Everything You Ever Wanted to Know About Introduction toAfraid to Ask SSRL S But Were SAXS at AX

John A Pople
Stanford Synchrotron Radiation Laboratory, Stanford Linear Accelerator Center, Stanford CA 94309

Scattering or Microscopy?
Microscopy good for: Local detail Surface detail Faithfully represents local complexities

E.g. if objective is to monitor the degree to which Mickeys nose(s) and ears hold to a circular micromorphology use microscopy not scattering

Scattering or Microscopy?
Scattering good for:
Global parameters, distributions; 1st order Different sample states Non destructive sample preparation In-situ transitional studies

Solid

Melted & Sheared

Recrystallized

Complementary Scattering and Microscopy

Ag-Au dealloyed in 70% HNO 3
1000.00 1 min 5 min 15 min 60 min 720 min

5 mins in conc HNO3

200 nm

100.00

60 mins

10.00 L o g In t

1.00 0.01 0.10

0.1

0.01 Log Q

Forming a bi-continuous porous network with ligament width on the nanoscale by removing the less noble element from a binary alloy, in this case Ag-Au (multiple films for trans scattering)

Scattering: Neutrons or Photons?

X-rays Sensitive to electron density contrast Neutrons Sensitive to nuclear scattering length contrast Neutron scattering: Deuteration allows species selection X-ray scattering: Relatively small sample quantities required Relatively fast data acquisition times - allows time resolved effects to be characterized

Scattering: Neutrons or Photons?

Neutrons: Deuteration allows species selection
This essentially permits a dramatic alteration to the visibility of the tagged elements in terms of their contribution to the reciprocal space scattering pattern

Atom
1H 2D

Scattering length Incoherent scattering (x 1012 cm2) (x 1024 cm2) -0.374 80 0.667 2

Scattering: Neutrons or Photons?

Photos of deformation

SANS patterns

= 0%

= 300%

Scattering: Neutrons or Photons?

X-rays: Order of magnitude better spatial resolution Fast data acquisition times for time resolved data

Oscillatory Shearing of lyotropic HPC a liquid crystal polymer

X-ray Scattering: Transmission or Reflection?

Need to be conscious of: Constituent elements, i.e. absorption cutoffs Multiple scattering Area of interest: surface effect or bulk effect Transmission geometry appropriate for: Extracting bulk parameters, especially in deformation Weakly scattering samples: can vary path length

X-ray Scattering: Transmission or Reflection?

Reflection geometry appropriate for: Films on a substrate (whether opaque or not) Probing surface interactions

Rheology of Straight and Branched Fatty Alcohols

Study phase transitions of Langmuir monolayers of mixed fatty alcohols in terms of molecular branching and surface tension linear eicosanol (C20H42O, MW = 298)
00

Linear Eicosanol
00 00

00

00

00

increasing surface pressure: 0 to 40 mN/m

14

13

q (/nm)

15

16

branched eicosanol (C20H42O, MW = 298) Surface tension sensor

Gold mirror x-ray path

Langmuir trough

X-ray Scattering: SAXS or WAXS?

No fundamental difference in physics: a consequence of chemistry

WAXS patterns contain data concerning correlations on an intramolecular, inter-atomic level SAXS patterns contain data concerning correlations on an inter-molecular level: necessarily samples where there is macromolecular or aggregate order As synthesis design/control improves, SAXS becomes more relevant than ever before

X-ray Scattering: SAXS or WAXS?

Experimental consequences WAXS: Detector close to sample, consider: Distortion of reciprocal space mapping Thermal effects when heating sample No ion chamber for absorption SAXS: Detector far from sample, consider: Absorption from intermediate space Interception of appropriate q range

Recognizing Reciprocal Space Patterns: Indexing

Face centered cubic pattern from diblock copolymer gel

Recognizing Reciprocal Space Patterns: Indexing

Real space packing Hexagonal

Face centered cubic Reciprocal space image (unoriented domains) Normalized 1; =4/3; =8/3 peak positions

Body centered cubic

1; =2; =3

1; =3; =4

Recognizing Reciprocal Space Patterns: Preferential Orientation

Real space packing

Reciprocal space Randomly image aligned rods

Preferentially aligned rods

Hydrated DNA

Extracting Physical Parameters from X-ray data

I(q)

I()

Extracting Physical Parameters from X-ray data

Molecular size: Radius of gyration (Rg)

ln I(q)

I(q) = I(0) exp [-q2Rg2 / 3]

q2

Rg2 ln I(q) / q2 Guinier region: q < 1 / Rg

Guinier plot

Extracting Physical Parameters from X-ray data

Molecular conformation: Scaling exponent
Guinier plateau Gradient of profile in intermediate region implies fractal dimension of scattering unit

ln I(q)

Intermediate region

Rod Coil in good solvent Sphere

q-1 q-5/3 q-4

ln q

Molecular Conformation in Dentin

John H Kinney
Department of Preventive and Restorative Dental Sciences, University of California, San Francisco, CA 94143

DEJ

pulp

SAXS pattern

Molecular Conformation in Dentin

2.2
16G213 16G224 17G246

2 1.8

Scaling exponent

1.6 1.4 1.2 1 0 0.5 1 1.5 2

Distance from pulp (mm)

Molecular Conformation in Dentin

Shape change of mineral crystallites from needle-like to plate-like from pulp to dentin-enamel junction (DEJ).

Scaling exponent

2.2 1.8 1.4 1

plate-like

needle-like
40

DEJ
35

pulp

0.5 1 1.5 2 Distance from pulp (mm)

I(q)

30

25

3 3
0.2

Control tooth 4 5 6 DI tooth

0.4 q / nm-1 0.6 0.8

20

Dentinogenesis imperfecta (DI) teeth shown to exhibit impaired development of intrafibrillar mineral: characteristic scattering peaks are absent from the diseased tooth.

15

10

Extracting Physical Parameters from X-ray data

Molecular conformation: Persistence length of coiled chain I(q) q2 Kratky plot

q*

persistence length = 6 / ( q*)

Extracting Physical Parameters from X-ray data

Molecular orientation: Orientation parameter P2 <P2n(cos )> = I(s,) P2n(cos ) sin d I(s,) sin d I() Normalized: -0.5 < P2 < 1

q
0 0

Azimuthal profile

Molecular Orientation in Injection Moldings

Measuring the degree and inclination of preferential molecular orientation in a piece of injection molded plastic (e.g. hip replacement joints). ~ 1500 WAXS patterns Marks the injection point Orientation parameters: 0 < P2 < 0.3 Axis of orientation

SSRL Beamline 1-4: SAXS Materials Science ion chambers shutter X-rays

N2 supply

sample stage CCD detector

guard slits

beam defining slits

optical rail & table