Saxs 2005

1. Materials Characterization Lab
www.mri.psu.edu/mcl
SMALL ANGLE XRAY SCATTERING (SAXS)
AUGUST 10, 2005
Mark S. Angelone
[email protected]

2. Materials Characterization Lab
www.mri.psu.edu/mcl
250 MRL
August 17
9:45 AM
Particle Characterization
114 MRI Bldg
August 24
9:45 AM
X-ray photoelectron spectroscopy (XPS/ESCA)
114 MRI Bldg
August 24
11:00 AM
Auger Electron Spectroscopy (AES)
541 Deike Bldg.
July 27
9:45 AM
Chemical analysis (ICP, ICP-MS)
541 Deike Bldg.
August 10
9:45 AM
Small angle x-ray scattering (SAXS)
114 MRI Bldg
August 3
9:45 AM
Atomic Force Microscopy (AFM)
250 MRL Bldg.
July 20
9:45 AM
Orientation imaging microscopy (OIM/EBSD)
114 MRI Bldg
July 13
11:00 AM
TEM sample preparation
114 MRI Bldg
July 13
9:45 AM
Focused Ion Beam (FIB)
250 MRL Bldg.
July 6
10:15 AM
High temperature sintering lab (20 min lecture only)
250 MRL bldg.
July 6
9:45 AM
Dielectric Characterization (25 min lecture only)
250 MRL Bldg.
June 29
9:45 AM
X-ray Diffraction (XRD)
541 Deike Bldg.
June 22
11:00 AM
Analytical SEM
541 Deike Bldg.
June 22
9:45 AM
Scanning electron microscopy (SEM)
114 MRI Bldg
June 15
9:45 AM
Transmission Electron Microscopy (TEM/STEM)
250 MRL Bldg.
June 8
9:45 AM
Thermal analysis (TGA, DTA, DSC)
Location
Date
Time
Technique
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
Summer Characterization Open Houses Summer Characterization Open Houses

3. Materials Characterization Lab
www.mri.psu.edu/mcl
Beaver
Stadium
Park Ave.
Park Ave.
Porter Road
Pollock Road
University Drive
College Ave.
Shortlidge Road
North
Burrowes Road
0
0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
Centre
Community
Hospital
E&ES Bldg: SEM
Hosler Bldg: SEM,AFM,ESEM, FE- SEM, EPMA, ICP, ICP-MS,BET, SAXS
MRI Bldg: XPS/ESCA, FIB SIMS, TEM, HR- TEM, FE-Auger, AFM, XRD
Atherton Street
(322 Business)
MRL Bldg: SEM, XRD, OIM, DTA,
DSC, TGA, FTIR,
Raman, AFM, Powder,
dielectric, prep, shop,
IC, UV-Vis
Hastings Road
Penn Stater
Hotel
0
0
Materials Characterization Lab Locations
Route 322
I-99
0
0
Steidle Bldg: Nanoindenter
Deike Bldg:

4. Materials Characterization Lab
www.mri.psu.edu/mcl
•Facilities/Instruments
•User Training
•Operators/Analyst for hire
•24/7
•Online bookings
•User fees
•website/contacts to get started
MCL SERVICES

5. Materials Characterization Lab
www.mri.psu.edu/mcl
200 mesh
400 mesh

6. Materials Characterization Lab
www.mri.psu.edu/mcl
Scattering ‘Live’ Demo
Real Space Reciprocal Space
d
1
d
2
= d
1
/2
SOURCE
Scattered Beam (1
st
order)
Direct Beam -------
Scattered Beam (1
st
order)
SD
TAN θ=
SD/D
Smaller
For
Larger d
Sample/Detector D
θ
θ
Smaller d yields larger SD

7. Materials Characterization Lab
www.mri.psu.edu/mcl
ηλ= 2 d sin θ
Bragg Scattering (WAXS-XRD)
λ= Cu Kα= 1.5401 Å
q =(4π/λ) sin θ= 2 π/d
d2θ
10Å (0.001 Micron)
50Å
100Å
300Å
600Å
1000Å
8.84º
1.17 º
0.88 º
0.29 º
0.15 º
0.09 º
0.628 A
-1
0.126 A
-1
0.063 A
-1
0.021 A
-1
0.010 A
-1
0.006 A
-1
WAXS (Cu Ka, 2-160 2
θ
)
Laboratory SAXS
Synchrotron SAXS/SANS
Sub Angstrom - 10Å
10Å - 1000Å
10Å – several 1000Å
Atomic Structures
Nano/ Colloidal
Structures
(PSU)

8. Materials Characterization Lab
www.mri.psu.edu/mcl
What kinds of materials?
Compiled by Earle Ryba

9. Materials Characterization Lab
www.mri.psu.edu/mcl
What kinds of materials?

10. Materials Characterization Lab
www.mri.psu.edu/mcl
What kinds of materials?

11. Materials Characterization Lab
www.mri.psu.edu/mcl
Examples from literature
Polymer dendrimers
dilute solns in CH
3
OH to get dendrite sizes
dilute so dendrimers don’t correlate
Alkanediols
solns in water to study clustering
heavy water improves contrast (sans)
Water-based polymer latexes
use anionic surfactant to suspend in water
Macromolecular foams
wafers cut & immersed in toluene to get swelling
banded matls are translated in situ
Microemulsions
oils in water to get droplet size

12. Materials Characterization Lab
www.mri.psu.edu/mcl
Examples from literature
CVD SiGe films
µ-thin films stacked to get Ge heterogeneity
Nanotubes
use surfactant in water & sonicate; place in quartz cells
to study nanotube aggregation
Powders
thin-walled capillaries
Polymers
study crystallization processes in situ in hot cell

13. Materials Characterization Lab
www.mri.psu.edu/mcl
Examples from literature
Thin films on glass substrates
as is, but requires grazing incidence
Random crystalline block copolymers
rheology study in situ in rotating parallel disk cell
to get crystal alignment and grain rotations
Splat-cooled glass
in situannealing study to follow pptn of PbTe
nano-crystals

14. Materials Characterization Lab
www.mri.psu.edu/mcl
Examples from literature
Blown polymer films
special cell for in situstudies
Liq. Crystals
special magnetic cell for molecule rotation
Ionomers
cell w/ kapton windows
Hi pressure studies
diamond windows

15. Materials Characterization Lab
www.mri.psu.edu/mcl
Mouse bone

16. Materials Characterization Lab
www.mri.psu.edu/mcl
Real Space
ρ(r)
r
F.T.
Reciprocal Space
⏐A⏐
1/r (q)
⏐A⏐
2
Γ(r)
q
I.F.T .
1/r (q)
r
Reciprocal Space
Real Space
I(q)
Not Possible By Direct Calc
Calc – Scattering Theory – F.T.
Calc – Auto Correlation Function of ρ(r)
Large r
Particulate shapes
Phase mix
Large period structures
Small r
Atomic positions
•Crystals
•amorphous
Amplitude/Phase
Spectra of scattering
from individual scatters
(continuous/discrete)
Large r
Correlation function, radial
distribution
Small r
Pair (Radial) distribution: Short
range atomic ordering
(amorphous materials)
Patterson function: Interatomic
vectors (crystals)
Large r (SAXS) Diffuse scatter
Small r (WAXS) Diffraction dominates
for xtals, diffuse scatter for liquids,
amorphous solids
Observed scattering
intensity-
Noise/truncation
effects

17. Materials Characterization Lab
www.mri.psu.edu/mcl
Analytical
Interpretation
Model ρ(r) →calculate I(q)→fit to observed I(q)
Or
Model ρ(r) →calculate Γ(r) →fit to F.T. of observed I(q)
(models cast in parameters of size, shape, dispersity, thermo mixing
energy, etc.)

18. Materials Characterization Lab
www.mri.psu.edu/mcl
Common SAXS Models
DILTUE PARTICULATE SYSTEM
•Mono or poly dispersed
•No interparticle scattering effects
SAXS Interpretation yields •Size/dispersity for known shapes
•Rg for unknown shapes
•Can incorporate dense packing effects into model

19. Materials Characterization Lab
www.mri.psu.edu/mcl
Dilute Particulate models

20. Materials Characterization Lab
www.mri.psu.edu/mcl
Dilute Particulate models

21. Materials Characterization Lab
www.mri.psu.edu/mcl
Dilute Particulate Models

22. Materials Characterization Lab
www.mri.psu.edu/mcl
Common SAXS Models
Non Particulate 2 Phase System
•2 intermixed phases without host or matrix
SAXS Interpretation yields
•Phase volume fraction, domain size,
•information on interphase boundary
(sharp or diffuse)

23. Materials Characterization Lab
www.mri.psu.edu/mcl
Common SAXS Models
Periodic Systems
•Lamellar stacks, ordered copolymers, biologic
Periodic and ordered structures
WAXS methods apply but with emphasis on
deviations from ordered structures

24. Materials Characterization Lab
www.mri.psu.edu/mcl

25. Materials Characterization Lab
www.mri.psu.edu/mcl
Photoresist grating

26. Materials Characterization Lab
www.mri.psu.edu/mcl
Common SAXS Models
Soluble Blend System
•Single disordered phase dissolved molecularly with
density inhomogeneity
(miscible polymers, block copolymers, polymer solns)
SAXS Interpretation yields
•Solution properties
(could be treated as dilute system but blend model formulated
for more direct treatment of thermodynamic properties
rather than size and shape)

27. Materials Characterization Lab
www.mri.psu.edu/mcl
TWO IMPORTANT GENERAL MODEL RESULTS
(some interpretation without models)
•GUINIER LAW
•POROD LAW

28. Materials Characterization Lab
www.mri.psu.edu/mcl
GUINIER LAW
•Even for unknown, irregular or ‘non-describable shapes; scattering has
predictable form at low q

29. Materials Characterization Lab
www.mri.psu.edu/mcl
GUINIER LAW
Valid for
•q << 1/R
g
•Dilute system
•Isotropic (random particle orientation)
•Solvent scattering subtracted

30. Materials Characterization Lab
www.mri.psu.edu/mcl
POROD LAW
•Predictable relationship between I(q) and total interface area
in 2 phase systems at high q
•Can obtain total interface area for absolute intensities or specific
surface area (S/V) for relative measure of
scattered intensity
•Deviations from Porod Law indicate and give information on
diffuse interphase boundaries
•

31. Materials Characterization Lab
www.mri.psu.edu/mcl
INSTRUMENTS FOR SAXS
•KRATKY CAMERA
•PINHOLE CAMERA
•LABORATORY SOURCES
•SYNCHROTRON SOURCES

32. Materials Characterization Lab
www.mri.psu.edu/mcl
KRATKY CAMERA

33. Materials Characterization Lab
www.mri.psu.edu/mcl
INSTRUMENTS FOR SAXS
•Scattering in transmission mode
•Source is critical
•1-2mm ideal thickness for polymers/organics
•Monochromatic
•Intense
•Collimated
•Small cross section (pinhole)

34. Materials Characterization Lab
www.mri.psu.edu/mcl
BEAM CONDITIONING

35. Materials Characterization Lab
www.mri.psu.edu/mcl
MOLMET (PSU) SAXS

36. Materials Characterization Lab
www.mri.psu.edu/mcl

37. Materials Characterization Lab
www.mri.psu.edu/mcl
INSTRUMENTS FOR SAXS
•Scattering in transmission mode
•Source is critical
•Evacuated beam path
•Sample holders
•Detectors
•1-2mm ideal thickness for polymers/organics
•Monochromatic
•Intense
•Collimated
•Small cross section (pinhole)
•Film, plates, PSD, Area

38. Materials Characterization Lab
www.mri.psu.edu/mcl
Sample holders

39. Materials Characterization Lab
www.mri.psu.edu/mcl
Multi-wire Area Detector

40. Materials Characterization Lab
www.mri.psu.edu/mcl
EXAMPLES

41. Materials Characterization Lab
www.mri.psu.edu/mcl
r
Calibrates center and q on 58.37 A d-space
Silver Behenate Standard

42. Materials Characterization Lab
www.mri.psu.edu/mcl
SAXS of 60PMVP-I in NMF
0.00 0.02 0.04 0.06 0.08 0.10
1000
1500
2000
2500
3000
3500
I(q), normalized intensity, (A.U.)
q, (Angstrom
-1
)
2.5 mg/ml 5.0mg/ml 10.0mg/ml 20.0 mg/ml
60PMVP-I/EG
concentration:
0.01 0.1 1
100
Correlation length, ξ ( Angstrom)
Concentration, c (M)
Slope = -0.4
500
60PMVP-I/NMF
Polyelectrolytes in Solution
Shichen Dou; PSU Colby group

43. Materials Characterization Lab
www.mri.psu.edu/mcl
Core-Shell latex spheres

44. Materials Characterization Lab
www.mri.psu.edu/mcl
Supercritical Fluid Treatment of Polymers
Poly(aryl ether ether ketone) PEEK
high performance thermoplastic with high
impact strength, tensile yield strength and
thermal and chemical resistance
Group studied methyl substituted PEEK annealed in air
and supercritical CO2 to control crystallization
and reduce processing costs.
unpublished Queen’s University, Ontario

45. Materials Characterization Lab
www.mri.psu.edu/mcl

46. Materials Characterization Lab
www.mri.psu.edu/mcl

47. Materials Characterization Lab
www.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalysts
for fuel cell applications
Random pore model;
three supports
Stevens, et al, CARBON 41 (2003)

48. Materials Characterization Lab
www.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalysts
for fuel cell applications
Stevens, et al, CARBON 41 (2003)
SAXS: Pt loadings by mass/ 2 supports

49. Materials Characterization Lab
www.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalysts
for fuel cell applications
Stevens, et al, CARBON 41 (2003)
Pt Size Distribution: Pt loadings by mass/ 2 supports

50. Materials Characterization Lab
www.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalysts
for fuel cell applications
Stevens, et al, CARBON 41 (2003)
•This study used moderately small angle so that size
agreed with WAXS/Scherrer but SAXS best at smaller size
•Generally, WAXS/Scherrer not effective in large sizes (no line
broadening, xtal domain vs. grain domain, no distribution info)
•TEM/SEM: specific areas vs. average important to catalyst
properties

51. Materials Characterization Lab
www.mri.psu.edu/mcl
Deformation Stage SAXS
Toughened Polystyrene
unstressed stressed

52. Materials Characterization Lab
www.mri.psu.edu/mcl
Come see the PSU MCL Molmet SAXS Room 6/7 Hosler