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Materials Characterization Labwww.mri.psu.edu/mcl
SMALL ANGLE XRAY SCATTERING (SAXS)
AUGUST 10, 2005
Mark S. [email protected]
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Materials Characterization Labwww.mri.psu.edu/mcl
250 MRLAugust 179:45 AMParticle Characterization
114 MRI BldgAugust 249:45 AMX-ray photoelectron spectroscopy (XPS/ESCA)
114 MRI BldgAugust 2411:00 AMAuger Electron Spectroscopy (AES)
541 Deike Bldg.July 279:45 AMChemical analysis (ICP, ICP-MS)
541 Deike Bldg.August 109:45 AMSmall angle x-ray scattering (SAXS)
114 MRI Bldg August 39:45 AMAtomic Force Microscopy (AFM)
250 MRL Bldg.July 209:45 AMOrientation imaging microscopy (OIM/EBSD)
114 MRI BldgJuly 1311:00 AMTEM sample preparation
114 MRI BldgJuly 139:45 AMFocused Ion Beam (FIB)
250 MRL Bldg.July 610:15 AMHigh temperature sintering lab (20 min lecture only)
250 MRL bldg.July 69:45 AMDielectric Characterization (25 min lecture only)
250 MRL Bldg.June 299:45 AMX-ray Diffraction (XRD)
541 Deike Bldg.June 2211:00 AMAnalytical SEM
541 Deike Bldg.June 229:45 AMScanning electron microscopy (SEM)
114 MRI BldgJune 159:45 AMTransmission Electron Microscopy (TEM/STEM)
250 MRL Bldg.June 89:45 AMThermal analysis (TGA, DTA, DSC)
LocationDateTimeTechnique
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 HousesSummer Characterization Open Houses
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Materials Characterization Labwww.mri.psu.edu/mcl
BeaverStadium
Park Ave.
Park Ave.
Porter RoadPollock Road
University Drive
College Ave.
Shortlidge Road North
Bur ro w
es Ro ad
00
00
00
00
00
00
00
00
00
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
00
Materials Characterization Lab Locations
Route 322
I-99 00
Steidle Bldg:Nanoindenter
Deike Bldg:
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Materials Characterization Labwww.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
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Materials Characterization Labwww.mri.psu.edu/mcl
200 mesh
400 mesh
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Materials Characterization Labwww.mri.psu.edu/mcl
Scattering ‘Live’ DemoReal Space Reciprocal Space
d1
d2 = d1/2
SOURCE
Scattered Beam (1st order)
Direct Beam - - - - - - -
Scattered Beam (1st order)SD
TAN θ = SD/D
SmallerFor
Larger dSample/Detector D
θ
θ
Smaller d yields larger SD
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Materials Characterization Labwww.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/dd 2θ
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 2θ)Laboratory SAXSSynchrotron SAXS/SANS
Sub Angstrom - 10Å10Å - 1000Å10Å – several 1000Å
Atomic StructuresNano/ Colloidal
Structures(PSU)
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Materials Characterization Labwww.mri.psu.edu/mcl
What kinds of materials?
Compiled by Earle Ryba
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Materials Characterization Labwww.mri.psu.edu/mcl
What kinds of materials?
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Materials Characterization Labwww.mri.psu.edu/mcl
What kinds of materials?
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Materials Characterization Labwww.mri.psu.edu/mcl
Examples from literature
Polymer dendrimersdilute solns in CH3OH to get dendrite sizes
dilute so dendrimers don’t correlate
Alkanediolssolns in water to study clustering
heavy water improves contrast (sans)
Water-based polymer latexesuse anionic surfactant to suspend in water
Macromolecular foamswafers cut & immersed in toluene to get swelling
banded matls are translated in situ
Microemulsionsoils in water to get droplet size
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Materials Characterization Labwww.mri.psu.edu/mcl
Examples from literature
CVD SiGe filmsµ-thin films stacked to get Ge heterogeneity
Nanotubesuse surfactant in water & sonicate; place in quartz cellsto study nanotube aggregation
Powders thin-walled capillaries
Polymersstudy crystallization processes in situ in hot cell
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Materials Characterization Labwww.mri.psu.edu/mcl
Examples from literature
Thin films on glass substratesas is, but requires grazing incidence
Random crystalline block copolymersrheology study in situ in rotating parallel disk cellto get crystal alignment and grain rotations
Splat-cooled glassin situ annealing study to follow pptn of PbTenano-crystals
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Materials Characterization Labwww.mri.psu.edu/mcl
Examples from literature
Blown polymer filmsspecial cell for in situ studies
Liq. Crystalsspecial magnetic cell for molecule rotation
Ionomerscell w/ kapton windows
Hi pressure studiesdiamond windows
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Materials Characterization Labwww.mri.psu.edu/mcl
Mouse bone
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Materials Characterization Labwww.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 SpaceReal Space
I(q)
Not Possible By Direct CalcCalc – Scattering Theory – F.T.
Calc – Auto Correlation Function of ρ (r)
Large rParticulate shapesPhase mixLarge period structures
Small rAtomic positions
•Crystals•amorphous
Amplitude/PhaseSpectra of scatteringfrom individual scatters(continuous/discrete)
Large rCorrelation function, radial distribution
Small rPair (Radial) distribution: Short range atomic ordering (amorphous materials)
Patterson function: Interatomicvectors (crystals)
Large r (SAXS) Diffuse scatterSmall r (WAXS) Diffraction dominatesfor xtals, diffuse scatter for liquids, amorphous solids
Observed scattering intensity-Noise/truncation effects
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Materials Characterization Labwww.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 mixingenergy, etc.)
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Materials Characterization Labwww.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
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Materials Characterization Labwww.mri.psu.edu/mcl
Dilute Particulate models
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Materials Characterization Labwww.mri.psu.edu/mcl
Dilute Particulate models
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Materials Characterization Labwww.mri.psu.edu/mcl
Dilute Particulate Models
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Materials Characterization Labwww.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)
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Materials Characterization Labwww.mri.psu.edu/mcl
Common SAXS Models
Periodic Systems
•Lamellar stacks, ordered copolymers, biologicPeriodic and ordered structures
WAXS methods apply but with emphasis on deviations from ordered structures
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
Photoresist grating
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Materials Characterization Labwww.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 formulatedfor more direct treatment of thermodynamic properties
rather than size and shape)
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Materials Characterization Labwww.mri.psu.edu/mcl
TWO IMPORTANT GENERAL MODEL RESULTS(some interpretation without models)
•GUINIER LAW
•POROD LAW
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Materials Characterization Labwww.mri.psu.edu/mcl
GUINIER LAW
•Even for unknown, irregular or ‘non-describable shapes; scattering has predictable form at low q
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Materials Characterization Labwww.mri.psu.edu/mcl
GUINIER LAW
Valid for
•q << 1/Rg
•Dilute system
•Isotropic (random particle orientation)
•Solvent scattering subtracted
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Materials Characterization Labwww.mri.psu.edu/mcl
POROD LAW
•Predictable relationship between I(q) and total interface areain 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 ondiffuse interphase boundaries
•
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Materials Characterization Labwww.mri.psu.edu/mcl
INSTRUMENTS FOR SAXS
•KRATKY CAMERA
•PINHOLE CAMERA
•LABORATORY SOURCES
•SYNCHROTRON SOURCES
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Materials Characterization Labwww.mri.psu.edu/mcl
KRATKY CAMERA
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Materials Characterization Labwww.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)
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Materials Characterization Labwww.mri.psu.edu/mcl
BEAM CONDITIONING
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Materials Characterization Labwww.mri.psu.edu/mcl
MOLMET (PSU) SAXS
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.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
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Materials Characterization Labwww.mri.psu.edu/mcl
Sample holders
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Materials Characterization Labwww.mri.psu.edu/mcl
Multi-wire Area Detector
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Materials Characterization Labwww.mri.psu.edu/mcl
EXAMPLES
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Materials Characterization Labwww.mri.psu.edu/mcl
r
Calibrates center and q on 58.37 A d-space
Silver Behenate Standard
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Materials Characterization Labwww.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),
norm
aliz
ed in
tens
ity, (
A.U
.)
q, (Angstrom-1)
2.5 mg/ml 5.0mg/ml 10.0mg/ml 20.0 mg/ml
60PMVP-I/EGconcentration:
0.01 0.1 1
100
Cor
rela
tion
leng
th, ξ
( A
ngst
rom
)
Concentration, c (M)
Slope = -0.4
50060PMVP-I/NMF
Polyelectrolytes in Solution
Shichen Dou; PSU Colby group
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Materials Characterization Labwww.mri.psu.edu/mcl
Core-Shell latex spheres
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Materials Characterization Labwww.mri.psu.edu/mcl
Supercritical Fluid Treatment of PolymersPoly(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
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalystsfor fuel cell applications
Random pore model;three supports
Stevens, et al, CARBON 41 (2003)
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Materials Characterization Labwww.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalystsfor fuel cell applications
Stevens, et al, CARBON 41 (2003)
SAXS: Pt loadings by mass/ 2 supports
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Materials Characterization Labwww.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalystsfor fuel cell applications
Stevens, et al, CARBON 41 (2003)
Pt Size Distribution: Pt loadings by mass/ 2 supports
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Materials Characterization Labwww.mri.psu.edu/mcl
Pt particle size in carbon-supported Pt electrocatalystsfor 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
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Materials Characterization Labwww.mri.psu.edu/mcl
Deformation Stage SAXS
Toughened Polystyrene
unstressed stressed
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Materials Characterization Labwww.mri.psu.edu/mcl
Come see the PSU MCL Molmet SAXS Room 6/7 Hosler