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 its diameter (radius) Other properties of sphere are easily computed from its size:
1 3 2 m = d 3 V = d S = 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 ) = 3D
d(H) hydrodynamic diameter, D translational diffusion coefficient, k Boltzmanns constant, T temperature, - 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 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)

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+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.

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 d3). 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 d6 from Rayleighs 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?

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
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 Mass of the solid, g

Specific Surface Area, m /g =

2

Porosity, % =

Porosity
Pore size and its distribution

X 100 Volume of solid (including pores)

Volume of pores

Specific Pore volume, cm3/g

=
Total pore volume, cm3 Mass of the solid, g

Concept of Porosity: Open vs. Closed Pores

Inter-connected (open) Closed

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

Passing (open)

Dead end (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 Zeolite, Activated carbon, Metal organic framework 2 nm Mesopores Macropores

Mesoporous silica, Activated carbon

Sintered metals and ceramics

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, 603619 (1985).

Shapes of Pores
Cylindrical Slits

Conical

Pore Shapes

Spherical or Ink Bottle

Interstices

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 Angle Neutron scattering

Mercury porosimetry

Techniques

TEM

Small angle X-ray scattering

SEM

Techniques for Porosity Analysis

Gas adsorption

Small Angle Neutron scattering

Can measure only open pores Pore size : 0.4 nm 50 nm Easy Established technique

Mercury porosimetry

Techniques

TEM

Small angle X-ray scattering

SEM

Techniques for Porosity Analysis

Gas adsorption Small Angle Neutron scattering

Mercury porosimetry

Similar to gas

Techniques

adsorption Can measure only open pores Pore size >1.5 nm Easy Established technique

TEM

Small angle X-ray scattering

SEM

Techniques for Porosity Analysis

Gas adsorption Small Angle Neutron scattering

Mercury porosimetry

Provide information

Techniques

TEM

Small angle X-ray scattering

regarding pore connectivity Pore size can be measured if the materials contains ordered pores Rarely used for pore analysis

SEM

Techniques for Porosity Analysis

Gas adsorption Small Angle Neutron scattering

Mercury porosimetry

Techniques

TEM

Small angle X-ray scattering

SEM

Pore size > 5nm Rarely used for pore

analysis

Techniques for Porosity Analysis

Gas adsorption Small Angle Neutron scattering

Mercury porosimetry

Techniques

TEM

Small angle X-ray scattering

Any pore size Open + Close

porosity

SEM

Techniques for Porosity Analysis

Gas adsorption Small Angle Neutron scattering

Mercury porosimetry

Any pore size Open & Close

porosity Costly

Techniques

TEM

Small angle 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
WEAK, LONG RANGE BONDING Van der Waals interactions NOT SURFACE SPECIFIC Physisorption takes place between all molecules on any surface providing the temperature is low enough. Hads = 5 .. 50 kJ mol-1

CHEMISORPTION
STRONG, SHORT RANGE BONDING Chemical bonding involved. SURFACE SPECIFIC E.g. Chemisorption of hydrogen takes place on transition metals but not on gold or mercury.

Hads = 50 .. 500 kJ mol-1

Non activated with equilibrium achieved relatively Can be activated, in which case equilibrium can be quickly. Increasing temperature always reduces slow and increasing temperature can favour adsorption. surface coverage. No surface reactions. Surface reactions may take place:- Dissociation, reconstruction, catalysis. MONOLAYER ADSORPTION Langmuir Isotherm is used to model adsorption equilibrium.
http://www.soton.ac.uk

MULTILAYER ADSORPTION BET Isotherm used to model adsorption equilibrium.

Adsorption Process
Gas molecules admitted under increasing pressure to a clean, cold surface.

1 1

2 2

3 3

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

1. Diffusion to adsorbent surface 2. Migration into pores of adsorbent 3. Monolayer builds up of adsorbate

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

Adsorption Process
V V
a

= f (W , T , I , P) = volume of gas adsorbed;

where
a

W = weight of adsorbent; P = pressure of the adsorbate; T = temperatu re; I = interactio n between adsorbate and adsorbent. If W, T, and I are made constant, the above equation can be written as :

Adsorbate

p Equation of adsorption = f o Va p isotherm where Adsorbent p pressure of adsorbate = o & J. E. p saturated pressure of adsorptive S. Lowell 3rd Ed.Shields, Powder Surface Area and Porosity, Chapman & Hall, New York, 1991

Gas Sorption: Isotherm

Desorption isotherm Adsorption isotherm
p V a = f po where p pressure of adsorbate o = p saturated pressure of adsorptive

p po

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.

Va

Gas Sorption: Isotherm

Type I or Langmuir 1

Concave to the P/Po axis Exhibited by microporous solids ( < 2nm )

Va

P/Po

Type II B

Exhibited by nonporous or macroporous solids ( > 50nm ) Unrestricted monolayer-multilayer adsorption Point B indicates the relative pressure at which monolayer coverage is complete
1
S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed. Chapman & Hall, New York, 1991

Va

P/Po

Gas Sorption: Isotherm

Va
Type III

Convex to the P/Po axis Exhibited by nonporous solids

P/Po

Type IV

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

Va

P/P

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

Gas Sorption: Isotherm

Va
Type V

Highly uncommon Exhibited by mesoporous solids

P/Po

Va

Type VI

Exhibited by nonporous solids with an almost completely uniform surface

P/Po

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

Gas Sorption: Hysteresis

Va

Hysteresis

P/Po

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

P/Po

P/Po

P/Po

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 = + Va ( P P o ) Vm C Vm C P o 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 = relative pressure of adsorbate. Po

S.Brunauer, P.Emmett, E.Teller Adsorption of Gases in Multimolecular Layers, J. Am. Chem. Soc., 1938, 60 (2), pp 309319

Adsorbate

(a)

Adsorbent

(b) (c)

Modification of Langmuir isotherm Both monolayer and multilayer adsorption Assumptions: gas molecules physically adsorb on a solid in layers infinitely; there is no interaction between each adsorption layer; the Langmuir theory can be applied to each layer.

Specific Surface Area Calculation

P (C 1) P 1 = o + o Va ( P P ) VmC P VmC
At least three data points in the relative pressure range 0.05 to 0.30

Y = mX + i
1 Vm = m +i
Total surface area =
1 V[(Po/P)-1]

Vm N av Acs Weight of adsorbate

0-1

0-2

0-3
P/Po

Total surface area SSA (Specific surface area) = Weight of sample

Single Point BET

Single-point method offers the advantage of simplicity and speed, often with little loss in accuracy.

A relative pressure of 0.3 gives good general agreement with the multi-point method. Correction of single point error at P/P0 = 0.3 by multiplying the single point BET value by C/C-2 decreases the difference.
Sample No. Multi-point BET (m2/g) 4.923 4.286 8.056 5.957 Uncorrected single-point (m2/g) 4.241 3.664 6.867 5.194 Uncorrected Corrected difference single point (%) (m2/g) -13.9 -14.5 -14.8 -12.8 4.948 4.275 8.011 6.060 Corrected difference (%) 0.51 -0.26 -0.56 +1.73

Vm = Va (1 P P

i.e. Vm = 1/slope

1 2 3 4

Pore Size Distribution

The distribution of pore Broad pore size volume with respect to pore distribution size is called a pore size Narrow pore size distribution.
distribution

Va

Pore volume = Va
d

Pore diameter, d

Unimodal pore size distribution

Va

Multimodal pore size distribution

Pore diameter, d

Pore Size Distribution

Va

Adsorption or desorption isotherm. The desorption isotherm is preferred over adsorption isotherm.
(P/Po)des (P/Po)ads P/Po 1

Gdes = RT(lnPdes - lnP0) Gads = RT(lnPads - lnP0)

Gdes < Gads

Pore Size: Kelvin Equation

p 2V ln o = cos p r k RT where p pressure of adsorbate = o saturated pressure of adsorbate ; p = liquid surface tension; V = molar volume of condensed adsorbate;

rk

T = temperatu re; = contact angle between th e solid and condensed phase.

Multilayer formation occurs in parallel to = mean radius of curvature of the liquid meniscus; capillary condensation. k Capillary condensation R = real gas constant; is described by the Kelvin equation.

Pore Size: Kelvin Equation

Prior to condensation, some adsorption has taken place on the walls of the pore, rk does not represent the actual pore radius.

rk

t
Adsorbed layer

rp = rk + t
Actual radius of the pore Kelvin radius of the pore Thickness of the adsorbed layer

Methods for Calculation of Pore Size Distribution

BJH (Barrett, Halenda) method Joyner and Mesoporous solids DH (Dollimore Heal) method Dubinin-Astakhov method HK (Horvath-Kawazoe) method Saito-Foley method NLDFT (Non Local Density Functional Theory) and Monte Carlo simulation method Microporous and Mesoporous solids Microporous solids

Porosity Analyzer

Outgassing station

Analysis station Liquid nitrogen bath

Steps for Measurement

1. Sample Preparation

2. Adsorption Analysis

3. Interpretation

Sample Preparation (Outgassing)

Vacuum Helium Adsorbate

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.

Po Sample Cell Outgassing station Analysis station

Adsorption Analysis
Vacuum Helium Adsorbate

Po Sample Cell Outgassing station Analysis station

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

Interpretation
Points P/Po Volume adsorbed
Pore size & distribution

1 2 3

UT TP U O

Pore shape

Results

Pore volume

Weight of sample

Specific surface area

Common Adsorbates
Gas N2 Ar CO2 CO Kr O2 C4H10

Temperature -195.8 oC (liquid nitrogen) -183 oC (liquid argon). -183 oC (liquid argon). -195.8 oC (liquid nitrogen)

Cross sectional area (nm2) 0.162 0.142 0.195 0.163 0.205 0.141 0.469

-78 oC, -25 oC, 0 oC -183 oC (liquid argon) -195.8 oC (liquid nitrogen) -183 oC (liquid argon) 0 oC, 25 oC

Choice of Adsorptive
0.55 0.50 Cross-sectional area, nm 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00
Nit rog Ca en rbo nm on oo xid e Ca rbo nd iox ide n-b uta ne Ar go n Kr yp ton Ox yg en
2

N2(g) in N2(l) is the most commonly used adsorbate. Not completely inert. Dipole movement and thus can have localized adsorption. Cross-sectional area of 0.162 nm2 is questionable.

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 Cross-sectional area, nm 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00
Nit rog Ca en rbo nm on oo xid e Ca rbo nd iox ide n-b uta ne Ar go n Kr yp ton Ox yg en
2

Ar(g) in Ar(l) is preferable but because of unavailability of Ar(l) (87K), N2(l) (77 K) is used. Ar can reach to somewhat smaller pores than N2. Accurate measurement of micropores is possible using Ar.

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 Cross-sectional area, nm 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00
Nit rog Ca en rbo nm on oo xid e Ca rbo nd iox ide n-b uta ne Ar go n Kr yp ton Ox yg en

In case of activated carbon, CO2 is often the most preferred adsorbate. Adsorption analysis of CO2 takes less time. Limited to micropore analysis.

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

Validity of BET - Method

The BET method depends on the cross-sectional area of adsorbate. Monolayer structure is same on all the surface. Localized monolayer coverage.
P 1 (C 1) P = + V ( P P o ) VmC VmC P o

SSA =

V Lav A M

Adsorbate

Adsorbent
K. S. W. Sing, The Use of Nitrogen Adsorption for the Characterisation of Porous Materials, Colloids and Surfaces, 187 188, 2001, 3 - 9

Validity of Kelvin Equation

ln

p p

2V = cos o r k RT

rk

Is relation between the meniscus curvature and the pore size and shape valid? Is it applicable for micropores and narrow mesopores? Does surface tension varies with pore width?

F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic Press, 203, 1999

Shape of Microporous Materials

Type I isotherms dont have hysteresis.
Type I or Langmuir 1

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.

Va

P/Po

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
Based on ..
de Boers t-method
Polanyi

Methods

Assumption Pore Shape

Brunauer MP method Dubinin-Astakhov method

Cylindrical or Slit shaped -

potential theory Independent of Kelvin equation and Powl method Independent of Kelvin equation HK method

HK (Horvath-Kawazoe) method

Slit

Everett

Saito-Foley method

Cylindrical

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
Methods Assumption Pore Shape
BJH (Barrett, Joyner and Halenda) method DH (Dollimore Heal) method Cylindrical, Slit-shaped Cylindrical

50 nm

Based on ..
Kelvin equation t-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
Methods Assumption Pore Shape
NLDFT (Non Local Density Functional Theory) and Monte Carlo simulation method Cylindrical and slit

50 nm

Based on ..
Statistical thermodynamics

P. A. Webb, C. Orr, Analytical Methods in Fine Particle Technology, Micromeritics, 53 152, 1997 Quantachrome Autosorb-I Operational Manual