Advanced Analytical Techniques in Chemical and Materials Engineering Research

1. Analysis in ProcESS Xuan Wang Department of Chemical Engineering Department of Metallurgy and Materials Engineering 23/01/2013

2. Table of content • Introduction • ICP-MS • Introduction • Principles • Influence • Sample preparation • AAS • FT-IR • PerkinElmer GC lab • Mercury Analyzer • Contact Angle Analyzer

3. Introduction • ProcESS --- Process Engineering for Sustainable Systems • Research focuses on: • Process intensification • Solid waste treatment • Surface and interphase analysis • Advanced separation processes using membrane technology • Various analytical equipments: • ICP-MS, AAS, FT-IR, GC, Mercury Analyzer, Contact Angle Analyzer…

4. ICP-MS • Inductively Coupled Plasma • Mass Spectrometry • Producer: Thermo Scientific • Type: X series • Contact: Michèle Vanroelen • (michele.vanroelen@cit.kuleuven.be) • Advantages: • Quantitative and semi-quantitative analysis • Detection limits at or below ppt level for much of the periodic table • 8 orders of magnitude analytical range • High productivity • Isotopic analysis

5. (PerkinElmer) Remark: Method Detection Limit (MDL) is generally 2-10 times more than Instrumental Detection Limit (IDL) PerkinElmer, Inc

6. Principles • Ionization of atoms • At certain time, only ions with one • certain mass-to-charge ratio can • pass through and be detected. (PerkinElmer) mass spectrometer RF Load Coils ICP Torch Argon Plasma Cones Solid Atoms Schematic representation of a quadrupole ICP- MS Ions Aerosol Gas

7. Influence Residual signal (rlative to the signal in 0.14 M HNO3) for several elements present in 0.5 M H2SO4 matrix as a function of the mass number of the nuclide. (Vanhaecke F., Vanhoe H., Dams R., Vandecasteele C. , Talanta, 1992, 39) Matrix effects: signal suppression or enhancement caused by overloading of plasma, cooling effects, changes of ionization, blockage of cones, change of ion sampling, etc. Remedy: internal standard (Be, Ga, In, Tl).

8. Influence • Use of HNO3 • Select isotopes (65Cu instead of 63Cu (ArNa+)) • Mathematical correction • Modify sample preparation (USGS) Spectral interferences: interferences between ions with similar atomic mass. Remedy:

9. Influence Partially blocked orifice (Kym Jarvis. Presentation for Nuclear Spectrometry Users Forum, May 2005) Cone blockage The small orifice (~ 1mm) on the cones can be blocked if too much total dissolved solids (TDS) in the solution. This can cause decreased sensitivity and detection capability Remedy: diluted feeding solution (TDS no more than 0.2%)

10. Sample preparation Preparation • Sample digestion • Three acids digestion • Microwave digestion • Lithium metaborate fusion digestion • Sample dilution • Standard preparation

11. Sample digestion Caution: highly corrosive acids applied and protection needed • Three acids digestion • 0.1 g finely ground sample added in Teflon beaker with heating on the bottom and lid on the top • Three acids: • HNO3: oxidation, dissolving oxides and hydroxides • HClO4: oxidation, dissolving organics • HF: dissolving silicate are added, 5 ml each, by sequential order until the previous one boiled down. • If the sample is not completely dissolved, more cycles of the process (without HClO4) are needed until the complete dissolution of sample.

12. Sample digestion • Micro wave digestion: • Acid digestion carried out in microwave transparent inert material vessels, where pressure is introduced • High temperature (260-300 °C) • High digestion quality • Reduced acid consumption • Reduced digestion time (20-60 minutes)

13. Sample digestion • Lithium metaborate fusion digestion: • Thoroughly mix 0.1 g finely ground sample with 1.0 g of lithium metaborate (LiBO2) • Put the mixture in a graphite crucible and insert crucible into an oven at 1000 °C for 15 minutes • Pour the melt mixture into 100 ml 5 vol% nitric acid solution • Stir at least 15 minutes until all solid dissolved then filtrate the solution for dilution and measurement

14. Sample preparation • Sample dilution: • The digested solution normally need to be dilute • Concentration not larger than 1000 ppb • Concentration not lower than detection limit • Normally 2 vol% HNO3 is added • Standard preparation: • Chose concentration of elements according the element concentration in diluted sample • Addition of internal standards (e.g. Be, Ga, In and Tl) • 3 or 5 calibration points, including one blank

15. AAS Principle: absorption of EM-radiation characteristic for electron transition in the outer shell of an atom of an element. (http://web.vscht.cz/poustkaj) Atomic Absorption Spectroscopy

16. AAS • Measurement of almost all metals, metalloids and some non-metals (B, Si, P) • Sample: • Solution in diluted acids • Diluted biological fluids • Suspensions of solid samples (slurries) • Flame AAS (in CIT): measurement of higher concentration (10-100 ppm) – high temperature flame (N2O) • Measurement time 3-10 seconds • Contact: Michèle Vanroelen (michele.vanroelen@cit.kuleuven.be)

17. FT-IR Principle: absorption of IR-radiation results in changes of vibrational energy of molecules. (Thermo Nicolet, co.) Fourier Transform InfraRed (with diamond ATR)

18. FT-IR Contact: Christine Wouters(christine.wouters@cit.kuleuven.be ) Identification of unknown pure (organic) compounds Identification of functional groups Sample: liquid, solid (in solution), solid. Fast measurement, in a matter of seconds Less suited for quantitative analysis, detection limits around 2 %

19. PerkinElmer GC lab • GC-MS • GasChromatographMass Spectrometry • Analysis of PCBs, phenols, trizaines, organophosphorus • and organochlorine pesticides, PAHs, mono-aromatic • hydrocarbons. • GC-FID/ECD • GasChromatographFlame Ionization Detector • and Electron Capture Detector • Analysis of PCBs, phenols, organochlorine pesticides, • mono-aromatic hydrocarbons, aspecific solvents, • mineral oil, volatile organic acids.

20. PerkinElmer GC lab • GC-FID • GasChromatographFlame Ionization Detector • Analysis of phenols, mono-aromatic hydrocarbons, • aspecific solvents, mineral oil, volatile organic acids. • GC-FID/NPD • GasChromatographFlame Ionization Detector and • Nitrogen Phosphorus Detector • Analysis of phenols, triazines, organophosphorus • pesticides, mono-aromatic hydrocarbons, aspecific • solvents, mineral oil, volatile organic acids. Contact: Christine Wouters (christine.wouters@cit.kuleuven.be )

21. Mercury analyzer • Design for all types of sample: • Environmental samples • (water, soil, plants, etc) • -Human samples • (hair, blood, urine, etc) • Vapour generation technique • (remove most chemical interferences) • Atomic fluorescence spectrometry • (mercury analysis down to ppt level) • Contact: Tom Van Gerven • (thomas.vangerven@cit.kuleuven.be ) (not operational yet by the moment, part of RARE3 project)

22. Contact Angle Analyzer KRÜSS Dsa10-MK2 Contact: Bart Van der Bruggen (bart.vanderbruggen@cit.kuleuven.be )

23. Contact • ICP-MS • AAS • FT-IR • PerkinElmer GC lab • Mercury Analyzer • Contact Angle Analyzer Michèle Vanroelen (michele.vanroelen@cit.kuleuven.be) Christine Wouters (christine.wouters@cit.kuleuven.be ) Tom Van Gerven (thomas.vangerven@cit.kuleuven.be ) Bart Van der Bruggen (bart.vanderbruggen@cit.kuleuven.be )

24. Many thanks!