Laser ablation ICP spectrometry

• Main Author: Jansen, Andrew
• Published: Sheffield Hallam University 1998
• Subjects: 667.9; Coating depth measurement
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.245345

This thesis reports investigations into laser ablation inductively coupled plasma emission spectrometry for rapid elemental analysis of a diverse range of samples: glasses, aqueous solutions, oils, coated steels and glasses, and biological samples. Bulk analysis of glasses for major, minor and trace elements is reported. Results showed that element emission responses are dependent upon laser operating conditions. With optimised operating conditions of a Q switched laser operating at 60 J for 5 s ablation time with the laser defocused by 5 mm above the sample surface. The limits of detection are in the sub ug g -1 level with precision ranging from 6.6 %RSD for a non volatile element such as boron to 23 %RSD for a volatile element silver. Although the principal aim of using aqueous multielement solutions as novel calibration standards for quantitative analysis of other liquids was not achieved, optimised laser operating parameters needed for microsampling of aqueous solutions and analytical performance data were obtained. The optimum laser operating conditions for a 20 ul sample were found to be the same as for glasses and were as follows: a Q switched laser operating at 60 J for a 5 s ablation time with the laser defocused by 5 mm above the sample surface. Transport efficiencies of approximately 30 % can be achieved, compared to < 1% by pneumatic nebulisation. Also there was no differential loss of elements by laser ablation which may occur with electrothermal vaporisation. Limits of detection were found to be in the sub ug ml -1 level. Precisions were typically between 6.6 and 12 %RSD. The main cause for lack of precision was spattering of the sample. Microsampling of oils by laser ablation proved to be an effective and accurate technique for rapid determination of element concentration without the need for sample filtration or digestion. Precision proved to be better than for aqueous solutions, typically from 3 to 7 %RSD, because of a reduction in spattering. The same optimum laser operating conditions used for aqueous solutions were identical for oils. This thesis reports the first experiments to fully utilise laser ablation as a routine method for quantitative measurement of coating depth for coated steels and glasses. It was found that the peak width at half the maximum height was proportional to the coating thickness (over a range of 1 to 10 um). With optimised laser operating conditions a depth resolution of less than 1 um was achieved. The optimum laser operating conditions were as follows: a Q switched laser ran continuously with a laser lamp energy of 60 J at 10 Hz pulse repetition rate. Finally experiments show the great potential for the use of laser ablation as a microsampling technique for microtome tissue samples. Micro depth analysis of nickel distribution in skin shows that the technique could differentiate between two skin samples with different nickel concentrations. The use of gel multielement standards as a novel calibration technique for analysis of microtome tissue samples has also been demonstrated. Optimum laser operating condition were to use a moderate laser energy of 750 V with the laser defocused 5 mm above the sample surface.