S. Michael Angel

Standoff Detection of High Explosive Materials at 50 Meters in Ambient Light Conditions Using a Small Raman Instrument

We have designed and demonstrated a standoff Raman system for detecting high explosive materials at distances up to 50 meters in ambient light conditions. In the system, light is collected using an 8-in. Schmidt–Cassegrain telescope fiber-coupled to an f/1.8 spectrograph with a gated intensified charge-coupled device (ICCD) detector. A frequency-doubled Nd: YAG (532 nm) pulsed (10 Hz) laser is used as the excitation source for measuring remote spectra of samples containing up to 8% explosive materials. The explosives RDX, TNT, and PETN as well as nitrate- and chlorate-containing materials were used to evaluate the performance of the system with samples placed at distances of 27 and 50 meters. Laser power studies were performed to determine the effects of laser heating and photodegradation on the samples. Raman signal levels were found to increase linearly with increasing laser energy up to ∼3 × 106 W/cm2 for all samples except TNT, which showed some evidence of photo- or thermal degradation at higher laser power densities. Detector gate width studies showed that Raman spectra could be acquired in high levels of ambient light using a 10 microsecond gate width.

Dual-Pulse LIBS Using a Pre-Ablation Spark for Enhanced Ablation and Emission

In this paper we report the first observations of dual-pulse laser-induced breakdown spectroscopy (LIBS) signal enhancements by using a pre-ablation spark. In this technique a laser pulse is brought in parallel to the sample surface and focused a few millimeters above it to form an air plasma or air spark. A few microseconds later a second laser pulse, which is focused on the sample, ablates sample material and forms the LIBS plasma from which analyte emission occurs. In this way, large LIBS signal enhancements, 11-to 33-fold, are observed for copper and lead, respectively, relative to the signal in the absence of the air spark. In all cases where enhanced LIBS signals are seen, greatly enhanced sample ablation also occurs.

Effect of Pulse Delay Time on a Pre-ablation Dual-Pulse LIBS Plasma

In this paper, we investigate the effect of dual-pulse timing on material ablation, plasma temperature, and plasma size for pre-ablation spark dual-pulse laser-induced breakdown spectroscopy (LIBS). Although the plasma temperature increases for dual-pulse excitation, the signal enhancement is most easily attributed to increased sample ablation. Plasma images show that the magnitude of the enhancement can be affected by the collection optic and by the collection geometry. Enhancements calculated using the total integrated intensity of the plasma are comparable to those measured using fiber-optic collection.

Dual-pulse laser-induced breakdown spectroscopy with combinations of femtosecond and nanosecond laser pulses

Nanosecond and femtosecond laser pulses were combined in an orthogonal preablation spark dual-pulse laser-induced breakdown spectroscopy (LIBS) configuration. Even without full optimization of interpulse alignment, ablation focus, large signal, signal-to-noise ratio, and signal-to-background ratio enhancements were observed for both copper and aluminum targets. Despite the preliminary nature of this study, these results have significant implications in the attempt to explain the sources of dual-pulse LIBS enhancements.

Multilayer sol/gel membranes for optical sensing applications: single layer pH and dual layer CO2 and NH3 sensors

Organo-silica sol-gel membranes have been prepared and demonstrated in a single layer format for pH measurement and multiple-layer format for both carbon dioxide and ammonia. The sensors are simple and versatile since the same chemistry and membranes are used for each sensor. The sensors use hydroxypyrenetrisulfonic acid (HPTS) as the indicator immobilized in a base-catalyzed sol-gel containing poly(dimethyl)siloxane, aminopropyltriethoxysilane (APTES) and tetraethylorthosilicate (TEOS). This indicator gel is over coated with a hydrophobic sol-gel to reduce cross reactivity to pH when either CO(2) or NH(3) are examined. The gels are very stable and the sensors retain response up to a 12-month period. Sensors can be stored in buffer or dry without loss of function and have response times to that are comparable to literature values.

Enhancement of Aluminum, Titanium, and Iron in Glass Using Pre-Ablation Spark Dual-Pulse LIBS

In this paper, we report the first enhanced emission for elements in a nonmetal or nonconducting matrix, glass, with the use of a pre-ablation spark. The glass samples used in this work are prototypes of samples used to immobilize inorganic waste at the Savannah River Site Vitrification Facility. We have found that using a pre-ablation spark results in larger signal enhancements, 11- to 20-fold for titanium, aluminum, and iron in glass compared to the metal under the same experimental conditions. We also demonstrate that this method is more sensitive than single-pulse LIBS experiments for the direct solid sampling of vitrified waste glass.

Energy Dependence of Emission Intensity and Temperature in a LIBS Plasma Using Femtosecond Excitation

In this paper, we investigate the effect of laser energy on laser-induced breakdown emission intensity and average temperature in a short-pulse plasma generated by using 140 fs laser excitation. Both line emission and continuum background intensity and plasma temperature decrease very rapidly after excitation compared to the more conventional nanosecond pulse excitation. Both emission intensity and plasma temperature increase with increasing laser energy. However, the intensity increase appears to be mostly related to the amount of material ablated. Also, nongated laser-induced breakdown spectroscopy (LIBS) is demonstrated using a high-pulse (1 kHz) pulse repetition rate.

Remote Pulsed Laser Raman Spectroscopy System for Mineral Analysis on Planetary Surfaces to 66 Meters

There is a need for an instrument that can be used for remote in situ identification of biogenic and a-biogenic minerals, various types of ices, and organic and inorganic materials on planetary surfaces. In this paper, we explore the use of remote pulsed laser Raman spectroscopy for mineral analysis at distances from 10 to 66 m on planetary surfaces. We have constructed a remote Raman system utilizing a small pulsed Nd:YAG laser and a 5-in. telescope coupled to a spectrograph with an optical fiber. The performance of our system is demonstrated by presenting spectra of benzene and marble (calcium carbonate) while varying the integration time (i.e., number of laser shots), as well as single laser shot spectra of marble while decreasing laser power. Finally, Raman spectra of representatives of several different mineral groups are presented, including hydrated substances, carbonates, silicates (e.g., olivine, pyroxene, feldspars, etc.), water, and ice.

Novel Probe for Laser-Induced Breakdown Spectroscopy and Raman Measurements Using an Imaging Optical Fiber

A fiber-optic probe designed for remote laser-induced breakdown spectroscopy (LIBS), Raman spectroscopy, and Raman imaging has been developed for the microanalysis of solid samples. The probe incorporates both single-strand optical fibers and an image guide and allows atomic emission and Raman analysis of any spot on a solid sample within a 5 mm diameter field of view. The real-time sample imaging aspects of the probe are demonstrated by measuring LIBS spectra from different regions of a granite sample and by measuring the Raman spectra of individual TiO2 and Sr(NO3)2 particles on a soil substrate. The ability to obtain remote Raman images of the TiO2 and Sr(NO3)2 particles on the soil substrate is also demonstrated. In this paper we discuss the design and implementation of the fiber-optic probe for obtaining LIBS spectra, Raman spectra, and Raman images.

Laser-induced breakdown spectroscopy of bulk aqueous solutions at oceanic pressures: evaluation of key measurement parameters.

The development of in situ chemical sensors is critical for present-day expeditionary oceanography and the new mode of ocean observing systems that we are entering. New sensors take a significant amount of time to develop; therefore, validation of techniques in the laboratory for use in the ocean environment is necessary. Laser-induced breakdown spectroscopy (LIBS) is a promising in situ technique for oceanography. Laboratory investigations on the feasibility of using LIBS to detect analytes in bulk liquids at oceanic pressures were carried out. LIBS was successfully used to detect dissolved Na, Mn, Ca, K, and Li at pressures up to 2.76 x 10(7) Pa. The effects of pressure, laser-pulse energy, interpulse delay, gate delay, temperature, and NaCl concentration on the LIBS signal were examined. An optimal range of laser-pulse energies was found to exist for analyte detection in bulk aqueous solutions at both low and high pressures. No pressure effect was seen on the emission intensity for Ca and Na, and an increase in emission intensity with increased pressure was seen for Mn. Using the dual-pulse technique for several analytes, a very short interpulse delay resulted in the greatest emission intensity. The presence of NaCl enhanced the emission intensity for Ca, but had no effect on peak intensity of Mn or K. Overall, increased pressure, the addition of NaCl to a solution, and temperature did not inhibit detection of analytes in solution and sometimes even enhanced the ability to detect the analytes. The results suggest that LIBS is a viable chemical sensing method for in situ analyte detection in high-pressure environments such as the deep ocean.