Mercury Porosimetry

By
Vinodhini B
Vishwanathan S K

Contents
Pores Classifications-Porosity
Methods of Porosity Measurements

Mercury Porosimetry Method

Washburn Equation

Hysteresis
Advantages Disadvantages-Applications

What are Porous Materials?

Non-porous solid

Porous solid

Porous materials have high specific surface area and

pore volume.

Size of Pores (IUPAC Standard)

Micropores
Zeolite,
Activated
carbon,
Metal organic
framework

Mesopores

Macropores

Mesoporous silica,
Activated carbon

2 nm

Pores are classified according to the sizes:

< 2 nm micropores,
2-50 nm mesopores,
>50 nm macrospores.

Sintered metals
and ceramics

50 nm

Types Of Pores

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)

Shapes of Pores
Cylindrical

Conical

Slits

Pore
Shapes
Interstices

Spherical or
Ink Bottle

Measurement of Porosity
Parameters used to measure porosity; specific surface area, specific pore
volume ,and pore size and its distribution.
Specific Surface Area,

m2/g

Total surface area, m2

Mass of the solid, g

Porosity, % =
Volume of pores

Porosity
Pore size &
its distribution

X 100

Volume of solid (including pores)

Specific Pore volume, cm3/g

=

Total pore volume, cm3

Mass of the solid, g

Laboratory Measurements
Direct Measurement Method
Imbibition Method
Mercury Porosimetry Method

Gas expansion method

Density Method
Petrographic Method

Bulk Volume Measurement

Mercury Porosimetry
Extremely useful characterization technique for porous

materials.

Pores b/w 500m-3.5nm can be investigated.

Only method that provides information about

Pore size distribution,

Porosity ,
Skeletal & Apparent density and
Surface area of the sample.

Purity of Mercury
Hydraulic oil should not be recycled , it

contaminate the mercury and changes its dielectric

and flow properties.

Contamination of mercury affects the contact

angles and surface tension values.

Mercury-Acid washed, dried and distilled

preferably doubly- or triply-distilled.

It is always advisable to use fresh mercury for

every measurement.

Sample Preparation
Porous materials are prone to adsorb water or other

chemicals, which should be removed during the initial

evacuation of the sample.

One of the key parameter here is the sample weight.

Instrumentation
Reservoir of mercury to which a graduated barrel

with a piston is attached.

Penetrometer-sample of known weight is placed.

The sample cell is surrounded by hydraulic fluid.

After evacuating the air around the specimen

with the vacuum pump and the penetrometer is

filled with mercury up to the reference level.

Schematic diagram

Working Principle
At normal pressures Hg will not enter the pores of

most samples.
From the Hg displacement, bulk volume of the
sample is calculated.
The pressure on the Hg is then raised further, forcing
the mercury into the pores of the sample .At
sufficiently high pressure, the mercury will invade all
the pores.
The amount of mercury lost into the sample provides
the pore volume directly.
The porosity can then be calculated from the bulk
volume and the pore volume.

Pressure Range
Low Pressure System
The first data point is usually taken at a pressure of
3000 to 4000 Pa or higher.
High Pressure System
Pressure given to the hydraulic oil surrounding the
sample cell in an isostatic way up to 414 Mpa.

Mercury Injection Apparatus

 Mercury will enter the capillary at the threshold

pressure, but will not advance.

The mercury level increase is depend on an excess
pressure applied , above the threshold pressure
For the increased level the distance - time relationship is

 The distance - time relationship for mercury in tubes of five

different sizes is shown fig below, E.g., More than 100 seconds
are needed to travel 3 cm in a tube of 0.5m radius.

Washburn equation
The relationship between the applied pressure (p) and

the pore size (d),

d= (4/p) cos
where,
-surface tension of mercury,
-contact angle between solid and mercury

The value of Vi(Hg) at the applied pressure Pi

apparently gives the cumulative volume of all available

pores of radius d.

Hysteresis
Wardlaw at 1988 proposed mercury entrapment leads

to hysteresis between the mercury intrusion and

extrusion curves.
Explanations proposed are:
a) Contact angle hysteresis
b) Ink bottle theory
c) Percolation -connectivity model

Hysteresis

a) Contact angle hysteresis

The surface roughness or the impurities on the
mercury or solid surface could certainly affect the
contact angle.

b) Ink Bottle Theory

The opening of a pore is smaller than the actual cavity.
So mercury entering into the pore cavity depends on
the neck size and not the actual cavity size.
c) Connectivity Model
Uses network of pores.
An extension of ink bottle theory

Percent Porosity

Where,
Va -Hg volume intruded at any given pressure
Vb -Hg volume intruded at a user-defined Intrapore
Filling Pressure Limit
Vc -Hg volume intruded at the max. experimental
pressure

The PMI Mercury Intrusion

Porosimeter
Equipment

PMI Mercury Porosimeter Data

Report
Pore Volume vs. Diameter
Delta Volume histogram
Pore Distribution (histogram)
Percent Total Pore Volume
Pore Distribution (pressure and diameter)
Particle Size Distribution (histogram)
Percent Porosity and Density
Cumulative Surface Area
Porosimetry Text Data

Advantages
Speed and simplicity.
grain size and pore throat size distribution of the

sample can be calculated.

Can analyse lower porosity values than other methods.
Low-pressure mercury porosimetry determines
macropores (pore diameter 14 200 m).
High-pressure porosimetry determines mesopores and
macropores (pore diameter 3 nm 14 m).
it can be done on small irregular samples.

Limitations & Disadvantages

Mercury porosimetry does not actually measures the

internal pore size, determines the largest connection

(throat or pore channel)
Cost of distilled Mercury is high.
The assumption of a constant value of surface tension
and angle of contact for mercury.
The Pores are not usually circular in shape, so the
results can only be comparative
Sample must be disposed of safely after the test.

Applications
Characterization of carbon blacks, pharmaceutical

samples.
Distribution of porous bead cellulose.
Determination of Maltose.

Distribution of foamed chitosan.

Determination of Cement Particles.

Thought for the Day