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 Mesoporous silica, Activated carbon Macropores

Sintered metals and ceramics

2 nm

50 nm

Pores are classified according to the sizes: < 2 nm micropores, 2-50 nm mesopores, >50 nm macrospores.

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 Slits

Conical

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

Volume of solid (including pores)

X 100

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