Analysis of High Purity Zinc by Glow Discharge

Analysis of High Purity Zinc by Glow Discharge Mass Spectrometry for Use in Thermometry T. Gusarova, B. Lange, H. Kipphardt, R. Matschat and U. Panne Federal Institute for Materials Research and Testing (BAM) Working Group “Primary Calibration Materials; Trace Analysis” Physikalisch. Technische Bundesanstalt Federal Institute for Materials Research and Testing BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Content PTB + BAM co-operation work GD-MS: basic principles, advantages and limitations Calibration with pellets (sample preparation) Calibration with Zinc Certified Reference Materials Pure zinc samples, used in thermometry Conclusions Prospects BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Co-operation work Temperature PTB and BAM: joint development of a basis for creation of fix points based on certified pure materials taking into account national and international regulations estimating corresponding uncertainty Solid state Ultra-high purity materials Trace element mass fraction Multielement ultra-trace determination (μg/kg, ng/kg) Method traceable to SI – precondition for certification of RM BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Glow Discharge Mass Spectrometry (GD-MS) Multielement Solid sampling No sample preparation No losses of analytes No chemical contamination of the sample Less time is needed Decreased non-spectral Interferences (compared to ICP-MS) BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Main advantages of Finnigan ELEMENT GD (Thermo Fisher Scientific) Magnet ESA Faraday SEM Cup Detection System Ion Transfer Optics GD Ion Source (with Sample Holder) Grimm-type ion source High sputter rate, short analysis time High sample throughput (6 Samples per hour) More than 12 orders of BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Quantification with Element GD Quantitative Semiquantitative Traceable to SI IBR Standard RSF Indirect Direct Calibration with RM Calibration with doped pellets BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Preparation of Zn Pellets by wet doping Doping Mixing 52 elements shaking in 3 dimensions of space 1% HNO 3 Pressing ~ 1 g of the powder in pellets into a sample steel ring under 90 k. N/cm 2 Sample diameter ≈ 12 mm Thickness ≈ 2 mm BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne Analysing EUROMET-732 23 -24 November 2006

Observation of intensity-time behaviour of different elements Doped with powders: grain size between 3 and 900 μm 123 Sb 70 μm 10 ppm 58 Ni 3 -7 μm 1 ppm 56 Fe > 840 μm 50 ppm Doped with liquids Pre-sputter time 5 ppm matrix 5 ppm Measurement time 114 Cd 64 Zn 24 Mg Pre-sputter time Measurement time BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Analysing data Mass fractions of trace elements in the pellets 10 mg/kg; 5 mg/kg; 1 mg/kg; 500 µg/kg; 100 µg/kg; 50 µg/kg; 10 µg/kg; 5 µg/kg; blank Zn powder 99, 999% pure <150 micron Parameters Voltage ~500 V Current 20 m. A Ar Gas Flow 375 ml/min Peltier Cooling 20 °C Low Resolution (LR) ≈ 400 Medium Resolution (MR) ≈ 4000 High Resolution (HR) ≈ 10000 BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Calibration with doped pellets BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Calibration with doped pellets BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Zn Certified Reference Materials Voltage Current Ar Gas Flow Peltier Cooling ~500 V 20 m. A 375 ml/min 20 °C Trace element mass fraction in mg/kg ± uncertainty mg/kg BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

CRMs measurements BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Procedure for samples analysis 1. 114 Cd Scanning (6 – 239 u) ↓ 112 Cd elements of interest 116 Cd 111 Cd 113 Cd 38 Ar 40 Ar 2. Pellet preparation 3. Compiling of measurement method and parameter optimisation 4. Calibration of Element GD with pellets 5. Sample measurements BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Comparison of materials for thermometric use PTB-Zn 1 and PTB-Zn 2 a can be easily distinguished. That might also be visible in the temperature measurements Limits of detection (6 s) for most of the elements are < 1 mg/kg (many of them go down to µg/kg level) These limits of detection could be in future improved with enhancement of the sensitivity of the method by special calibration of detection system and other measures. BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Analysis of In In-Sample in sample holder Light optical microscope image BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Enhancement of signal sensitivity of Glow Discharge Optical Emission Spectroscopy Titanium in pure copper Sample with a hole a. u. Flat sample mass fraction, mg/kg BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Conclusions Pellets doped with solutions can be successefully used for the calibration of GD-MS It is the most accurate calibration procedure to obtain small uncertainty (compared to factor 2 or even more uncertainty by use of RSF approach) In this way direct traceability of the measurement results to SI is achieved – this procedure is a precondition for the certification of reference materials (CRMs) with GD-MS CRMs of pure zinc were also measured. The measurement results were in good agreement with the calibration curves of Zn-pellets A procedure for the analysis of materials used for fix-point cells is being worked out Two samples of fix-point materials from different producers were compared First investigations with In samples were carried out Another analytical techniques such GD-OES will be improved and tried to be used for the analysis of the fix-point materials BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Prospects Preparation of doped In-pellets and calibration for In matrix Analysis of the material for fix-points-cells Graphite analysis Comparison of analyses with ICP-MS, -ICP-MS, GD-OES and GD-MS LA Determination of non-metallic elements (O, S…) Expansion of GD-MS to analysis of other materials BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006

Thank youfor your attention Thank you financial support … Dr. Fischer, J. Dr. Rudtsch, S. Fahr, M. Dr. Lange, B. Dr. Hodoroaba, V. -D. Dr. Kipphardt, H. … and help during investigations! BAM Division I. 1 Dr. Matschat, R. Richard-Willstaetter-Strasse 11 12489 Berlin, Germany Prof. Dr. Panne, U. Contact: tamara. gusarova@bam. de or heinrich. kipphardt@bam. de BAM I. 1 Inorganic Chemical Analysis; Reference Materials T. Gusarova, B. Lange, H. Kipphardt, R. Matschat, U. Panne EUROMET-732 23 -24 November 2006