Xrd 2005
Upcoming SlideShare
Loading in...5
×

Like this? Share it with your network

Share
  • Full Name Full Name Comment goes here.
    Are you sure you want to
    Your message goes here
No Downloads

Views

Total Views
3,862
On Slideshare
3,858
From Embeds
4
Number of Embeds
1

Actions

Shares
Downloads
295
Comments
1
Likes
3

Embeds 4

http://www.slideshare.net 4

Report content

Flagged as inappropriate Flag as inappropriate
Flag as inappropriate

Select your reason for flagging this presentation as inappropriate.

Cancel
    No notes for slide

Transcript

  • 1. Materials Characterization Lab www.mri.psu.edu/mcl X-Ray Diffraction Nichole Wonderling 159 Materials Research Laboratory University Park, PA. 16802 nmw10@psu.edu 814-863-1369 Wednesday, June 29, 2005
  • 2. Materials Characterization Lab www.mri.psu.edu/mcl Summer Characterization Open Houses Technique Time Date Location Thermal analysis (TGA, DTA, DSC) 9:45 AM June 8 250 MRL Bldg. Transmission Electron Microscopy (TEM/STEM) 9:45 AM June 15 114 MRI Bldg Scanning electron microscopy (SEM) 9:45 AM June 22 541 Deike Bldg. Analytical SEM 11:00 AM June 22 541 Deike Bldg. X-ray Diffraction (XRD) 9:45 AM June 29 250 MRL Bldg. Dielectric Characterization (25 min lecture only) 9:45 AM July 6 250 MRL bldg. High temperature sintering lab (20 min lecture only) 10:15 AM July 6 250 MRL Bldg. Focused Ion Beam (FIB) 9:45 AM July 13 114 MRI Bldg TEM sample preparation 11:00 AM July 13 114 MRI Bldg Orientation imaging microscopy (OIM/EBSD) 9:45 AM July 20 250 MRL Bldg. Chemical analysis (ICP, ICP-MS) 9:45 AM July 27 541 Deike Bldg. Atomic Force Microscopy (AFM) 9:45 AM August 3 114 MRI Bldg Small angle x-ray scattering (SAXS) 9:45 AM August 10 541 Deike Bldg. Particle Characterization 9:45 AM August 17 250 MRL X-ray photoelectron spectroscopy (XPS/ESCA) 9:45 AM August 24 114 MRI Bldg Auger Electron Spectroscopy (AES) 11:00 AM August 24 114 MRI Bldg NOTE LOCATIONS: The MRI Bldg is in the Innovation Park near the Penn Stater Hotel; MRL Bldg. is on Hastings Road. More information: www.mri.psu.edu/mcl
  • 3. Materials Characterization Lab www.mri.psu.edu/mcl Materials Characterization Lab Locations Bldg Telephone MRL 863-7844 MRI 865-0337 MRI Bldg: Hosler 865-1981 XPS/ESCA, SIMS, E&ES 863-4225 TEM, HR-TEM, FE- Auger, AFM, XRD MRL Bldg: Hosler Bldg: SEM, XRD, OIM, DTA, SEM, ESEM, FE- DSC, TGA, FTIR, Penn Stater SEM, EPMA, ICP, Hotel AFM, Powder, E&ES Bldg: ICP-MS,BET, dielectric, prep, shop, SEM SAXS,XRD IC, UV-Vis Route 322 Steidle Bldg: Atherton Street Nanoindenter (322 Business) I-99 Park Ave. 0 0 0 0 0 0 0 Ave. 0 0 0 0 0 Park 0 Beaver 0 0 Stadium 0 0 0 Centre 0 0 Porter Road Community Univ Shortlidg Hospital 0 0 Burrowes Road ersi ty D e Pollock Road Road rive North Hastin Deike Bldg: gs Ro ad College Ave.
  • 4. Materials Characterization Lab www.mri.psu.edu/mcl Outline History / Theory Instrumentation Strengths / Limitations MCL Instruments /Capabilities Applications at PSU Software How to Get Started Sample Prep Campus and Other Resources Lab Tour
  • 5. Materials Characterization Lab www.mri.psu.edu/mcl HISTORY
  • 6. Materials Characterization Lab www.mri.psu.edu/mcl Wavelength Range of X-rays Encyclopedia Britannica, Inc.
  • 7. Materials Characterization Lab www.mri.psu.edu/mcl The Discovery of X-Rays • On 8 Nov, 1895, Wilhelm Conrad Röntgen (accidentally) discovered an image cast from his cathode ray generator, projected far beyond the possible range of the cathode rays (now known as an electron beam). Further investigation showed that the rays were generated at the point of contact of the cathode ray beam on the interior of the vacuum tube, that they were not deflected by magnetic fields, and they penetrated many kinds of matter. • A week after his discovery, Rontgen took an X-ray photograph of his wife's hand which clearly revealed her wedding ring and her bones. The photograph electrified the general public and aroused great scientific interest in the new form of radiation. Röntgen named the new form of radiation X-radiation (X standing for quot;Unknownquot;). http://inventors.about.com/library/inventors/blxray.htm
  • 8. Materials Characterization Lab www.mri.psu.edu/mcl It was the Rage…….. Edison Get your bone portrait! An x-ray “studio” nails Images are copyrighted by Radiology Centennial, Inc and used with permission
  • 9. Materials Characterization Lab www.mri.psu.edu/mcl Laue - 1912 Showed that if a beam of X rays passed through a crystal, diffraction would take place and a pattern would be formed on a photographic plate placed at a right angle to the direction of the rays. Today, known as the Laue pattern Max von Laue
  • 10. Materials Characterization Lab www.mri.psu.edu/mcl A few months later – Two Braggs Father Son Sir William Lawrence Bragg Sir William Henry Bragg http://www.britannica.com/nobel/micro/83_18.html
  • 11. Materials Characterization Lab www.mri.psu.edu/mcl THEORY
  • 12. Materials Characterization Lab www.mri.psu.edu/mcl Young Bragg • Believing that Laue's explanation was incorrect in detail, he carried out a series of experiments, the result of which he published the Bragg equation – He was 15 years old when he did this!
  • 13. Materials Characterization Lab www.mri.psu.edu/mcl Bragg’s Law - defined Assume n=1 for the first order reflection (hkl=111) Tells us at what angles X rays will be diffracted by a crystal when the X-ray wavelength and distance between the crystal atoms are known Wavelength X-ray incidence angle 1.54 A for Cu (known value) (known value) Lattice inter-planar spacing of the crystal (calculate)
  • 14. Materials Characterization Lab www.mri.psu.edu/mcl Bragg’s Law Assumptions: Monochromatic beam Parallel beam http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/bragg.html
  • 15. Materials Characterization Lab www.mri.psu.edu/mcl Eventually……… Bragg-Brentano Diffractometer and The Diffraction Pattern [s o lid - 2 R - 2 .r a w ] 3000 2500 2000 I t niyC u t ) s n s ( on et 1500 1000 500 0 10 20 30 Tw o - Th e ta ( d e g )
  • 16. Materials Characterization Lab www.mri.psu.edu/mcl Development of Modern Spectrometers
  • 17. Materials Characterization Lab www.mri.psu.edu/mcl Invention of the X-ray Tube • Ductile • William D. Coolidge's name is inseparably linked with Tungsten the X-ray tube-popularly at General called the 'Coolidge tube.' Electric This invention completely revolutionized the generation of X-rays and remains to this day the model upon which all X-ray tubes are patterned. http://inventors.about.com/gi/dynamic/offsite.htm?site=http://www.invent.org/hall%5Fof%5Ffame/1%5F1%5F6%5Fdetail.asp%3FvInventorID=33
  • 18. Materials Characterization Lab www.mri.psu.edu/mcl Modern X-Ray Tube • In an X-ray tube, the high voltage Cross Section maintained across the electrodes draws electrons toward a metal target (the anode). X-rays are produced at the point of impact, and radiate in all directions. http://pubs.usgs.gov/of/of01-041/htmldocs/xrpd.htm
  • 19. Materials Characterization Lab www.mri.psu.edu/mcl Schematic of Bragg-Brentano Diffractometer First was introduced by North American Philips in 1947 Construction and geometry today differ little today from the early diffractometers BUT…..Significant advances in: detection and counting systems, automation, and analysis of the data (computers) From the Siemens (now Bruker AXS) manual for the D5000
  • 20. Materials Characterization Lab www.mri.psu.edu/mcl Types of X-ray Diffraction Instruments
  • 21. Materials Characterization Lab www.mri.psu.edu/mcl Two Types of Instrumentation • Powder • Single Crystal
  • 22. Materials Characterization Lab www.mri.psu.edu/mcl Types of Patterns From an From a Oriented Single powder crystal [s o lid - 2 R - 2 .r a w ] 3000 2500 2000 I t niyC u t ) s n s ( on et 1500 1000 500 From a randomly 0 10 20 30 Tw o - Th e ta ( d e g ) Oriented powder
  • 23. Materials Characterization Lab www.mri.psu.edu/mcl Powder Diffraction • Use Powder when working with: – Essentially anything that can be ground to a powdered form • Rocks, cements, pharmaceuticals, etc – Materials for which you wish to know the compounds present – not just the elements - (and perhaps how much of each compound if a mixture)
  • 24. Materials Characterization Lab www.mri.psu.edu/mcl Compounds “I have iron oxide. I want to know if it is in the form of FeO (wuestite) or Fe2O3 (hematite).” Wuestite - cubic Hematite - hexagonal FeO Fe2O3
  • 25. Materials Characterization Lab www.mri.psu.edu/mcl Single Crystal Diffraction • Use Single Crystal when working with: – Obviously when you have “single crystals” – When you want to know the structure of a crystal – information such as - bond lengths - bond angles - atom positions
  • 26. Materials Characterization Lab www.mri.psu.edu/mcl Strengths / Limitations of Powder Diffraction
  • 27. Materials Characterization Lab www.mri.psu.edu/mcl Strengths of Powder X-ray Diffraction • Non-destructive – small amount of sample • Relatively rapid • Identification of compounds / phases – not just elements • Quantification of concentration of phases – (sometimes) • Classically for powders, but solids possible too • Gives information regarding crystallinity, size/strain, crystallite size, and orientation Limitations of Powder X-ray Diffraction • Bulk technique – generally – unless a camera is uses • Not a “stand-alone” technique – often need chemical data • Complicated spectra – multiphase materials – identification / quantification can be difficult
  • 28. Materials Characterization Lab www.mri.psu.edu/mcl MCL Instruments / Capabilities
  • 29. Materials Characterization Lab www.mri.psu.edu/mcl Powder Diffraction
  • 30. Materials Characterization Lab www.mri.psu.edu/mcl Scintag ……Scintag 1 Both horizontal θ/2θ geometry -tube is stationary - detector and sample move Both used for basic powder Diffraction. Scintag 2……… Both located in 158 MRL building
  • 31. Materials Characterization Lab www.mri.psu.edu/mcl Scintag (cont’d) ……..Scintag 3 Vertical θ/θ geometry - sample is stationary - tube and detector move Hot (up to 1500C), Cold (to Liquid nitrogen -196C), and sample rotation stages available Located in 158 MRL
  • 32. Materials Characterization Lab www.mri.psu.edu/mcl Philips X’Pert Has both focusing and parallel beam optics. Located in Room 158 MRL building
  • 33. Materials Characterization Lab www.mri.psu.edu/mcl Single Crystal Diffractometers
  • 34. Materials Characterization Lab www.mri.psu.edu/mcl Laue Multiwire Laboratories Consists of a position sensitive x- ray proportional counter connected to a computer system - orients and characterizes single crystals quickly in real-time. Laue patterns can be easily stored, displayed, and printed - completely avoiding the use of film. Located in 156 MRL
  • 35. Materials Characterization Lab www.mri.psu.edu/mcl Philips High Resolution 4-Circle Located in room MRI building
  • 36. Materials Characterization Lab www.mri.psu.edu/mcl Bruker 4-Circle Located in 156 MRL
  • 37. Materials Characterization Lab www.mri.psu.edu/mcl Applications at PSU
  • 38. Materials Characterization Lab www.mri.psu.edu/mcl Oxidation States of Copper As a fungicide on roofing materials The major phase is quartz, (red) also a significant [522-03.raw] , SCAN: 5.0/70.0/0.02/2(s ec ), Cu(35k V,30mA), I(max )=2806, 07/03/03 08:20 46-1045> Quartz, syn - SiO2 amount of Cu, 44-0706> CuO - Copper Oxide 400 85-1326> Copper - Cu (green). 78-2076> Cuprite - Cu2O Cu 350 Perhaps, some Cu2O, CuO Cu2O 300 SiO2 (blue), but Cu2O CuO SiO2 directly overlaps SiO2 Intensity(Counts) 250 the SiO2 lines. SiO2 200 Cu2O There is no CuO 150 detected. 100 Other unidentified CuO 50 phases also present. 0 34 35 36 37 38 39 40 41 42 43 44 Two-Theta (deg)
  • 39. Materials Characterization Lab www.mri.psu.edu/mcl Pyrite • Example of the mineral pyrite, FeS2, that was found at a local road construction site. [pyrite sample.raw] , SCAN: 20.0/60.0/0.02/2(sec), Cu, I(max)=2179, 02/26/04 15:20 (Eq. 1) FeS2 + 7/2O2 + H2O = 42-1340> Pyrite - FeS2 46-1045> Quartz, syn - SiO2 350 Fe2+ + 2SO42- + 2H+ 300 (Eq. 2) Fe2+ + 1/4O2 + 3/2H2O 250 Intensity(Counts) = FeOOHppt + 2H+ 200 150 (Eq. 3) FeS2 + 15/4O2 + 100 7/2H2O = Fe(OH)3ppt + 2SO42- 50 + 4H+ 0 25 30 35 40 45 50 Two-Theta (deg)
  • 40. Materials Characterization Lab www.mri.psu.edu/mcl Crystallite Size Measurement Rh-Ni CeO2 powders τ Kλ = Decreasing [1%R h5%N i-C eO2- Aldr ic h( 4degper min) .r aw ] , SC AN : 5.0/70.0/0.02/4(s ec ), C u( 35k V,30mA), I(max )=480, 05/13/04 08:39 500 43-1002> Cerianite-(Ce), syn - CeO2 _______ crystallite 400 Intensity(Counts) 300 size β cos θ 200 100 τ = particle size 0 10 20 30 40 50 60 70 Two-Theta (deg) K = shape factor [1%Rh5%Ni-CeO2-600C calcined (4degpermin).raw] , SCAN: 5.0/70.0/0.02/4(sec), Cu(35kV,30mA), I(max)=288, 05/13/04 09:50 300 43-1002> Cerianite-(Ce), syn - CeO2 47-1049> Bunsenite, syn - NiO 250 (typically 0.85-0.9) 200 Intensity(Counts) λ = wavelength (Angstroms) 150 100 β = corrected FWHM (radians) 50 0 10 20 30 40 50 60 70 Two-Theta (deg) θ = ½ 2θ (peak position) [1%Rh5%Ni-CeO2-Rhodia(4degpermin).raw] , SCAN: 5.0/70.0/0.02/4(sec), Cu(35kV,30mA), I(max)=208, 05/13/04 07:55 43-1002> Cerianite-(Ce), syn - CeO2 200 Good for particle sizes < 150 500A and no strain. I ntensit y(Count s) 100 If strain, other Methods: 50 Warren / Averbach 0 10 20 30 40 50 60 70 Two-Theta (deg) Williamson-Hall plot
  • 41. Materials Characterization Lab www.mri.psu.edu/mcl Grazing Angle Geometry W Lα Pt (111) Pt 32.2 57.4 (111) ATN (110) Cu Kβ ATN (211) Pt (111) 46.0 32.2 ATN (200) ATN (110) Si (200) 46.0 57.4 ATN (200) ATN (211) X Grazing angle mode Normal Powder mode Reflected X-rays Incident x-rays ATN film Pt Silicon
  • 42. Materials Characterization Lab www.mri.psu.edu/mcl
  • 43. Materials Characterization Lab www.mri.psu.edu/mcl Software
  • 44. Materials Characterization Lab www.mri.psu.edu/mcl Jade • Currently using Jade 7.1+ software manufactured by MDI, Inc. – Capabilities include (not inclusive): • Full Search / Match of current ICDD (2004) and ICSD (2005) databases for phase ID • Whole Pattern Profile Fitting / Rietveld Refinement • RIR Quantitative (Easy Quant) • Crystallite Size Estimate / Strain • 3-D Crystal Structure Viewer
  • 45. Materials Characterization Lab www.mri.psu.edu/mcl Quantitative Analysis – by Rietveld NH4Al(SO4)2 and CuSO4 co-precipitated [NH4Al(SO4)-CuSO4-mixture.raw] 750 Intensity(Counts) 500 250 0 97-001-7679> Chalcanthite - Cu S O4 (H2 O)5 97-007-7246> Tschermigite - (N H4) Al (S O4)2 (H2 O)12 8 9 10 11 12 13 14 15 16 17 18 Two-Theta (deg)
  • 46. Materials Characterization Lab www.mri.psu.edu/mcl Rietveld Refinement • Quantify monoclinic and tetragonal zirconia – only the 100% tetragonal peak visible / clear from overlap [powder ZrO2.raw ] , SCAN : 5.0/70.0/0.02/2(s ec ), C u(35k V,30mA), I(max )=2435, 03/04/04 14:58 37-1484> Baddeleyite, syn - ZrO2 50-1089> ZrO2 - Zirconium Oxide red=monoclinic 1000 blue=tetragonal 500 2 9 .5 2 9 .6 2 9 .7 2 9 .8 2 9 .9 3 0 .0 3 0 .1 3 0 .2 3 0 .3 3 0 .4 3 0 .5 3 0 .6 3 0 .7 3 0 .8 Intensity(Counts) 0 15 20 25 30 35 40 Goal: To quantif y the amount of tetragonal ZrO2 in a mixture of tetragonal and monoclinic ZrO2. 1000 500 0 45 50 55 60 65 Two-Theta (deg)
  • 47. Materials Characterization Lab www.mri.psu.edu/mcl Quantitative Analysis – RIR Method Jade’s “Easy QUANT”
  • 48. Materials Characterization Lab www.mri.psu.edu/mcl How to Get Started
  • 49. Materials Characterization Lab www.mri.psu.edu/mcl Environmental Health and Safety X-ray safety training course http://www.ehs.psu.edu/radprot/x-ray_safety_training.cfm
  • 50. Materials Characterization Lab www.mri.psu.edu/mcl Dosimetry • Worn on the wrist closest to the x-ray source (varies by instrument) – issued once each quarter Thin strip of specially formulated aluminum oxide (Al2O3) crystalline material. During analysis, the Al2O3 strip is stimulated with selected frequencies of laser light causing it to luminesce in proportion to the amount of radiation exposure.
  • 51. Materials Characterization Lab www.mri.psu.edu/mcl Who Do I Contact to use X-ray Diffraction Equipment at PSU?
  • 52. Materials Characterization Lab www.mri.psu.edu/mcl MCL Contacts (For equipment in the MRL building) Nichole Wonderling nmw10@psu.edu 159 MRL Building 863-1369 (For equipment in Hosler and MRI buildings) Mark Angelone John Cantolina msa3@psu.edu jjc16@psu.edu 310 Hosler Building 310 Hosler Building 883-9350 883-8358
  • 53. Materials Characterization Lab www.mri.psu.edu/mcl Sample Preparation
  • 54. Materials Characterization Lab www.mri.psu.edu/mcl In Search of the Elusive “Perfect” Powder Sample • A “Representative” sample
  • 55. Materials Characterization Lab www.mri.psu.edu/mcl The Elusive “Perfect” Powder Sample How do I get a “representative” sample?
  • 56. Materials Characterization Lab www.mri.psu.edu/mcl The Elusive “Perfect” Powder Sample • A “Representative” sample • Sufficient number of crystallites Particle Size POWDER ?
  • 57. Materials Characterization Lab www.mri.psu.edu/mcl Make mine a powder…… You may be lucky and have one of these…….. Or maybe a SPEX Shatterbox You have… the XRD’s Best friend……… The trusty mortar and Picture of SPEX Shatterbox from Georgia State, Geology dept. web site http://www2.gsu.edu/~wwwgeo/pages_03/lab/xRayFluorescence.htm pestle.
  • 58. Materials Characterization Lab www.mri.psu.edu/mcl The Elusive “Perfect” Powder Sample Particle Size < 325 mesh or < 400 mesh (38-44 micron) – for Qualitative Work 10 micron or less for Quantitative Work – very difficult if not Somehow…….it needs to impossible by hand! go through here!
  • 59. Materials Characterization Lab www.mri.psu.edu/mcl The Elusive “Perfect” Powder Sample • A “Representative” sample • Sufficient number of crystallites Particle Size • Total randomness of the crystallite orientations How the Sample is Introduced to the Instrument
  • 60. Materials Characterization Lab www.mri.psu.edu/mcl Zero Background Holders (ZBH) Flat Silicon ZBH Quartz ZBH with cavity Cut parallel to Si (510) Cut 6 º from (0001) Si (511) – also available, but has peak at 96ºθ See www.gemdugout.com for additional information
  • 61. Materials Characterization Lab www.mri.psu.edu/mcl Flat Quartz ZBH Vaseline Mount Smear Mount
  • 62. Materials Characterization Lab www.mri.psu.edu/mcl Back Filled Sample Holder
  • 63. Materials Characterization Lab www.mri.psu.edu/mcl Side Drift Mount Disassembled Assembled Designed to reduce preferred orientation – great for clay samples, (and others with peaks at low 2-theta angles)
  • 64. Materials Characterization Lab www.mri.psu.edu/mcl The Elusive “Perfect” Powder Sample • A “Representative” sample • Sufficient number of crystallites Particle Size • Total randomness of the crystallite orientations How the Sample is Introduced to the Instrument • Sufficient intensity – limit of detection ~5% Enough sample area presented to the beam and enough of the phase of interest present
  • 65. Materials Characterization Lab www.mri.psu.edu/mcl “Real World” Samples Some things can’t practically be powders: Hope diamond films pellets crystals mineral specimens There are techniques available to deal with many of these – ask! galena
  • 66. Materials Characterization Lab www.mri.psu.edu/mcl Plastic box - Shimmed Pellet Pellet Mount Mount
  • 67. Materials Characterization Lab www.mri.psu.edu/mcl Campus and Other Resources
  • 68. Materials Characterization Lab www.mri.psu.edu/mcl Courses • MATSE 430 Materials Characterization – Fall semester only, 3 credit course, instructor Elizabeth Dickey Books “Elements of X-ray Diffraction,” Cullity and Stock “Introduction to X-ray Powder Diffractometry,” Jenkins and Snyder “Fundamentals of Powder Diffraction and Structural Characterization of Materials,” Pecharsky and Vitalij “A Practical Guide for the Preparation of Specimens for X-ray Fluorescence and X-ray Diffraction Analysis,” Buhrke, Jenkins, Smith
  • 69. Materials Characterization Lab www.mri.psu.edu/mcl Journals “Powder Diffraction” “Acta Crystallographica” “Zeitschrift für Kristalographie” On-line http://www.ccp14.ac.uk/ http://www.icdd.com/
  • 70. Materials Characterization Lab www.mri.psu.edu/mcl Faculty Experts at PSU • Elizabeth Dickey, 195 MRI • Peter Heaney, 309 Deike Building • Gerald Johnson, Jr.; Prof. Emeritus, 153 MRL • Earl Ryba, 304B Steidle Building • Barry Scheetz, 107 MRL
  • 71. Materials Characterization Lab www.mri.psu.edu/mcl Lab Tour