Qualitative and Quantitative Chemical Investigation of Orthopedic Alloys by Combining Wet Digestion, Spectroanalytical Methods and Direct Solid Analysis

In this study, two laser-based techniques, laser-induced breakdown spectroscopy (LIBS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) were used for analytical signal evaluation of Ti, Al, and V and investigation of possible harmful elements eventually present as minor elements in Ti alloys. Due to the lack of certified reference materials, samples were also analyzed by wavelength dispersive X-ray fluorescence (WDXRF) and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted digestion. To maximize the efficiency of LIBS and LA-ICP-MS, operational conditions were adjusted aiming to find optimal analytical performance. LIBS showed several Ti emission lines and few signals for Al and V. LA-ICP-MS was able to detect all three major constituents. For quantitative analysis, the correlation of intensity signals from LIBS analysis with reference values obtained by ICP OES was not successful, showing that there are still difficulties for quantification using solid samples. Measurements using ICP OES showed that additionally to major constituents, only Fe was present in concentrations around 0.2%. Analysis by WDXRF confirmed the presence of Fe. Results using both methods, i.e., ICP OES and WDXRF, were in good agreement.

本研究采用两种基于激光的分析技术，即激光诱导击穿光谱（Laser-induced breakdown spectroscopy, LIBS）与激光剥蚀-电感耦合等离子体质谱法（Laser ablation-inductively coupled plasma-mass spectrometry, LA-ICP-MS），对钛（Ti）、铝（Al）、钒（V）的分析信号进行评估，并探究钛合金中可能以微量杂质形式存在的潜在有害元素。鉴于缺乏有证标准物质，本研究还采用波长色散X射线荧光光谱法（Wavelength dispersive X-ray fluorescence, WDXRF）以及经微波辅助消解后的电感耦合等离子体光发射光谱法（Inductively coupled plasma optical emission spectrometry, ICP OES）对样品开展分析。为最大化LIBS与LA-ICP-MS的分析效率，对其操作条件进行优化以获取最优的分析性能。LIBS可检测到多条钛的特征发射谱线，但仅能获取少量铝与钒的信号；而LA-ICP-MS则可同时检出三种主要组成元素。在定量分析方面，LIBS的强度信号与ICP OES得到的参考值未呈现良好相关性，这表明采用固体样品进行定量分析仍存在一定困难。ICP OES的检测结果显示，除三种主要组成元素外，仅铁（Fe）的浓度约为0.2%。WDXRF分析结果证实了铁元素的存在。ICP OES与WDXRF两种方法的检测结果具有良好的一致性。