X-Ray 2023

4.
X-RAY ANALYSES OF POLYMERS

Characterization of Polymers - Methods
Methods of Polymer
Characterization
Spectroscopy Chromatographic
methods: methods:
UV-VIS, FT-IR, GC, GPC, MALDI
NMR, EPR
Microscopy
Thermal methods:
methods: PLM, SEM,
TEM, AFM
DSC, TGA,
DMA
Light
Scattering
Mechanical methods;
Tensile, shear and
X-ray methods:
impact strengths,
WAXS, SAXS
moduli, etc
(static, dynamic)
Planning of the Segment
1. Introduction to X-ray techniques and relation with other methods
2. Basic definitions of X-ray. Moduli in an X-ray apparatus
3. Basic theory of X-ray scattering

4. Examples of nanostructure characterization in polymers
Caracterização de Polímeros 2023-24 3

X-ray experiments – visualizing the
small invisible
The use of X-ray
absorption for imaging.
Images in normal scale are
produced. No
magnification, no data
about the structure of the
material.
Phase contrast due to
different
absorption capability
Phase contrast due to different

absorption capability
X-ray experiments – visualizing the big
invisible
Phase contrast due to different

emission capability
Diffraction vs Real imaging
Polymers
Biological materials
Metals, alloys
Nanopowders
Solutions with sufficient
scattering volume
Patterns caused by the nano-structure but not depicting the

sample morphology
Caracterização directly !
de Polímeros 2023-24 6
Hierarchical Structures – Observation
and Structural Characterization
DNA molecule - direct observation by high

resolution electron microscope
Place cursor on image
to animate it.
X-ray pattern of DNA – Watson/Crick

and its analysis
Morphology of Polymers – Introduction:
Aggregates of Polymer Chains
Single Crystals - Macroscopic
Al2O3 single crystals
The Culinan diamond

Single Crystal Structure

Single Crystals in Polymers
•Single Crystals

Ordering in Polymers – chain folding
Chain folding: Chain folding:

regular Random switchboard
• Single Crystals
• Lamellar Cyrstals from the Melt
Two-phase model for a

semcrystalline polymer:
The concept of the Long period
L = l a + lc

Crystalline in Polymers - Scheme
Low crystallinity High crystallinity
Fringed micelle model A lamellar stack

Crystalline Polymers – Semicrystalline!
Some polymers are semicrystalline Materials – PE, PA6, PET….
Features:
• Imperfect crystal morphology. Polymer crystals are small and defective
(known since 1957);
• Partial crystalline structure, e.g., coexistence of crystalline and
amorphous phases
• Crystallinity Index Xc (masss) or Vc (volume):
- Xc = Mc /M wherein Mc = mass of the crystaline phase; M = total sample mass
Same with the volume!

Crystalline Polymers - Spherullites
- Spherullites - Spherullite Growth

Crystalline Polymers
- Spherullites
Kepler & Anderson, Adv. In Physics, 1992, 41, 1, 1-57

Spherulites in Semicrystalline Polymer - Microscopy

Crystalline Polymers – Oriented Morphologies

Fibril
Crystalline
Lamella


Lamellar Stakes in Polymers - SAXS
L = la + lc
Model of a
semicrystalline
polymer

Crystalline Polymers – Orders of Magnitude
Orders of Magnitude in Polymers

X-rays – The WAXS and SAXS modes
WAXS
diffraction at crystal lattice
diffraction angles: 2-170° (d = 5-10 Å)
SAXS
scattering at particles or
incident electron density changes
d
scattering angles: 0-2°
X-ray beam
(L = 30 – 500 Å )

WAXS and SAXS Structure Determination
WAXS
SAXS

Basic Theory of X-ray Scattering
Diffraction
Types of X by the
– ray
experiments
crystalline lattice
(WAXS and SAXS)
Absorption by the Inducing of secondary X-

material ray radiation in the
(X-ray defectoscopy) material
(X-ray spectral analysis)
Structure determination by X-
ray scattering methods
Diffraction by the
crystalline lattice
(WAXS and SAXS)
Crystalline lattice Defects in the

parameters crystalline lattice
(WAXS) (SAXS, WAXS)
Size of the Degree of Orientation of

crystallites crystallinity the crystallites
(SAXS) (WAXS) (WAXS, SAXS)

Polymer Monocrystals –
visible by electron
microscopy
Crystallographic information from X-ray studies

Crystalline lattice and unit cell - definitions

Crystalline lattice types:
Triclinic a ≠ b ≠ c; α ≠ β ≠ γ
Monoclinic: a ≠ b ≠ c; α = β = 90 ≠ γ
Orthorhombic: a ≠ b ≠ c; α = β = γ = 90
Tetragonal: a = b ≠ c; α = β = γ = 90
Trigonal: a = b = c; α = β = γ ≠ 90
Hexagonal: a = b ≠ c; α = β = 90; γ = 120
Cubic: a = b = c; α = β = γ = 90
If we know the unit cell

parameters, we can describe
the whole crystal.

Examples of Lattice Indexing
Triclinic (a ≠ b ≠ c, α ≠ β ≠ γ) unit cell .
http://www.doitpoms.ac.uk/tlplib/miller_indices/lattice_examples.php
Caracterização de Polímeros 2023-24

4. Basic Theory of X-ray Scattering
Examples of Lattice Indexing

PA66
PEAD
Alexander, "X-Ray Diffraction Methods in

PBTD Polymer Science"

Bigger Orders - SAXS
kebab
stacked lamellae shish
Lamellar structure and orientation – 2D SAXS

Lamellar Stakes in Polymers - SAXS
kebab
stacked lamellae
shish
http://www.chemie.uni-hamburg.de/tmc/stribeck/focus/index_e.html
Why X-ray methods for structure characterization?
Non-destructive methods – easy (or none) sample preparation.
Deep insight into the structure in various length-scales at the same time
– from 0.5 to 1000 nm.
Obtaining of averaged structural data (over an area of up to several mm2
Some limitations:
Indirect method (structure not seen directly)

Relatively complex data handling
Necessity of adequate models for data interpretation

X-rays – Basic definitions
The interaction of X-rays with matter leads to two principal effects:
Absorption of X-rays.
Scattering of X-rays.
X-Ray Scattering could be two types:
Without changes of the X-ray wavelength (so-called Rayleigh scattering or

coherent scattering). No exchange of energy occurs between the X-ray photons and
the electrons of the sample (elastic interaction). Only the coherent scattering gives
rise to systematic interference effects between rays scattered by different volume
elements.
With small changes of the X-ray wavelength (so-called Compton's (incoherent)

scattering. Gives rise to the continuous background in the X-ray patterns. Energy
transfer occurs between the photons and the electrons of the sample

Nature of X-rays
Relation to the other radiation types

Type of radiation Wavelength Frequency Corresponding transitions
(m) (Hz)
Gamma rays 10-12–10-10 1020–1018 Nuclear
X-rays 10-10–10-8 1018–1016 Of the internal electrons
UV and visible 10-8–10-6 1016–1014 Of the external electrons
IR 10-6–10-4 10-14-1012 Vibrational (IR)
Microwaves 10-4–10-1 1012-109 Of radicals (EPR - electron
paramagnetic resonance)
Radio waves >10-1 >109 Rotational (NMR)
Nature of X-rays
X-rays are short-wavelength electromagnetic waves (EM).
Electric vector: E = A0 sin[2px/l -2pnt]

Magnetic vector: B = B0 cos[2px/l -2pnt]
The magnetic and electric waves are out of phase by 90º.

E and A are vectors. l is the wavelength, n is the frequency
l and n are related by the velocity of the EM wave,

which in vacuum is close to the speed of light, c.
l = c/n (c = 3 x 108 m/s)
EM radiation can always be assumed to travel in a straight line.

Nature of X-rays
EM radiation (including X-rays) has an energy and can be

considered also as a flux of a number of particles with no mass
called photons whose energy is given by the Planck's law:
E = hn = hc/l (h = 6.63x10-34J.s
In agreement with the wave-photon dualism, EM radiation

can be regarded either as a flux of photons or as a
package of waves.
Nature of X-rays
In-phase waves: all their maximums coincide in space.
Coherent beam: contains in-phase waves only.

Incoherent waves can interfere with each other leading to
reduction (destructive interference) or increase (constructive
interference) of the amplitude of the electric vector E.
Well-collimated beam: contains waves progressing in the

same direction.
Divergence of the beam: well-collimated beams have low
divergence and vice versa.
Monochromatic X-ray beam contains only waves characterized

by the same frequency or wavelength.
Bragg Law
Definition: For an incident, well-collimated X-ray wave of

monochromatic wavelength λ coherent diffracted waves are
produced at an angle 2q from the incident direction, if the
diffracting material has domains, which interact with the radiation
and are spaced at a distance d:
l 1
d =
2 sin q
Any X-ray equipment must have: 1. Source of monochromatic X-

rays; 2. X-rays collimation system; 3. Detector for revealing the
scattering pattern. Caracterização de Polímeros 2023-24 41
X-rays – Basic setups
Grazing incidence Bragg - Brentano
θ
2θ
www.gisaxs.de
Transmission
mode

X-rays – The X-ray scattering setup
Principal Components of an X-ray setup – transmittance mode

beamstop
x-ray x-ray x-ray
source optics beam specimen Short SD
Detector distances - WAXS
4-20 cm
Large SD
distances - SAXS
80 - 300 cm
X-rays – The X-ray scattering setup
Bragg - Brentano
SDD = Constant
θ
2θ
X-ray setups - The commercial Bruker
AXS NanoStar
X-ray source with

X-coupled Göbel Mirrors
Versatile Pinhole Sample chamber

optics 2-D detector
And beam stop

X-ray setups - The commercial Bruker
AXS WSAXS
X-ray source with

X-coupled Göbel Mirrors
Versatile Pinhole Sample chamber

optics 2-D detector
And beam stop
Transmission
mode
X-ray setups – transmission mode
details
◼ 100 mm
WAXS
◼ 40 mm
◼ 650 mm
SWAXS

details
◼ 106 cm
SAXS
Typical resolution for the NanoSTAR with Cu radiation:

Distance Attainable
Accessible q-range
Sample – Detector Resolution Rmax
1060 mm qmin = 0.008 Å-1 Rmax = 785 Å
650 mm qmin = 0.01 Å-1 Rmax = 628 Å
100 mm 0.07 Å-1 – 3.00 Å-1 3 Å - 90 Å
40 mm qmax = 2.8 Å-1 Rmin = 2 Å
X-rays – How to produce X-rays?
These high-frequency (1016 – 1018 Hz) electromagnetic radiation is

caused by a change in the momentum of a charged particle (e.g.,
electron) by:
- Bombarding a metal target by high-speed electrons (vacuum tube);
- Accelerating electrons in vacuum and suddenly changing their path

(synchrotron);
- Decelerating electrons by special coatings (old TV screens);
- Nuclear explosions and cosmic events.
X-ray have extremely high penetration ability. Most materials (with

the exception of the heaviest metals) are transparent for them.
details
Incident charged particle of high energy

K-shell electron
L-shell electron
Atom of the metal target

Theoretical Aspects of X-ray formation

White radiation – the halo. Results from
deceleration of incoming electrons after
hitting the target;
Monochromatic radiation – the peaks. Results
from rearrangement of the orbital electrons of
the target.
L–K Kα
M–K Kβ

X-ray generators – the Vacuum Tube
S – Evacuated space between

the electrodes;
e – Accelerated electrones;
P – High voltage contact;
T – Anode;
B – Berrylium filters
X – X-rays

X-ray generators – Rotating anode X-ray tube
X-rays outlet
Advantages:
- Longer anode life;
- Higher energy beam (>3-30 times as
compared to VT)
- Simultaneous work of 2 devices (in
some constructions)
Disdvantage:
- Very complex construction (more than
350 parts). Caracterização de Polímeros 2023-24 53
The Synchrotron
C – Cavities ; M - magnets
- Continuous spectrum – from infrared to hard X-
ray;
- Very high intensity and brightness of the source in
comparison with the conventional X-ray sources
(thousand of times!!);
- High collimation of the beam;
- Well-defined time structure.
Very complex and costly equipment,

Caracterização highly
de Polímeros trained personnel required.54
2023-24
2
1
1. Accelerator of particles
2. Storage ring
3
3. Bending magnet
4. Beamline compartments
5. Command centre
5
4
Detecting X-rays
Detecting X-rays – 2D detectors
PET fibre PET film

(oriented) (isotropic)
WAXS
SAXS
HDPE fibre HDPE film
(oriented) (isotropic)

Stress-induced orientation with
crystallization - WAXS


Extracting Information from the X-ray
Patterns - WAXS
[1 0 0 ]
[1 0 1]
[1 -1 0]
[0 -1 1]
[1 1 1]
X = 47 %
c
10 15 20 25 30 35
2 Theta, degrees
1. Sample orientation – isotropic

2. Calculation of the crystalline lattice parameters
3. Calculation of the crystallinity index

Patterns - WAXS
1. Sample orientation – fibre axis vertical

2. Calculation of the crystalline lattice parameters
3. Calculation of the crystallinity index
(different section necessary)
4. Calculation of the degree of orientation –
Herman’s orientation function
PET fibre
(oriented)
f = 1, 0 , -1/2
0 1 2 3 4 5 6
-1
Scattering vector s, nm
Equatorial section
5. Extracting Information from the X-ray
Patterns - WAXS
Crystalline phase thickness & transcrytallization
B - the half width at half height

0.9l
t= l - X-ray wavelength
B cos q B
Q - half of the diffraction angle related
to the WAXS peak
a b
Oriented PET (a) and PA12 (b)
Annealing a 1:1 blend of PET:PA12 at

240ºC for 4 (c) or 8h (d) and cooling
c d to 25ºC cause selective melting and
recrystallization of PA12. The novel
PA12 crystallites are rotated to 90º in
respect to the original orientation in b.

5. Extracting Information from the X-ray
Patterns - SAXS
Equatorial
Fibre axis Section smax-1 = LB = lc + la
700
600
500
400
300
200
100
HDPE fibre HDPE film 0.00 0.05 0.10 0.15 0.20
(oriented) (isotropic) s, Å-1
LB – Bragg´s
Long spacing
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

Azimuthal angle, in radians

Patterns - SAXS
L = la + lc
Model of a
semicrystalline
Polymer – the lamella

Patterns - SAXS
Sizes of the amorphous and crystalline phases
Isotropic
PET film
1000
1
LB =
s max
Intensity, a.u.
500
0.00 0.05 0.10 0.15 0.20
2D SAXS s, nm
-1
pattern
Raw SAXS curve

Patterns - SAXS

1.0
g 1,r
=

0
( I − I b )q 2 cos(qr ) exp( 2 q 2 )dq

0.5
Q
0
( I − I b )q 2 dq
g/Q
0.0
-0.5
0 50 100 150 200 250 300

Distance, angstr.
1D Correlation
Function

Patterns - SAXS

g 1,r
=
0
Gq cos(qr ) exp( 2 q 2 )dq

Q
 (I − I
0
b )q 2 dq
0.002
0.001
g/Q
0.000
-0.001
0 50 100 150 200 250 300

Distance, angstr.
Interface Distribution
Function
Patterns - SAXS
Structural parameters of different PET films

PET sample type LB, Å LCm, Å LCM, Å LI, Å la, Å lc, Å
As quenched –* – – – – –
As quenched, thermo oxid. 104 –** – – – –
3h at 185ºC 135 106 110 92 40 52
3h at 185ºC, thermo oxidation 124 98 98 84 30 54
3h at 230ºC 134 114 113 108 46 62
3h at 230ºC, fast, thermooxid. 128 106 110 98 38 60
3h at 230ºC, slow thermooxid. 130 108 109 95 37 58

Patterns - SAXS
Absence of SAXS peaks I(s) = I(0) exp(-s2Rg2/3)
GUINIER PLOT
Intensity, a.u.
Monotonous decay SAXS –

Non-correlated particles
Scattering vector, s
Patterns - SAXS
Guinier region Rg

Patterns - WAXS
WAXS under stretching – real time
35
30
25
20
Load
15
10
-5
0.0 0.2 0.4 0.6 0.8 1.0
Stress-strain curve
%strain

Patterns
SAXS under stretching – real time
35
30
25
20
Load
15
10
-5
0.0 0.2 0.4 0.6 0.8 1.0
Stress-strain curve%strain

Diffraction
Types of X by the
– ray
experiments
crystalline lattice
(WAXS and SAXS)
Absorption by the Inducing of secondary X-

material ray radiation in the
(X-ray defectoscopy) material
(X-ray spectral analysis)
Structure determination by X-
ray scattering methods
Diffraction by the
crystalline lattice
(WAXS and SAXS)
Crystalline lattice Defects in the

parameters crystalline lattice
(WAXS) (SAXS, WAXS)
Size of the Degree of Orientation of

crystallites crystallinity the crystallites
(SAXS) (WAXS) (WAXS, SAXS)

Supplementary material
X ray theory

The scattering from one electron
E1, ⊥ = E0 (e2 / mc2 ) / R

E1,II = E0 (e2 / mc2 ) cos 2q / R
1 + cos 2
2q
I = EE * = I1 = I 0 (e 2 / mc 2 ) 2
2R2
The scattering from a single electron corresponds
to a spherical wave, emanating from the
electron
The scattering from many electrons
XY = rS0; PQ = rS1
[[PQ – XY]/λ = r(S1 – S0)/λ = sr
s = (S1 – S0) /λ
E = E1e 0 + E1epirs
k
E
The structural factor F F= =  e 2pirk s
E1 1
Emax = Q.E1 (Q = number of electrons)
E = F.E1 (E – actual amplitude; F = Emax/E1; F< Q) F ( s) =   (r )e 2pirsdVr
Vr
i = FF*/V
Fourier Transformations
 (r ) =  F ( s)e −2pirsdVs  (r ) = F (s)

Vs
F (s) =  (r )
F ( s ) =   ( r )e 2pirs
dVr
Vr
The function ρ(r) is in the real space and is characterized by

Cartesian coordinates – x, y, z.
The function F(s) is in an imaginary space (s – space), also called

reciprocal space. Its Cartesian coordinate system has coordinates
ξ, η and ζ, whereby:
sr = xξ + yη + zζ
Reciprocal lattice
The vector s [hkl] from the

origin to any point of the
reciprocal lattice is
perpendicular to a set of
parallel planes in the real
lattice. These planes
Real space intersect a, b and c axes
lattice Reciprocal
lattice at points a/h, b/k and c/l.
d space
s space
Basic properties of the reciprocal
lattice (3D): d = s-1
a* axis is perpendicular to b and c axes;
b* axis is perpendicular to c and a axes;
c* axis is perpendicular toCaracterização
a and bdeaxes Polímeros 2023-24 79
The convolution operation
F(x) - the line profile of a

pattern obtained at ideal
conditions.
G(x) - distortion (apparative)
function
H(x) - resultant function

H ( x) =  F ( x − x)G( x)dx
−
1D convolution of G(x) and F (x)
H (r ) =  F (r − r )G (r )dV r 3D convolution of G(r) and F(r)

Vr 
Q(r ) =   (r)  (r + r )dVr  3D convolution of (r) and (-r)

Vr
(autoconvolution)
Q(r) is related to the scattering strength

Supplementary material
WAXS applications in polymers

3 In-situ MFC - idea
S. Fakirov et al (1992) Polymer 33:877–880
Theoretical Scheme Selective

Melting of
Polymer 1 Fibrilation
Fibrilization Polymer 2
(2) (3)
Polymer2
Crystallization
(4)
Homogenization
(1)
TCL formation
Polymer 2
Polymer 1 = PA6 (may contain up to 7.5% MMT, Cloisite® or Nanomer®)

Polymer 2 = HDPE
Compatibilizer YP (HDPE-MAH)
4 MFC morphology – TEM, SEM
Fibril Ǿ = 100-400 nm 500 nm
OP 80/20/0
Fibril Ǿ = 500-800 nm 5 μm Fibril Ǿ = 1500-1800 nm 20 μm
UDP MFC 80/20/0 UDP MFC 80/20/0 + 5 % MMT

Separation of the iso- and anisotropic scattering
Initial pattern POLAR -- Isotropic
Stonybrook
scattering Technology and
Oriented Applied Research Inc.
scattering
HDPE/PA6/YP
80/20/0
- =
70/20/10
- =
7000
1D WAXS –peak fitting a
1 -(200) a-PA6
6000
2 -(001) g-PA6
3 -(110) HDPE
5000 4 -(200) g-PA6
Intensity, counts
(110) HDPE
5 -(002) a-PA6
4000
6 -(200) HDPE 1D WAXS
7 -(210) HDPE Oriented scattering (110) HDPE
3000
4 HDPE/PA6/YP PA6, % HDPE, % PA6/HDPE (200) HDPE
2000
2
5 (200) HDPE 80/20/0 55.7 44.3 1.257 (200) a PA6
1000 1
(210) HDPE
70/20/10 50.8 49.2 1.032
0
10 15 20 25 30 Caracterização
35 de Polímeros 2023-24 84
Diffraction an gle 2q, deg rees
Modeling on the basis of WAXS/SAXS
After extruder die After final During After

cold drawing compression compression
molding at 160ºC molding
Globular Both PA and HDPE Shell –core
PA phase HDPE fibrilized isotropization PA6 fibrils
VPA6 glob. = VPA6 fib.

Estimation of TCL by WAXS
2R1
Components of the WAXS
2R2 oriented scattering
TCL = R2 – R1
HDPE/PA6/YP PA6, % HDPE, % f
2R1 = ? 80/20/0 55.7 44.3 1.26: 1
L 70/20/10 50.8 49.2 1.03 : 1
HDPE/PA12/YP PA12, % HDPE, % f

Z
I ~ Vi .el
i
s
el = N A . M . m
MM
90/10/0 65.3 34.7 1.911
80/20/0 73.8 26.2 2.817
70/20/10 66.0 34.0 1.941
75/20/5 67.4 32.6 2.067
VPA6 = p .R .L 2
1 77.5/20/2.5 68.9 31.1 2.215
65/30/5 71.1 28.9 2.460
VTCL = p .L.(R22 − R12 )

HDPE/PA6/YP/MMT PA6, % HDPE, % f
80/20/0/4 NM 37.6 37.3 1.00
80/20/0/4 CL 30.8 35.3 0.87
80/20/0/5 NM 33.8 32.1 1.05
k = elPA6 elPE f 80/20/0/5 CL 31.7 39.0 0.81
2 R1 = 2 R2  80/20/0/7.5 NM 32.6 27.9 1.17
f = I sPA6 I sPE k+ f 77.5/20/2.5/ 5 NM 32.3 29.0 1.11

Reinforcing Fibril Structure by WAXS
HDPE/PA6/YP, no MMT HDPE/PA6/YP, with MMT
UDP MFC 80/20/0/ 5% NM UDP MFC 80/20/0/ 5% CL
UDP MFC 80/20/0 UDP MFC 70/20/10
2R2 = 1050 nm 2R2 = 1320 nm

2R2 = 750 nm 2R2 = 500 nm
2R1 = 550 nm 2R1 = 738 nm

2R1 = 350
TCL = 100 nm TCL = 75 nm TCL = 156 nm
2R1 = 864 nm
UDP MFC 80/20/0/ 7.5% NM TCL = 228 nm

HDPE/PA12/YP, no MMT
2R2 = 1750 nm
UDP MFC 80/20/0 UDP MFC 70/20/10
UDP MFC 77.5/20/2.5 7.5 NM
2R2 = 625 nm 2R2 = 560 nm
2R2 = 1200 nm
2R1 = 539 nm 2R1 = 457 nm

TCL = 43 nm TCL = 52 nm
2R1 = 1260 nm 2R1 = 854 nm
TCL = 245 nm TCL = 173 nm
Reinforcing Fibril Structure by WAXS
HDPE/PA6/YP, no MMT
(TEM image)
HDPE/PA6/YP, no MMT
(model)
UDP MFC 80/20/0
2R2 = 750 nm
2R1 = 550 nm
TCL = 100 nm
ca. 520 nm
ca. 90 nm
P03 microfocus beamline
Y1; X 1
Y3; X 1-11
5/5μm
Scanning along
X Caracterização de Polímeros 2023-24 90
x11
Scanning along
Y11; X1-10 Y
y11
x01
Y10; X1-10
y01
Y09; X1-10
Y08; X1-10 Y07; X1-10

Distribution of non-exfolliated MMT Thickness distribution of the PAMC layer

PA6/Cloisite 15A
PA6/Graphite

PA6/Cu PA6/Al
PA6/Fe3O4 PA6/Fe

X-Ray 2023

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4.

X-RAY ANALYSES OF POLYMERS

1. Introduction to X-ray techniques and relation with other methods

2. Basic definitions of X-ray. Moduli in an X-ray apparatus

3. Basic theory of X-ray scattering

Caracterização de Polímeros 2023-24 3

Phase contrast due to different

Phase contrast due to different

Patterns caused by the nano-structure but not depicting the

DNA molecule - direct observation by high

X-ray pattern of DNA – Watson/Crick

Al2O3 single crystals

The Culinan diamond

Caracterização de Polímeros 2023-24 11

Caracterização de Polímeros 2023-24 12

Chain folding: Chain folding:

• Lamellar Cyrstals from the Melt

Two-phase model for a

The concept of the Long period

Caracterização de Polímeros 2023-24 13

Low crystallinity High crystallinity

Fringed micelle model A lamellar stack

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Some polymers are semicrystalline Materials – PE, PA6, PET….

• Crystallinity Index Xc (masss) or Vc (volume):

- Xc = Mc /M wherein Mc = mass of the crystaline phase; M = total sample mass

Same with the volume!

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- Spherullites - Spherullite Growth

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Kepler & Anderson, Adv. In Physics, 1992, 41, 1, 1-57

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Spherulites in Semicrystalline Polymer - Microscopy

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Orders of Magnitude in Polymers

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Absorption by the Inducing of secondary X-

Crystalline lattice Defects in the

Size of the Degree of Orientation of

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Crystallographic information from X-ray studies

Crystalline lattice and unit cell - definitions

If we know the unit cell

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Examples of Lattice Indexing

Triclinic (a ≠ b ≠ c, α ≠ β ≠ γ) unit cell .

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Examples of Lattice Indexing

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Alexander, "X-Ray Diffraction Methods in

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stacked lamellae shish

Lamellar structure and orientation – 2D SAXS

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Why X-ray methods for structure characterization?

Non-destructive methods – easy (or none) sample preparation.