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quantitative analysis by x-ray diffraction

quantitative determinations of the amounts of different minerals in a soil on the basis of


simple comparison of diffraction in mass absorption coefficients of different of the minerals, in
particle orientations, in sample weights, in hydration, and in other factors. In some cases, estimates
based on x-ray data alone are at best semi quantitative ; however, in others techniques that account
for differences in mass absorption characteristics and utilize comparisons with known mixtures or
internal standards may give good results. Soils containing only two or three well crystallized mineral
components are more easily analyzed than those with multimineral compositions and mixed
layering.

A theory for quantitative analysis based on linear interaction between mineral pairs is
described by Moore (1968). Methods for determination of interaction coefficients are
given.Experimental accuracy to within 2 percent appears possible. A method based on the use of at
least two synthetic mixtures to bracket the background x-ray intensity and composition of the
unknown is described by Buck (1973)

For a more detailed treatment x-ray diffraction theory, identification criteria, and techniques,
particularly as related to the study of clays, the reader is referred to Klug and Alexander (1954),Cullity
(1956), Brown (1961), Whittig (1965) , Grim (1968), and Carroll (1970)

5.6 DIFFERENTIAL THERMAL ANALYSIS

Principle

Thermal techniques have been used for the study of soils and clay minerals. Differential
thermal analysis (DTA) has found the widest application, and consists of simultaneously heating a
test sample and a thermally inert subtance rate ( usually about 10C/min) to over 1000C and
continuously measuring differences in temperature between the sample and the inert material.
Differences in temperature between the sample and the inert substance reflect reactions in the
sample brought about by the heating. Thermogravimetric analyses, in which

Table 5.3 x-ray

Table 5.4

Changes in weight caused by loss of water or CO2 or gain in oxygen are determined, are also used to
some axtent, but will not be disscused herein.

The results of differential thermal analysis are generally presented as a plot of the difference
in temperature between sample and inert material (T) versus temperature (T) as indicated in
Fig.5.8. Endothermic reactions are those wherein the sample takes up heat, and in exothermic
reactions, heat is liberated. Analysis of test result consists in comparing the sample curve with those
for known materials so that each deflection can accounted for.

Apparatus

Apparatus for DTA consists of a sample holder, usually ceramic, nickel, or platinum; a
furnance; a temperatu controller to provide a contant rate of heating; thermocouples for
measurement of temperature and the difference in temperature between the sample and inert
reference material; and a recorder for the thermocouple output. The amount of sample required is
of order of one gram. Figure 5.9 is a schematic diagram of the apparatus. Although the temperatures
at which thermal reactions take place are a function only if the sample, the size and shape of the
reaction peaks depend also on the thermal characteristics of the apparatus and the heating rate.
Thus, there is some difficulty in comparing quantitatively the result from different apparatus.

Fig 5.8

Reactions giving thermal peaks

The important thermal reactions giving rise to peaks on a thermogram are :

1. Dehydration. Water may be present in two forms in addition to free pore water : adsorbed
water or water hydration, which is driven off at 100 to 300c and crystal lattice water in the
form of (OH) ions, the removal of which is termed dehydroxylation (Barshad, 1965).
Dehydroxylation causes a complete destruction of mineral structures; whereas removal of
adsorbed water is a reversible process. The temperature at which the major amount of
crystal water is lost is the most indicative property for identification of minerals. Dehydration
reactions are endothermic
Fig.59
2. Crystallization. New crytals can form from amorphous materials or from old crystals
destroyed at a lower temperature. Crystallization reactions usually are accompanied by an
energy loss and thus are exothermic
3. Phases changes. Some crystal strustures change from one form to another at a specific
temperature and the energy of transformation shows up as a peak on the thermogram.
Quartz changes from the to form (reversible) at 573c. The peak for the quartz phase
change is sharp (fig. 5.10), and its amplitude is nearly in direct proportion to the amount of
quartz present. The quartz peak is frequently masked within the peak for some other
reacting material. The quartz may be readily identified, however, by determining the
thermogram during cooling of the sample or by letting. It cool first and then rerunning it. The
other minerals are destroyed during the initial run while the quartz reaction is reversible
4. Oxidation. Exothermic oxidation reactions may take place such as the combustion of organic
matter or the oxidation of Fe2+ to Fe3+. Organic metter oxidizes in the range of about 250 to
450c
Useful information about the shape, texture, size, and size distribution of silt and sand grains
may be obtained directly without formal previous training in petrographic techniques. Some
background is needed to identify the variuos minerals; however, relatively simple diagnostic crtiteria
that can be used for identification of over 80 percent of the coarse grains in most soils have been
given by Cady(1965). These criteria are based on such factors as color, reflactive index, birefringence,
cleavage, and particle morphology. The nature of surface texture, the presence of coatings,layers of
decomposition, and so on, are useful both for interpretation of the history of a soil and as a guide to
the soundness and durability of the particles.

5.8 ELECTRON MICROSCOPY

The electron microscope is a valuable tool for the study of soils, because with modern
electron microscopes, it is possible to resolve distances to less than 100A, thus making study of small
clay particles possible. Electron diffraction study of single particles also is possible. Electron
diffraction is similar to X ray diffraction except an electron beam instead of an x ray beam is used.

Magnetic lenses, which refract an electron beam, form the basis of the transmission electron
microscope optical system. An elctron beam is focused on the specimen, which is usually a replica of
the surface strusture of the material under study. Some of the electrons are scattered from the
specimen, and different parts of the specimen appear light or dark in proportion to the amount of
scettering. After passing through a serial of lenses, the image is displayed on a flourescent screen for
viewing. Probably the most critial aspect of successful transmision electron microscopy is specimen
preparation. Some of the available techniques that have been used for study of discrete particles and
surface structures of particle asseblanges are reviewed by Kittrick (1965).

The scanning electron microscope (SEM) represents a rether recent development. With this
instrument, secondary electrons emitted from a sample surface form what appear to be three
dimensional images. The SEM has a magnification range of X20 to X150000 and a depth of field some
300 times greater than that of the light microscope. These characteristics, coupled with the fact that
clay particles themselves and freacture surfaces through soil masses may be viewed directly, as
opposed to the study of raplicated surfaces in the transmission electron microscope, have led to
almost exlusive use of the SEM for electron microscope study of clay. Examples of electron
photomicrographs of clays and soils are given in chapter 3,8, and 11. Principles of electron
microscopy techniques, and additional examples are presented by McCrone and Delly (1973)

5.9 QUANTITATIVE ESTIMATION OF SOIL COMPONENTS

Qualitative x ray diffraction and few simple tests generally suffice to indicate the minerals
present in a soil. More data are needed, however, for more precise quantitative estimetes. As a rule,
the number of different analyses needed is equal to the number of mineral species present (Barshad,
1965). The results of glycol adsorption,cation exchange capacity, X ray diffraction, differential thermal
analysis, and the various chemical tests noted in Section 5.4 all give data that may be used for
quantitative estimations. Table 5.5 summarizes some of the partinent identification criteria and
indicates referance values for the clay minerals. Quantitative estimates may be made based on
measured quantities and reference values (Lambe and Martin, 1954;Barshad, 1965).
After the quantities of organic metter, carbonates,free oxides, and non clay minerals have
been determined, the presentages of clay minerals are estimated using the appropriate glycol
adsorption, cation excange capacity, K2O, and DTA data. The nonclays can be identified, and their
abundance determined using the microscope, grain size distribution analysis, X ray diffraction, and
DTA. The amount of illite is estimeted from the K 2O content since this is the only clay mineral
containing potassium. The amount of kaolinite is most reliably determined from the 600 C DTA
endotherm amplitude. If the presence of montmorillionite,chlorite,and/or vermiculite has been
indicated by X ray, then quantitative estimates are made based on the glycol adsorption and excange
capacity data. The total excange capacity and glycol retention is ascribed to the clay minerals, and
the measured values must be accounted for in terms of proportionate contributions by the different
clay minerals present. In some cases these values may be used to provide a check on each other.

As simple example, assume that quartz, illite, and montorillonite (smectite) are identified in
the -2m fraction of a soil. Additional data indicate 4,0 percent K 2O,ethylene glycol retention of
100mg/g, and a cation exchange capacity of 35 meq/100 g. Them assuming 9 percent as an average
value of K2O for pure illite (table 5.5), the content of illite is estimeted at 4,0/9,0 of 44 percent.
Because only the illite and montmorillonite will contribute to the glycol adsorption, the amount of
montmorillonite may be estimated

0,44 X 60 + M X 300 = 100

10026,4
M= =25
300

The remaining 31 percent can be ascribed to quartz and other non clay components. For this clay
mineral composition, the theoretical cation excange capacity should be, based on the referance
values in table 5.5 :

0,44 x 25 +0,25 x 85 = 11 + 21 = 33 meq/100 g

Table 5.5

This compares favorably with the measured quantity of 35 meq/100 g. Thus, the composition of the
clay size fraction is

Illite 44%

Montmorillonte 25%

Quartz and other non clay 31%

In most instances, a semiquantitative analysis is sufficient for most application. This may be
done as follows. The silt and sand fraction can be examined by microscope and the approximate
proportion of non clay minerals determined. The amount of clay size material, -2 m, can be
determined by grain size distribution analysis. As a first approximation, it may be assumed that the
amount of clay mineral equals at least the amound of clay size. This assumption is justifield for the
following reasons. It is known that non clay size fraction. On the other hand, for most soils, the
amount of clay mineral exceeds the amount of clay size. This most probably results from
cementation of small clay particles into aggregates larger than 2m in diameter. The approximate
proportions of the different clay mineral in the clay fraction can be estimated from the relative
intensities of the X-ray diffraction reflections for each mineral. Greater precision may be obtained by
application of one of the techniques noted earlierfor quantitive analysis by X-ray diffraction. The
presence of organic matter an carbonates can be easily detected using the tests listed in section 5.4.

5.10 NATURE OF SOIL FINES

In a series of five papers, Lambe and Martin (1953-1957) reported compositional data and
their relationship to engineering properties for a large number of soils. These soils were
predominantly those from civil engineering projects from all over the world, but the largest group
came from the United States. In many instances they were associated with special soil engineering
problems. In 137 soils, the percentage of the following minerals was

Quartz 45%

Illite 66%

Fe2O3 58%

Smectite 46%

Organic matter 45%

Carbonates 28%

Kaolinite 23%

Feldspars 21%

Chlorite 21%

Halloysite 10%

Gibbsite 10%

Mica 6%

Vermiculite 4%

This shows clearly the prevalance of quartz as the dominant non clay and illite as the dominant clay
mineral in soils. More tha one of the clay minerals occurred in about 70 percent of the soils studied,
and the clay mineral were usually interstratified.
Vermiculite. Although an expansive mineral, the greater interplayer ordering in vermiculite result in
less variability in basal spacing as a result of heating and drying than occurs in the smestite minerals.
When Mg-saturated, the hydration states of vermiculite yield a discrete set of basal spacings,
resulting from a changing, but ordered, arrangement of Mg cations and water in the interlayer
complex. When fully saturated, the d-spacing is 14,8 AA , which reduces to 11,6 AA when heatedat 70C.
All interlayer water can be expelled at 500C, but rehydration is rapid on cooling. Permanent
dehydration and collapse to 9,02A ca be achived by heating to 700C

Chlorite minerals. The basal specing of the chlorite minerals is fixed at 14A because of the
strong ordering of the interplayer complex. Chlorite often have a clear sequence of four or five basal
reflections. The third order reflection at 4,7A is quite often strong. Iron-rich chlorites have a weak
first order reflection but strong second oder and, thus , may be confusedwith caolinite. The facts that
chlorite is destroyed when treated with 1N HCL at 60C while kaolinite is unaffected and that kaolinite
is destroyed but chlorite may not be affected on heating to 600C are useful for distinguishing the two
clay types.

Table 5.3 is summarization of basal spacings and effects of glycol treatment and heating
which can be used for X-ray identification. Regularly interstratified mixtures of clay minerals are also
frequently encountered. Basal spacings useful for identification of some of the common interlayered
mixtures are listed in table 5.4

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