THE TECHNIQUES

USED IN
DETERMINATION OF
SOLID SURFARCE
AREAS
Specific surface area is defined as the surface area per unit of mass, typically expressed in square
centimetres per gram (cm2/g) or square meters per kilogram (m2/kg). Surface size and surface quality are
two of the most important parameters of organic and inorganic solid materials as hardened cement paste
and concrete. Gas sorption techniques are based on physical adsorption of gases or vapours on the
surfaces of solids. In contrast to chemical adsorption, also called chemisorption or irreversible adsorption,
during physical adsorption the sorbed molecules are not restrained to specific sites on the surface of the
measured solid and are free to cover the whole surface. The term “sorption” is used to describe the
interaction of a gas with a solid surface. This interaction may be in the form of adsorption, absorption, or
capillary condensation.

Techniques in Concrete Science and Technology

TECHNIQUES OF SURFACE AREA MEASUREMENT

In the area of cement and concrete research, two main types of materials need to be characterized:
powder materials such as cement, flash and silica fume (micro silica), and solid materials such as
hardened cement paste and concrete. The surface area of the powder material is of importance due to its
effect on the reactivity.

1. Blaine method (ASTM C204-94)- Lea and Nurse method,

is used to determine surface area. For powders finer than Portland cement (silica fume or fly ash)
nitrogen adsorption or mercury intrusion porosimeter are used to determine the surface area.

porosity by monitoring the pore size filled with a liquid at an applied pressure, and others use the
deflection of electron and neutron beams.2.1

2. Gas Sorption Techniques

Gas sorption techniques are based on physical adsorption of gases orvapors on surfaces of solids. In
contrast to chemical adsorption, also called chemisorption or irreversible adsorption, during physical
adsorption thesorbed molecules are not restrained to specific sites on the surface of the measured solid

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and are free to cover the whole surface. For this reason, determination of surface areas is possible.
Physical adsorption is fully reversible and, with the exception of small pores, equilibrium can be easily
achieved since no activation energy is involved. Because physical adsorption does not occur at elevated
temperatures, sufficiently clean surfaces can be prepared prior to the actual low-temperature surface
area measurements. Although numerous methods for surface area measurements based on physical
adsorption of gases were developed, the best-known method for determination of surface areas of
porous solids is the so-called

3. BET method

grounded on the work of Braeuer, Emmett, and Teller.[2][3] Since its development in the late 1930s,
this method became the most universally used method for surface area determination of such
diverse materials as catalysts, carbon blacks, finely divided silica, and hydrated cement pastes and
components. The BET methodology gives surface areas two to three times higher than the Lea and
Nurse and Blaine methods discussed above. The BET theory makes two basic assumptions regarding
the heat of adsorption:

(i) It is constant throughout the formation of the first layer of adsorbed gas.
(ii) In the second and higher layers it is equal to the heat of liquefaction.

More about the accuracy of these BET assumptions can be A plot of the amount of gas adsorbed at a
certain temperature against the relative pressure is called a sorption isotherm. It is usually presented as
the volume of adsorbed gas versus the relative pressure, p/po, see Fig. 2.[12] From such a plot the
amount of gas needed to form a monolayer cane determined and, assuming the cross-sectional area of
the sorbate molecule, the surface area of the measured solid can be calculated. The relative humidity at
which a monolayer completely covers the solid surface depends both on the nature of the used sportive
gas and the nature of the solid. The gas interacting with the surface is usually referred to in the literature
as a sorbate. The BET method as well as some previous related work is based on the experimental
establishment of the relationship between the pressure of gas that is in equilibrium with a solid surface
and the volume of the gas adsorbed at the particular pressure at the surface. The theoretical basis for this
approach is the Langmuir theory based on the kinetic theory of gases.

4. Gas sorption techniques

are based on the assumption that gas mol-edulis are strongly attracted and adsorbed on a virgin surface.
The method assumes also that the sorbent molecules have access to the walls of the pores. As a
monolayer of the sorbent gas forms on the surface the repulsion of the previously adsorbed gas
molecules makes the formation of a second and subsequent layers less likely. This process is gas pressure
dependent, thus with increased relative pressure the degree of gas adsorption increases. Gas molecules
may be adsorbed in subsequent layers before the underlying layer is completely covered. The method
does not make any assumptions regarding the pore size or pore size distribution

5. Mercury Intrusion Porosimeter (MIP)

One of the best-known techniques used for determination of particle size or pore size distribution
that can also be used to indirectly determine the surface area is the Mercury Intrusion Porosimeter.
MIP is based on the relationship between pressure and the corresponding volume of pores filled with

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 a non-wetting liquid. Due to the high pressure needed to infiltrate the pores, this method is applied
mainly to hydrated cement paste and concrete both of which can withstand the applied pressure
without much damage tithe measured microstructure. The liquid typically used is mercury. It is a
non-wetting liquid. The method uses two major assumptions:

(I) the surface tension and the wetting angle are constant throughout the tested specimen, and
(ii) all pores have the shape of an ice cream cone. The first assumption may not be accurate
because the contact angle changes with the changing pore solution in the tested material. The
second assumption causes the space behind the neck of the ink-bottle to be treated as a cylinder
with radius of the pore opening. The pressures typically applied during testing ranges

6.Wagner Turbidimeter

The primary use of this technique is in measurement of surfaces of powders. The Wagner turbidimetry is
based on measurement of the terminal free fall velocity governed by Stake’s law. By using a beam of
light, the concentration of particles suspended in kerosene is measured by determining the percentage of
light transmitted through the suspension toa photocell.The method was adapted by ASTM as Standard
Test Method.The technique usually gives consistent results, the main error being the assumption of
uniform distribution of particles smaller than 7.5 µmother use of the average particle size of 3.8 µm
below the 7.5 µm is an overestimation resulting in the lower calculated surface area. The assumption
that the average particle below 7.5 µm is 3.8 µm is overestimated; thus, the calculated surface areas are
too low. Because it is these finest pores that govern the specific surface area, their influence on the
calculated results is overwhelming; a modification to reduce this error was proposed.

7.Permeability Methods

Permeability measurements are applicable for situations when the flow through a material is caused
mainly by pressure gradient. If this assumption is true, permeability is the property of a porous material
which characterizes the ease with which a fluid may be made to flow through the material. The
coefficient of permeability can thus be related to the surface area of the tested material. The relationship
that governs the flow through porous media.

The principal equation=

where: Qis the flow raitas the cross-sectional area/∆Lis the pressure gradient. Lea and Nurse applied
Darcy’s law to describe the surface area of materials.The surface is then calculated as:

It has two main advantages: the method is simple and fast. The main disadvantage, not critical in
determine-nation of cement fineness, is its poor accuracy which becomes worse with increasing
variability of the particle size, pore tortuously, and surface area.The use of permeability methods requires
complete drying of the pore structure.

8.Small Angle X-Ray Scattering (SAXS)

and Small Angle Neutron Scattering (SANS)The basic principle of SAXS and SANS is the scattering of the
beam of radiation as it passes through a material. At low angles the scattering is particularly noticeable
and can be monitored to describe the inhomogeneities or boundaries in a two-phase system (e.g., solid
and air, or solid and water). Figure 4 shows schematics of an x-ray scattering arrangement.

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9.Nuclear Magnetic Resonance (NMR)

One of the new techniques for determination of the total pore volume and surface areas is NMR,
specifically the technique referred to as spin-spin relaxation.[10][40] The method is based on the
relaxation of longitudinal or transverse magnetization at the interface between a solid and the liquid, in
other words, on the dependence of the exact resonance frequency upon the local magnetic field. Its use
for surface area determination is based on two principles:

In the region containing evaporable water, the first molecular layer on the hydrated surface has a
uniform, well-defined relaxation time All conditions for fast exchange of water present in the first surface
layer and of the remaining evaporable water in the pore structure are met the absorption spectrum of a
material will depend on the environment of the protons in the sample, thus the technique allows
estimation of the water mobility or its state in the sample.

10.Image Analysis Image

analyses of visible light (optical) or backscattered electron images of specially pre-treated samples can
be, in principle, used for determination of pore size distributions and surface areas. However, as
discussed elsewhere in this book (Ch. 19), in addition to some advantages(e.g., no need for drying), the
technique suffers from several disadvantages:•Two-dimensional images have to be recalculated into
three-dimensional pore distribution data.

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