea (AgNPs-FCg) appeared in the wavelength range of 410-460 nm. Scanning electron microscopy energy-dispersive X-ray spectrometry (SEM-EDS) revealed the agglomeration and spherical shapes of AgNPs-LCg and AgNPs-FCg with diameters ranging from 87.85 to 256.7 nm. Zeta potentials were observed in the range of -41.8 to -25.1 mV. The Kirby-Bauer disc diffusion assay revealed AgNPs-FCg as the most potent antimicrobial agent with inhibition zones of 12.05 ± 0.58, 11.29 ± 0.45, and 9.02 ± 0.10 mm for Escherichia coli, Staphylococcus aureus, and Candida albicans, respectively. In conclusion, aqueous extract from the leaves or flowers of Calotropis gigantea may be used in the green synthesis of AgNPs with broad-spectrum antimicrobial activities.

Development of Chitosan/Rice Husk-Based Silica Composite Membranes for Biodiesel Purification.

Inorganic-organic composite membranes (IOCMs) are an alternative separation method developed for their straightforward process, economic benefits, and ease of scaling up. The IOCMs in this study were prepared from a biopolymer chitosan matrix and rice husk-based silica filler to remove impurities from crude biodiesel. The IOCMs were prepared through phase inversions, in which the priorly prepared silica particles were dispersed in the dope solution of chitosan. The maximum loading of the silica particles was 60%, capable of reducing the soap level, free glycerol level, and acid number from 547.9 to 12.2 mg/L, 54 to 0.041%, and 2.02 to 1.12 mgKOH/g. These reduced impurity values have satisfied the standardized quality. The chemical composition and morphology of the IOCM was characterized using Fourier-transform infrared spectroscopy and scanning electron microscope-energy dispersive X-Ray spectroscopy. The IOCM water absorption-based porosity and swelling degree were studied as well. Further investigation using isothermal modeling revealed the adsorption dependency against the Sips model equation (R2 = 0.99 and root-mean-square errors = 1.77 × 10-8). Even though regeneration is still a challenging factor in this study, the IOCM prepared from chitosan and rice husk-derived silica particles could be used in crude biodiesel purification.

Synthesis of Chitosan-Silver Nanoparticle Composite Spheres and Their Antimicrobial Activities.

Synthesis of silver nanoparticles-chitosan composite particles sphere (AgNPs-chi-spheres) has been completed and its characterization was fulfilled by UV-vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and zetasizer nano. UV-vis spectroscopy characterization showed that AgNPs-chi-spheres gave optimum absorption at a wavelength of 410 nm. The XRD spectra showed that the structure of AgNPs-chi-spheres were crystalline and spherical. Characterization by SEM showed that AgNPs-chi-spheres, with the addition of 20% of NaOH, resulted in the lowest average particle sizes of 46.91 nm. EDX analysis also showed that AgNPs-chi-spheres, with the addition of a 20% NaOH concentration, produced particles with regular spheres, a smooth and relatively nonporous structure. The analysis using zetasizer nano showed that the zeta potential value and the polydispersity index value of the AgNPs-chi-sphere tended to increase with an increased NaOH concentration. The results of the microbial activity screening showed that the AgNP-chi-Spheres with highest concentration of NaOH, produced the highest inhibition zone diameters against S. aureus, E. coli, and C. albicans, with inhibition zone diameters of 19.5, 18.56, and 12.25 nm, respectively.

Characteristics of laser induced breakdown investigated by a compact, nongated optical multichannel analyzer system and its potential application.

Laser induced breakdown is a highly temporally and spatially dynamic phenomenon, normally studied using a highly temporally resolved optical detector system. In this work, a compact, low cost optical multichannel analyzer (OMA) system without a built-in temporal gating device and thus operated under a free running mode was used to investigate the characteristics of laser induced plasma. A Nd-YAG laser beam was used as the excitation source from several samples, namely, copper, zinc, and aluminum plates. The characteristics of the plasma emission produced under various experimental parameters, including the pulse energy, surrounding gas pressure, and collection fiber position, were examined. It was found that the essential features of emission spectra can be investigated even using the ungated, compact OMA system even without a highly temporally resolved gating system. The plasma emission characteristics critically depend on the experimental parameters. A quality emission spectrum, featuring a high intensity with a low background, can be obtained using the ungated, compact OMA system under optimized conditions, namely, a pulse energy of approximately 8 mJ, a surrounding gas pressure of 10 Torr, and a collection fiber position of more than 5 mm above the surface of the sample. The features of the emission spectra detected under optimized conditions are only similar to those obtained using a sophisticated, gated OMA system. The characteristics of the emission spectra are in good agreement with the previous assumption of the shockwave role in plasma excitation. Having quality emission spectra under the optimized conditions, a preliminary practical laser induced breakdown spectroscopy (LIBS) analysis using the ungated, compact OMA system was performed on several samples, such as standard brass, commercial pure gold, and natural stone samples. The aluminum emission lines are strongly detected from the standard brass sample (C1118) containing aluminum at 2.8%. The LIBS system also unequivocally revealed a qualitatively abandoned impurity presence in the purportedly pure commercial gold sample. It also effectively confirmed qualitatively a Cu presence in the blinking spots of the natural stone collected from a traditional mining site in Aceh. This result implies the effectiveness of the LIBS using the ungated, compact OMA system for quick, practical analysis.

Suppression of self-absorption in laser-induced breakdown spectroscopy using a double pulse orthogonal configuration to create vacuum-like conditions in atmospheric air pressure.

Self-absorption, which is known to severely disturb identification of the emission peak intensity in emission-based spectroscopy, was first studied using ordinary single pulse laser-induced breakdown spectroscopy (LIBS). It was found that severe self-absorption, with an evident self-reversal, occurs in the resonance emission lines of high concentration Na, K, and Al, and thus it is impossible to obtain the linear calibration curve required for quantitative analysis. To overcome this problem, we introduce a double pulse orthogonal technique in which the first laser is fired in a parallel orientation at a varied distance of 2-6 mm from the sample surface. It is well known that the strong shock wave generated by this laser irradiation temporarily creates a vacuum-like condition immediately in front of the sample surface. This action is followed by a second laser irradiation oriented perpendicular to the sample surface. The sample ablated by the second laser irradiation expands following the shockwave excitation process in the vacuum-like air atmosphere created by the first laser. The obtained spectra of the resonance emission lines of high concentration Na, K, and Al are free from the self-reversal and weakly affected by the self-absorption effect. A linear calibration curve that intercepts near zero point for K element over a wide concentration range is also demonstrated in this study. This simple modification is considered notably helpful in overcoming the self-absorption that occurs in ordinary single pulse atmospheric pressure LIBS.

Emission Spectrochemical Analysis of Soft Samples Including Raw Fish by Employing Laser-Induced Breakdown Spectroscopy with a Subtarget at Low-Pressure Helium Gas.

Laser-induced breakdown spectroscopy (LIBS) to detect the light elements such as lithium (Li) and boron (B) and heavy elements such as copper (Cu) and lead (Pb) in raw fish samples is reported in this work. This is made possible by understanding that the soft target absorbs recoil energy and as a result, the ablated atoms gushing from the soft target do not acquire sufficient speed to form a shock wave. In order to overcome this problem, we set a subtarget on the back of the soft target so as to produce the repulsion force by which the gushing speed of the ablated atoms is increased, yielding a sufficiently high plasma temperature or sufficiently large thermal energy needed for the excitation of the ablated atoms. Excellent spectral qualities of various soft samples such as margarine, butter, peanut butter, strawberry jam, raw tuna, raw gindara, and raw salmon are presented. Furthermore, a linear calibration curve with a zero intercept is also obtained for Li, Cu, and Pb. The detection limit of Li, Cu, and Pb is found to be around 0.1 mg/L. This modification of LIBS for soft samples by using a subtarget effect clearly promises a rapid and in situ soft sample analysis since there is practically no sample digestion in the analysis.

Underlying Physical Process for the Unusual Spectral Quality of Double Pulse Laser Spectroscopy in He Gas.

This study is aimed at elucidating the physical processes responsible for the excellent spectral qualities in terms of full width at half-maximum (fwhm) and signal-to-noise (S/N) ratio shown in a special double pulse laser-induced spectroscopy. Apart from the use of atmospheric He ambient gas, the achievement is due to the first laser for generating He gas plasma and the subsequent use of the second laser pulse for target ablation, in opposite order of the two-laser operations in conventional double pulse LIBS. This setup allows adjustments of the many experimental parameters to yield the optimal condition resulting in 0.03 nm fwhm and around 1000× S/N ratio of Cu I 521.8 nm and far surpasses the spectral qualities obtained by other techniques. This is obtained by allowing the crucial separation of the target plasma from the He gas plasma and thereby enabling the He-assisted excitation (HAE) to play its full and unique role of nonthermal excitation, taking advantage of metastable excited He atoms in the He plasma and the Penning-like energy transfer process. This excellent performance is further verified by its successful application analysis of Cr in low alloy steel samples, with the presence of smooth linear calibration lines, signifying the absence of the self-absorption effect well-known in ordinary LIBS.

H-D Analysis Employing Low-Pressure microjoule Picosecond Laser-Induced Breakdown Spectroscopy.

An experimental study is conducted in search of the much needed experimental method for practical and minimally destructive analysis of hydrogen (H) and deuterium (D) in a nuclear power plant. For this purpose, a picosecond (ps) Nd:YAG laser is employed and operated with 300-500 µJ output energies in a variety of ambient gases at various gas pressures. The sample chamber used is specially designed small quartz tube with an open end that can be tightly fitted to the sample surface. It is found that ambient Ar gas at reduced pressure of around 0.13 kPa gives the best spectral quality featuring fully resolved H and D emission lines with clearly detectable intensities and practically free from surface water interference. The D emission intensities measured from zircaloy plates containing various concentrations of D impurity are shown to yield a linear calibration line with extrapolated zero intercept, offering its potential application to quantitative analysis. The estimated detection limit of less than 10 ppm is well below the sensitivity limit of around 600 ppm required for the regular inspection of zircaloy tubes in a heavy water nuclear power plant. The use of the exceedingly low laser energy is shown to offer an additional advantage of minimum destructive effect marked by the resulted tiny craters of about 5 µm diameter with 25 µm depth. These results promise the potential development of the desired alternative analytical tool for regular in situ and real time inspection of the zircaloy tubes in a heavy water power plant.

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.

A comparative study of pressure-dependent emission characteristics in different gas plasmas induced by nanosecond and picosecond neodymium-doped yttrium aluminum garnet (Nd:YAG) lasers.

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.

New technique for the direct analysis of food powders confined in a small hole using transversely excited atmospheric CO(2) laser-induced gas plasma.

Taking advantage of the differences between the interactions of transversely excited atmospheric (TEA) CO(2) 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 CO(2) 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.

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.

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.

Quantitative hydrogen analysis of zircaloy-4 using low-pressure laser plasma technique.

It is found in this work that variation of laser power density in low-pressure plasma spectrochemical analysis of hydrogen affects sensitively the hydrogen emission intensity from the unwanted and yet ubiquitous presence of ambient water. A special experimental setup has been devised to allow the simple condition of focusing/defocusing the laser beam on the sample surface. When applied to zircaloy-4 samples prepared with various hydrogen impurity concentrations using low-pressure helium surrounding gas, good-quality hydrogen emission lines of very high signal to background ratios were obtained with high reproducibility under weakly focused or largely defocused laser irradiation. These measurements resulted in a linear calibration line with nonzero intercept representing the residual contribution from the recalcitrant water molecules. It was further shown that this can be evaluated and taken into account by means of the measured intensity ratio between the oxygen and zirconium emission lines. We have demonstrated the applicability of this experimental approach for quantitative determination of hydrogen impurity concentrations in the samples considered.