GeoEnvironmental Research Group Laboratory Manual 2008

X-ray diffraction
The X-ray diffraction (XRD) analysis was undertaken to investigate qualitatively the
composition of the clay mineralogy in the soil samples. The main purpose of this study
was to identify the clay mineralogy of the soil samples. It is important to identify clay
minerals, for example kaolinite, illite, montmorillonite, chlorite etc. as they may
influence the behaviours and properties of the clay materials. The cation exchange
capacity, specific surface area, plasticity, and retention capability very much dependent
on clay mineralogy.

a. Sample preparation
The glass slide method was utilised in this study because of its ease of application (Figure
3.18). All of the sample preparation must be accomplished with a minimum of chemical
and physical damage to the clay minerals present. The rule is to do as little as possible to
the sample before presenting it to the x-ray beam. Organic-free soils less than 63m
(after the organic test from Section 3.3.1) were used. According to Moore and Reynolds
(1989), organic matter can produce broad x-ray diffraction peaks, and may increase the
background, and inhibit dispersal of other minerals.
Ceramic
Glass
Suspension

Figure 3.18. The suspension on the glass slide is hold by the surface tension. The ceramic/tile is
used to catch the spills.

About 1g of soil was then placed into 10ml measuring cylinder. About 5ml of distilled
water was then added in to it and was mixed thoroughly using a glass rod. After 15-20
minutes, the upper solution was then pipetted (using an eyedropper) and placed slowly on
the clean glass slide so that the liquid covered the entire surface of the slide. A porous
ceramic plate was used under the slide to catch any spills. It was assumed, according to
Stokes Law, that the solution that was sampled contained the clay particles of less than 2
GeoEnvironmental Research Group Laboratory Manual 2008
m. The slide was dried at the room temperature. High drying temperature should not
be used because poorly crystallised clay minerals in soils can be damaged by high
temperature. Several treatments have been undertaken to verify the clay minerals in the
soil. These treatments were: -

Glycol treatment
The sample was exposed to the vapour of the reagent ethylene glycol solvation. It was
dried in the oven at 60
o
C and then re-analysed to determine the presence of
montmorilonite. Montmorillonite is easily identified by comparing patterns of air-dried
and ethylene glycol-solvated preparations. The glycol-treated preparations give a very
strong 001 reflection at about 5.2
o
2 (16.9 ), which, in the air-dried condition, shifts to
about 6
o
(15 ) (Moore and Reynolds, 1989).

Heat treatment
The slide was heated in the furnace at a temperature of 550
o
C for 30-40 minutes to verify
the chlorite and kaolinite peaks. Heating chlorite to 550
o
C for 1 hour causes
dehydroxylation of the hydroxide sheet with attendant changes in the diffraction pattern.
The intensity of the 001 reflection increases greatly and shifts to about 6.3 to 6.4
0
2, and
the 002, 003 and 004 reflections are much weakened. At this temperature, kaolinite
becomes amorphous to X-rays and its diffraction pattern disappears. This test may
suggest that chlorite is present or that chlorite is absent (Moore and Reynolds, 1989).

Hydrochloric acid treatment
0.2g of organic-free soil sample was placed into the centrifuge tube. About 5ml of
concentrated hydrochloric (HCl) was added and heated for 10-15 minutes. It was washed
with distilled water for 3-4 times to neutralise the acid. The sample was centrifuged, the
wash water was discarded and the soil left was oven dried and powdered. The sample
was then used for preparation of another glass slide. This treatment was used to destroy
the chlorite peaks and to distinguish chlorite from kaolinite.

GeoEnvironmental Research Group Laboratory Manual 2008
b. Qualitative analysis
The clay minerals were identified using the X-ray diffraction patterns (diffractogram)
which by the peaks position, intensity, shape and breadth. Peak position is determined
using Braggs law which is written as n =2dsin . Most of the important clay peaks are
at the 2 values of 40
o
or less; therefore, is 20
o
or less. The identification of clay
minerals was accomplished by careful consideration of peak positions and intensities.
The qualitative identification procedure began by searching for a mineral that explains
the strongest peak or peaks, then confirming the choice by finding the positions of
weaker peaks for the same mineral. Once a set of peaks was confirmed as belonging to a
mineral, these peaks were eliminated from consideration. From the remaining peaks, a
mineral that will explain the strongest remaining peak or peaks was searched and then
confirmed by looking for its peaks of lesser intensity. This method was repeated until all
peaks were identified.

The determinations of clay minerals were based on the treatment results described earlier.
Illite and glauconite profiles are unaffected by ethylene glycol solvation and heating to
550
o
C. Glauconite has a higher 001/003 intensity ratio than illite, but the main difference
is the very week or non-existent gluconite 002 reflection whose weakness is caused by
heavy scattering from octahedral iron (Moore and Reynolds, 1989).

Chlorite has a basal series of diffraction peaks based on a first-order reflection of 14.2 .
Kaolinite has reflections based on a 7.1 structure. Most kaolinites have the 002 peak at
24.9
0
2, and chlorite has its 004 reflection at 25.1
0
2. Positive identification of chlorite
is provided by peaks at 6.2 and 18.8
0
2, but these peaks are often weak and may not be
detectable if the chlorite concentration is low. The chlorite and kaolinite can be
differentiate by treated chemically or heated and then re-examined. Montmorillonite is
easily identified by comparing diffraction patterns of air-dried and ethylene glycol-
solvated preparations (Moore and Reynolds, 1989).



GeoEnvironmental Research Group Laboratory Manual 2008

Table 3.10. An identification of clay minerals based on observation after treatments.
Mineral name Air dried Heated 550
o
C Glycolation Acid
Montmorillonite 15.0 10.0 16.9 Unchanged
Illite 10.0 Unchanged Unchanged Unchanged
Kaolinite 7.1 Peak disappeared Unchanged Unchanged
Chlorite 14.2 Unchanged Unchanged Peak disappeared