X-ray Diffraction

for powder sample

Rigaku Corporation
Application laboratory
Keigo Nagao

Todays topics (AM)

z Features of Rigaku TTRAX
z Basics of powder XRD
Feature of XRD
Evaluation item

z Texture analysis for bulk sample

Measurement and Process

z SAXS for nano-size sample

Principle and Optics
Application

Feature of TTRAX

Rigaku TTRAX
2

X-ray
source

Detector

Sample holder
In-Plane measurement
(2/scan)

Horizontal goniometer
High power X-ray source
Parallel beam method
In-Plane axis

Feature of TTRAX

In case the sample isnt set to horizontal.

Hard-to-pack sample

Thin layer sample

Semi-liquid sample

Feature of TTRAX

In Horizontal goniometer
Hard-to-pack sample

Independent on
sample condition

Thin layer sample

Semi-liquid sample

Feature of TTRAX

High power X-ray source

Rotating anode X-ray tube
1018kW

Sealed-off X-ray tube

23kW
Cooling
water
Be
window

Target

Feature of TTRAX

Geometry for powder sample

z Focusing method

Parallel Beam
Detector

RS

X-ray source
DS

X-ray source
Detector

SS

DS
Multi layer
Miller

Parallel slit analyzer

Sample

Sample

Focusing method

Parallel beam

Systematic error

1. Flat sample
2. Umbrella effect
3. Adsorption effect
4. Eccentric error

Umbrella effect

Intensity

Strong

medium

Feature of TTRAX

Cross Beam Optics

Rigaku patented technology
BB and PB geometries are simultaneously mounted, aligned, and selectable.
X-ray source
BB selection slit

PB selection slit

Multilayer mirror
Sample
Focusing geometry (BB)

Sample
Parallel beam geometry (PB)

Feature of TTRAX

Measurement of rough sample surface

Focusing method
Parallel beam
Sample : Zeolite

Flat

10

11

12

13

14Rough 5

2(deg)

10

11

12

13

14

2(deg)

Hold of peak shape, peak position and FWHM

Feature of TTRAX

Free from Eccentric error (Parallel beam)

0 order
detector

X-ray source

2
Receiving slit : open
Parallel slit analyzer
X
2-

Datum surface
Eccentric surface

2
2

Basics of XRD
Interaction of substance and X-ray :1

Braggs condition of diffraction

z The conditions for a reflected ( diffracted ) beam are given
by the relation

2dsin = n

Braggs equation

2dsin =

X-ray wavelength
n1,2,3

dInterplanar spacing
Bragg angle

Basics of XRD
Interaction of substance and X-ray :2

X-ray diffuse scattering

Scattering angle
( 2 = 0~10 deg. )

Sample

1000
Intensity ( a.u. )

X-ray

100
10
1
0.1
0

10

2 (deg.)

Basics of XRD
Interaction of substance and X-ray :3

Reflection and interference

Two beams reflected on the
surface and the interface
interfere each other.

X-ray reflectivity profile

reflection
0

10

refraction

-1

10
Reflectivity

-2

10

-3

10

refraction

reflection
-4

10

2/ (degree)

Basics of XRD

Evaluation item in powder sample

z more than 2=5deg
Peak
Peakpositions
positions
ddvalues
values: : Phase
PhaseIdentification
Identification
Lattice
Latticeconstant
constant
ddshift
shift : : Residual
Residualstress
stress
Solid
Solidsolution
solution

Intensity
Intensityvs.
vs.Orientation
Orientation
Preferred
Preferredorientation
orientation
Fiber
structure
Fiber structure
Pole
Polefigure
figure

FWHM
FWHM
Crystal
Crystalquality
quality
Crystallite
Crystallitesize
size
Lattice
Latticestrain
strain

Integrated
IntegratedInt.
Int.
ofofamorphous
amorphous

Crystallinity

: :Quantitative
Quantitativeanalysis
analysis

Intensity

Integrated
IntegratedInt.
Int.
ofofcrystal
crystal

Angle2

Basics of XRD

Phase Identification in X-ray diffraction

Intensity ( counts )

z The powder diffraction pattern is characteristic of the substance

z The diffraction pattern indicates the state of chemical combination

Anatase
(Photocatalyst etc)

TiO2

2 ( deg. )

Rutile
(Cosmetic etc)

Basics of XRD

Quantitative analysis(RIR method)

The concentration of each phase is calculated by
integrated intensity and RIR value
Polymorphs of TiO2
Rutile (RIR:3.40)
Anatase (RIR:3.30)
Brookite
Preparation
Rutile:Anatase=3:1
Result
Rutile: 71.6wt%
Anatase: 28.4wt%

Basics of XRD

Crystallite size
Polycrystal
There is one or multiple crystalline in one particle.

Small angle
X-ray scattering

Crystallite size

Particle
size

The width of
diffracted line
Scherrer method
Hall method

Basics of XRD

Crystallite size -MoThe width of diffracted line broaden in crystallite size

less than 100nm(1000)
Debye ring
12.0

Mo

(CPS)
Intensity(cps)

10.0

900

900

100

8.0
6.0
58.0 58.1 58.2 58.3 58.4 58.5 58.6 58.7 58.8 58.9 59.0 59.1 59.2 59.3

100

4.0
2.0
x10^3

I
40

Molybdenum - Mo
50

60

70

80

2(deg)

Basics of XRD

Crystallinity
Plastic wrap

Crystallinity .

10

40-1995> (CH2)x - N-Paraffin

15

20

25

30
2(deg)

35

40

45

Basics of XRD

Change of lattice constant

Monitoring the change of lattice constant in real time
in situ measurement

3500

Intensity(CPS)

3000

2dsin=
35.12 35.16

Al2O3
25.56 25.58

2500
2000
1500

900

25

1000
500
0
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

2(deg)

10

Basics of XRD

Stress and interplanar spacing

Compressive stress

d1

d1 > d2 > d3 > d4

d2

d3

Tensile stress

d1

d4

d1 < d2 <d3 < d4

d2

d3

d4

Braggs condition of diffraction

2d sin = n

Basics of XRD

Peak shift and sin2diagram

N(N)

Normal line of sample surface :N

=0
=0

:N

Intensity(counts)

Normal line of lattice plane

2(deg)

sin2

11

Basics of XRD

Calculation of stress value

(stress value) K

sin2 Slope of sin2 diagram

-E
cos0
Kstress constant)
180
21
Material-specific value
Eyoungs modulus, poisson ratio,
0diffraction angle in stress free condition
N

SC

XG

N
tension

SC

XG

minus psi

plus psi

compress

2
compress

tension

Iso-inclination method(Fixed Psi)

sin2 0

sin2

Basics of XRD

Measurement of residual stress

z Iron plate

Before rubbing
Sample

After rubbing

12

Texture evaluation and

pole figure analysis
for bulk sample

Texture evaluation

Texture and substance

Nonoriented samplebrick, concrete, (powder)
Oriented samplealuminium foil
iron plate
plastic bottle
Single crystalsilicon waferdiamondquartz

13

Texture evaluation

What is oriented sample?

The condition that a lattice plane faces to the same direction

Metal orientation
(rolled sample)

Approximate equivalent
to single crystal

Uni-axial
orientation

(Epitaxial film)

fiber orientation

Texture evaluation

2D image and 2-I diffraction pattern

oriented

nonoriented

2D image

Diffraction
pattern
2

14

Texture evaluation

What is the purpose of texture?

Which plane is faced to Rolling direction and Normal direction?
X

Y
a

Texture evaluation

Spherical projection method and

Stereographic projection method
3D is described with 2D

Stereographic
projection figure

Spherical projection method

Stereographic projection method

15

Texture evaluation

Pole figure
RDRolling direction
X

TD
Transverse
direction

Z
TD

NDNormal direction

Texture evaluation
Sample behavior
in Reflection method and Transmission method

Reflection
method

Beta rotation at each alpha angle

Alpha:5deg step
(ex.15208590deg)
Beta: 5deg step
(ex.05355360deg/ angle)

rotation
rotation

Transmission
method

Sample is moved centering around purple line

16

Texture evaluation

Orientation analysis :step1

Pole figure of (111) in rolled Cu-Zn(70-30)
20 RD

90

Wulff net.

62

The angle between RD and each pole is

estimated with Wulff net.

Texture evaluation

Orientation analysis :step2

Polar net

90

35

The angle between ND and each pole is

estimated with Polar net.

17

Texture evaluation

Orientation analysis :step3

Angle between plane in (h1k1l1) and (h2k2l2) of cubic crystal
(h1k1l1)
100
110

100
0
90
45
90

111

54.7

210

26.6
63.4
90
35.3
65.9

211

(h2k2l2)

ND

RD

110
0
60
90
35.3
90
18.4
50.8
71.5
30
54.7
73.2
90

111

0
70.5
109.5
39.2
75.0
19.5
61.9
90

210

211

0
36.9
53.1
24.1
43.1
56.8

0
33.6
48.2

Texture evaluation

Orientation analysis :step4

Angle between plane of cubic

111110=35.590

ND

111211=19.561.990

RD

Rotate standard (110) projection of cubic crystal

35degree clockwise.
RD is [112]
This texture is (110)[112]. (hkl)[uvw]=h*u+k*v+l*w=0
ND

RD

18

Texture evaluation

Process by stereographic objection figure

Rotate 35degree

[112]

RD

[112]

Standard (110)objection of cubic crystal

Small angle X-ray scattering

for nano-size sample

19

Small angle X-ray scattering

Purpose of SAXS
Small Angle X-ray Scattering

z Particle size estimation (X-ray scattering)

z Phase identification (X-ray diffraction)

Particle size
the distribution

molecular
structure

Small angle X-ray scattering

Principle of SAXS

X-ray

Scattering angle
( 2 = 0~10 deg. )

Sample

Scattering

Diffraction 2dsin=n
1000
Intensity ( a.u. )

Intensity ( a.u. )

1000
100
10
1
0.1

100
10
1
0.1

5
2 (deg.)

10

2 (deg.)

20

Small angle X-ray scattering

Particle information
z Particle size and particle distribution

Intensity ( a.u. )

1000

Shape of SAXS profile

: Breadth of distribution

100
10
1

Slope of SAXS profile : Average size

0.1
0

10

2 (deg.)

Small angle X-ray scattering

Phase information
z Long-period structure
1000
Intensity ( a.u. )

Peak position of SAXS

: Structure and Interval

100

1/3
1/2

10
1
0.1
0

2 (deg.)

21

Small angle X-ray scattering

Instrument for SAXS

Ultima

TTRAX III

NANO-Viewer

Small angle X-ray scattering

Point focus optics

z NANO-Viewer ( 2D-SAXS System )

Semiconductor
2D detector Pilatus100k

2D image

X-ray
source

1st slit

2nd slit

2D detector

3rd slit

Sample

3slits optics

22

Small angle X-ray scattering

NANO-Solver

Intensity ( a.u. )

Distribution ( a.u. )

z Automatic particle size & distribution estimation !

4 6 8
2 (deg.)

0
5
10
Particle / Pore size ( nm )

10

size
distribution

SAXS
profile

Closely particle

sphere

cylinder

Core/shell

Small angle X-ray scattering

Relations of size and profiles

Intensity (a.u.)

z Size : 60nm

Intensity (a.u.)

z Size : 3nm

4
6
2 (deg.)

10

4
6
2 (deg.)

10

Normalized dispersion : 10 %

23

Small angle X-ray scattering

Relations of dispersion and profiles

z Dispersion : 90 %

Intensity (a.u.)

Intensity (a.u.)

z Dispersion : 10 %

4
6
2 (deg.)

10

4
6
2 (deg.)

10

Average diameter : 3 nm

Small angle X-ray scattering

Applications of SAXS
Particle size estimation
( transmission mode )

24

Small angle X-ray scattering

SAXS profiles and size distribution

z Au nanoparticles
No.1
No.2
No.3

104
103
102
101
100
0

4
6
2 (deg.)

No.1
No.2
No.3

Distribution( a.u.)

Intensity (CPS)

105

2
4
6
8
Particle size ( nm )

10

Small angle X-ray scattering

Comparison of TEM image

TEM image

SAXS

No.2

No.3

Distribution( a.u.)

No.1

No.1
No.2
No.3

4
6
8
Particle size ( nm )

10

25

Small angle X-ray scattering

Nano size of porous silica

Intensity (a.u.)

Intensity (a.u.)

z Mesoporous silica

2
3
2 (deg.)

2
3
2 (deg.)

26