The Rigaku SAXS Solution Portfolio. Rigaku Innovative Technologies Inc. Paul Ulrich PENNARTZ

Transcription

1 The Rigaku SAXS Solution Portfolio Rigaku Innovative Technologies Inc. Paul Ulrich PENNARTZ

2 Scaling of SAXS/WAXS

3 Principle of SAXS X-ray Sample Beam Stop Scattering angle ( 2q = 0~10 deg. ) Important: Important:

4 Rigaku SAXS Portfolio * Ultima IV & SmartLab S-MAX 3000 NANOPIX NanoMAX & NanoMAX IQ

5 Ultima IV/SmartLab SAXS X-ray Sample

6 Application Tree Composit materials Polymers in Solution Metal powders, bulks Anisotropic Scatterers Nanoparticles in solution Isotropic Scatterers Cracks, pores etc. Bones, cotton, carbon composites Nanoparticles Surfaces Polymers Application Ultima IV & SmartLab SAXS

7 NANOPIX Nano Particle Inspection X-ray tool : NANOPIX

8 NANOPIX Concept "Easy operation for experts and non-expert" The analysis of the main use purpose and method in a small-angle scattering analysis. Small-angle scattering analysis apparatus that has greatly improved the usability of the main purpose SAXS application. Target Market Professional user and entry user. The entry user has a steep learning curve. Structure scientist interested in nano-scale materials (size distribution analysis, preferred orientation, shape crystallinity) General Features Material science applications, solution scattering including nanoparticle and polymers (fully cover all SAXS applications) Q min starting at about 0.02 nm -1 (very low-q measurement capability) The system is fully motorized and controlled by software. Sample-to-detector distance is easily changed by manual movement. Position of sample is measured and sent to PC.

9 Pinhole SAXS System X-ray Sample Beam Stop + Detector

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11 Application Tree Composit materials Polymers in Solution Metal powders, bulks Anisotropic Scatterers Nanoparticles in solution Isotropic Scatterers Cracks, pores etc. Bones, cotton, carbon composites Nanoparticles Surfaces Polymers Application NANOPIX

12 Sources X-ray generated Synchroton Lab Source Divergence Low, almost parallel Divergent in all directions Energy Adjustable in wide area Depending on target mostly Kα or Kα 1 Polarisation Intensity Yes, almost 100% within storage ring direction Very high photon/second/sterad/δe No, almost not polarized at all High 10 9 depending on source Pulsed source Yes, second pulses No, continuous emission Availability At research centers In your lab (typical basement)

13 Lab X-ray Sources by Rigaku Focal Spot Max. Power Anode Material MM003i 30 µm 30 W Cu, Mo, Ag MM µm 40 W Cu MM x 1000 µm 9000 W Cu, Cr, Fe, Co, Ni, Ag, Mo, Au, W MM µm 1200 W Cu, Mo, Cr FR-E 70 µm 2475 W Cu, Cr

14 2D Focusing Monochromators Synthetic Multilayers with Graded Index Kirkpatrick-Baez Scheme Cross-Coupled Side-by-side optical systems Confocal First reflection zone Second reflection zone Each mirror reflects one vector component independently Elliptical mirrors focus the beam and parabolic mirrors collimate the beam Large capture angle Symmetric magnification Compact Easy alignment

15 Detectors HyPix HyPix-6000 Direct photon counting Efficiency: >99% (Cu, Co) 100x100 mm 2 pixel size No point spread function Resolution = pixel size Zero background

16 Detectors Technology Rigaku HyPix-3000 Hybrid pixel array Rigaku HyPix-6000 Hybrid pixel array Size 38.5 x 77.5 mm 2 77 x 77.5 mm 2 Area 2,984 mm 2 5,968 mm 2 Pixel size 100 x 100 mm x 100 mm 2 Point spread function - - XRF suppression YES YES Energy discriminator Count rate (Local) 2 1 >1 Mcps >1 Mcps Background <0.1 cps <0.1 cps 0D mode YES YES 1D mode YES YES 2D mode YES YES

17 Rigaku's fundamental technologies Beam module Two-dimentional detector High perfomance pinhole slit (Optinal) Vaccum path and sample stage

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19 Beam module NANOPIX beam module X-ray source (selectable) MM007 (Standard) and FR-X (Optional) Multilayer mirror for Cu Newly desigend CMF

20 2 pinhole collimation Source Pinhole slit combination (selectable) 2 pinhole (high performance pinhole) and 3 pinhole (Pt pinhole) configurations are selectable, and no need to adjust the pinholes. CMF Detector Source CMF 1st slit 3 pinhole collimation 3rd (2nd) slit Beam stop Detector 1st slit 2nd slit Beam stop 3rd slit Pinhole slit coliation is fully motorized.

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22 Sample stage Vaccum path and sample stage Sample-to-detector distance is easilly changed Sample stage position is easilly changed sample stage

23 Sample stage Standard sample holder Kinematic base

24 System length The system performance is selectable 2.0 m 3.0 m

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27 Samples of applications SAXS studies of anisotropic sample - rat tail collagen 2D SAXS scattering patterns from rat tail collagen (left) and integrated 1D profile I vs Q(right). The Q min can reach to 0.05nm -1 and first peak corresponding to ~63nm can be clearly measured. If Q min is as large as 0.069nm -1 this first peak can t be clearly determined.

28 SAXS/WAXS in Biominerization Simultaneous SAXS and WAXS Studies of Bones Simultaneous 2D SAXS( left) and WAXS(right) patterns from bones

29 The following results are obtained by Dr. Cincia Gianini ICCS Bari/Italy

30 Research Theme: Bone XMI-LAB allows to collect scanning small and wide angle X-ray scattering (scanning SWAXS) Studies of healthy and pathologic human bone sections : dwarfism syndrome, coxarthrosis and Paget s disease. Inspection of the structural and morphological order of bone at the nanoscale Partner: RIZZOLI - BOLOGNA FR-E+ SuperBright Data are collected with a high brilliance synctrotron like microsource (FR-E+ SuperBrigth)coupled with a 3-pinhole SWAXS camera. Fiber-like hierachical materials (collagen cellulose) Typical outcome: a. CPL microscopy b. WAXS microscopy c. SAXS microscopy Map of mono-oriented interfibrillar aligned mineral nanocrystals Map of the collagen fiber by SAXS Microscopy

31 SAXS in Nanocomposites Simultaneous SAXS and WAXS Studies of Nanocomposites---SAXS Data The SAXS pattern of PP(left) and the plots of unwrapped azimuth angle in degree vs. Q (right). The SAXS data reveal that PP has an ordered structure with strong orientation. The sample - detector distance is 820mm

32 SAXS/WAXS in Nanocomposites Simultaneous SAXS and WAXS Studies of Nanocomposites---WAXS data The WAXS pattern of PP(left) and the plot of azimuthally averaged I vs. Q (right). Ordered structure was observed. The data were collected at sample-detector distance of 40mm.

33 Eggiman, Tate & Hillhouse, Chem. Mater. Grazing Incidence SAXS 2D SAXS upon Substrate Rotation: from TSAXS to GISAXS

34 GISAXS Study of a 3D Ordered Assembly of Iron Oxide Nanocrystals. Altamura D., Holy V., Siliqi D., Cozzoli D., Fan L., Gozzo F., and Giannini C. 2014

35 Samples of applications GISAXS Studies of Copolymer Thin Films 2D GISAXS pattern from a copolymer thin film. Such materials with weak scattering ability is always challenge for laboratory GISAXS. The Rigaku S-Max3000 can determine their morphology The peak positions are Qxy= 0.043, 0.075, A -1 The ratio follows 1:3 1/2 : 4 1/ 2, indicating a hexagonal structure

36 NanoMAX NanoMAX IQ

37 NanoMAX & NanoMAX-IQ X-ray Sample

38 Application Tree Composit materials Polymers in Solution Metal powders, bulks Anisotropic Scatterers Nanoparticles in solution Isotropic Scatterers Cracks, pores etc. Bones, cotton, carbon composites Nanoparticles Surfaces Polymers Application NanoMAX & NanoMAX-IQ

39 NanoMAX Hardware Overview Beam stop (Pin Diode) Kratky Block Detector Attenuator 4 Jaw slits Detector Sample holder Kratky Block

40 Inter-relationship of q and flux Photo of the 2dk block Top view of 2d kratky block at varied q min

41 Inter-relationship of q and flux X-ray source (CMF) Low q min (Low flux) Sample Mid q min (Mid flux) High q min (High flux) SMAX HF 2DK+FR-E 1-0,005 7E-17 0,005 0,01 0,015 Minimum q vers. flux (q A -1 )

42 NanoMAX Detector Sensor: Reversed biased silicon diode array Active area: 83.8 mm x 33.5 mm Pixel Size: 172 µm x 172 µm Count rate: up to 2 x 10 6 photons/sec/pixel DQE: CuKa Cooling: Air cooled

43 NanoMAX and SMAX Data Quality Comparison SMAX3000 Rg ; 15.0(0.65) Points ; NanoMAX+FR-E Rg ; 15.1(0.039) Points ; 6-38

44 NanoMAX examples System/Lysozyme As a highly diluted sample Exposure time (min) concentration (mg/ml) NanoMAX S-MAX A A -1

45 Silverbehenate on different SAXS machines 0.25 A -1 S-MAX A -1 NanoMAX NanoMAX-IQ 4,9 A -1

46 Sample Holders

47 Acknowledgements This presentation was only possible due to the support of my colleagues at Rigaku. Dr. Licai Jiang Mr. Nick Grupido Dr. Petra Pennartz Dr. Mike Degen and many others But also I will not forget my friends and customers at ETH Zurich/CH, Prof. R. Mezzenga, Dr. T. Sanches-Ferrer AMI/Fribourg/CH, Dr. S. Balog RWTH/Aachen/D, Dr. Th. Eckert ICCS Bari/I, Prof. C. Giannini and all members of their teams and many others

48 Typical Models Shapeless Spheres Clustered spheres (Debye model) Cylinders Core/shell spheres

49 Raw data (1) Real Life SAXS Data SAXSGUI Reduced data (2) SAXSGUI analyzed data (3) Result (4) Core Shell structure

50 Raw data (1) Real Life SAXS Data SAXSGUI Reduced data (2) SAXSGUI analyzed data (3) center to center Result (4) Particles approx 275 Ang size, Center to Center distance of particles Approx. 36 Ang can be interpreted from fringes in data analysis.

51 Why SAXS now? ln(i) q 2 I Log(I) P(r) SAXS pattern Guinier plot q [Å -1 ] Kratky plot Pair distribution function q 2 [Å -2 ] q [Å -1 ] r [Å] Journal of Structural Biology 172 (2010)

52 Any Questions?