MATE 280 Characterization of Powders and Porous Materials
MATE 280 Characterization of Powders and Porous Materials
MATE 280 Characterization of Powders and Porous Materials
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?
1 3
V d 3 S d 2
m d
6 6
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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.
kT
d (H )
3D
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
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.
Porosity, % =
Volume of pores
X 100
Porosity Volume of solid (including pores)
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
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 angle
TEM X-ray
scattering
SEM
Techniques for Porosity Analysis
Gas
adsorption
SEM
Techniques for Porosity Analysis
Gas
adsorption
Small
Mercury Angle
porosimetry Neutron
scattering
Techniques
Small angle
TEM X-ray
scattering
Small
Mercury Angle
porosimetry Neutron
scattering
Techniques
SEM
Techniques for Porosity Analysis
Gas
adsorption
Techniques
Small angle
TEM X-ray
scattering
SEM
Theory of Adsorption
Adsorption Process
Adsorptive - adsorbate before being adsorbed on the surface
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.
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.
http://www.soton.ac.uk
Adsorption Process
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
P/Po 1
Exhibited by mesoporous
Type IV solids
Va
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
P/Po 1
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
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
Assumptions:
homogeneous surface (all adsorption
sites energetically identical)
Y mX i
1
Vm 1
mi V[(Po/P)-1]
Vm N av Acs
Total surface area
Weight of adsorbate
0-1 0-2 0-3
P/Po
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.
Volume
Points P/Po
adsorbed
UT
1 T P
U
2 O Pore shape Results Pore volume
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.
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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.
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Ca
rbo
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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.
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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
2 nm 50 nm
Methods Assumption
Pore Shape Based on ..
2 nm 50 nm
Methods Assumption
Pore Shape Based on ..
Cylindrical t-method
DH (Dollimore Heal) method
2 nm 50 nm
Methods Assumption
Pore Shape Based on ..