The Plasma Spectroscopic Study of Dergaon Meteorite, India.

Meteorites are the recoverable portions of asteroids that reach the surface of the Earth. Meteorites are rare extraterrestrial objects studied extensively to improve our understanding of planetary evolution. In this work, we used calibration-free laser-induced breakdown spectroscopy (CF-LIBS) to evaluate the quantitative elemental and molecular analyses of the Dergaon meteorite, a H 4-5 chondrite fall sample from Assam, India. Spectral signatures of H, N, O, Na, Mg, Al, Si, P, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, andIrweredetected. Along with the atomic emission, this work reports the molecular emission from FeO molecules. The concentration of the measured elements obtained using CF-LIBS is in close agreement with earlier reports. The elements H, N, and O and their concentrations are estimated by using CF-LIBS for the first time. This study applies laser spectroscopy to establish the presence of Ni, Cr, Co, and Ir in meteorites. The elemental analysis forms the basis for the establishment of the potential molecular composition of the Dergaon meteorite. Moreover, the elemental analysis approach bodes well for in-situ analyses of extraterrestrial objects including applications in planetary rover missions.

Laser-Plasma Spectroscopy of Hydroxyl with Applications.

This article discusses laser-induced laboratory-air plasma measurements and analysis of hydroxyl (OH) ultraviolet spectra. The computations of the OH spectra utilize line strength data that were developed previously and that are now communicated for the first time. The line strengths have been utilized extensively in interpretation of recorded molecular emission spectra and have been well-tested in laser-induced fluorescence applications for the purpose of temperature inferences from recorded data. Moreover, new experiments with Q-switched laser pulses illustrate occurrence of molecular recombination spectra for time delays of the order of several dozen of microseconds after plasma initiation. The OH signals occur due to the natural humidity in laboratory air. Centrifugal stretching of the Franck-Condon factors and r-centroids are included in the process of determining the line strengths that are communicated as a Supplementary File. Laser spectroscopy applications of detailed OH computations include laser-induced plasma and combustion analyses, to name but two applications. This work also includes literature references that address various diagnosis applications.

Laser-Plasma Spatiotemporal Cyanide Spectroscopy and Applications.

This article reports new measurements of laser-induced plasma hypersonic expansion measurements of diatomic molecular cyanide (CN). Focused, high-peak-power 1064 nm Q-switched radiation of the order of 1 TW/cm 2 generated optical breakdown plasma in a cell containing a 1:1 molar gas mixture of N 2 and CO 2 at a fixed pressure of 1.1 × 10 5 Pascal and in a 100 mL/min flow of the mixture. Line-of-sight (LOS) analysis of recorded molecular spectra indicated the outgoing shockwave at expansion speeds well in excess of Mach 5. Spectra of atomic carbon confirmed increased electron density near the shockwave, and, equally, molecular CN spectra revealed higher excitation temperature near the shockwave. Results were consistent with corresponding high-speed shadowgraphs obtained by visualization with an effective shutter speed of 5 nanoseconds. In addition, LOS analysis and the application of integral inversion techniques allow inferences about the spatiotemporal plasma distribution.

Mapping of Uranium in Surrogate Nuclear Debris Using Laser-Induced Breakdown Spectroscopy (LIBS).

This work describes the use of a laser-induced breakdown spectroscopy (LIBS) system to conduct macroscopic elemental mapping of uranium and iron on the exterior surface and interior center cross-section of surrogate nuclear debris for the first time. The results suggest that similar LIBS systems could be packaged for use as an effective instrument for screening samples during collection activities in the field or to conduct process control measurements during the production of debris surrogates. The technique focuses on the mitigation of chemical and physical matrix effects of four uranium atomic emission lines, relatively free of interferences and of good analytical value. At a spatial resolution of 0.5 mm, a material fractionation pattern in the surrogate debris is identified and discussed in terms of constituent melting temperatures and thermal gradients experienced.

Emission spectroscopy of expanding laser-induced gaseous hydrogen-nitrogen plasma.

Microplasma is generated in an ultra-high-pure H2 and N2 gas mixture with a Nd:YAG laser device that is operated at the fundamental wavelength of 1064 nm. The gas mixture ratio of H2 and N2 is 9 to 1 at a pressure of 1.21 ± 0.03 105 Pa inside a chamber. A Czerny-Turner-type spectrometer and an intensified charge-coupled device are utilized for the recording of plasma emission spectra. The line-of-sight measurements are Abel inverted to determine the radial distributions of electron number density and temperature. Recently derived empirical formulas are utilized for the extraction of values for electron density. The Boltzmann plot and line-to-continuum methods are implemented for the diagnostic of electron excitation temperature. The expansion speed of the plasma kernel maximum electron temperature amounts to 1 km/s at a time delay of 300 ns. The microplasma, initiated by focusing 14 ns, 140 mJ pulses, can be described by an isentropic expansion model.

Laser-induced optical breakdown spectroscopy of polymer materials based on evaluation of molecular emission bands.

Laser-induced breakdown spectroscopy (LIBS) for composition analysis of polymer materials results in optical spectra containing atomic and ionic emission lines as well as molecular emission bands. In the present work, the molecular bands are analyzed to obtain spectroscopic information about the plasma state in an effort to quantify the content of different elements in the polymers. Polyethylene (PE) and a rubber material from tire production are investigated employing 157nmF2 laser and 532nm Nd:YAG laser ablation in nitrogen and argon gas background or in air. The optical detection reaches from ultraviolet (UV) over the visible (VIS) to the near infrared (NIR) spectral range. In the UV/VIS range, intense molecular emissions, C2 Swan and CN violet bands, are measured with an Echelle spectrometer equipped with an intensified CCD camera. The measured molecular emission spectra can be fitted by vibrational-rotational transitions by open access programs and data sets with good agreement between measured and fitted spectra. The fits allow determining vibrational-rotational temperatures. A comparison to electronic temperatures Te derived earlier from atomic carbon vacuum-UV (VUV) emission lines show differences, which can be related to different locations of the atomic and molecular species in the expanding plasma plume. In the NIR spectral region, we also observe the CN red bands with a conventional CDD Czerny Turner spectrometer. The emission of the three strong atomic sulfur lines between 920 and 925nm is overlapped by these bands. Fitting of the CN red bands allows a separation of both spectral contributions. This makes a quantitative evaluation of sulfur contents in the start material in the order of 1wt% feasible.

Measurement of Strontium Monoxide in Methane-Air Flames.

The spectroscopy of alkaline earth metal compounds is stimulated by the use of these compounds in practical areas ranging from technology to medicine. Applications in the field of pyrotechnics were the motivation for a series of flame emission spectroscopy experiments with strontium-containing compounds. Specifically, strontium monoxide (SrO) was studied as a candidate radiator for the diagnosis of methane-air flames. Strontium monoxide emissions have been observed in flames with temperatures in the range 1200 K to 1600 K for two compounds: strontium hydroxide and strontium chloride. Comparisons are made of the measured SrO spectra to simulated spectra in the near-infrared region of 700 nm to 900 nm.

Aluminum monoxide emission measurements in a laser-induced plasma.

We report temperature inferences from time-resolved emission spectra of a micro-sized plasma following laser ablation of an aluminum sample. The laser-induced breakdown event is created with the use of nanosecond pulsed laser radiation. Plasma temperatures are inferred from the aluminum monoxide spectroscopic emissions of the aluminum sample by fitting experimental to theoretically calculated spectra with a nonlinear fitting algorithm. The synthetic spectra used as a comparison for the experimental spectra are generated from accurate line strengths of aluminum monoxide bands. The inferred plasma temperatures are found to be 5315 ± 100 K at 20 µs following breakdown. At later time delays of 45 and 70 µs following breakdown, the plasma temperatures are found to be 4875 ± 95 and 4390 ± 80 K, respectively. Error analysis of the inferred temperatures is performed with the fitting algorithm.

Laser-induced plasma spectroscopy of hydrogen Balmer series in laboratory air.

Stark-broadened emission profiles for the hydrogen alpha and beta Balmer series lines in plasma are measured to characterize electron density and temperature. Plasma is generated using a typical laser-induced breakdown spectroscopy (LIBS) arrangement that employs a focused Q-switched neodymium-doped yttrium aluminum garnet (Nd : YAG) laser, operating at the fundamental wavelength of 1064 nm. The temporal evolution of the hydrogen Balmer series lines is explored using LIBS. Spectra from the plasma are measured following laser-induced optical breakdown in laboratory air. The electron density is primarily inferred from the Stark-broadened experimental data collected at various time delays. Due to the presence of nitrogen and oxygen in air, the hydrogen alpha and beta lines become clearly discernible from background radiation for time delays of 0.4 and 1.4 µs, respectively.

A fundamental understanding of the dependence of the laser-induced breakdown spectroscopy (LIBS) signal strength on the complex focusing dynamics of femtosecond laser pulses on either side of the focus.

We correlate the focusing dynamics of 50 femtosecond (fs) laser radiation as it interacts with a silicon sample to laser-induced breakdown spectroscopy (LIBS) signal strength. Presented are concentric ring-shaped variations in the electric field in the prefocus region due to lens aberrations and nonsymmetry between the prefocus and post-focus beam profile as a result of continuum generation, occurring around the focus. Experimental results show different signal trends for both atmospheric and vacuum conditions, attributed to the existence of a continuum for the former. Lens aberrations effects on the LIBS signal strength are investigated using a plano-convex spherical lens and an aspherized achromatic lens. High-resolution scanning electron micrographs of the silicon surface after ablation, along with theoretical simulations, reveal the electric field patterns near the focus. The research results contribute to fundamental understanding of the basic physics of ultrashort, femtosecond laser radiation interacting with materials.

Aluminum flame temperature measurements in solid propellant combustion.

The temperature in an aluminized propellant is determined as a function of height and plume depth from diatomic AlO and thermal emission spectra. Higher in the plume, 305 and 508 mm from the burning surface, measured AlO emission spectra show an average temperature with 1σ errors of 2980 ± 80 K. Lower in the plume, 152 mm from the burning surface, an average AlO emission temperature of 2450 ± 100 K is inferred. The thermal emission analysis yields higher temperatures when using constant emissivity. Particle size effects along the plume are investigated using wavelength-dependent emissivity models.

Carbon swan spectra measurements following breakdown of nitro compound explosive simulants.

Our measurements of micro-plasma following laser-induced optical breakdown of nitro compound explosive simulants, here 3-nitrobenzoic acid, show well-developed molecular spectra during the first several hundreds of nanoseconds. Analysis of recorded carbon spectra is accomplished using accurate line strengths for the diatomic molecular Swan system. Presence of hydrogen-beta allows us to infer electron density in the plasma evolution. Computational challenges include accounting for background variation and appropriate modeling of hydrogen embedded in molecular spectra. Recorded and computed spectra agree nicely for time delays on the order of 1.6 µs from optical breakdown when using a single temperature for local thermodynamic equilibrium plasma.

Measurement and analysis of atomic hydrogen and diatomic molecular AlO, C2, CN, and TiO spectra following laser-induced optical breakdown.

In this work, we present time-resolved measurements of atomic and diatomic spectra following laser-induced optical breakdown. A typical LIBS arrangement is used. Here we operate a Nd:YAG laser at a frequency of 10 Hz at the fundamental wavelength of 1,064 nm. The 14 nsec pulses with anenergy of 190 mJ/pulse are focused to a 50 µm spot size to generate a plasma from optical breakdown or laser ablation in air. The microplasma is imaged onto the entrance slit of a 0.6 m spectrometer, and spectra are recorded using an 1,800 grooves/mm grating an intensified linear diode array and optical multichannel analyzer (OMA) or an ICCD. Of interest are Stark-broadened atomic lines of the hydrogen Balmer series to infer electron density. We also elaborate on temperature measurements from diatomic emission spectra of aluminum monoxide (AlO), carbon (C2), cyanogen (CN), and titanium monoxide (TiO). The experimental procedures include wavelength and sensitivity calibrations. Analysis of the recorded molecular spectra is accomplished by the fitting of data with tabulated line strengths. Furthermore, Monte-Carlo type simulations are performed to estimate the error margins. Time-resolved measurements are essential for the transient plasma commonly encountered in LIBS.

Optical diagnostic and therapy applications of femtosecond laser radiation using lens-axicon focusing.

Diagnostic modalities by means of optical and/or near infrared femtosecond radiation through biological media can in principle be adapted to therapeutic applications. Of specific interest are soft tissue diagnostics and subsequent therapy through hard tissue such as bone. Femto-second laser pulses are delivered to hydroxyapatite representing bone, and photo-acoustic spectroscopy is presented in order to identify the location of optical anomalies in an otherwise homogeneous medium. Imaging through bone is being considered for diagnostic, and potentially therapeutic, applications related to brain tumors. The use of mesomeric optics such as lens-axicon combinations is of interest to achieve the favorable distribution of focused radiation. Direct therapy by increasing local temperature to induce hyperthermia is one mode of brain tumor therapy. This can be enhanced by seeding the tumor with nanoparticles. Opto-acoustic imaging using femtosecond laser radiation is a further opportunity for diagnosis.

Measurement and analysis of titanium monoxide spectra in laser-induced plasma.

We present results including measurement and analysis of titanium monoxide. Pulsed, nanosecond Nd:YAG laser radiation is used in a typical laser-induced breakdown spectroscopy arrangement to record the spectra. This scheme provides experiments analogous to pulsed laser deposition tactics and allows for time-resolved spectroscopic analysis. The computed spectra are generated from a new, accurate line-strength file that allows us to accurately predict γ (A3Φ→X3Δ) and γ' (B3Π→X3Δ) spectral signatures. We infer temperature on the order of 3600±700 K and 4200±800 K at time delays of 52 and 72 µs, respectively. Current interest in this work includes titania (TiO2) nanoparticle generation for thin film applications.

Analysis of time-resolved superposed atomic hydrogen Balmer lines and molecular diatomic carbon spectra.

We present analysis of superposition spectra following laser-induced breakdown (LIB) of methane. Both hydrogen-beta and hydrogen-gamma lines contain discernible contributions from diatomic carbon emissions for time delays of 1 to 2 µs from pulsed, 8 ns, infrared Nd:YAG laser radiation LIB. Analysis of the atomic lines and molecular C(2) spectra reveal electron and molecular excitation temperatures of typically 13,000 and 5000 K, respectively.

Computation of AlO B2Σ+ → X2Σ+ emission spectra.

Application of molecular spectroscopy to analytical chemistry usually requires accurate description of the particular transition of interest. In this communication we describe the creation of a list of spectral lines. Following the introduction and definition of the line strength, we present a recipe for computation of diatomic-line-strengths, including the Hönl-London factor and electric dipole line strength for each spectral line. The diatomic eigenfunction is discussed including Hund's case basis functions. In our data tables we prefer use of Hund's case (a) basis, and we apply the usual Born-Oppenheimer approximation for the electronic-vibrational strengths. This allows us to generate the table of line strengths that we frequently apply for spectroscopic temperature determination. Using these line-strength tables, we present theoretical AlO emission spectra for the B-X system of AlO. These emission spectra are computed for temperatures of 3000 and 6000 K and for typical spectroscopic resolution used in laser-induced optical breakdown studies.

Time-resolved spectroscopy measurements of hydrogen-alpha, -beta, and -gamma emissions.

Hydrogen emission spectroscopy results are reported following laser-induced optical breakdown with infrared Nd:YAG laser radiation focused into a pulsed methane flow. Measurements of Stark-broadened atomic hydrogen-alpha, -beta, and -gamma lines show electron number densities of 0.3 to 4x10(17) cm(-3) for time delays of 2.1 to 0.4 micros after laser-induced optical breakdown. In methane flow, recombination molecular spectra of the Delta nu = +2 progression of the C(2) Swan system are discernable in the H(beta) and H(gamma) plasma emissions within the first few microseconds. The recorded atomic spectra indicate the occurrence of hydrogen self-absorption for pulsed CH(4) flow pressures of 2.7x10(5) Pa (25 psig) and 6.5x10(5) Pa (80 psig).

Measurements of aluminum and hydrogen microplasma.

We report time-averaged and time-resolved emission spectra subsequent to laser-induced optical breakdown of aluminum in laboratory air and in hydrogen gas. The microplasma generated by nominal 10 ns IR laser radiation shows Stark-broadened and shifted atomic lines. An analysis of the H(alpha) and H(beta) Balmer series lines and selected aluminum lines allows one to determine electron number density in the range of 0.01 - 10 x 10(18) cm(-3) early in the plasma decay. Atomic and molecular features are investigated for diagnostic applications in laser material processing.