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. The surface is the only way for a solid to interact with its surroundings.
Consequentially, various physical properties of a solid such as dissolution, thermal properties, moisture
retention etc. as well as its participation in chemical reactions as a reagent or catalyst is also governed by
the surface. Thus the characterization of the surface is essential to predict the nature of a solid for its
potential applications. Amongst various characterization techniques, determination of surface area is of
significant importance as it gives a measure of the exposure a solid does have towards its surroundings.

Measurement of surface area of a solid can be performed using various techniques such as light
scattering, laser diffraction or gas adsorption. First two techniques are essentially particle sizing
techniques which considers all particles have regular surface and completely overlook the possibility of
presence of pores resulting in underestimation of the surface area. To countermeasure this limitation of
conventional particle sizing techniques, gas adsorption is considered to be the better alternative as
depending upon the size of the pores, appropriate gas molecules can be used to enter the pores, sit on
the inner surface and measuring the amount of gas used up in covering the surface, the surface area of a
particular solid can be measured with greater accuracy.

Adsorption, the phenomenon exploited for surface area measurement is the adhesion of atoms, ions or
molecules from a gas, liquid or dissolved solid (adsorbate) to a surface (adsorbent) that creates a film of

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the adsorbate on the surface of the adsorbent. It is a consequence of excess energy associated with every
bulk surface and mainly characterized by van der Waals’ forces. The adsorption of gases and solutes is
usually described through isotherms, that is, the amount of adsorbate on the adsorbent as a function of
its pressure (if gas) or concentration (for liquid phase solutes) at constant temperature.

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
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

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 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. Brunauer–Emmett–Teller (BET)
theory aims to explain the physical adsorption of gas molecules (N2, Ar, Kr, CO2, H2, CH4, H2O etc.) on a
solid surface and serves as the basis for an important analysis technique for the measurement of the
specific surface area of materials. The specific surface area is usually calculated by using BET theory from
the gas adsorption isotherm data. The BET model states that the adsorptive starts to adsorb on the
strong energy sites on the surface first, and then, as the pressure is increased, the adsorptive adsorbs on
the next energy level sites. The model also takes account of the 2nd, 3rd and higher layer adsorption. This
BET theory for multi-layer adsorption is the expansion of Langmuir equation, which is for the single layer
adsorption.

The theory is based on following assumptions:

 Homogeneous surface of the solid

 No lateral interactions between molecules
 Uppermost layer is in equilibrium with vapour phase
 First layer: Heat of adsorption
 Higher layers; Heat of condensation
 At saturation pressure, the number of layers becomes infinite

The calculation is based on a linear section of the isotherm at relative pressure range 0.05-0.35

The equation derived from the BET theory is;

(P/P0)/W(1-P/P0) = [(C-1)/WmC] (P/P0) + 1/WmC,

Where, P = partial pressure of N2, P0 = N2 equilibrium vapour pressure, W= mass absorbed of N2, Wm =
mass of the monolayer and C is the BET constant

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 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.Intrusion Porosimeter Mercury (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 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 to a 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. Surface Area
f
6
Measurements S=6 ⋅ 10 ⋅ F ⋅
Σ
d⋅f

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where: S is the specific surface area in m2 kg-1

F is an empirical constant that takes into account the assumed pore shape distribution specific surface
area

f is the weight fraction of material consisting of grains assumed to have a diameter d, in µm

r is the density, given in kg m-3

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=

k ⋅ ΔP
Q= A ⋅
ΔL

where: Qis the flow rate

A is the cross-sectional area

ΔP/∆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.

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

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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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