M. Ya. Grishin

Compact diode-pumped Nd:YAG laser for remote analysis of low-alloy steels by laser-induced breakdown spectroscopy

A low weight diode-pumped Nd:YAG laser (400 g, 1064 nm, 5 ns, 130 mJ per pulse) was developed for a compact laser-induced breakdown spectroscopy (LIBS) system to be installed on a robotized arm. Fiber optics delivery vs. conventional LIBS were compared for C, Si, Mn and Cr analysis in low-alloy steels. Fiber optics transformed the multimode laser beam to a flat-top beam with an improved fluence profile stability, resulting in shallow and more reproducible craters. A fast imaging study revealed that plasma generated by fiber optic pulses was plane-shaped, more uniform and dissipated two-fold faster compared with the plasma induced by direct laser beam focusing. Greater peak fluence for conventional LIBS provided plasma with 20–100 times more intensive emission due to the greater ablated mass, higher temperature and electron density. Improved reproducibility of shot-to-shot measurements was observed for plasma induced by fiber optic pulses, due to more stable ablation. The analytical capabilities of LIBS were compared for fiber optics vs. conventional LIBS in terms of calibration curve linearity, limits of detection and the root mean square error of the cross-validation procedure. Limits of detection for Si, Cr and Mn were always better for direct laser beam focusing; however, more importantly, the conventional LIBS system provided quantitative analysis for carbon in low-alloy steels (0.025–0.5% wt) with acceptable detection limits (55 ppm) while fiber optic pulses produced too-low intensity plasma.

Laser induced breakdown spectroscopy for multielement analysis of powdered materials used in additive technologies

ABSTRACT Additive manufacturing technologies utilizing metal parts production with layer by layer printing are of high demand for different fields of science and technology. Analytical chemistry is challenged to provide multielemental quantitative analysis of any metal powders within a few minutes and onsite to fulfil the requirements for high quality metal parts production. Powder materials utilized in additive technologies were quantitatively analyzed by laser induced breakdown spectroscopy for the first time. Laser induced breakdown spectroscopy mapping of loose metal powder attached to the double-sided adhesive tape provided high reproducibility of measurements even for powder mixtures with large difference of particles densities (tungsten carbide particles in nickel alloy powder). Laser induced breakdown spectroscopy analytical capabilities were estimated for tungsten and carbon analysis by calibration curve construction and accuracy estimation by leave-one-out cross-validation procedure. Laser induced breakdown spectroscopy and X-ray fluorescence spectroscopy techniques comparison revealed better results for laser induced breakdown spectroscopy analysis. Improved accuracy of analysis and capability to quantify light elements (carbon, etc.) demonstrated the potential of laser induced breakdown spectroscopy as a promising technique for express onsite multielement analysis of powder materials utilized in additive technologies.

Optimizing laser crater enhanced Raman scattering spectroscopy

The laser crater enhanced Raman scattering (LCERS) spectroscopy technique has been systematically studied for chosen sampling strategy and influence of powder material properties on spectra intensity enhancement. The same nanosecond pulsed solid state Nd:YAG laser (532 nm, 10 ns, 0.1-1.5 mJ/pulse) was used for laser crater production and Raman scattering experiments for l-aspartic acid powder. Increased sampling area inside crater cavity is the key factor for Raman signal improvement for the LCERS technique, thus Raman signal enhancement was studied as a function of numerous experimental parameters including lens-to-sample distance, wavelength (532 and 1064 nm) and laser pulse energy utilized for crater production. Combining laser pulses of 1064 and 532 nm wavelengths for crater ablation was shown to be an effective way for additional LCERS signal improvement. Powder material properties (particle size distribution, powder compactness) were demonstrated to affect LCERS measurements with better results achieved for smaller particles and lower compactness.

Lidar sensing of ship wakes

Detection of ship wakes is utterly important for ship traffic monitoring, security of sea borders, etc. Among standard detection methods there are radar and acoustic sensing, photographing, hyperspectral measurements, and water sample analysis. However, these methods are hardly suitable for detecting wakes of light high-speed boats. An alternative is optical methods, in particular laser remote sensing. In this work, laboratory experiments on laser remote sensing of water perturbed by a propeller rotating at up to 20 000 rpm are described. A long (over 5 h) decrease in the integral of the band of OH stretching vibrations inH2Omolecules in the Raman scattering spectrum and a blueshift of theOHband center by 2.5 to 3 cm−1 are demonstrated.

Ice thickness measurements by Raman&Rayleigh scattering technique

An efficient technique for ice thickness measurements by Raman&Rayleigh scattering is suggested. The elastic scattering is used for air-to-sample borders indication but fails to detect floating ice border. The Raman spectroscopy is used to detect interfaces between transparent materials such as ice-water interface. This approach is a promising express and non-invasive technique for remote thickness measurements in field experiments.

Bimodal dependence of light scattering/fluctuations on the concentration of aqueous solutions

Two concentration ranges (from 10−5 to 10−9 and from 10−13 to 10−18 M) corresponding to enhanced fluctuations of Rayleigh and Raman scattering of second-harmonic (527 nm) pulses of YVO4:Nd3+ laser are found for aqueous solutions of antioxidant potassium phenosan. A correlation is revealed between the rise in elastic Rayleigh scattering intensity and its fluctuations and the shift of the center of OH Raman band of water toward the ice component characteristic frequency (3200 cm−1). The development of phase-equilibrium instabilities is analyzed based on the model of fluctuations of the number of hydrogen bonds on the assumption of formation/destruction of ordered hydration layer of phenosan molecules in water.

Laser remote sensing of an algal bloom in a freshwater reservoir

Laser remote sensing of an algal bloom in a freshwater reservoir on the Volga River in central Russia was carried out. The compact Raman lidar was installed on a small ship to probe the properties of the surface water layer in different typical regions of Gorky Water Reservoir. Elastic and Raman scattering as well as chlorophyll fluorescence were quantified, mapped and compared with data acquired by a commercial salinity, temperature and depth probe (STD probe) equipped with a blue-green algae sensor. Good correlation between lidar and STD measurements was established.

Nonmonotonic concentration dependences of elastic light scattering and its fluctuations in aqueous solutions

A nonmonotonic bimodal dependence of elastic, Rayleigh scattering on the potassium phenosan concentration in an aqueous solution has been revealed. A similar dependence has been found, for the first time, for scattering amplitude fluctuations. The observed correlation is indicative of structural transitions in hydration shells of potassium phenosan, which are responsible for the increase and scatter of their size comparable with the wavelength (527 nm) of a laser spectrometer.