Improving LIBS analysis of non-flat heterogeneous samples by signals mapping.

Heterogeneous material analysis by the laser-induced breakdown spectroscopy (LIBS) technique is challenging in real practice due to requirements for representative sampling and non-flat surfaces of the samples. Methods complementary to LIBS (plasma imaging, plasma acoustics, sample surface color imaging) have been introduced to improve zinc (Zn) determination in soybean grist material by LIBS. The detailed statistical study revealed that atomic/ionic lines emission and other LIBS signals were distributed normally except for acoustics signals. The correlation between LIBS and complementary signals was rather poor due to the large variability of the particle properties of soybean grist material. Still, analyte line normalization on plasma background emission was rather simple and effective for Zn analysis but required a few hundred spot samplings for representative Zn quantification. Non-flat heterogeneous samples (soybean grist pellets) were analyzed by LIBS mapping but it was demonstrated that the choice of sampling area is crucial for reliably analyte determination.

Combining thermal imaging and spectral pyrometry for express temperature mapping in additive manufacturing.

A compact and low-cost two-dimensional (2D) thermal imager was developed for real-time temperature mapping of a melt pool during coaxial laser cladding (the additive manufacturing technique). The device combines a color CMOS camera and a compact spectrometer. The spectrometer was utilized for internal calibration and validation of a 2D temperature map that was acquired by the CMOS camera. The remarkable feature of the thermal imager is that camera images are calibrated directly during the measurement process utilizing spectral pyrometry. Additionally, the spectrometer decreased a potential systematic error due to a spectrum contribution from atomic/ionic lines emission. The spectral pyrometry provided temperature accuracy measurements of ±23K while two-dimensional (2D) temperature mapping by two-color pyrometry accuracy was estimated as ±38K in the range of 1700-3500 K. The system has been installed at a coaxial laser cladding head for real-time temperature mapping. The system was developed for measuring a melt pool during laser cladding production of a high wear-resistant coating (tungsten carbide particles in a nickel matrix). Tungsten carbides powder flow rate has been changed sequentially from 5 to 27 g/min by powder feeder programming, which resulted in a variation of melt pool dimensions and temperature maps during the cladding process.

In situ laser-induced breakdown spectroscopy measurements during laser welding of superalloy.

Laser-induced breakdown spectroscopy (LIBS) has been utilized for in situ diagnostics of the laser welding process. The influence of different weld spot areas (melt pool, solid weld) on LIBS signals and plasma properties has been studied in detail. Liquid metal sampling and high target surface temperature of the melt enhance LIBS plasma intensity and increase plasma temperature. The influence of laser welding process parameters on LIBS measurements has been studied in order to differentiate optimal and defective laser welding. In case of defective laser welding, the melt pool was intensively boiling, so we have observed greater LIBS signals but poor reproducibility. For the first time, the LIBS technique was demonstrated to detect defective laser welding during in situ measurements utilizing atomic and ionic line comparison by paired sample t-test hypotheses testing.

Surface plasma influence on nanosecond laser ablation.

The comparison of laser ablation and plasma evolution has been carried out for a molten steel sample in the absence and in the presence of surface plasma. A continuous wave (cw) laser beam was utilized for local melting of a steel (Fe>99 wt.%) sample, but it also induced a surface plasma according to optical emission spectroscopy. The cw laser was switched off for a few milliseconds to dissipate the surface plasma, but the surface temperature did not change according to optical pyrometer measurements. Molten metal was ablated by a nanosecond Nd:YAG laser pulse during cw laser operation and when it was switched off for 5 milliseconds. Comparison of laser ablation and plasma evolution in the presence and in the absence of the near-surface plasma induced by the cw laser beam has been carried out. Time-integrated plasma imaging detected slightly greater emissivity of the plasma induced during cw laser operation. The cw laser operation resulted in a twofold enhancement of the intensity of atomic lines in the spectra as well as slower decay of plasma emission. Plume temperature and electron density were slightly greater at early stages of plume expansion in surface plasma.

Optimizing laser crater enhanced Raman spectroscopy.

Raman signal enhancement by laser crater production was systematically studied for 785 nm continuous wave laser pumping. Laser craters were produced in L-aspartic acid powder by a nanosecond pulsed solid state neodymium-doped yttrium aluminum garnet laser (532 nm, 8 ns, 1 mJ/pulse), while Raman spectra were then acquired by using a commercial spectrometer with 785 nm laser beam pumping. The Raman signal enhancement effect was studied in terms of the number of ablating pulses used, the lens-to-sample distance, and the crater-center-laser-spot offset. The influence of the experiment parameters on Raman signal enhancement was studied for different powder materials. Maximum Raman signal enhancement reached 11 fold for loose powders but decreased twice for pressed tablets. Raman signal enhancement was demonstrated for several diverse powder materials like gypsum or ammonium nitrate with better results achieved for the samples tending to give narrow and deep craters upon the laser ablation stage. Alternative ways of cavity production (steel needle tapping and hole drilling) were compared with the laser cratering technique in terms of Raman signal enhancement. Drilling was found to give the poorest enhancement of the Raman signal, while both laser ablation and steel needle tapping provided comparable results. Here, we have demonstrated for the first time, to the best of our knowledge, that a Raman signal can be enhanced 10 fold with the aid of simple cavity production by steel needle tapping in rough highly reflective materials. Though laser crater enhancement Raman spectroscopy requires an additional pulsed laser, this technique is more appropriate for automatization compared to the needle tapping approach.

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.

Laser-induced breakdown spectroscopy for three-dimensional elemental mapping of composite materials synthesized by additive technologies.

Three-dimensional multi-elemental mapping of composite wear-resistant coatings by laser-induced breakdown spectroscopy has been demonstrated for the first time, to the best of our knowledge. Individual clads of 1560 nickel alloy reinforced with tungsten carbide were synthesized by a co-axial laser cladding technique. Electron energy dispersive x-ray spectroscopy revealed elemental maps for major elements (W, Ni, Co, Cr, Fe) but failed to measure silicon and carbon. Laser-induced breakdown spectroscopy was utilized for elemental mapping of carbon and all other elements of interest. It was demonstrated that three-dimensional elemental profiling for a few tens of micrometers requires substantial laser spot overlapping during the scanning procedure in order to achieve good accuracy of depth measurements. Elemental maps for nickel, iron, chromium, silicon, tungsten, and carbon were quantified for 900 µm×900 µm×45 µm volume with 30 µm lateral and 4 µm depth resolution in the case of tungsten carbide particles in nickel alloy.

Multiple increase in productivity of the yeast at reducing the fraction of D2O in water.

We found a two-fold increase in the productivity of baker's yeast grown on a nutrient mixture prepared in light water with a D2O content (127 ppm) smaller than in the distilled water (150 ppm). The number of water monomers that provides the biosynthetic activity (water transport through membrane channels) of yeast cells with an increased CO2 yield was determined for the first time. We established that the selectivity of cell membrane channels in water of different composition depends not only on the motion of ortho-and para-spin H2O isomers in solution, as was shown earlier, but also on the concentration of D2O.

Double nanosecond pulses generation in ytterbium fiber laser.

Double pulse generation mode for nanosecond ytterbium fiber laser was developed. Two sequential 60-200 ns laser pulses with variable delay between them were generated by acousto-optic modulator opening with continuous diode pumping. A custom radio frequency generator was developed to produce two sequential "opening" radio pulses with a delay of 0.2-1 µs. It was demonstrated that double pulse generation did not decrease the average laser power while providing the control over the laser pulse power profile. Surprisingly, a greater peak power in the double pulse mode was observed for the second laser pulse. Laser crater studies and plasma emission measurements revealed an improved efficiency of laser ablation in the double pulse mode.

[Functional characteristics of yeast cells in nutrient aqueous solution enriched with ortho-H2O isomers].

It has been experimentally established that cultivation of yeast cells in depleted, dietary or normal nutrient aqueous solutions enriched with ortho-H2O spin isomers is accompanied by an increase in the amount of carbon dioxide produced by the cells and an increase in their biomass. It has been revealed that the rate of metabolic processes and biological activity depends on the quality of nutrition and enhances in time in both nutrient solutions. In contrast, the reproductive function and the rate of cell division are insusceptible to the components of nutrition, but intensified in a solution enriched with ortho-H2O similar to retardation of aging. The observed effects are discussed in assumption that an increase of a portion of ortho-H2O molecules occurs in the neighborhood of water channels in the cell membrane that let through only monomers of H2O and determine the rate of metabolic processes.

[H2O ortho-para spin conversion in aqueous solutions as a quantum factor of Konovalov paradox].

Recently academician Konovalov and co-workers observed an increase in electroconductivity and biological activity simultaneously with diffusion slowing (or nanoobject diameter increasing) and extremes of other parameters (ζ-potential, surface tension, pH, optical activity) in low concentration aqueous solutions. This phenomenon completely disappeared when samples were shielded against external electromagnetic fields by a Faraday cage. A conventional theory of water and water solutions couldn't explain "Konovalov paradox" observed in numerous experiments (representative sampling about 60 samples and 7 parameters). The new approach was suggested to describe the physics of water and explain "Konovalov paradox". The proposed concept takes into account the quantum differences of ortho-para spin isomers of H2O in bulk water (rotational spin-selectivity upon hydration and spontaneous formation of ice-like structures, quantum beats and spin conversion induced in the presence of a resonant electromagnetic radiation). A size-dependent self-assembly of amorphous complexes of H2O molecules more than 275 leading to the ice Ih structure observed in the previous experiments supports this concept.

[Effect of quantum differences of ortho and para H2O spin-isomers on water properties: biophysical aspect].

Quantum differences of ortho/para H2O spin-isomers are considered as a key factor that determines water property taking into account the ortho/para conversion and the unbalanced. (1:1) ortho/para ratio in water. The biophysical mechanism of jump in the permeability of erythrocytes at the level of microcapillary at 36.6 degrees C in water-based physiological solution and at 37.4 degrees C in heavy water is proposed and discussed.

[Quantum differences of ortho/para H2O2 spin-isomers as a factor of the femtosecond charge separation kinetics modulation in reaction centers of purple bacteria].

We have proposed the mechanism of coherent modulations of the P* state in the transient absorption spectra of the reaction center isolated from purple bacteria. Two water molecules, located between special pair, Ba, Bb chlorophylls and histidine L173 and M202, are supposed to be ortho-H2O and para-H2O isomers with different magnetic properties. The distinctive modulation frequencies were labeling as rotational resonances of ortho-H2O. According to our assumption, the interaction of rotational modes of water isomers with the charge-transfer states is a reason of coherent modulations of kinetics. We have modified a Hamiltonian system in order to take into account the rotational modes of ortho-H2O. Evolution of the density matrix was calculated in Liouville space. The Redfield relaxation theory for molecular aggregates was used to model kinetics up to 3 ps.

[Weak coherent radiation of OH and ortho- H2O space masers as a carrier in biocommunication: the ortho/para-conversion of H2O spin isomers?].

A conception of biocommunication based on the principle of radiophysics stating that the carrier modulation takes place at the resonance frequency in the transmission-receiver system has been substantiated and proved. The coherent radiation of space OH-masers (1.6-1.7 GHz) and ortho-H2O-maser (22.3 GHz) is proposed as a source of the carrier frequency. The narrow lines of rotational transition of H2O and OH molecules in liquid water were proposed to be considered as an analog of selective resonances of transmitter and receiver in radiocommunication. The possibility of the ortho-para conversion of H2O spin isomers, induced by weak electromagnetic fields, is discussed.

[Spin isomeric selectivity of water molecules upon DNA hydration].

Four-wave photon coherent scattering of laser emission was used to study the influence of DNA on the content of quasi-free ortho and para isomers of water molecules in its aqueous solution. It was shown that the concentration of quasi-free molecules that form the rotational spectrum of spin isomers increases considerably in the hydrational shell of the DNA molecule as compared to pure water. The increase in the concentration of spin isomers occurs disproportionally. In the presence of DNA, the intensity of the rotational spectrum of orthoisomers is on the average much greater than that of para isomers. It was also demonstrated that the character of hydration and the ortho/para ratio change noticeably upon DNA denaturation, which may be evidence of changes in preferable solvation of DNA during its denaturation. The data obtained allowed us to assume that the stability of different biologically important states of macromolecules can be changed by varying the relative concentration of water spin isomers in solution.

Amplitude and polarization instability of picosecond light pulses exciting a semiconductor optical resonator.

The first results of our study of nonlinear shift, distortion of form, and destruction of picosecond light pulses interacting with a nonlinear Fabry-Perot resonator in a strongly nonstationary regime are reported. Polarization instability of the light pulse transmitted through a nonlinear resonator has been observed.