Combining Measurement Methods The Benefit of Fast Analytical Instruments

Transcription

1 Combining Measurement Methods The Benefit of Fast Analytical Instruments Jana Bergholtz, Daniel Goran, Stephan Boehm, René Chemnitzer Bruker Nano GmbH, Berlin, Webinar, October 25 th, 2012 Innovation with Integrity

2 Speakers Dr. Jana Bergholtz Application Scientist EDS Bruker Nano GmbH Stephan Boehm Project Manager Micro-CT for SEM Bruker Nano GmbH Dr. Daniel Goran Product Manager EBSD Bruker Nano GmbH Dr. René Chemnitzer Application Scientist ICP-MS Bruker Daltonik GmbH 25/10/2012 2

3 Let s Imagine the Following Scenario EDS Solar nebula Lab Manager Customer brings you meteorite samples to analyze Impact plume 25/10/2012 3

4 Focus of this Webinar Advantages and limitations of some typical analytical instruments (Micro-CT, µ-xrf, EDS, EBSD, LA-ICP-MS) In which situations does it make sense to combine different methods? EDS How far can you take it? (high-speed µ-xrf and EDS, chemical information in 3D!) 25/10/2012 4

5 Instruments/Methods 3D Structural Information SkyScan 1173 Micro-CT kv microfocus X-ray source 3D spatial resolution: 4 8 µm Object sizes: up to 140 mm Ø, 200 mm in length Micro-CT for SEM Uses SEM e- beam to generate X-rays 3D spatial resolution: nm Object sizes: mm Ø, 10 mm in length 25/10/2012 5

6 Instruments/Methods Chemical Information M4 Tornado (µ-xrf) Uses X-ray source to generate X-rays Spatial resolution: 25 µm XFlash detector (EDS) Uses SEM e-beam to generate X-rays Spatial resolution: 20 nm 0.8 µm Advanced silicon drift detector technology for fast element mappings and analyses On- and offline data mining with powerful software tools such as HyperMap 25/10/2012 6

7 Instruments/Methods Chemical and Crystallographic Information XFlash detector (EDS) Uses SEM e-beam to generate X-rays Spatial resolution: 20 nm 0.8 µm e - Flash detector (EBSD) Scattered electrons (Kichuchi bands) hit phosphor screen and are imaged by a fast CCD camera Simultaneous acquisition of EDS and EBSD provides the basis for advanced phase identification 25/10/2012 7

8 Instruments/Methods Chemical and Crystallographic Information XFlash detector (EDS) Uses SEM e-beam to generate X-rays Spatial resolution: 20 nm 0.8 µm e - Flash detector (EBSD) Scattered electrons (Kichuchi bands) hit phosphor screen and are imaged by a fast CCD camera Simultaneous acquisition of EDS and EBSD provides the basis for advanced phase identification 25/10/2012 8

9 Instruments/Methods Chemical and Isotopic Information Laser Ablation- EDS Uses a focused laser beam to ablate material Spatial resolution: typical crater sizes µm in diameter ICP-MS Inductively coupled plasma used to ionize the sample Mass spectrometer gives very high sensitivity and quasisimultaneous analysis of elements/isotopes of interest 25/10/2012 9

10 Back to the Meteorite Sample Analytical Questions What would we like to see? Round objects: Abundance? Sizes? Shapes? What are they made of? Do they all have the same chemical composition? Do we find any evidence that tells us how they were formed? What does the material in between the round objects (matrix) look like? Micro-CT µ-xrf, EDS EBSD, LA-ICP-MS Micro-CT for SEM Meteorite sample 25/10/

11 X-ray Computed Tomography (CT) 3D Structural Information Stephan Boehm Project Manager Micro-CT for SEM

12 X-ray Computed Tomography (CT) Working Principle X-ray Microfocus Computed Tomography (Micro-CT) Non-destructive experimental technique Shows the 3D internal microstructure Micrometer accuracy Object rotates between static X-ray source and detector 25/10/

13 X-ray Computed Tomography (CT) Abundance/Sizes of the Round Objects Measurement conditions: 130 kv, 60 µa 180 CT-Scan, approx. 8h Resolution: 13 µm High absorption material, difficult reconstruction Meteorite sample SkyScan 1173 Micro-CT 25/10/

14 X-ray Computed Tomography (CT) Abundance/Sizes of the Round Objects Measurement conditions: 130 kv, 60 µa 180 CT-Scan, approx. 8h Resolution: 13 µm High absorption material, difficult reconstruction Results: Round particles are there (dense) Between round objects: less dense material Data set can be used for shape analysis Meteorite sample, 3D reconstruction with amira 25/10/

15 µ-xrf and EDS 2D (and 3D) Chemical Information Dr. Jana Bergholtz Application Scientist EDS

16 Micro X-Ray Fluorescence (µ-xrf) Chemical Information µ-xrf with optics conventional XRF µm spot Element distribution analysis in a heterogeneous sample mm analysis area homogeneous material 25/10/

17 Micro X-Ray Fluorescence (µ-xrf) Chemical Information µ-xrf with optics µm spot Element distribution analysis in a heterogeneous sample M4 TORNADO Advanced silicon drift (and dual) detector technology Hybrid signal processing: high pulse throughput (up to 500 kcps) TurboSpeed stage on the fly measurements Quick data handling 25/10/

18 Energy Dispersive Spectrometry (EDS) Chemical Information XFlash 6 detectors Advanced silicon drift (and multi-) detector technology Available with various active areas (10, 30, 60 and 100 mm²) and energy resolutions down to 121 ev for Mn Kα Largest solid angles and more efficient collection of X-rays through slim-line technology Hybrid signal processing for highest pulse throughput Quick online/offline data mining (e.g. HyperMap) XFlash 6 detector series Optimized detector to sample distance through slim-line technology 25/10/

19 EDS vs. µ-xrf Advantages and Limitations XFlash detector (EDS on SEM) M4 Tornado (µ-xrf) Excitation by electrons X-rays Elements Be Am Mg Am Spatial resolution 20 nm 0.8 µm 25 µm Typical scan area µm mosaic/tiling: up to 5 cm Sample preparation flat surface, good polish, carbon coat up to 20x15.5 cm flat surface 25/10/

20 EDS vs. µ-xrf Advantages and Limitations 25/10/

21 EDS vs. µ-xrf Advantages and Limitations 25/10/

22 EDS and µ-xrf Software HyperMap 25/10/

23 Micro X-Ray Fluorescence (µ-xrf) What are the round objects made of? Measurement conditions: 30 kv, 600 µa, ~150 kcps on Fe 931x806 pixel 80 min 25/10/

24 Micro X-Ray Fluorescence (µ-xrf) What are the round objects made of? Mass percent (%) Metal Particles: Different Fe/Ni ratios Different abundances of S-rich grains S Cr Fe Co Ni /10/

25 EDS vs. µ-xrf What are the round objects made of? EDS/SEM Measurement conditions: 20 kv, 30 na, ~300 kcps 800x600 pixel, 20 min 5 mm µ-xrf 5 mm 100 µm 25/10/

26 EDS vs. µ-xrf What are the round objects made of? EDS/SEM Metal Particles: Better spatial resolution: now we can analyze metal and sulfide grains separately 5 mm µ-xrf 5 mm 100 µm 25/10/

27 EDS vs. µ-xrf What are the round objects made of? EDS/SEM Metal Particles: Better spatial resolution: now we can analyze metal and sulfide grains separately 5 mm µ-xrf mm 100 µm 25/10/

28 EDS vs. µ-xrf What are the round objects made of? 5 mm EDS/SEM Silicate chondrules: Better spatial resolution: now we can resolve the structures µ-xrf 5 mm 100 µm 25/10/

29 EDS vs. µ-xrf What are the round objects made of? 5 mm EDS/SEM Silicate chondrules: Better spatial resolution: now we can resolve the structures and quantify different phases µ-xrf 5 mm 100 µm 25/10/

30 EDS vs. µ-xrf What are the round objects made of? 5 mm EDS/SEM Silicate chondrules: Better spatial resolution: now we can resolve the structures and quantify different phases µ-xrf 5 mm 100 µm 25/10/

31 Quick Review Combining the Results of Micro-CT, µ-xrf and EDS Combining the results CT scan, 8 hours: Abundance, sizes and shapes of round objects µ-xrf mapping, 80 min: Round objects are mostly metal particles consisting of Fe, Ni and S (but also silicate spherules = chondrules) Metal particles show different Fe/Ni ratios and different abundance of sulfides EDS mapping, 20 min: Analyze metal and sulfides separately Resolve different phases within silicate chondrules 25/10/

32 Limitations of Combining Micro-CT Data with 2D µ-xrf and 2D EDS Are 2D data representative for the 3D sample? Are we missing out on important information (i.e. particles with a certain composition may have a specific size or shape)? 25/10/

33 Chemical Data in 3D? Sure if we are allowed to destroy your sample Isn t it possible to obtain chemical information in 3D? 25/10/

34 Chemical Data in 3D? Sure if we are allowed to destroy your sample Isn t it possible to obtain chemical information in 3D? Absorption of X-rays already presents a challenge for quantitative EDS analysis when using samples with a rough surface This explains why you cannot do chemical analysis in 3D without removing layers from your sample 25/10/

35 Chemical Data in 3D? Sure if we are allowed to destroy your sample Isn t it possible to obtain chemical information in 3D? 25/10/

36 Chemical Data in 3D? Sure if we are allowed to destroy your sample Isn t it possible to obtain chemical information in 3D? Sample digitalization Mapping collected on each layer For each layer: HyperMap database We transform the sample into a data matrix. 25/10/

37 Chemical Data in 3D 3D µ-xrf and 3D EDS Gujba sample was embedded in epoxy together with two Aluminum wegdes (to determine the sectioning depth) Specific grinding/polishing protocols for the different sectioning steps µ-xrf (Volume 1) µ-xrf (Volume 2) EDS Volume ~2200 mm mm mm 3 Number of layers Sectioning depth 148 µm 48 µm 4 µm Total depth 5.18 mm 1.78 mm 80 µm Time spent on grinding/polishing ~20 min ~15 min ~15 min 25/10/

38 Chemical Data in 3D 3D µ-xrf µ-xrf (Vol. 1) Volume ~2200 mm 3 Layers 36 Total depth 5.18 mm Voxel size 32x32x148 µm 2D resolution 931x806 pixel Instrument M4 Tornado HV 30 kv Beam current 600 µa ICR ~150 kcps on Fe 3D reconstruction with amira Aquisition time Total time 80 min ~60 h 25/10/

39 Chemical Data in 3D 3D µ-xrf µ-xrf (Vol. 2) Volume 41.5 mm 3 Layers 38 Total depth 1.78 mm Voxel size 6x6x48 µm 2D resolution 808x803 pixel Instrument M4 Tornado HV 30 kv Beam current 600 µa ICR ~150 kcps on Fe 3D reconstruction with amira Aquisition time Total time 60 min ~50 h 25/10/

40 Chemical Data in 3D 3D µ-xrf µ-xrf (Vol. 2) Volume 41.5 mm 3 Layers 38 Total depth 1.78 mm Voxel size 6x6x48 µm 2D resolution 808x803 pixel Instrument M4 Tornado HV 30 kv Beam current 600 µa ICR ~150 kcps on Fe Aquisition time 60 min Total time ~50 h 3D reconstruction with amira 25/10/

41 Chemical Data in 3D 3D µ-xrf and 3D EDS 5 mm 3D reconstruction with amira µ-xrf (Volume 1) µ-xrf (Volume 2) EDS Volume ~2200 mm mm mm 3 Number of layers Sectioning depth 148 µm 48 µm 4 µm Total depth 5.18 mm 1.78 mm 80 µm Time spent on grinding/polishing ~20 min ~15 min ~15 min 25/10/

42 Chemical Data in 3D 3D EDS EDS Volume 0.6 mm 3 Layers 21 Total depth 80 µm Voxel size 1.6x1.6x4 µm 2D resolution Instrument HV Beam current ICR Aquisition time Total time 2400x1200 pixel XFlash 6 60 EDS- SDD on a Hitachi SU 6600 FE-SEM 15 kv 5 na ~130 kcps on Fe 90 min ~40 h 3D reconstruction with amira 25/10/

43 Chemical Data in 3D 3D EDS 3D reconstruction with amira EDS Volume 0.6 mm 3 Layers 21 Total depth 80 µm Voxel size 1.6x1.6x4 µm 2D resolution Instrument HV Beam current ICR Aquisition time Total time 2400x1200 pixel XFlash 6 60 EDS- SDD on a Hitachi SU 6600 FE-SEM 15 kv 5 na ~130 kcps on Fe 90 min ~40 h 25/10/

44 Quick Review Combining 3D µ-xrf and 3D EDS Results 3D µ-xrf data cube, 60 hours, incl. sectioning: We get structural along with chemical information Metal particles show different Fe/Ni ratios and different abundances of sulfides Limitation: resolving the sizes and structures of sulfide grains 3D EDS data cube, 40 hours, incl. sectioning: Bowl-shaped structures of arcuate sulfides become visible Limitation: scan area Can we find any evidence that tells us how these different metal particles and sulfide structures were formed? 25/10/

45 EBSD Combined with EDS Crystallographic and Chemical Information Dr. Daniel Goran Product Manager EBSD

46 EBSD/EDS Integration Introduction EBSD/EDS integration e - Flash EBSD detectors XFlash EDS detectors Unique hardware design features allowing optimum signal at practically any WD Simultaneous data acquisition (EBSP and full spectrum) for up to 900 points/s Advanced phase ID, on-/offline (see previous webinar) Online/Offline automatic EDS assisted phase discrimination EBSD/EDS detector setup inside SEM chamber 25/10/

47 EBSD/EDS Integration Location of Measurement EDS/SEM 5 mm µ-xrf 100 µm 5 mm Simultaneous EBSD/EDS measurements 25/10/

48 EBSD/EDS Integration Phase ID and Distribution Analysis EBSD/EDS integration e - Flash HR and XFlash 6 30 Online phase identification Forsterite Mg 2 SiO 4 (SG:62) Simultaneous EBSD/EDS measurements at ~70 pps Raw phase map 25/10/

49 EBSD/EDS Integration Phase ID and Distribution Analysis EBSD/EDS integration e - Flash HR and XFlash 6 30 Online phase identification Forsterite Mg 2 SiO 4 (SG:62) Simultaneous EBSD/EDS measurements at ~70 pps Offline phase identification and ultrafast re-indexing for map completion Phase distribution analysis Ferrite (SG:229) Diopside (SG:15) Forsterite (SG:62) Orthopyroxene (SG:61) Troilite 2H (SG:190) Final phase map 25/10/

50 Offline Data Processing Data Interpretation EBSD data interpretation e - Flash HR and XFlash 6 30 Online phase identification Forsterite Mg 2 SiO 4 (SG:62) Simultaneous EBSD/EDS measurements at ~70 pps Offline phase identification and ultrafast re-indexing for map completion Study the deformation state Orientation distribution map (IPFz) 25/10/

51 Offline Data Processing Location of Measurement 5 mm Simultaneous EBSD/EDS measurements 25/10/

52 Offline Data Processing Deformation State Analysis EBSD data interpretation Study the deformation state Correlated misorientation angle distribution histogram Grain Orientation average misorientation distribution map map 25/10/

53 Offline Data Processing Grain Boundary Analysis EBSD data interpretation Study the deformation state Grain boundary analysis Boundaries <15 deg. Boundaries >15 deg. Grain boundaries map 25/10/

54 Offline Data Processing Grain Size Analysis EBSD data interpretation Study the deformation state Grain boundary analysis Grain size analysis ~32000 grains average equivalent diameter area weighted statistics Grains map (grains in random colors) 25/10/

55 Laser Ablation-ICP-MS Chemical and Isotopic Information Dr. René Chemnitzer Application Scientist ICP-MS

56 Laser Ablation-ICP-MS Chemical and Isotopic Information Laser Ablation- EDS Uses a focused laser beam to ablate material Spatial resolution: typical crater sizes µm in diameter Object sizes: different ablation cells available ICP-MS Inductively coupled plasma used to ionize the sample completely Quasi-simultaneous analysis of elements/isotopes of interest mass spectrometer gives very high sensitivity and large dynamic range 25/10/

57 Laser Ablation-ICP-MS Chemical and Isotopic Information Laser 193 nm ArF Excimer Laser Geolas Pro ICP-MS Bruker aurora M90 ICP-MS Efficient Plasma complete decomposition of particles through interlaced coils Sensitivity, trace elements in limited amount of sample 90 ion mirror optic Fast Scanning speed 0.2 ms dwell time Isotopic information used e.g. for age determination 25/10/

58 LA-ICP-MS vs. µ-xrf and EDS Advantages and Limitations ICP-MS Mass range m/z Isotopic information High sensitivity even for light elements Detection limits in the low ppm range No simultaneuos detection of all elements Number of elements/isotopes per laser shot is limited 25/10/

59 Results LA-ICP-MS, SEM and EDS 1000 µm 25/10/

60 Results LA-ICP-MS, SEM and EDS 25/10/

61 Results LA-ICP-MS, SEM and EDS Different particles show same elemental composition Except 3C and 3D: high Cr, much less Co and Ni (not shown, 2 3% instead of 6.5%) 4A and 4B less Cr 4C and 5 equal Cr and Co conc. 4C higher Cu Wt% 25/10/

62 Results LA-ICP-MS, SEM and EDS 193 nm Excimer Laser Geolas Pro Spotsize: µm 100 pulses with 25 ns duration Energy density: 5 J/cm 2, frequency: 10 Hz 100 µm CI 25/10/

63 Quick Review EBSD and LA-ICP-MS Results EBSD: Metal particles are fine-grained Metal shows evidence for shock deformation and subsequent annealing LA-ICP-MS: Metal particles show solar composition when sulfides are included Remaining question: What about the material in between the big round metal particles? What is that made of? 25/10/

64 Micro-CT for SEM Combined with EDS Structural and Chemical Information Stephan Boehm Project Manager Micro-CT for SEM

65 Micro-CT for SEM SEM Topology and chemical composition of surface layers X-ray CT internal microstructure of the sample 25/10/

66 Micro-CT for SEM Advantages and Limitations Benefits Nanotomography (700 nm resolution, pixel sizes from 8 µm down to 350 nm) for a relatively low price Implementable on most types of SEMs Full software package for reconstruction, viewing and analysis Easy to mount, only one flange on specimen chamber and two USB ports on PC needed 25/10/

67 Micro-CT for SEM Advantages and Limitations Disadvantages SEM CT add-on is limited to low Z materials, because the maximum electron energy and thus the maximum energy of the X-rays that can be generated is 30 kev in most SEMs Limited to relatively small samples ( mm in diameter, max. 10 mm height) System performance is depended on the SEM type/model required e-beam current: typically more than 100 na 25/10/

68 Micro-CT for SEM Working Principle 1. Objective lens 2. Electron beam 3. Target 4. X-ray beam 5. Object 6. 2D X-ray detector Prepared lamella of Gujba sample with sample holder 25/10/

69 Micro-CT for SEM Combined with EDS Structural and Chemical Information Piece of meteorite Lamella (2x2x5 mm³) from Gujba meteorite sample prepared for investigation with Micro-CT for SEM to show the three-dimensional internal microstructure. 25/10/

70 Micro-CT for SEM Combined with EDS Structural and Chemical Information Volume rendered 3D model of the Gujba lamella 3D reconstruction with amira 25/10/

71 Micro-CT for SEM Combined with EDS Structural and Chemical Information Micro-CT for SEM Brass target, 30 kv, 600 na 180 CT-scan, approx. 11 h Resolution: 1.7 µa EDS Excitation voltage: 20 kv Map size: 800x600 pixel / 998x749 µm Pixel size: 1.2 µm Measurement time: 42 min Input count rate: ~ 40 kcps 25/10/

72 Summary Solar nebula EDS Now we understand, why the scientists are debating so much about the thermal history of the Gujba meteorite! Impact plume 25/10/

73 Summary If you want to get the most out of your sample, you cannot just rely on one single method you need to combine different analytical methods At Bruker, we are developing our instruments and software having in mind that: you want your analyses done quickly you want to combine different methods for your analytical task We work closely with you and help you developing innovative analytical answers to new analytical challenges 25/10/

74 Copyright 2012 Bruker Corporation. All rights reserved. Innovation with Integrity