Sutarno KM 1

Characterization
of Materials
Why Porous Materials?
Porous materials are also of scientific and technological
importance because of their vast ability to adsorb and interact
with atoms, ions and molecules on their large interior surfaces
and in the nanometer sized pore space.
They offer new opportunities in areas of inclusion chemistry,
guest-host synthesis and molecular manipulations and
reaction in the nanoscale for making nanoparticles, nanowires
and other quantum nanostructures.

3
What are Porous Materials?
Porous materials are defined as solids containing pores.
Porous materials have porosity of 0.2-0.95.
Nature abhors a vacuum - always find ways to fill void
space.
The interaction of the voids with guest species is the
subject of adsorption, catalysis, transport phenomena,
etc.
4
Main Characteristics of Powders and
Porous Solids
Particle size
Surface area
Porosity
5
Why Do We Care About Particle Size and
Surface Area?
These characteristics control many properties of materials:
Flowability;
Filter-ability
Viscosity-Reology;
Agglomeration;
Dusting tendency;
Settling rate;
Activity/Reactivity rate (e.g. of catalyst);
Dissolution rate (of pharmaceutical);
Gas absorption;
Hydration rate (of cement);
Moisture absorption;
Entry into lungs (shape dependency too);
Combustion rate (of fuel)
Etc

6
What is Particle Size?
SEM of real ibuprofen particles
7
A Concept of Equivalent Sphere
3
6
1
d V t =
Due to symmetry, size of sphere is
completely determined by only
one parameter its diameter
(radius)
Other properties of sphere are
easily computed from its size:

Sphere is just a convenient model!
This is why it is found throughout
the particle size analysis

2
d S t =
3
6
d m t
=
8
Different Equivalent Spheres
9
Particle Size Measurement Techniques
Direct observation (image analysis)
Sieving;
Sedimentation settling rate;
Coulter counter electrozone sensing;
Gas adsorption BET (SSA back extrapolation to
size);
Permeability (gas or liquid) e.g. Blaine, FSSS
Light scattering laser diffraction and Photon
Correlation Spectroscopy / Dynamic Light Scattering
10
And What Do They Measure?
Direct observation (image analysis) usually some 2-D
representation of a particle. Which dimension is
viable?;
Sieving combination of particle size and shape;
Sedimentation settling rate. Stokes Law (spheres,
straight line settling);
Coulter counter electrozone sensing;
Gas absorption / Permeability surface area.
Extrapolate to average particle size only. BET (SSA
back extrapolation to size);
Light scattering equivalent scatterers;
11
Particle Size by Direct Observation
Google for
ImageJ
12
Dynamic Light Scattering (DLS)
DLS measures Brownian motion and relates this to the size of the
particles.

The larger the particle the slower the Brownian motion will be. Smaller
particles are kicked further by the solvent molecules and move more
rapidly.

The velocity of Brownian motion is defined by a property known as the
translational diffusion coefficient (D).

The size of a particle is calculated from the translational diffusion
coefficient by using the Stokes-Einstein equation:

d(H) hydrodynamic diameter, D translational diffusion coefficient, k
Boltzmanns constant, T temperature, - viscosity
D
kT
H d
tq 3
) ( =
13
What Do We Measure in DLS?
The diameter that is measured in DLS is
a value that refers to how a particle
diffuses within a fluid so it is referred to
as a hydrodynamic diameter
The diameter that is obtained by this
technique is the diameter of a sphere
that has the same translational diffusion
coefficient as the particle
The translational diffusion coefficient
will depend not only on the size of the
particle core, but also on any surface
structure, as well as the concentration
and type of ions in the medium

Particle core
Shell formed by solvent particles,
ions etc. Low conductivity medium
will produce an extended double
layer of ions around the particle,
reducing the diffusion speed and
resulting in a larger, apparent
hydrodynamic diameter.
Thus, the measurements are
usually done in 10mM
NaCl (ISO13321 Part 8 1996)
14
How DLS Works
The dark spaces in the speckle pattern produced by light scattering are where the phase
additions of the scattered light are mutually destructive. The bright spots of light in the
speckle pattern are where the light scattered from the particles arrives with the same
phase and interfere constructively.
The observed signal depends on the phase addition of the scattered light falling on the
detector. In example A, two beams interfere and cancel each other out resulting in a
decreased intensity detected. In example B, two beams interfere and enhance each
other resulting in an increased intensity detected.

15
How DLS Works
For a system of particles undergoing Brownian motion, a speckle pattern is
observed where the position of each speckle is seen to be in constant motion. This
is because the phase addition from the moving particles is constantly evolving and
forming new patterns.
The rate at which these intensity fluctuations occur will depend on the size of the
particles. Figure above schematically illustrates typical intensity fluctuations arising
from a dispersion of large particles and a dispersion of small particles.
The small particles cause the intensity to fluctuate more rapidly than the large
ones.
It is possible to directly measure the spectrum of frequencies contained in the
intensity fluctuations arising from the Brownian motion of particles, but it is
inefficient to do so. The best way is to use a device called a digital auto correlator.
16
How an Auto Correlator Works
If the intensity of a signal is compared with itself at a particular point in time and a time much
later, then for a randomly fluctuating signal it is obvious that the intensities are not going to be
related in any way, i.e. there will be no correlation between the two signals.
However, if the intensity of signal at time t is compared to the intensity a very small time later
(t+t), there will be a strong relationship or correlation between the intensities of two signals.
Perfect correlation is indicated by unity (1.00) and no correlation is indicated by zero (0.00).
If the signals at t+2t, t+3t, t+4t etc. are compared with the signal at t, the correlation of a
signal arriving from a random source will decrease with time until at some time, effectively t = ,
there will be no correlation.
If the particles are large the signal will be changing slowly and the correlation will persist for a long
time. If the particles are small and moving rapidly then correlation will reduce more quickly.
17
Different Forms of Particle Size Distribution
Consider 2 populations of spherical particles of diameter 5nm and 50nm present in equal numbers.
If a number distribution of these 2 particle populations is plotted, a plot consisting of 2 peaks
(positioned at 5 and 50nm) of a 1 to 1 ratio would be obtained.
If this number distribution was converted into volume, then the 2 peaks would change to a 1:1000 ratio
(because the volume of a sphere is proportional to d
3
).
If this was further converted into an intensity distribution, a 1:1000000 ratio between the 2 peaks would
be obtained (because the intensity of scattering is proportional to d
6
from Rayleighs approximation).
In DLS, the distribution obtained from a measurement is based on intensity.
18
Schematics of Zetasizer Nano
19
20
Measurement of Porosity and
Specific Surface Area by
Gas Adsorption
21
F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous
Solids, Academic Press, 1-25, 1999
What are Porous Materials?
Non-porous solid
Low specific surface area
Low specific pore volume
Porous solid
High specific surface area
High specific pore volume

Porous materials have highly developed internal surface area that can be
used to perform specific function.
Almost all solids are porous except for ceramics fired at extremely high
temperatures

22
23
24
25
26
Measure of Porosity
Pore size and
its distribution
Specific Surface Area, m
2
/g =
Porosity
There are three parameters used as a measure of porosity; specific surface
area, specific pore volume or porosity, and pore size and its distribution.
Mass of the solid, g
Total surface area, m
2
Specific Pore volume, cm
3
/g
Mass of the solid, g
Total pore volume, cm
3
=
Porosity, % =
Volume of solid (including pores)
Volume of pores
X 100
27
28
Types of Pores
Concept of Porosity: Open vs. Closed Pores
Dead end
(open)
Closed
Inter-connected
(open)
Passing
(open)
Open pores are accessible
whereas closed pores are
inaccessible pores. Open pores
can be inter-connected, passing
or dead end.
29
Size of Pores (IUPAC Standard)
2 nm 50 nm
Micropores
Mesopores Macropores
Zeolite,
Activated
carbon,
Metal organic
framework
Mesoporous silica,
Activated carbon
Sintered metals
and ceramics
Porous material are classified according to the size of pores: material with
pores less than 2 nm are called micropores, materials with pores between 2
and 50 nm are called mesopores, and material with pores greater than 50 nm
are macrospores
Sing, K. S. W. et al. Reporting Physisorption Data for Gas/Solid Systems. Pure &
Appl. Chem. 57, 603-619 (1985). 30
Shapes of Pores
Conical
Interstices
Slits
Cylindrical
Spherical or
Ink Bottle
Pore
Shapes
31
Experimental Techniques
32
Techniques for Porosity Analysis
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
33
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
Can measure only open pores
Pore size : 0.4 nm 50 nm
Easy
Established technique
34
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
Similar to gas
adsorption
Can measure only
open pores
Pore size >1.5 nm
Easy
Established technique
35
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
Provide information
regarding pore
connectivity
Pore size can be
measured if the
materials contains
ordered pores
Rarely used for pore
analysis
36
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
Pore size > 5nm
Rarely used for pore
analysis
37
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
Any pore size
Open + Close
porosity
38
Mercury
porosimetry
TEM
SEM
Small angle
X-ray
scattering
Small
Angle
Neutron
scattering
Gas
adsorption
Techniques
Any pore size
Open & Close
porosity
Costly
39
Theory of Adsorption
40
Adsorption Process
Adsorption is brought by the forces acting between the solid and the
molecules of the gas. These forces are of two kinds: physical
(physiosorption) and chemical (chemisorption)
Adsorbent - the solid where adsorption takes place
Adsorbate - the gas adsorbed on the
surface of solids
Adsorptive - adsorbate before being adsorbed on the surface
41
PHYSISORPTION CHEMISORPTION
WEAK, LONG RANGE BONDING
Van der Waals interactions
STRONG, SHORT RANGE BONDING
Chemical bonding involved.
NOT SURFACE SPECIFIC
Physisorption takes place between all
molecules on any surface providing the
temperature is low enough.
SURFACE SPECIFIC
E.g. Chemisorption of hydrogen takes place on
transition metals but not on gold or mercury.
H
ads
= 5 .. 50 kJ mol-1 H
ads
= 50 .. 500 kJ mol
-1

Non activated with equilibrium achieved
relatively quickly. Increasing temperature
always reduces surface coverage.
Can be activated, in which case equilibrium can
be slow and increasing temperature can favour
adsorption.
No surface reactions. Surface reactions may take place:- Dissociation,
reconstruction, catalysis.
MULTILAYER ADSORPTION
BET Isotherm used to model adsorption
equilibrium.
MONOLAYER ADSORPTION
Langmuir Isotherm is used to model adsorption
equilibrium.
Physisorption vs. Chemisorption
http://www.soton.ac.uk 42
Adsorption Process
1. Diffusion to adsorbent surface
2. Migration into pores of adsorbent
3. Monolayer builds up of adsorbate

1 2 3
Gas molecules admitted
under increasing pressure to
a clean, cold surface.

Data treatment techniques
find the quantity of gas that
forms the first layer.

1 2 3
S. Lowell & J. E. Shields, Powder Surface
Area and Porosity, 3rd Ed. Chapman & Hall,
New York, 1991
43
Adsorption Process
adsorptive of pressure saturated
adsorbate of pressure

where
: as written be can equation
above the constant, made are I and T, W, If
adsorbent. and adsorbate between n interactio
re; temperatu
adsorbate; the of pressure
adsorbent; of weight
adsorbed; gas of volume
where
) , , , (
=
|
|
.
|
\
|
=
=
=
=
=
=
=
p
p
p
p
f
I
T
P
W
P I T W f
o
o
V
V
V
a
a
a
Equation of adsorption
isotherm
Adsorbent
Adsorbate
S. Lowell & J. E. Shields, Powder Surface Area and
Porosity, 3rd Ed. Chapman & Hall, New York, 1991
44
Gas Sorption: Isotherm
adsorptive of pressure saturated
adsorbate of pressure

where
=
|
|
.
|
\
|
=
p
p
p
p
f
o
o
V
a
Adsorption isotherm
Isotherm is a measure
of the volume of gas
adsorbed at a constant
temperature as a
function of gas
pressure.
Isotherms can be
grouped into six
classes.
V
a

Desorption isotherm
p
p
o
45
46
S. Lowell & J. E. Shields, Powder Surface Area and Porosity,
3rd Ed. Chapman & Hall, New York, 1991
V
a

1
P/P
o
Type I
or
Langmuir
Concave to the P/P
o
axis
Exhibited by microporous
solids ( < 2nm )
Exhibited by nonporous or
macroporous solids ( > 50nm )
Unrestricted monolayer-multilayer
adsorption
Point B indicates the relative
pressure at which monolayer
coverage is complete

1
P/P
o
Type II
B
V
a

47
V
a

1
P/P
o
Type III
Convex to the P/P
o
axis
Exhibited by nonporous solids
P/P
o
V
a

1
Type IV
Exhibited by mesoporous
solids
Initial part of the type IV follows
the same path as the type II

S. Lowell & J. E. Shields, Powder Surface Area and Porosity,
3rd Ed. Chapman & Hall, New York, 1991
48
V
a

1
P/P
o
Type V
Highly uncommon
Exhibited by mesoporous solids
S. Lowell & J. E. Shields, Powder Surface Area and
Porosity, 3rd Ed. Chapman & Hall, New York, 1991
1
P/P
o
Type VI
Exhibited by nonporous solids
with an almost completely
uniform surface

V
a

49
Gas Sorption: Hysteresis
Hysteresis indicates the presence of mesopores.
Hysteresis gives information regarding pore shapes.
Types I, II and III isotherms are generally reversible but type I
can have a hysteresis. Types IV and V exhibit hysteresis.
1
P/P
o
Hysteresis
V
a

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991
50
Gas Sorption: Hysteresis
Cylindrical Slits
Conical
Bottle neck
V
a

1
P/P
o
Type A Type B
1
P/P
o
1
P/P
o
Type C Type D
1
P/P
o
Type
E
1
P/P
o
51
Adsorption Theories: Langmuir
adsorbate. of pressure
and constant; empirical
monolayer; form to required gas of volume
; pressure at adsorbed gas of volume
where
1
=
=
=
=
+ =
P
b
V
P V
V
P
b V V
P
m
a
m m a
Assumptions:
homogeneous surface (all adsorption
sites energetically identical)
monolayer adsorption (no multilayer
adsorption)
no interaction between adsorbed
molecules
Adsorbate
Adsorbent
I. Langmuir The Constitution and Fundamental
Properties of Solids and Liquids. Part I. Solids.
J. Am. Chem. Soc., 1916, 38 (11), 2221-2295
52
Adsorption Theories: BET
adsorbate. of pressure relative
and layer); 1st of adsorption of energy to (related constant BET C
monolayer; form to required gas of volume
; pressure at adsorbed gas of volume
where
) 1 ( 1
) (
=
=
=
=
|
.
|
\
|
+ =
o
m
a
o
m m
o
a
P
P
V
P V
P
P
C V
C
C V P P V
P
Modification of Langmuir
isotherm
Both monolayer and multilayer
adsorption
Assumptions:
(a) gas molecules physically
adsorb on a solid in layers
infinitely;
(b) there is no interaction between
each adsorption layer;
(c) the Langmuir theory can be
applied to each layer.

Adsorbate
Adsorbent
S.Brunauer, P.Emmett, E.Teller Adsorption
of Gases in Multimolecular Layers, J. Am.
Chem. Soc., 1938, 60 (2), pp 309319
53
Specific Surface Area Calculation
C V P
P
C V
C
P P V
P
m
o
m
o
a
1 ) 1 (
) (
+
|
.
|
\
|
i mX Y + =
i m
V
m
+
=
1
adsorbate of Weight
area surface Total
cs av m
A N V
=
P/P
o
1
V[(P
o
/P)-1]
0-1 0-2 0-3
At least three data points in the
relative pressure range 0.05 to 0.30
sample of Weight
area surface Total
area) surface (Specific SSA =
54
Porosity Analyzer
Analysis station
Outgassing station
Liquid nitrogen
bath
61
Steps for Measurement
3. Interpretation
2. Adsorption Analysis
1. Sample Preparation

62
Sample Preparation (Outgassing)
Surface contamination is
removed by application
of:
Temperature
Flowing gas (helium or
nitrogen) or vacuum

Backfill can be done
using helium or adsorbate
gas.

According to IUPAC
standards, materials
should be outgassed for
at least 16 hours.

Adsorbate
Helium
Vacuum
P
o
Outgassing
station
Analysis station
Sample
Cell

63
Adsorption Analysis
Adsorbate (nitrogen,
argon, carbon dioxide,
krypton)
Analysis temperature
(liquid nitrogen, liquid
argon, 0
o
C)
Quantity of sample (1
mg sample is sufficient)
Number of points
(single point, five
points, seven points,
eleven points, full
analysis)

Adsorbate
Helium
Vacuum
P
o
Outgassing
station
Analysis station
Sample
Cell

64
Interpretation
Points P/P
o
Volume
adsorbed

1
2
3
Pore shape
Specific
surface area
Pore volume
Pore size
&
distribution
Results
Weight of sample
65
Common Adsorbates
Gas Temperature Cross sectional
area (nm
2
)
N
2
-195.8
o
C (liquid nitrogen)
-183
o
C (liquid argon).
0.162
Ar -183
o
C (liquid argon).
-195.8
o
C (liquid nitrogen)
0.142
CO
2
-78
o
C, -25
o
C, 0
o
C 0.195
CO -183
o
C (liquid argon) 0.163
Kr -195.8
o
C (liquid nitrogen) 0.205
O
2
-183
o
C (liquid argon) 0.141
C
4
H
10
0
o
C, 25
o
C 0.469
66
Choice of Adsorptive
O
x
y
g
e
n
A
r
g
o
n
N
i
t
r
o
g
e
n
C
a
r
b
o
n

m
o
n
o
o
x
i
d
e
C
a
r
b
o
n

d
i
o
x
i
d
e
K
r
y
p
t
o
n
n
-
b
u
t
a
n
e
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
C
r
o
s
s
-
s
e
c
t
i
o
n
a
l

a
r
e
a
,

n
m
2
N
2(g)
in N
2(l)
is the most
commonly used
adsorbate.
Not completely inert.
Dipole movement and
thus can have
localized adsorption.
Cross-sectional area of
0.162 nm
2
is
questionable.
S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd
Ed. Chapman & Hall, New York, 1991
Quantachrome Autosorb-I Operational Manual

67
O
x
y
g
e
n
A
r
g
o
n
N
i
t
r
o
g
e
n
C
a
r
b
o
n

m
o
n
o
o
x
i
d
e
C
a
r
b
o
n

d
i
o
x
i
d
e
K
r
y
p
t
o
n
n
-
b
u
t
a
n
e
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
C
r
o
s
s
-
s
e
c
t
i
o
n
a
l

a
r
e
a
,

n
m
2

Ar
(g)
in Ar
(l)
is preferable
but because of
unavailability of Ar
(l)
(87K),
N
2(l)
(77 K) is used.
Ar can reach to somewhat
smaller pores than N
2
.
Accurate measurement of
micropores is possible
using Ar.

68
O
x
y
g
e
n
A
r
g
o
n
N
i
t
r
o
g
e
n
C
a
r
b
o
n

m
o
n
o
o
x
i
d
e
C
a
r
b
o
n

d
i
o
x
i
d
e
K
r
y
p
t
o
n
n
-
b
u
t
a
n
e
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
C
r
o
s
s
-
s
e
c
t
i
o
n
a
l

a
r
e
a
,

n
m
2

In case of activated
carbon, CO
2
is often
the most preferred
adsorbate.
Adsorption analysis of
CO
2
takes less time.
Limited to micropore
analysis.
69
Shape of Microporous Materials
Type I isotherms dont have
hysteresis.

Pore shape cannot be
determined by isotherm.

As various methods for pore
size calculation are based on
shape of pores, reliability of
pore size calculation is
questionable.
V
a

1
P/Po
Type I
or
Langmuir
72
Methods

Assumption
Pore Shape Based on ..
Brunauer MP method Cylindrical or Slit shaped de Boers t-method
Dubinin-Astakhov method - Polanyi potential
theory
Independent of
Kelvin equation
HK (Horvath-Kawazoe) method Slit Everett and Powl
method
Independent of
Kelvin equation
Saito-Foley method Cylindrical HK method
2 nm
50 nm
Micropores
Choice of Method
P. A. Webb, C. Orr, Analytical Methods in Fine Particle Technology, Micromeritics, 53 152, 1997

73
2 nm 50 nm
Micropores
Methods

Assumption
BJH (Barrett, Joyner and
Halenda) method
Cylindrical, Slit-shaped Kelvin equation
DH (Dollimore Heal) method
Cylindrical t-method
Choice of Method

74
50 nm
2 nm
Micropores
Methods

Assumption
NLDFT (Non Local Density
Functional Theory) and Monte
Carlo simulation method

Cylindrical and slit Statistical
thermodynamics
Choice of Method

75

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