Characterization of

Powders, Porous Solids

and Suspensions
Lecture 8
Main Characteristics of Powders
and Porous Solids

 Particle size
 Surface area
 Porosity
Why 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…
What is Particle Size?

SEM of real ibuprofen particles

A Concept of Equivalent Sphere
 Due to symmetry, size of sphere is
completely determined by only
one parameter – it’s diameter
(radius)
 Other properties of sphere are
easily computed from its size:

1  3
V  d 3 S  d 2
m d
6 6

 Sphere is just a convenient model!

This is why it is found throughout
the particle size analysis
Different Equivalent Spheres
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
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;
Particle Size by Direct Observation

Google for
ImageJ
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:

kT
d (H ) 
3D
d(H) – hydrodynamic diameter, D – translational diffusion coefficient, k
– Boltzmann’s constant, T – temperature, η - viscosity
What 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 Particle core
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 Shell formed by solvent particles,
 The translational diffusion coefficient ions etc. Low conductivity medium
will produce an extended double
will depend not only on the size of layer of ions around the particle,
the particle “core”, but also on any reducing the diffusion speed and
resulting in a larger, apparent
surface structure, as well as the hydrodynamic diameter.
concentration and type of ions in the Thus, the measurements are
medium usually done in 10mM
NaCl (ISO13321 Part 8 1996)
 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.
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.
 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+δt), 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+2δt, t+3δt, t+4δt 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.
 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 Rayleigh’s
approximation).
 In DLS, the distribution obtained from a measurement is based on intensity.
Schematics of Zetasizer Nano
Measurement of Porosity and
Specific Surface Area by
Gas Adsorption
What are Porous Materials?

Porous solid
Non-porous solid
 High specific surface area
 Low specific surface area
 High specific pore volume
 Low 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
F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous
Solids, Academic Press, 1-25, 1999
 Measure of 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.

Total surface area, m2

Specific Surface Area, m /g =
2

Mass of the solid, g

Porosity, % =
Volume of pores
X 100
Porosity Volume of solid (including pores)

Pore size and

its distribution Specific Pore volume, cm3/g
Total pore volume, cm3
=
Mass of the solid, g
 Concept of Porosity: Open vs.
Closed Pores
Inter-connected Closed
(open)

Open pores are accessible

whereas closed pores are
inaccessible pores. Open pores
can be inter-connected, passing
or dead end.

Passing Dead end

(open) (open)

F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous

Solids, Academic Press, 1-25, 1999
Size of Pores (IUPAC Standard)

Micropores Mesopores Macropores

Zeolite, Mesoporous silica, Sintered metals

Activated Activated carbon and ceramics
carbon,
Metal organic
framework
2 nm 50 nm

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).
Shapes of Pores
Cylindrical Slits

Pore
Conical Shapes

Interstices
Spherical or
Ink Bottle

F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic

Press, 1-25, 1999
Experimental Techniques
Techniques for Porosity Analysis
Gas
adsorption

Small
Mercury Angle
porosimetry Neutron
scattering

Techniques

Small angle
TEM X-ray
scattering

SEM
Techniques for Porosity Analysis
 Can measure only open pores
 Pore size : 0.4 nm – 50 nm
Gas
adsorption  Easy
 Established technique
Small
Mercury Angle
porosimetry Neutron
scattering

Techniques

Small angle
TEM X-ray
scattering

SEM
Techniques for Porosity Analysis
Gas
adsorption

Small  Similar to gas

Mercury Angle
porosimetry Neutron adsorption
scattering  Can measure only
open pores
 Pore size >1.5 nm
Techniques  Easy
 Established technique

Small angle
TEM X-ray
scattering

SEM
Techniques for Porosity Analysis
Gas
adsorption

Small  Provide information

Mercury Angle
porosimetry Neutron regarding pore
scattering connectivity
 Pore size can be
measured if the
Techniques materials contains
ordered pores
 Rarely used for pore
Small angle analysis
TEM X-ray
scattering

SEM
Techniques for Porosity Analysis
Gas
adsorption

Small
Mercury Angle
porosimetry Neutron
scattering

Techniques

Small angle
TEM X-ray
scattering

SEM  Pore size > 5nm

 Rarely used for pore
analysis
Techniques for Porosity Analysis
Gas
adsorption

Small
Mercury Angle
porosimetry Neutron
scattering

Techniques

Small angle  Any pore size

TEM X-ray
scattering
 Open + Close
porosity

SEM
Techniques for Porosity Analysis
Gas
adsorption

Small  Any pore size

Mercury Angle  Open & Close
porosimetry Neutron porosity
scattering  Costly

Techniques

Small angle
TEM X-ray
scattering

SEM
Theory of Adsorption
 Adsorption Process
Adsorptive - adsorbate before being adsorbed on the surface

Adsorbate - the gas adsorbed on the

surface of solids

Adsorbent - the solid where adsorption takes place

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)
Physisorption vs Chemisorption
PHYSISORPTION CHEMISORPTION
WEAK, LONG RANGE BONDING STRONG, SHORT RANGE BONDING
Van der Waals interactions Chemical bonding involved.

NOT SURFACE SPECIFIC SURFACE SPECIFIC

Physisorption takes place between all E.g. Chemisorption of hydrogen takes place on
molecules on any surface providing the transition metals but not on gold or mercury.
temperature is low enough.

ΔHads = 5 ….. 50 kJ mol-1 ΔHads = 50 ….. 500 kJ mol-1

Non activated with equilibrium achieved Can be activated, in which case equilibrium can
relatively quickly. Increasing temperature be slow and increasing temperature can favour
always reduces surface coverage. adsorption.

No surface reactions. Surface reactions may take place:-

Dissociation, reconstruction, catalysis.

MULTILAYER ADSORPTION MONOLAYER ADSORPTION

BET Isotherm used to model adsorption Langmuir Isotherm is used to model adsorption
equilibrium. equilibrium.

http://www.soton.ac.uk
Adsorption Process

Gas molecules admitted

under increasing pressure to
a clean, cold surface.
1 2 3 Data treatment techniques
find the quantity of gas that
1 2 3 forms the first layer.

1. Diffusion to adsorbent surface

2. Migration into pores of adsorbent S. Lowell & J. E. Shields, Powder Surface
3. Monolayer builds up of adsorbate Area and Porosity, 3rd Ed. Chapman & Hall,
New York, 1991
Adsorption Process
V a
 f (W , T , I , P)
where
V a
 volume of gas adsorbed;
W  weight of adsorbent; Adsorbate
P  pressure of the adsorbate;
T  temperature;
I  interaction between adsorbate and adsorbent.
If W, T, and I are made constant, the above
equation can be written as :
 p
  Equation of adsorption
V a  po 
 f
isotherm
 
where Adsorbent
p pressure of adsorbate
o 
p saturated pressure of adsorptive S. Lowell & J. E. Shields, Powder Surface Area
and Porosity, 3rd Ed. Chapman & Hall, New York,
1991
 Gas Sorption: Isotherm
 p
V a  f  po 
 
where
Desorption isotherm
p pressure of adsorbate
o 
p saturated pressure of adsorptive
Adsorption isotherm
Isotherm is a measure
Va

of the volume of gas

adsorbed at a constant
temperature as a
function of gas
pressure.
Isotherms can be
p
grouped into six
po
classes.
 Gas Sorption: Isotherm
Concave to the P/Po axis
Va

Type I Exhibited by microporous

or solids ( < 2nm )
Langmuir

P/Po 1
Exhibited by nonporous or
macroporous solids ( > 50nm )
Unrestricted monolayer-multilayer
adsorption
Va

Type II
Point B indicates the relative
B pressure at which monolayer
coverage is complete

P/Po 1 S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991
 Gas Sorption: Isotherm

Type III Convex to the P/Po axis

Va

Exhibited by nonporous solids

P/Po 1

Exhibited by mesoporous
Type IV solids
Va

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.
P/P o 1 Chapman & Hall, New York, 1991
 Gas Sorption: Isotherm
Type V
Highly uncommon
Va

Exhibited by mesoporous solids

P/Po 1

Exhibited by nonporous solids

Type VI with an almost completely uniform
Va

surface

P/Po 1 S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991
 Gas Sorption: Hysteresis

Hysteresis
Va

P/Po 1

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.

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991
 Gas Sorption: Hysteresis
Type A Type B Type C Type D Type E
Va

P/Po 1 P/Po 1 P/Po 1 1 P/Po 1

P/Po

Cylindrical Slits Conical Bottle neck

 Adsorption Theories: Langmuir
P 1 P
 
Va Vmb Vm
where
Adsorbate Va  volume of gas adsorbed at pressure P;
Vm  volume of gas required to form monolayer;
b  empirical constant; and
P  pressure of adsorbate.

Assumptions:
 homogeneous surface (all adsorption
sites energetically identical)

Adsorbent  monolayer adsorption (no multilayer

adsorption)
 no interaction between adsorbed
I. Langmuir The Constitution and Fundamental
Properties of Solids and Liquids. Part I. Solids.molecules
J. Am. Chem. Soc., 1916, 38 (11), 2221-2295
 Adsorption Theories: BET
P 1 (C  1)  P 
    S.Brunauer, P.Emmett, E.Teller Adsorption
Va ( P  P o ) Vm C Vm C  P o  of Gases in Multimolecular Layers, J. Am.
Chem. Soc., 1938, 60 (2), pp 309–319
where
Va  volume of gas adsorbed at pressure P;
Vm  volume of gas required to form monolayer;
C  BET constant (related to energy of adsorption of 1st layer); and
P  Modification of Langmuir
o
 relative pressure of adsorbate.
P isotherm
 Both monolayer and multilayer
adsorption
 Assumptions:
Adsorbate
(a) gas molecules physically
adsorb on a solid in layers
infinitely;
(b) there is no interaction between
Adsorbent each adsorption layer;
(c) the Langmuir theory can be
applied to each layer.
Specific Surface Area Calculation
P (C  1)  P  1
  o  At least three data points in the
Va ( P  P ) VmC  P  VmC
o
relative pressure range 0.05 to 0.30

Y  mX  i
1
Vm  1
mi V[(Po/P)-1]

Vm N av Acs
Total surface area 
Weight of adsorbate
0-1 0-2 0-3
P/Po

Total surface area

SSA (Specific surface area) 
Weight of sample
Porosity Analyzer

Outgassing station

Analysis station

Liquid nitrogen
bath
Steps for Measurement
1. Sample Preparation

2. Adsorption Analysis

3. Interpretation
Sample Preparation (Outgassing)
Vacuum
 Surface contamination is
Helium removed by application
of:
Adsorbate  Temperature
 Flowing gas (helium or
nitrogen) or vacuum
Po
 Backfill can be done
Sample using helium or adsorbate
Cell gas.

Outgassing  According to IUPAC

station
standards, materials
should be outgassed for
Analysis station
at least 16 hours.
 Adsorption Analysis
Vacuum

Helium  Adsorbate (nitrogen,

argon, carbon dioxide,
Adsorbate krypton)
 Analysis temperature
(liquid nitrogen, liquid
Po argon, 0 oC)
 Quantity of sample (1
Sample mg sample is sufficient)
Cell
 Number of points
(single point, five
Outgassing
station points, seven points,
eleven points, full
Analysis station analysis)
Interpretation
Pore size
&
distribution

Volume
Points P/Po
adsorbed

UT
1 T P
U
2 O Pore shape Results Pore volume

Weight of sample Specific

surface area
Common Adsorbates

Gas Temperature Cross sectional

area (nm2)
N2  -195.8 oC (liquid nitrogen) 0.162
 -183 oC (liquid argon).

Ar  -183 oC (liquid argon). 0.142

 -195.8 oC (liquid nitrogen)

CO2  -78 oC, -25 oC, 0 oC 0.195

CO  -183 oC (liquid argon) 0.163
Kr  -195.8 oC (liquid nitrogen) 0.205
O2  -183 oC (liquid argon) 0.141
C4H10  0 oC, 25 oC 0.469
 Choice of Adsorptive
0.55
0.50  N2(g) in N2(l) is the most
0.45 commonly used
2
Cross-sectional area, nm

0.40
0.35
adsorbate.
0.30
 Not completely inert.
0.25  Dipole movement and
0.20 thus can have
0.15
localized adsorption.
0.10
0.05
 Cross-sectional area of
0.00 0.162 nm2 is
questionable.
e

ide

ne
en

en

ton
xid
go

uta
yg

rog

iox

yp
Ar

oo
Ox

n-b
Kr
Nit

nd
on

rbo
nm

Ca
rbo
Ca

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd
Ed. Chapman & Hall, New York, 1991
Quantachrome Autosorb-I Operational Manual
 Choice of Adsorptive
0.55
0.50  Ar(g) in Ar(l) is preferable
0.45
but because of
2
Cross-sectional area, nm

0.40
0.35 unavailability of Ar(l) (87K),
0.30 N2(l) (77 K) is used.
0.25
0.20
 Ar can reach to somewhat
0.15 smaller pores than N2.
0.10  Accurate measurement of
0.05
micropores is possible
0.00
using Ar.
e

ide

ne
en

en

ton
xid
go

uta
yg

rog

iox

yp
Ar

oo
Ox

n-b
Kr
Nit

nd
on

rbo
nm

Ca
rbo
Ca

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd
Ed. Chapman & Hall, New York, 1991
Quantachrome Autosorb-I Operational Manual
 Choice of Adsorptive
0.55
0.50
0.45
 In case of activated
2
Cross-sectional area, nm

0.40
0.35
carbon, CO2 is often
0.30 the most preferred
0.25
adsorbate.
0.20
 Adsorption analysis of
0.15
0.10 CO2 takes less time.
0.05  Limited to micropore
0.00
analysis.
e

ide

ne
en

en

ton
xid
go

uta
yg

rog

iox

yp
Ar

oo
Ox

n-b
Kr
Nit

nd
on

rbo
nm

Ca
rbo
Ca

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd
Ed. Chapman & Hall, New York, 1991
Quantachrome Autosorb-I Operational Manual
Shape of Microporous Materials

Type I isotherms don’t have

hysteresis.

Pore shape cannot be

Va

Type I determined by isotherm.

or
Langmuir
As various methods for pore
size calculation are based on
P/Po 1 shape of pores, reliability of pore
size calculation is questionable.

F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous

Solids, Academic Press, 439-446, 1999
 Choice of Method
Micropores Mesopores Macropores

2 nm 50 nm
Methods Assumption
Pore Shape Based on ..

Brunauer MP method Cylindrical or Slit shaped de Boer’s 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

P. A. Webb, C. Orr, Analytical Methods in Fine Particle Technology, Micromeritics, 53

– 152, 1997
Quantachrome Autosorb-I Operational Manual
 Choice of Method
Micropores Mesopores Macropores

2 nm 50 nm

Methods Assumption
Pore Shape Based on ..

BJH (Barrett, Joyner and Cylindrical, Slit-shaped Kelvin equation

Halenda) method

Cylindrical t-method
DH (Dollimore Heal) method

P. A. Webb, C. Orr, Analytical Methods in Fine Particle Technology, Micromeritics, 53

– 152, 1997
Quantachrome Autosorb-I Operational Manual
 Choice of Method
Micropores Mesopores Macropores

2 nm 50 nm

Methods Assumption
Pore Shape Based on ..

NLDFT (Non Local Density Cylindrical and slit Statistical

Functional Theory) and Monte thermodynamics
Carlo simulation method

P. A. Webb, C. Orr, Analytical Methods in Fine Particle Technology, Micromeritics, 53

– 152, 1997
Quantachrome Autosorb-I Operational Manual