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By Vinodhini B Vishwanathan S K
Contents
Pores Classifications-Porosity
Methods of Porosity Measurements
Hysteresis
Advantages Disadvantages-Applications
Non-porous solid
Porous solid
Porous materials have high specific surface area and pore volume.
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 pores are accessible whereas closed pores are inaccessible pores. Open pores can be inter-connected, passing or dead end.
Passing (open)
Shapes of Pores
Cylindrical Slits
Conical
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
Laboratory Measurements
Direct Measurement Method
Imbibition Method Mercury Porosimetry Method
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.
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.
Instrumentation
Reservoir of mercury to which a graduated barrel
Penetrometer-sample of known weight is placed. The sample cell is surrounded by hydraulic fluid.
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.
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
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
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
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
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.
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.