Instituto de Estructura de la Materia, CSIC - ALBA · Instituto de Estructura de la Materia, CSIC [email protected] SAXS Workshop Barcelona, 1st October 2014 . SAXS Workshop

Mari Cruz García Gutiérrez

Instituto de Estructura de la Materia, CSIC

[email protected]

SAXS Workshop

Barcelona, 1st October 2014

SAXS Workshop. Barcelona, 1st October 2014 [email protected]

Hierarchical structures and techniques

Basics about X-ray scattering and polymers

Wide angle X-ray scattering (WAXS) and small angle X-ray

scattering (SAXS)

Microfocus X-ray scattering (mWAXS y mSAXS)

Grazing incidence X-ray scattering (GIWAXS y GISAXS)

Crystallography Microstructure Structure

Proteins Virus

Bacterias

Granular

structures

Polymers

Atomic

structure

Porous

materials

10-11 10-9 10-7 10-5 10-3

Size (meters)

Length scales

SEM

Optic microscopy Techniques

WAXS SAXS Scanning X-ray

microdiffraction

Neutron

diffraction TEM

Electron

diffraction

AFM STM


10-8 m

5x10-10 m

Tg <T < Tm

X-ray scattering (WAXS)

Neutron scattering

SAXS; SANS;

AFM

10-5 m

Light scattering

Optic microscopy

AFM


sample X-ray source

2

SAXS interface : WAXS interface

2’

WAXS

SAXS

q (nm -1

)

0.0 0.5 1.0 1.5 2.0

I (a

rbb

itra

ry u

nits)

0.0

0.5

1.0

1.5

2.0

~ 10nm

s(nm-1)

1.0 1.5 2.0 2.5 3.0 3.5

I(a

.u.)

PBT

S (nm-1)

~ 5Å


Detector SAXS Detector WAXS Sample environment

Vacuum chamber



X-ray beam

rotating

cilinder

sample

detector

movement

at rest

PS in methanol


WAXS SAXS

: I Sics et al, Rev. Sci. Instrum.

71,1733 (2000)

DS

WAXS

q (Å-1

)

0.8 1.2 1.6 2.0

Inte

nsid

ad

SAXS

q (Å-1

)

0.02 0.04 0.06 0.08 0.10

I×q

2

DS

Log10

[F/Hz]

3 4 5 6

"

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.26

10

120

10

120

10

120

tie

mp

o

tie

mp

o

tie

mp

o

Structure Dynamics

Uniaxial deformation

SAXS/WAXS +

Raman

X-rays

Camera

Raman

Stress-strain

S. Ran et al, Rev. Sci. Instrum. 74, 3087 (2003)

Complementary information about

the structural evolution of

molecular chain in the amorphous

phase, mesophase and crystalline

phase.

BNL, Spring-8

Processing

SAXS/WAXS

S. Ran et al, Colloid Polym. Sci. 282, 802 (2004)

BNL



strain (%)

0 50 100 150 200 250 300 350 400 450

Str

ess (

MP

a)

0

2

4

6

8

10

12

14

(PBT-PTMO)

(PBT-PTMO)+0.2%SWCNT

(PBT-PTMO): 75.8 MPa

(PBT-PTMO)+SWCNT: 87.6 MPa

Young’s Modulus:

(PBT-PTMO): 8.4 MPa

(PBT-PTMO)+SWCNT: 9.1 MPa

Yield Strength:

(PBT-PTMO): 420%

(PBT-PTMO)+SWCNT: 170%

Elongation-to-break:

“Deformation behavior during cold drawing of nanocomposites based

on single wall carbon nanotubes and poly(ether ester) copolymers” J.J.

Hernández, M.C. García-Gutiérrez, et al.; Polymer 48, 3286 (2007)


strain (%)

0 50 100 150 200 250 300 350 400 450

Str

ess (

MP

a)

0

2

4

6

8

10

12

14

(PBT-PTMO)

(PBT-PTMO)+0.2%SWCNT

relaxed

Str

ess (

MP

a)

1 2 5 4 3 relaxed

SAXS

WAXS

2

3

4

5

1

3

4 5

2

6

relaxed

1 2 3 5

6 relaxed 4

(PBT-PTMO)

equator +- +-

(PBT-PTMO)+SWCNT


A

B

C

D

E

L

Leq

r

e

l

a

x

e

d

L’

Leq’

L>L’ Leq<Leq’

A

B

E

D

C

F

Copolymer Nanocomposite


focalized X-ray beam ( 0.5 mm)

video-microscope

scan in xyz

CCD

sample

Scanning set-up @ ID13 (ESRF)

SAXS

WAXS


3*3 mm

compression

6 1

2 UHMW-PE

C. Riekel, M.C. García-Gutiérrez, et al.;

Anal. & Bioanal. Chem. 376, 594 (2003)


2A 3

M. Kastler et al. Adv. Mater.

18, 2255 (2006)


30 mm

SEM

AAO Membrane + solution (30wt% PVDF-Dimethylacetamide)

5 mm

PVDF nanofibers


“Confinement-induced one-dimensional ferroelectric polymer

arrays” M.C. García-Gutiérrez, et al.; Nano Letters 10, 1472 (2010)

bulk nanoarray

q (nm-1

)

0 5 10 15 20 25 30 35

Inte

nsity (

a.

u.)

0

500

1000

1500

2000

2500

3000

3500

q (nm-1

)

0 5 10 15 20 25 30 35

Inte

nsity (

a.

u.)

0

50

100

150

200

250

300

bulk nanoarray

100

020

110

200 002

a form g form 020

002 / 110

022


2 mm SAXS

b

020

022 002 / 110

“Probing the internal structure of high-performance fibers by on-axis scanning

diffractometry” R. Davies et al. Macromolecules 40, 5038 (2007)

Tamaño de haz =

500nm

“X-ray microdiffraction study of SWCNT alignment

across a fiber” V. Pichot et al. EPL 79, 46002 (2007)

Beam size< 100 nm

“Coherent X-ray diffraction imaging with nanofocus illumination”

C.G. Schroer et al. PRL 101, 090801 (2008)



qz

qy

qz

qy

2p/d

qz

qy

2p/d

qz=2p/l sin (ai+af)

qy=2p/l sin(w)cos(af)

ai << 1

ai ~ ac

• GIWAXS/GISAXS → similar to WAXS/SAXS but in reflection geometry

• Length scales range: from Angstroms to several microns

• Structure and morphology: size, shape and order

• Depth sensibility (buried structures)

• Average of illuminated area (~ cm2)

• Real time experiments


X-rays

Detector

BW4 beamline @ HASYLAB, Hamburg

Sample environment



y

y=0mm Au Dy=50 mm

300mm 200mm 400mm

600mm

0.205

0.300

0.395

0.110

PS 3500mm

0 -0.098 0.098

qy [Å-1]

qz [Å-1]

800mm 900mm

X-ray

5mm

“Combinational investigation of the isolated nanoparticle to coalescent layer transition in a gradient

sputtered gold nanoparticle layer on top of polystyrene” S. Roth, et al.; Appl. Phys. Lett. 88, 021910 (2006)


Thin films: Spin-Coating

Thickness(~nm) : concentration; w

LIPSS: Interference between the incident light and the light dispersed by the surface.

L

Periodicity:

Laser parameters:

Wavelength (266 nm)

Fluence (~ mJ/cm2)

Number of pulses


Laser-Induced Periodic Surface Structures (LIPSS)

Laser-Induced Periodic Surface Structures (LIPSS)

Fluence:

7 mJ/cm2 100 pulses 600 pulses 3000 pulses

(a) (b)(a) (b)

Poly (trimethylene terephthalate) (PTT),

x=3

600 pulses

AFM

I. Martín-Fabiami, et al.; Langmuir 28, 7938 (2012)



Laser-Induced Periodic Surface Structures: GISAXS

Simulated GISAXS

H; R; W: Measured by AFM

H

2R

2W

In order to assess the level of order we used a one-

dimensional paracrystalline lattice

L

The probability of finding a particle at a distance L

is defined by a probabilistic function p(x)

paracrystalline distortion parameter: g= DL/L

DL

IsGISAXS http://www.insp.jussieu.fr/axe2/Oxydes/IsGISAXS/isgisaxs.htm, 2002

g→ 0


Nanoimprint lithography (NIL)

Clean room (IMB-CSIC)

RIE

Fabrication of mould:

Nanoimprint:

5x5 mm2

Mould

5x5 mm2

NIL


GISAXS: NIL vs LIPSS

LIPSS

Mould NIL

Experimental GISAXS:

Simulated GISAXS:

D.R. Rueda et al.; J. Appl. Cryst. 45, 1038 (2012)



• Europe: - ESRF: ID2, ID10, ID13, BM26

- Alba:NCD

- Diamond: I22

- Soleil: SWING

- BESSY: mSpot

- Elettra: BL5.2L

• UUEE: - APS: 1-ID, 8-ID, 18-ID

- ALS: 7.3.3

• Asia: - Spring-8: BL08B2, BL40B2, BL45XU


Condensed Matter Physics, G. Strobl, Springer.

Neutrons, X-rays and Light: Scattering Methods Applied to Soft

Condensed Matter P. Lindner, T. Zemb Ed., Elsevier: 2002.

Small Angle X-ray Scattering, O. Glatter, O. Kratky Ed., Academic

Press, London (1982).

Synchrotron Light to Explore Matter, ISBN 3-540-14888-4 ©

Copyright IMediaSoft® (Bucharest and Meylan) ESRF (Grenoble)

and Springer-Verlag (Berlin, Heidelberg) 2001.

Applications of Synchrotron Light to Scattering and Diffraction in

Materials and Life Sciences, T.A. Ezquerra, M.C. García-Gutiérrez, A.

Nogales, M.A. Gómez Ed., Lect. Notes Phys. 776 Springer, (Berlin,

Heidelberg) 2009.

AUSE: http://auseweb.wordpress.com/

ESUO:http://www.elettra.trieste.it/ELISA/index.php?n=Main.EuropeanSy

nchrotronUserOrganization


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Documents

Instituto de Estructura de la Materia, CSIC - ALBA · Instituto de Estructura de la Materia, CSIC [email protected] SAXS Workshop Barcelona, 1st October 2014 . SAXS Workshop