X-RAY DIFFRACTION (XRD) METHOD

Name of Test:

X-Ray Diffraction (XRD) Analysis

Details of specimen:

The powder diffraction method is an appropriate method for the characterization and
identification of polycrystalline phase especially cementitious system. Sample needs to be
ground as well as sieved through 75 µm sieve and used for XRD analysis. Mineralogical
characteristics of pozzolanic materials, ordinary Portland cement and Portland pozzolana
cements can be determined by using XRD.

Details of equipment:

X-ray diffraction technique is an effective tool to study the crystallography of materials and
phase compositions of a polycrystalline sample. The quantitative determination of phase
composition in the cement clinker by referencing the relative peak intensities, state of
crystallinity of different phases, determination of polymorphic changes, and other salient features
of individual phases can be studied by X-ray powder diffraction technique. XRD instrument is
shown in Figure 1. X diffraction instrument consists of X-ray tube source, divergence slit,
sample stage, detector and amplifier.
 Figure 1: XRD instrument at IIT Madras

Step by step procedure for testing:

Sample needs to be prepared as described earlier and taken on slide. The prepared sample
directly placed on the sample stage. X-ray beam is generated and allowed to pass through slits to
collimate the beam. X-ray beam interacts with specimen and gets diffracted. The diffracted rays
are allowed to passed through monochromators to eliminate the wavelength other than Kα
radiation. Detector is used to collect the diffracted rays. The detector records the diffraction
pattern taken from different angles. A spectrum of diffraction is plotted with intensity versus
detector angle 2θ to get a diffraction pattern of the tested sample. Every crystalline substance has
specific diffraction pattern and considered as a fingerprint of that substance. Identification of
detected phases is achieved by comparing the X-ray diffraction pattern with internationally
standard database like JCPDS (International Joint committee on Powder diffraction standards)
with the help of software tools such as X’Pert Highscore Plus. In addition, the amount of each
phase present in the polycrystalline sample can be calculated by the area under the corresponding
peak.
 X-RAY FLUORESCENCE SPECTROSCOPY
(XRF)

Name of Test:

Determination of oxide composition using X-ray fluorescence Spectroscopy (XRF)

Details of specimen:

Sample passing through 75 µm sieve is used for XRF analysis using Bruker S4-Pioneer
instrument. The powdered sample was pelletized with high purity boric acid for the
measurement.

Details of equipment:

X-ray fluorescence analysis is a reliable and rapid method that uses characteristic X-ray
(fluorescent X-ray) to find the elemental composition of the materials. X-ray fluorescence
spectrometer consists of X-ray tube (side window type or end window type) to generate X-ray,
sample chamber (two types; top-surface irradiation type and bottom-surface irradiation type),
and detector. The incident X-ray is generated from the X-ray tube by accelerating the electrons at
higher voltage and directed them to strike against a metal target. Generally tungsten, rhodium,
molybdenum and chrome are used as the metal target in the X-ray tube to generate incident
X-ray depending upon the types of analysis. The incident X-rays are focused towards the sample.
The electrons present in the outer shell transfer to the inner shell to fill the vacancy created by
the incident X-ray. Because of the energy difference, sample will emits fluorescent X-rays which
are the characteristics of the elements present in the sample. Therefore, relaxation of atoms is
achieved by the emission of the fluorescent X-rays.

Step by step procedure for testing:

Sample needs to be prepared as described earlier. Sample holder and placing of the sample in
sample chamber are shown in the Figures 2 and 3 respectively. The emitted X-rays can be
detected by an energy dispersive (or wave length dispersive) detector. The emitted radiation is
characteristic of a specific element. Elemental composition can be found from the net intensity of
energy peaks. From the elemental composition, oxide composition of bagasse ash and blended
cements were determined in the present study.

Figure 2: Sample holder and prepared sample for testing

Figure 3: Placing of sample in the sample chamber

 Figure 4: X-ray fluorescence spectrometer used for the study

SCANNING ELECTRON MICROSCOPY

(SEM)

Name of Test:

Microstructural analysis using Scanning electron microscopy

Details of specimen:

For SE mode:
Powder samples (SCM or cements)
The specimen preparation for secondary electron imaging involves just fracturing hardened
paste, mortar and concrete specimen and performing a sputter coating using gold or palladium.
For BSE mode: Polished specimens

Details of equipment:

Scanning electron microscope is used for microstructural characterization of cementitious

materials and hardened paste/mortar/concrete. Scanning electron microscope is widely used to
find morphological characteristics, composition and surface features (texture and topography) of
the sample with enhanced resolution. The scanning electron microscope consists of electron gun
(Thermionic guns or Field emission guns), condenser lenses, apertures, stigmator, scanning coil,
sample stage and vacuum system as shown in Figure 5 for the effective microscopic imaging.
Electron beam is generated from a tungsten filament (by heating the filament to high
temperature). Current of electron beam is controlled by Wehnelt electrode and directed towards
the sample for interaction.

Figure 5: Scanning electron microscope column

(http://science.howstuffworks.com/scanning-electron-microscope1.html)

A series of aperture and lenses are used to control the electron beam to achieve a better
interaction with sample. The incident electron beam interacts with sample and generates different
types of signals (secondary electrons, backscattered electrons, Auger electrons, X-rays).
Topographic contrast (surface texture and roughness) can be obtained by Secondary electrons
whereas compositional contrast is observed by backscattered electrons. Because of the electronic
transition and emission of X-rays, different elements present in the sample can be determined by
Energy dispersive X-ray analysis.

Step by step procedure for testing:

Secondary Mode (SE)

Supplementary cementitious materials, blended cements are directly spread on the sample holder
and the sample was coated with gold or palladium by sputter coating (see Figure 7) to achieve
better sample-electron beam interaction, high quality micrograph and avoid surface charging.
Moreover, carbon tape is used on the sample holder as shown Figure 6. For concrete study,
specimens are fractured at desired age and samples are immersed in acetone to stop further
hydration. Sample is directly placed with sample holder on the sample stage after coating to
observe morphology of the samples. Images captured in secondary mode of SEM are used to
study the topographical and morphological features of aggregates, cement, cement paste, mortar,
and concrete. Secondary electron study can throw light on mineralogical distribution of different
phases in the concrete and alterations upon any special exposures.

Figure 6: Sample holder and carbon tape

 Figure 7: Sputter coating equipment

Figure 8: Placing of sample on the sample stage of SEM

 Figure 9: Scanning electron microscope at IIT Madras

Specimen preparation for SEM-BSE

Specimen preparation for SEM-BSE involves a series of steps. To study the microstructure of
concrete at a particular age, the concrete after required curing is immersed in acetone for a
minimum duration of 24 hours, which expels the moisture from the concrete and subsequently
stops the hydration process. The respective samples thus obtained are then cut using a saw
(Figure 11) with a diamond blade of 1.2 mm thickness. The samples obtained with a size of
approximately 20 × 20 mm (Figure 12) are then epoxy-impregnated in a cylindrical mould, with
low viscosity epoxy resin and hardener (Figures 13 and 14). For this purpose, a vacuum
impregnator is used and specimens are moulded into the resin at 0.1 bar pressure. Specimens
obtained are then coarsely polished to remove the extra resin from the surface on a cast iron disc
with silicon carbide (SiC) powder and lubricant made out of 90 ml of carbide powder in one litre
of mixed glycerine/water (1:3). The coarse polishing is followed by fine polishing on a
lubricated cloth using polycrystalline diamond spray of 6 µm, 3 µm and 1 µm size (Figure 15).
Level of polishing is checked periodically by optical microscopy in reflected mode.
The polished specimens are then coated with gold or palladium to make the specimen conductive
prior to SEM imaging.

Figure 10: Specimens for microstructural studies by SEM

Figure 11: Cutting machine at IIT Madras

Figure 12: Specimens after cutting into 20 × 20 mm

Figure 13: Mould for epoxy mounting

Figure 14: Vacuum impregnator for epoxy mounting

Figure 15: Polishing of epoxy impregnated specimens

Figure 16: Polished specimens for SEM

 OPTICAL MICROSCOPY (OE)

Name of Test:

Polarized light microscopy

Details of specimen:

Standard thin sections of 30 µm

Details of equipment:

Microscopes are generally equipped with reflected and transmitted modes. Polished opaque
specimens can be viewed through reflected mode to study features such as different phases
present in the system, their interfaces and relative proportions. A transmitted mode is used to
study the mineralogy of thin sections in which semi-transparent specimens are viewed under the
microscope. Polarized light microscopy is used to study the properties of minerals. A typical
petrographic polarized light microscope with its parts is presented in Figure 17. Olympus BX41
polarized microscope equipped with digital camera is available at IIT Madras. The microscope
consists of reflected and transmitted modes with magnifications of 40, 100, 400 and 1000 X.
Petrographic microscope consists of eyepiece and objective lenses with coarse and fine focusing
facilities. It has a rotating stage and two polarizing filters, one below and another above the
stage. In general, the filter below the stage is known as ‘polarizer’ and one above the stage as
‘analyser’. If only the polarizer is used, the mode is called as Plane Polarized Light (PPL). If
both the polarizer and analyser are used, the mode is referred as Crossed Polarized Light (CPL)
or crossed nicols position. Images focused in optical microscope are captured by a mounted
camera or computer software.
 A B

Microscope used in this study

Figure 17: Polarized microscope; (a) Polarized light and microscope components
(http://www.microscopyu.com/articles/polarized/polarizedintro.html)
(b) Olympus BX41polarized microscope with digital camera available at IIT Madras

Step by step procedure for testing:

The respective samples of concrete are cut using a fine diamond saw (equipped in the machine)
to a possible minimum thickness. Then, a glass slide is ground on the surface on which the
sample was to be mounted in order to assure the bonding. The sample is then cemented on to the
roughened face of the glass slide using epoxy (approximately 5 µm in thickness) as shown in
Figure 18.
 Figure 18: Aggregate specimens cemented on to the glass slides

This slide needs to be transferred to a vacuum chamber and pressed from the top using the
pressing mechanism associated with the lid to expel any entrapped air. The samples obtained
from this procedure were ground using a grinding machine. During this process, the specimens
were held using a vacuum chuck supported by a vacuum pump (Figure 19). Then thin sections
are ground to the minimum possible thickness, the next step is to perform cast iron lapping with
silicon carbide (SiC) powder of # 1000 size with a lubricant made out of 90 ml of carbide
powder in one litre of mixed glycerine/water (1:3).

Figure 19: Vacuum chucks to hold thin section during grinding

The fine polishing is done using diamond sprays on a lubricated cloth, prior to the provision of a
glass cover over the thin section. The thickness of the section is measured using an electronic
Vernier calliper at every step of preparation. Figure 21 shows thin sections of aggregates
prepared for petrographic analysis. Similarly thin section can be prepared for concrete and
analysed using microscope.

Figure 20: Lapping thin sections after grinding

Figure 21: Thin sections of aggregates for petrographic analysis