Depth profiles of ceramic tiles by using orthogonal double‐pulse laser induced breakdown spectrometry

The potential of a double pulse (DP) excitation scheme for in‐depth characterization of ceramic samples using laser induced breakdown spectrometry (LIBS) has been demonstrated. For this purpose, two Q‐switched Nd:YAG lasers in orthogonal configuration were employed, the first one to ablate the sample (1064 nm) and the second one (532 nm) to excite the ablated material. Light emission was collected by a spectrograph and detected by an intensified charge‐coupled device (CCD) detector. Optimal conditions such as relative laser beam positions, laser pulse energies, inter‐pulse separation and CCD delay time were studied. Depth profiles were evaluated on the basis of various elemental compositions in both layers of ceramic samples. The depth resolution with DP configuration was improved by almost twofold as compared to the single‐pulse approach. The reproducibility of the depth profiles is also twice better with double pulse LIBS. Copyright © 2009 John Wiley & Sons, Ltd.     

Investigation of plasmas produced by laser ablation using single and double pulses for food analysis demonstrated by probing potato skins

We report on investigations of plasmas produced by laser ablation of fresh potatoes using infrared nanosecond laser radiation. A twin laser system consisting of two Nd:YAG oscillators was used to generate single or double pulses of adjustable interpulse delay. The potatoes were irradiated under ambient air with moderate pulse energies of about 10 mJ. The expansion dynamics of the ablation plume was characterized using fast imaging with a gated camera. In addition, time-resolved optical emission spectroscopy was applied to study the spectral line emission of the various plasma species. The electron density was deduced from Stark broadening, and the plasma temperature was inferred from the relative emission intensities of spectral lines. The relative concentrations of metals were estimated from the comparison of the measured emission spectra to the spectral radiance computed for a plasma in local thermal equilibrium. It is shown that the plasma produced by double pulses has a larger volume and a lower density. These properties lead to an increase of the signal-to-noise ratio by a factor of 2 and thus to an improved measurement sensitivity.     

Double pulse laser ablation and plasma: Laser induced breakdown spectroscopy signal enhancement

A review of recent results of the studies of double laser pulse plasma and ablation for laser induced breakdown spectroscopy applications is presented. The double pulse laser induced breakdown spectroscopy configuration was suggested with the aim of overcoming the sensitivity shortcomings of the conventional single pulse laser induced breakdown spectroscopy technique. Several configurations have been suggested for the realization of the double pulse laser induced breakdown spectroscopy technique: collinear, orthogonal pre-spark, orthogonal pre-heating and dual pulse crossed beam modes. In addition, combinations of laser pulses with different wavelengths, different energies and durations were studied, thus providing flexibility in the choice of wavelength, pulse width, energy and pulse sequence. The double pulse laser induced breakdown spectroscopy approach provides a significant enhancement in the intensity of laser induced breakdown spectroscopy emission lines up to two orders of magnitude greater than a conventional single pulse laser induced breakdown spectroscopy. The double pulse technique leads to a better coupling of the laser beam with the plasma plume and target material, thus providing a more temporally effective energy delivery to the plasma and target. The experimental results demonstrate that the maximum effect is obtained at some optimum separation delay time between pulses. The optimum value of the interpulse delay depends on several factors, such as the target material, the energy level of excited states responsible for the emission, and the type of enhancement process considered. Depending on the specified parameter, the enhancement effects were observed on different time scales ranging from the picosecond time level (e.g., ion yield, ablation mass) up to the hundred microsecond level (e.g., increased emission intensity for laser induced breakdown spectroscopy of submerged metal target in water). Several suggestions have been proposed to explain the mechanism of double pulse enhancement.     

A comparison of single and double pulse laser-induced breakdown spectroscopy of aluminum samples

Single and double pulse laser-induced breakdown spectroscopy (LIBS) was carried out on aluminum samples in air. In the case of double pulse excitation, experiments were conducted by using the same laser source operated at the same wavelength (1064 nm in most cases here presented). A lowering of the second pulse plasma threshold was observed, together with an overall enhancement in line emission for the investigated time delay between the two pulses (40–60 μs). The laser-induced plasma originated by a single and double pulse was investigated near ignition threshold with the aim to study possible dynamical mechanisms in different regimes. Currently available spectroscopic diagnostics of plasma, such as the line broadening and shift due Stark effects, have been used in the characterization in order to retrieve electron densities, while standard temperature measurements were based on Boltzmann plot. Plasma relevant parameters, such as temperature and electron density, have been measured in the plasma decay on a long time scale, and compared with crater shape (diameter and inferred volume). The comparison of double with single pulse laser excitation was carried out while keeping constant the energy per pulse; the influence of laser energy was investigated as well. Results here obtained suggest that use of the double pulse technique could significantly improve the analytical capabilities of LIBS technique in routine laboratory experiments.     

Quantitative analysis of arsenic in mine tailing soils using double pulse-laser induced breakdown spectroscopy

A double pulse-laser induced breakdown spectroscopy (DP-LIBS) was used to determine arsenic (As) concentration in 16 soil samples collected from 5 different mine tailing sites in Korea. We showed that the use of double pulse laser led to enhancements of signal intensity (by 13% on average) and signal-to-noise ratio of As emission lines (by 165% on average) with smaller relative standard deviation compared to single pulse laser approach. We believe this occurred because the second laser pulse in the rarefied atmosphere produced by the first pulse led to the increase of plasma temperature and populations of exited levels. An internal standardization method using a Fe emission line provided a better correlation and sensitivity between As concentration and the DP-LIBS signal than any other elements used. The Fe was known as one of the major components in current soil samples, and its concentration varied not substantially. The As concentration determined by the DP-LIBS was compared with that obtained by atomic absorption spectrometry (AAS) to evaluate the current LIBS system. They are correlated with a correlation coefficient of 0.94. The As concentration by the DP-LIBS was underestimated in the high concentration range (>1000 mg-As/kg). The loss of sensitivity that occurred at high concentrations could be explained by self-absorption in the generated plasma.     

Properties of Single- and Double-Lap Polymeric Joints Welded by a Diode Laser

Single-lap and double-lap polymeric joints of ultrahigh molecular weight polyethylene (UHMWPE) sheets, opportunely overlapped, were realized and studied. One of the polymer sheets was doped with carbon nanomaterials as a laser-absorbent filler. The joints were irradiated by a diode laser operating at 970 nm with maximum pulse energy of 200 mJ. Four types of weld seam geometries were realized in the overlapped area. Optical microscopy observations and mechanical shear and hardness tests were performed in order to characterize all the prepared joints. The maximum shear load was ≈210 N, reached generally in the double-lap joints. High loads in the single-lap joints were reached if high surface area of the welding and high filler amount in the polymer were present. Three parameters influenced the joint resistance: the joint configuration (single or double lap), the welding geometry, and the filler amount. The absorption of diode laser energy at the sheet interface induces a melting process that softens the polymeric sheets in the laser contact area. Finally, a comparison between the welding ability of the diode laser and of the Nd:Yag laser upon the polyethylene sheets is presented.     

Pulse shape analysis to reduce the background of BEGe detectors

A simple technique for pulse shape discrimination in HPGe-detectors of the so-called BEGe type, based on just one parameter obtained from one signal read out, is presented here. This technique allows discriminating between pulses generated when the deposited energy is located within a small region of about 1 mm³ from the pulses generated when the energy is deposited at different locations several mm or cm apart. Two possible applications using this technique are: (i) experiments that look for neutrinoless double β decay in ⁷⁶Ge, such as GERDA; (ii) γ spectrometry measurements where the Compton continuum can be reduced and the efficiency for cascading γ-rays can remain high. With this active background reduction technique a Compton suppression factor of about 3 was obtained. The detector response may be influenced by the detector size. The detector used for this study had a diameter of 6 cm, a thickness of 2.6 cm and a relative efficiency of 19%. The results obtained with this detector were consistent with the results obtained by Budjá? et al. [J Instrum 4:10, 2009] with a 50% relative efficiency BEGe detector.     

Pulse chirp effects in ultrafast laser-induced breakdown spectroscopy

When compared to many other sensitive methods for material detection, such as inductively coupled mass spectroscopy and thermal ionization mass spectroscopy, laser-induced breakdown spectroscopy (LIBS) typically exhibits a lower signal-to-noise ratio (SNR), resulting in higher detection limits. Increasing the SNR of LIBS would improve the ability to characterize the sample composition with increased accuracy and speed and reduce the amount of material needed to perform analysis. We have been investigating the effect of simple ultrashort laser pulse shaping on the SNR of LIBS. Our goal is to control the dynamics of the ionization and recombination processes in the laser-produced plasma to favorably affect the SNR associated with the line emission from the plasma. Pulse shaping is performed using an acousto-optic programmable dispersive filter. An adaptive learning algorithm is being developed to automate the pulse shape optimization process for maximization of LIBS SNR in nuclear security-relevant material characterization scenarios. We report a 27 % increase of the SNR for non-gated LIBS measurements of uranium by utilizing simple pulse shaping limited exclusively to excess quadratic spectral phase of the laser pulse.     

The Investigation on Ultrafast Pulse Formation in a Tm–Ho-Codoped Mode-Locking Fiber Oscillator

We experimentally investigate the formation of various pulses from a thulium–holmium (Tm–Ho)-codoped nonlinear polarization rotation (NPR) mode-locking fiber oscillator. The ultrafast fiber oscillator can simultaneously operate in the noise-like and soliton mode-locking regimes with two different emission wavelengths located around 1947 and 2010 nm, which are believed to be induced from the laser transition of Tm³⁺ and Ho³⁺ ions respectively. When the noise-like pulse (NLP) and soliton pulse (SP) co-exist inside the laser oscillator, a maximum output power of 295 mW is achieved with a pulse repetition rate of 19.85-MHz, corresponding to a total single pulse energy of 14.86 nJ. By adjusting the wave plates, the fiber oscillator could also deliver the dual-NLPs or dual-SPs at dual wavelengths, or single NLP and single SP at one wavelength. The highest 61-order harmonic soliton pulse and 33.4-nJ-NLP are also realized respectively with proper design of the fiber cavity.     

Improving the conversion efficiency of an organic distributed feedback laser by varying solvents of the laser gain layer

Control experiments were performed to improve the slope conversion efficiency of the organic distributed feedback laser by varying the dissolution solvents of the laser gain layer, a conjugated polymer poly(2-methoxy-5-(2?-ethyl-hexyloxy)-1,4-phenylene-vinylene) (MEH-PPV) in this work. The distributed feedback configuration of the laser was prepared by holographic photopolymerisation of the polymer/liquid crystal (HPDLC) mixture. Experimental results showed that the tetrahydrofuran (THF) solvent cast laser gain layer had a lower lasing threshold (0.28 μJ/pulse) and a higher slope conversion efficiency (7.8%) than that of the xylene solvent cast laser gain layer (0.5 μJ/pulse, 4.9%). Thin film waveguide characterisation demonstrated that the THF-cast film possessed a smaller waveguide loss (5.3 cm^?1) and larger net gain (17.1 cm^?1) than the xylene-cast film (8.3 cm^?1, 15.7 cm^?1). Absorbance and photoluminescence spectra indicated that the THF-cast film showed brighter luminescence at 620 nm and larger absorbance at 532 nm, indicating that the interchain interactions of the MEH-PPV is different, which plays the vital role in improving the optical performance of our organic DFB lasers.     

Comment on “three-dimensional analysis of laser induced plasmas in single and double pulse configuration”

Laser induced breakdown spectroscopy (LIBS) is an effective technique for real-time chemical analysis of samples in the laboratory and in the field. The performance of LIBS can be significantly improved by replacing the conventional LIBS configuration from single pulse laser to double pulse laser ablation. Corsi et al. showed that by firing two lasers with microsecond order delay can increase LIBS sensitivity [M. Corsi, G. Cristoforetti, M. Giuffrida, M. Hidalgo, S. Legnaioli, V. Palleschi, A. Salvetti, E. Tognoni, C. Vallebona, Three-dimensional analysis of laser induced plasmas in single and double pulse configuration, Spectrochimica Acta, Part B 59 (2004) 723–735] [1]. By studying plume evolution, they attribute this enhancement to the faster plume expansion in double pulse laser ablation. Blast wave theory was used in Corsi's paper to explain the higher expansion speed observed in double pulse laser ablation. However, it is questionable whether the blast wave theorem applies in laser ablation where the shockwave is driven by a vapor plume of mass. We introduce an alternative way to explain the faster plume expansion during double pulse laser through a more general thermodynamic relation.     

Dissociative ionization of ethanol by 400 nm femtosecond laser pulses

The dissociative ionization of ethanol in short-pulsed laser fields at approximately 400 nm is investigated. The yield ratio of the C-O bond breaking with respect to the C-C bond breaking increases sharply as the temporal width increases from 60 to 400 fs, and the yield ratio is two to three times as large as that at 800 nm in the entire pulse-width range of 60-580 fs. The enhancement of the C-O bond breaking of singly charged ethanol at 400 nm and the bond elongation prior to the Coulomb explosion of doubly charged ethanol occurring in the relatively weak light field intensity of 10(12)-10(13) W cm(2) is interpreted by the efficient light-induced coupling among the electronic states at the shorter wavelength of 400 nm. From the double pulse experiment, in which ethanol is irradiated with a pair of short pulses (<80 fs), the most efficient coupling occurs at Deltat=160 fs that is much earlier than Deltat=250 at 800 nm, where Deltat denotes the temporal separation of the two pulses, indicating that the nonadiabatic field-induced potential crossings of singly charged ethanol occurs much earlier at 400 nm than at 800 nm.     

Ultraviolet nanosecond laser ablation behavior of silver nanoparticle and melamine–formaldehyde resin-coated short sisal fiber-modified PLA composites

Nd:YAG laser (355 nm) induced surface modifications in polylactic acid (PLA), and its composites with silver nanoparticles (AgNPs, size range between 120 and 150 nm) with and without additional melamine–formaldehyde-coated short sisal fibers were studied as a function of laser pulse numbers. The AgNP content was varied (100, 300 and 500 ppm), whereas the sisal content kept as constant (9 mass%). The PLA-based systems with a fully amorphous matrix were irradiated with 1–256 laser pulses at a constant fluence of 0.32 µJ µm^?2. Changes in the irradiated surfaces were assessed and quantified by light and scanning electron microscopic pictures. Protrusion with bubbling, bubbled protrusion with cratering and crater formation with more or less bubbled ridges were found as characteristic ablation features. Bubbling was traced to entrapped gaseous products of PLA degradation, while the onset of ridges was ascribed to the melt flow of the PLA matrix caused by laser shock waves. The laser irradiation caused damage and ablation highly depended on the actual composition, which influenced the UV absorption at 355 nm, which was measured as well.     

Orthogonal Double-pulse versus Single-pulse laser ablation at different air pressures: A comparison of the mass removal mechanisms

The mass removal mechanisms occurring during the ablation of an aluminum target, induced by an Nd:YAG laser at λ = 1064 nm in air at different laser fluences, were investigated at different pressures and in the orthogonal double pulse configuration. Both the spectroscopic analysis of the plasma emission and the microscopic analysis of the craters, providing complementary information on the laser ablation process, were performed. The first technique allowed the calculation of the plasma thermodynamic parameters and an estimation of its atomized mass, while the latter led to the calculation of their volume, as well as a qualitative inspection of the craters profile and appearance. The results obtained at different fluences suggest a complex picture where the air pressure strongly drives the laser shielding effect, which in turn affects the relevance of melt displacement, melt expulsion and phase explosion mechanisms. The measurements performed in double pulse configuration suggest that in this case the ablation process is very similar to that induced at low air pressure. Phase explosion seems to occur in double pulse laser ablation while it seems inhibited in single pulse ablation at atmospheric pressure. Differently, melt splashing is much more efficient in single pulse ablation at atmospheric pressure than in double pulse ablation.     

A Complementary Metal Oxide Semiconductor sensor array based detection system for Laser Induced Breakdown Spectroscopy: Evaluation of calibration strategies and application for manganese determination in steel

This paper describes a low cost detection system for Laser Induced Breakdown Spectroscopy based on a simple spectrograph employing a conventional diffraction grating and a non-intensified, non-gated, non-cooled 1024 pixel Complementary Metal Oxide Semiconductor linear sensor array covering the spectral range from about 250 to 390 nm. It was employed in conjunction with a 1064 nm, 5 ns pulse duration Nd:YAG laser source for analyzing steel samples using the integration of 300 analysis pulses (35 mJ each). That led to gains in the signal-to-noise ratio of approximately 3 and 16 for Mn and Fe peaks, respectively, in addition to gains in the emission intensities of about 5.3, both in comparison with the integration of just 50 analysis pulses. The acquired emission spectra were used for Mn determination, in the range from 0.214 to 0.608% m/m as previously determined by ICP OES, evaluating different univariate (at different discrete wavelengths) and multivariate (over different spectral ranges) calibration strategies. The best results, using a PLS calibration model in the spectral range from 292.9 to 294.5 nm (related to Mn emission peaks), had relative errors of prediction of the Mn concentrations, for samples not employed in the calibration, from 0.3 to 7.3%, which are similar to or better than those obtained for Mn determination in steel using higher cost detection systems. The successful analytical application of the new detection system demonstrated that the performance of low cost detection systems can be very good for specific applications and that its low resolution and sensitivity can be at least partially compensated by the use of chemometrics and the integration of analysis pulses.     

Polarized gating assisted generation of the ultrashort extreme-ultraviolet sources

High-order harmonic emission and attosecond extreme-ultraviolet pulse generation have been theoretically investigated by controlling the two-color polarized laser field. The results show that when the polarized angle between the two pulses is arranged at \(\uptheta =0.2\uppi \) , not only the harmonic cutoff is extended, but also the modulation on the harmonic spectrum is decreased. Further, by optimizing the laser parameters, a supercontinuum with the 270 eV bandwidth can be obtained, which results in a series of isolated 38 as pulses. Finally, by investigating the pulse duration effect on the harmonic emission, we find that this two-color polarized gating scheme can also be achieved by the multi-cycle pulse region, which is much better for experimental realization.     

Simultaneous Determination of Trans-Cinnamaldehyde and Benzaldehyde in Different Real Samples by Differential Pulse Polarography and Study of Heat Stability of Trans-Cinnamaldehyde

Abstract

A simple, sensitive, and accurate differential pulse polarography method for simultaneous determination of trans-cinnamaldehyde and benzaldehyde in food and drug samples were developed. DC polarography, CV, and coulometric techniques were used for investigation the electrochemical behavior of both compounds. In phosphate buffer (pH = 8.2) and 10% v/v of methanol the differential pulse voltammograms of trans-cinnamaldehyde (?1.05 V) and benzaldehyde (?1.31 V) display reproducible peaks. Under these conditions a strict linearity between both analyte concentrations and their peaks height were observed. The detection limits were calculated to be 2.5 × 10^?8 and 1.2 × 10^?8 M for trans-cinnamaldehyde and benzaldehyde in pH = 8.2, respectively. The relative standard deviations for 1.0 × 10^?6 M of both analytes were 2.04 and 1.18. The heat stability of trans-cinnamaldehyde was studied, and it was found that trans-cinnamaldehyde undergoes a heat-induced decomposition at low temperature (>70°C) to produce benzaldehyde.     

Controlling the dissociative ionization of ethanol with 800 and 400 nm two-color femtosecond laser pulses

Ethanol molecules were irradiated with a pair of temporally overlapping ultrashort intense laser pulses (10(13)-10(14) Wcm(2)) with different colors of 400 and 800 nm, and the dissociative ionization processes have been investigated. The yield ratio of the C-O bond breaking with respect to the C-C bond breaking was varied in the range of 0.17-0.53 sensitively depending on the delay time between the two laser pulses, and the absolute value of the yield of the C-O bond breaking was found to be increased largely when the Fourier-transform limited 800 nm laser pulse overlaps the stretched 400 nm laser pulse, demonstrating an advantage of the two-color intense laser fields in controlling chemical bond breaking processes.     

Enhanced laser-induced breakdown spectroscopy using the combination of fourth-harmonic and fundamental Nd:YAG laser pulses

We have studied the combination of fourth-harmonic (266 nm) and fundamental (1064 nm) Nd:YAG laser pulses of the same irradiance. On a metallic target (Al), a sequence of ultraviolet (UV) and near-infrared (NIR) pulses produces deeper craters and can lead under certain conditions to analyte signal enhancements larger than those obtained with a NIR–NIR sequence. Compared to a single NIR pulse, signal enhancements by factors of approximately 30 for the Si I 288.16-nm line and 100 for the Al II 281.62-nm line were observed with double pulses of the same total energy. This effect correlates with a substantial increase in plasma temperature, with ionic lines and lines having a higher excitation energy experiencing a larger enhancement. Moreover, the optimal pulse separation is found to be larger for ionic than for neutral lines (∼3 compared to ∼0.1 μs). Another finding of this study concerns the combination of two different wavelengths (266 and 1064 nm) in a single ‘mixed-wavelength’ pulse, a scheme that also leads to an enhanced laser-induced breakdown spectroscopy (LIBS) sensitivity. It is proposed that the double-pulse and mixed-wavelength approaches are both capable of temperature and signal enhancement for the same reason: a larger portion of laser energy is absorbed in the plasma region containing the analyte atoms, instead of being absorbed at the sample surface or in the atmosphere.     

Matrix‐assisted laser desorption/ionization by using femtosecond laser pulses in the near‐infrared wavelength regime

We observe a substantial matrix‐assisted laser desorption/ionization (MALDI) signal when irradiating femtosecond laser pulses in the near‐infrared spectral range centered around 800 nm and using standard MALDI matrices with absorption bands in the ultraviolet (UV) regime. The laser pulse energy dependence of this novel phenomenon is investigated in comparison with MALDI with near‐UV laser pulses. Our observations show that multiphoton absorption/ionization could be a major issue among the MALDI processes when the sample is irradiated with ultra‐short laser pulses. Copyright © 2009 John Wiley & Sons, Ltd.