Spectroscopic analysis of fire suppressants and refrigerants by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy is evaluated as a means of detecting the fire suppressants CF(3)Br, C(3)F(7)H, and CF(4) and the refrigerant C(2)F(4)H(2). The feasibility of employing laser-induced breakdown spectroscopy for time- and space-resolved measurement of these agents during use, storage, and recharge is discussed. Data are presented that demonstrate the conditions necessary for optimal detection of these chemicals.     

Plasma-particle interactions in a laser-induced plasma: implications for laser-induced breakdown spectroscopy

The interaction between laser-induced plasmas and individual particles controls the rate of particle dissociation and subsequent atomic diffusion and emission processes, with implications for single-particle spectroscopy, as well as materials synthesis and other plasma sources. It is demonstrated through quantitative plasma imaging studies that discrete particles dissociate on a time scale of tens of microseconds within plasmas formed by 300-mJ Nd:YAG laser pulses. Significant spatial nonhomogeneity, as measured by localized atomic emission from particle-derived calcium atoms, persists on a comparable time scale, providing a measure of their average atomic diffusion rate of 0.04 m(2)/s. In addition, the resulting calcium atomic emission is explored using image analysis as well as traditional spectroscopic analysis.     

Multielemental chemical imaging using laser-induced breakdown spectrometry

Multichannel laser-induced breakdown spectrometry (LIBS) is used to generate selective chemical images for silver, titanium, and carbon from silicon photovoltaic cells. A 2.5 mJ pulsed nitrogen laser and a spectrometer using charge-coupled device detection were employed. LIBS images were acquired sequentially by moving the sample located on a motorized x-y translational stage step by step while storing the multichannel LIBS spectrum for each position of the sample, followed by computer-based reconstruction of two-dimensional selective images from intensity profiles at several wavelengths. Depth distributions of carbon impurities are also reported. Room temperature and atmospheric pressure operation as used here remove the restrictions on sample size exhibited by other surface analysis techniques used for imaging applications. Thus, the sample size in LIBS imaging is in principle unlimited. A LIBS experiment does not require a sample to be conductive. Therefore, virtually all materials can be imaged. Although LIBS is a typical example of destructive analytical technique, multichannel detection as demonstrated here confers the possibility to LIBS of obtaining multielement information from a given surface area. Lateral resolution of 80 μm and depth resolution of better than 13 nm were observed. The ultimate limitation to imaging the first layer of the surface in LIBS is the spectral signal-to-noise ratio as dictated by the ablation threshold of the material.     

Surface temperature-field imaging with laser-induced thermographic phosphorescence

A technique to remotely image temperature distributions of heated metallic surfaces is extended to higher temperatures. It uses a Dy(+3):YAG thermographic phosphor (TP) bonded to the surface and excited by radiation at 355 nm. Digital images of the emission from two excited states were recorded and divided by each other to correct by normalization for illumination and coating nonuniformities. Results show that the TP can survive heating and cooling cycles to 1400 K and that emitting states achieve thermodynamic equilibrium before radiating. Temperatures in the range of 300-1300 K were determined by normalization of pairs of emission images with a single calibration constant. Uncertainties of +/-7-13% at a spatial resolution of 20 microm and +/-0.7-4% at a resolution of 500 microm were achieved.     

Fraunhofer-type absorption lines in double-pulse laser-induced plasma

We studied the confocal double-pulse laser-induced plasma in the very beginning of its life. It was found that the second laser pulse fired 0.7 to 5 μs after the first pulse produces plasma which, during the first 0 to 20 ns, resembles solar configuration. There is a very hot and compact plasma core that radiates a broad continuum spectrum and a much larger and cooler outer shell. The light from the hot core passes through the cold outer shell and is partly absorbed by atoms and ions that are in ground (or close to ground) states. This produces absorption lines that are similar to Fraunhofer lines observed in the sun spectrum. The possibility to use these absorption lines for new direct and calibration free laser-induced breakdown spectroscopy analytical applications, both in laboratory and industrial conditions, is proved.     

Third-harmonic generation imaging of laser-induced breakdown in glass

We present the results of three-dimensional third-harmonic generation imaging of laser-induced breakdown in glass by focused microjoule femtosecond near-IR pulses. This technique has the potential to resolve three dimensionally microstructures that result from laser-induced breakdown. As a potential optical data storage approach it is shown that the same IR laser beam can be used for writing and, at a lower power, for reading. The induced microdamage is shown to be three dimensionally confined and to depend on the write power.     

Characteristics of laser-induced plasma from highT c superconductor

The spectroscopic analysis of the emission from the plasma produced by irradiating a highT _c superconducting GdBa₂Cu₃O₇ target with a high power Nd:YAG laser beam shows the existence of the bands from different oxides in addition to the lines from neutrals and ions of the constituent elements. The spectral emissions by oxide species in laser-induced plasma show considerable time delays as compared to those from neutral and ionic species. Recombination processes taking place during the cooling of the hot plasma, rather than the plasma expansion velocities, have been found to be responsible for the observed time delays in this case. The decays of emission intensities from various species are found to be non-exponential.     

Spectroscopic features of laser-induced breakdown in water and aqueous solutions in ultrasonic field

It is established that the action of ultrasound leads to both sharp enhancement of the acoustic emission and increase in the intensity of spectral lines of laser-excited elements dissolved in aqueous salt solutions (NaCl, NaHCO₃, CaCl₂), which provides a new method of combined laser–ultrasonic spark spectroscopy. The task of synchronization of the acoustic and optical emission has been solved, which reveals dependence of the intensity of spectral lines on the phase of ultrasonic wave action.     

Nondestructive laser-induced plasma formation at a target surface

The parameters of ultrashort laser pulses and the thermal characteristics of a metal target were determined, which provide that the laser-induced plasma formation at the target surface does not lead to damage of the metal surface. The results of calculations are compared to experimental data.     

Multispectral laser-induced fluorescence imaging system for large biological samples

A laser-induced fluorescence imaging system developed to capture multispectral fluorescence emission images simultaneously from a relatively large target object is described. With an expanded, 355-nm Nd:YAG laser as the excitation source, the system captures fluorescence emission images in the blue, green, red, and far-red regions of the spectrum centered at 450, 550, 678, and 730 nm, respectively, from a 30-cm-diameter target area in ambient light. Images of apples and of pork meat artificially contaminated with diluted animal feces have demonstrated the versatility of fluorescence imaging techniques for potential applications in food safety inspection. Regions of contamination, including sites that were not readily visible to the human eye, could easily be identified from the images.     

Temperature and pressure imaging using infrared planar laser-induced fluorescence

A new diagnostic technique for measurements of temperature and pressure distribution in gaseous flows has been developed. The technique, based on infrared planar laser-induced fluorescence (IR-PLIF), is applicable to all IR-active species. A simple two-line excitation approach is used for measurements of temperature, while pressure measurements utilize online excitation on one rotational line and offline excitation on another. A demonstration of the technique in a supersonic underexpanded jet of 30% CO2 and 70% N2 was performed, and the results are, to the best of our knowledge, the first demonstration of temperature and pressure imaging using IR-PLIF. The developed diagnostic shows potential for single-shot two-dimensional measurements of temperature and pressure in gaseous flows.     

Microanalysis by laser-induced plasma spectroscopy in the vacuum ultraviolet

A new setup for microanalysis by laser-induced plasma spectroscopy in the VUV range is presented and described in detail. The system features an integrated ablation and detection module with a newly designed VUV echelle system. The echelle permits a full spectral coverage between 150 and 300 nm with a resolving power lambda/Deltalambda between 11,000 and 15,000. At present, the ablation module permits a microanalysis with a crater size of 25 microm and a nominal depth resolution with an ablation rate of 150 nm/pulse. The VUV performance was demonstrated for bulk analysis of steel; detection limits for sulfur, carbon, and phosphorus were in the lower milligram per kilogram range. The VUV scanning and mapping performance for heterogeneous matrixes was illustrated for mineral bottom ash samples from a waste incineration process.     

Balmer series Hbeta measurements in a laser-induced hydrogen plasma

Stark-broadened emission profiles of the Balmer series Hbeta lines are measured subsequent to nanosecond laser-induced optical breakdown in gaseous hydrogen. Electron number densities are found from time-resolved spectra from Hbeta emissions to be in the range 10(15)-10(18) cm(-3). These results are compared with Halpha measurements for which number densities as high as 10(19) cm(-3) are determined from Stark widths and Stark shifts. Good agreement is reported for number densities inferred from Halpha and Hbeta emissions, down to an electron number density 3 x 10(16) cm(-3), by accurate treatment of ion dynamics in the theory.     

Synthesis and characterization of Ag-Ni bimetallic nanoparticles by laser-induced plasma

We present an approach in which laser ablation deposition is used to synthesize silver-nickel bimetallic nanoparticles. A variety of techniques, including scanning electron microscopy, energy disperse spectroscopy and X-ray photoelectron spectroscopy have been used to characterize the morphology, composition and construction of synthesized bimetallic nanoparticles, respectively. The formation mechanism of bimetallic nanoparticles has been discussed. The Raman spectra of silver-nickel bimetallic nanoparticles have been analyzed. Time-of-flight mass spectrometry has been applied to directly measure intermediate species. The results indicate that diatomic AgNi is the most abundant species and suggest that the AgNi is the most stable intermediate which may play an important role in the synthesis process. Emission spectra demonstrate that the electron temperature is in the range of 6000-10000 K during the ablation process and increases with the laser power density.     

Radiative model of post-breakdown laser-induced plasma expanding into ambient gas

The dynamics of the radiative plasma expansion into an ambient gas is considered. The model describes the evolution of the plasma emission spectrum and the dynamics of the resulting shock wave. The time frame for the applicability of the model is in the tens of nanoseconds after the laser pulse is terminated, until a few microseconds later when the plasma ceases to emit. It is assumed that local thermodynamic equilibrium is established and that the plume expands with spherical symmetry. The model outputs are spatial and temporal distributions of atoms, ions, and electron number densities, evolution of atom and ion line profiles, and the shock wave. The model should be applicable to spectroscopic analysis of the initial plasma state and plasma dynamics.     

Remote imaging laser-induced breakdown spectroscopy and laser-induced fluorescence spectroscopy using nanosecond pulses from a mobile lidar system

A mobile lidar system was used in remote imaging laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF) experiments. Also, computer-controlled remote ablation of a chosen area was demonstrated, relevant to cleaning of cultural heritage items. Nanosecond frequency-tripled Nd:YAG laser pulses at 355 nm were employed in experiments with a stand-off distance of 60 meters using pulse energies of up to 170 mJ. By coaxial transmission and common folding of the transmission and reception optical paths using a large computer-controlled mirror, full elemental imaging capability was achieved on composite targets. Different spectral identification algorithms were compared in producing thematic data based on plasma or fluorescence light.     

Spectroscopic diagnostics of the laser erosion plasma of lead

Time-averaged emission spectra of a laser erosion plasma formed during the action of a neodymium laser [W=(3–5)×10⁸ W/cm², λ_g=1.06 μm, τ=20 ns, f=12 Hz] on a lead target were measured for laser torch regions spaced by r=1 and 7 mm from the target. The spatial dynamics of population of the excited states and the electron temperature in the laser torch are analyzed.     

Experimental and theoretical investigation of laser-induced plasma of a titanium target

We present a theoretical approach to interpreting optical emission spectroscopy measurements for nonequilibrium conditions. In this approach both the fluid dynamics and the kinetics of laser-induced plasma are taken into account, and the results obtained by the numerical model are applied to the spectroscopic observation of the plasma induced by the interaction between a KrF laser and a metallic Ti target. We have generalized the theoretical method to calculate the initial conditions for the plume expansion that show the best agreement with experimental results.     

Analysis of solids by laser ablation and resonance-enhanced laser-induced plasma spectroscopy

An analytical technique based on resonance-enhanced laser-induced plasma spectroscopy was demonstrated. Pellets of potassium iodate containing trace amounts of sodium were ablated by a 532-nm laser pulse in air. After 30 ns, the plasma plume was intercepted by a 404.4-nm laser pulse to resonantly photoionize the potassium atoms in the vapor plume. The 589-nm emissions of the sodium were found to be significantly enhanced. The enhancement was shown to depend critically on the profile of the 532-nm beam as well as the spatial overlap of the two laser pulses. Using this double-pulse scheme, the mass detection limit for sodium was estimated to be about 200 pg, which was five times better than that obtained by using the 532-nm laser pulse alone.     

Minimally destructive analysis of aluminum alloys by resonance-enhanced laser-induced plasma spectroscopy

Aluminum alloys were analyzed for minor components and trace impurities using double pulse resonance-enhanced laser-induced plasma spectroscopy. The first laser pulse at 532 nm ablated the sample. The second laser pulse at 396.15 nm resonantly excited the Al atoms to rekindle the plasma plume. Emissions from Mg, Cu, Si, and Na were observed. At laser energies below the damage threshold, the analyte emissions were already orders of magnitude above the background noise. Nonresonant probes of comparable sensitivity would melt and deform the sample surface. Because of the lower etch rate of resonant probes, depth profiling at nanometer resolution was possible. Using this method, the variation of [Na] with depth was measured for high-purity samples. In contrast, nonresonant probes required 5 times the fluence and proportionally poorer resolution. Worse yet, the associated heating and laser remelting modified the [Na] profile.