RESUMEN
In the last few years, LIBS has become an established technique for the assessment of elemental concentrations in various sample types. However, for many applications knowledge about the overall elemental composition is not sufficient. In addition, detailed information about the elemental distribution within a heterogeneous sample is needed. LIBS has become of great interest in elemental imaging studies, since this technique allows to associate the obtained elemental composition information with the spatial coordinates of the investigated sample. The possibility of simultaneous multi-elemental analysis of major, minor, and trace constituents in almost all types of solid materials with no or negligible sample preparation combined with a high speed of analysis are benefits which make LIBS especially attractive when compared to other elemental imaging techniques. The first part of this review is aimed at providing information about the instrumental requirements necessary for successful LIBS imaging measurements and points out and discusses state-of-the-art LIBS instrumentation and upcoming developments. The second part is dedicated to data processing and evaluation of LIBS imaging data. This chapter is focused on different approaches of multivariate data evaluation and chemometrics which can be used e.g. for classification but also for the quantification of obtained LIBS imaging data. In the final part, current literature of different LIBS imaging applications ranging from bioimaging, geoscientific and cultural heritage studies to the field of materials science is summarized and reviewed.
RESUMEN
The increased demand for high purity nanoparticles (NPs) of defined geometry necessitates the continuous development of generation routes. One of the most promising physical techniques for producing metal, semiconductor or alloy NPs in the gas phase is spark discharge NP generation. The technique has a great potential for up-scaling without altering the particles. Despite the simplicity of the setup, the formation of NPs in a spark discharge takes place via complex multi-scale processes, which greatly hinders the investigation via conventional NP measurement techniques. In the present work, time-resolved optical emission spectroscopy (OES) was used to provide information on the species present in the spark from as early as approximately 100 ns after the initiation of the discharge. We demonstrate that operando emission spectroscopy can deliver valuable insights into NP formation. The emission spectra of the spark are used to identify, among others, the main stages of material erosion and to calculate the quenching rate of the generated metal vapour. We demonstrate that the alteration of key control parameters, that are typically used to optimize NP generation, clearly affect the emission spectra. We report for Cu and Au NPs that the intensity of spectral lines emitted by metal atoms levels off when spark energy is increased above an energy threshold, suggesting that the maximum concentration of metal vapour produced in the generator is limited. This explains the size variation of the generated NPs. We report a strong correlation between the optical and particle emission of the spark discharge generator, which demonstrate the suitability of OES as a valuable characterization tool that will allow for the more deliberate optimization of spark-based NP generation.
RESUMEN
Multi-pulse laser-induced breakdown spectroscopy (LIBS) in the collinear pulse configuration with time-integrating detection was performed on metallic samples in ambient air in an effort to clarify the contributing processes responsible for the signal enhancement observed in comparison with single-pulse excitation. Complementary experiments were also carried out on another LIBS setup using detection by an imaging spectrograph with high time resolution. The effects of laser bursts consisting of up to seven ns-range pulses from Nd-doped solid-state lasers operating at their fundamental wavelength and separated by 8.5-50 micros time gaps was studied. The ablation and emission characteristics of the generated plasmas were investigated using light profilometry, microscopy, plasma imaging, emission distribution mapping, time-resolved line emission monitoring, and plasma temperature calculations. The experimental data suggest that the two contributing processes mainly responsible for the signal enhancement effect are the plume reheating caused by the sequential laser pulses and, more dominantly, the increased material ablation attributed to the lower breakdown threshold for the preheated (molten) sample surface and/or the reduced background gas pressure behind the shockwave of preceding pulses.
RESUMEN
This paper proposes a quick, novel method for tin determination in organotin chemicals by slurry nebulization inductively coupled plasma atomic emission (ICP-AES) spectrometry. The method was tested by the measurement of five organotin carboxylate complexes of known composition for obtaining simple stoichiometric data. The slurries were prepared by first dissolving the organotins in an adequate solvent (methanol, pyridine or acetone) well miscible with water and then adding this solution drop-by-drop to a 0.005% TX-100 tenzide solution while maintaining intensive mixing. Dynamic laser light scattering experiments showed that the average equivalent particle size in the resulting slurry was approximately 0.3 mum for all samples and solvents. Under suitable ICP-AES measuring conditions, the signal recoveries were found to be between 101.8 and 106.6%, which allowed direct nebulization and calibration against aqueous solutions. Typically, 70 mug l(-1) detection limit and 1-5% relative S.D. on five replicates can be achieved by the described method.
RESUMEN
Adsorption isotherms have been determined for the intercalation of cadmium ions (Cd2+) into layered hydrophobized montmorillonite (HDP-M) and calumit (DBS-C) sheets dispersed in ethanol (1)-cyclohexane (2) mixtures. The amount of Cd2+ adsorbed depended strongly on the composition of the binary liquid; at an ethanol mole fraction of 0.05 (x1 = 0.05), 95% of the added Cd2+ is located in the ethanolic nanoreactor at the HDP-M (or DBS-C) surface. CdS nanoparticles have been generated in situ in ethanolic nanoreactors at the HDP-M and DBS-C surfaces. Absorption spectrophotometric measurements provided information on the number of CdS nanoparticles formed and on their absorption edges, bandgaps, and mean diameters. Good correlations have been obtained between the adsorption isotherms and the size (and the amount) of the CdS formed. X-ray diffractometry established that CdS nanoparticles stretched the HDP-M and DBS-C lamellas unevenly upon intercalation. Copyright 1999 Academic Press.
RESUMEN
Adsorption isotherms have been determined for the binding of Cd2+ onto the surfaces of hydrophilic A200 SiO2 and hydrophobic R972 SiO2 particles dispersed in ethanol (1>)-cyclohexane (2) mixtures at ethanol mole fractions of x1 = 0.05, 0.10, 0.20, and 0.40. CdS nanoparticles have been generated in situ within the ethanolic nanoreactors at surfaces of SiO2 particles in the different ethanol-cyclohexane binary liquids by the addition of hydrogen sulfide. Absorption spectra of the CdS particles provided information on their quantity, absorption edges, optical band gaps, and mean diameters. Good correlations have been obtained between the adsorption isotherms and size of the CdS particles as well as between the adsorption isotherms and the amount of CdS formed. The smallest CdS particles (ca. 6 nm diameter) have been obtained on the surfaces of SiO2 particles dispersed in ethanol (1>)-cyclohexane (2) mixtures at ethanol mole fractions of x1 = 0.05. More CdS particles have been observed to coat the hydrophilic A200 SiO2 than the hydrophobic R972 particles. In the x1 = 0.10 ethanol (1)-cyclohexane (2) liquid mixtures up to 10% of the SiO2 surface can be covered by CdS nanoparticles. Immersion wetting enthalpy measurements in methanol established the surface of the SiO2 particles to be hydrophilic, which became partially hydrophobic upon and the binding of cadmium ions and hence upon the subsequent formation of CdS. Copyright 1997 Academic Press. Copyright 1997Academic Press