Hills and Pettifer 1985 - The Clay Mineral Content of Various Rock Types, JCTB

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J. Chem. Tech. Biotechnol. 1985,35A, 168-180
The Clay Mineral Content of Various Rock Types

Compared with the Methylene Blue Value'
J. F. Hills and G . S. Pettifer
Wimpey Laboratories Limited, Beaconsfield Road, Hayes. Middlesex UBIOLS
The methylene blue test has been developed in France for giving an overall
assessment of the clay characteristics of an aggregate. The Department of the
Environment, Northern Ireland, introduced the test into a specification to indicate
the soundness of basalt and gritstone aggregates-the test being carried out on
finely ground samples. As the test was unfamiliar in the UK, it has been
investigated. A detailed and expanded test-method has been written and 28
samples, mainly from basic igneous rock sources, have been tested. Experiments
have shown that the particle size of the test-specimen affects the result (the 'blue
value'). The clay contents of the samples, and the swelling properties of the clay
minerals, have been determined by X-ray diffraction of the air-dry and glycolated
samples. Where the samples were of a suitable size, the water absorption has been
measured. The correlations between the blue value and the following parameters
are discussed: the clay content; the swelling properties; and the water absorption. It
is concluded that the methylene blue test, carried out on a powdered sample,
should not be used by itself to judge whether a source of aggregate should be
accepted or rejected.
Keywords: Aggregates; basalt; clay minerals; gritstone; laboratory tests; methylene
blue; petrography; rocks; soundness; X-ray diffraction.
1. Introduction
A methylene blue test is used in France for measuring the ionic adsorption capacity of soils and
aggregates.' The result of the test depends on both the quantity and the mineralogical nature of
the clay fraction of the sample tested and so gives an overall measure of the clay characteristics of
the sample.
The methylene blue test was recently introduced into a specification by the Department of the
Environment, Northern Ireland, to indicate the soundness of basalt and gritstone road aggregates
for use in sub-bases-the test being carried out on finely ground samples.2 As the test was
unfamiliar in the U K , experiments have been carried out to enable a detailed test method to be
written, and to find the effect of variables such as the particle size of the test sample. The test
method was then used on a limited range of samples, and the results ('blue value') compared
with data on the composition of the materials obtained by X-ray diffraction and thin-section
analysis, and. for 18 of the samples, with the water absorption of aggregate chippings or rock
specimens. Further, X-ray diffraction techniques were used to determine the type and swelling
properties of any clay minerals present.
The relationship between the blue value, clay mineral content and petrographic texture (i.e. the
internal structure of the rock and arrangement of the constituent minerals) has been investigated.
The validity of using the methylene blue test to predict the road performance of aggregates is
discussed.
"This paper was presented at the meeting of the Road and Building Materials Group of the Society of Chemical Industry
held in London on 9 February 1984.
168
19351836, 1985, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jctb.5040350404 by Texas A&M University Libraries, Wiley Online Library on [10/02/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Comparison of clay mineral content and methylene blue values of rocks 169
2. Materials and methods

2.1. Samples tested
The 28 samples tested are listed in Table 1, which shows the country of origin. The individual
sources, mostly working quarries, are designated by a letter of the alphabet. The rock type of the
samples is given in the second column of Table 2.
2.2. Methylene blue tests
The test method for the methylene blue test that was published by the Department of the
Environment, Northern Ireland, is reproduced in Appendix A . After some preliminary
experiments, a more detailed test method was written for use in the present investigation and this
is given in Appendix B. Particular attention was paid to the routine to be followed to determine
the end-point of the test.
The materials used in the methylene blue test are given in Table 3.
The methylene blue tests were initially carried out on material ground to pass the 0.425 mm
sieve, the size used in the measurement of plasticity. However, it was subsequently found that
higher blue values were obtained when the sample was ground finer than 0.075 mm. and this size
was then adopted as standard.
Table 1. List of samples tested

Sample Lab. ref. Country of
no. no. origin Quarry Sample type
1 3092 Turkey A Rock specimen
2 1577 Scotland B Type 1. 2&l0mm
3 1577lF Scotland B Fines from Type 1
4 2614 Scotland B Rock specimen
5 1434 Scotland C Type 1. 28-IUmm
6 14341F Scotland C Fines from Type 1
7 2212 Scotland D 20-14 m m
8 3093 N. Ireland E Blindings (>2.36 m m )
9 1421 N . Ireland F 14-10 m m
10 1420 N. Ireland G 14-10 mm
11 3094 N. Ireland G Rock specimen
12 2141 Scotland H 20-14 mm
13 2142 Scotland H 20-14 mm
14 1643 England I Limestone filler
15 2140 Scotland J 2(L14 mm
16 2139 Scotland J 20-14 mm
17 2138 Scotland J 2U-14 mm
18 1436 Scotland K 2&14 mm
19 1435 Scotland K Type 1, 28-10 mm
20 1435lF Scotland K Fines from Type 1
21 3095 Scotland K Rock specimen
22 2210 Scotland K Rock core
23 221 1 Scotland K Rock core
24 2213 Scotland L 2&14 mm
25 1433 Scotland M Type 1. 28-10 mm
26 14331F Scotland M Fines from Type 1
27 1432 Scotland M Waste, 28-10 m m
28 2194 England N Rock specimen
~ ~ ~~
'Type 1. 2X-10 mm' refers to the 28-10 m m fraction of material conforming lo

the Department of Transport 'Specification for Road and Bridge Works'. 1976.
Clause 803. Granular Subbase Material, Type 1
'Fines from Type 1' is a sub-sample sieved from the corresponding Type 1
sample, that passed either the 0.425 m m or the 0.075 mm aicvc (that is. it was not
ground in the laboratory).
Sample 14 was tested as received.
170 J. F. Hills and G . S. Pettifer
Table 2. Rcsults of X-ray ditfraction analyses and methylene blue tests

X~rabdiffraction analvsis
-
Swelling
index
Expansion (pcrcentage
Methylene blue
Water Total of basal of expansive
Sample absorption laver- swacing
. - on mineral times _______ value
ref. ('%dry Type and percentage of laitice glycolation expansion on Passing Passing
no. Rock type mass) layer-lattice minerals minerals (nm) giycolation) 0.425 rnm 0.075 mm
1 Olivine-basalt - None" 0 0.0 no - 0.10
2 Quartz-dolerite 1.0 Chlorite-smectite 10; 27 0.18 1.8 0.60 0.85
chlorite 15; mica 2
3 Quartz-dolerite - Chlorite-smectite 10; 31 0.18 1.8 1.00 1 25
chlorite 20; mica 1
4 Quartz-dolerite 0.6 Chlorite-smectite 10; 34 0.18 1.8 - 0.70
chlorite 20; mica 4"
5 Olivine-dolerite 1.3 Smectite 7 7 0.28 2.n 0.30 0.50
6 Olivine-dolerite - Smectite 20 20 0.28 5.6 0.85 1.10
7 Quartz-dolerite 1.7 Chlorite-smectitc 30: 41 0.18 5.4 - 1.10
chlorite 10; mica 1
8 Amygdaloidal basalt 28.0 Srnectite 50 50 0.23 I1 5 - xnoc
9 Greywacke 05 Chlorite 10; mica 5 0.0 0.0 0.20 0.30
10 Olivine-dolerite 1.4 Smectite 7 7 0.23 1.6 0.45 0.70
II Olivine-dolerite 0.6 Smectite 15: mica 1' 16 0.23 34 - 1.00
12 Sandstone 1.8 Chlorite 15; mica 5 (20)~ 0.0 0.0 -
0.60
13 Acid porphyrite 0.9 Chlorite 20, mica 3 (Wb 0.0 0.0 - 0.50
14 Limestone - Assumed noned 0 - 0.0 0.30 0.30
15 Quartz-dolerite 2.2 Chlorite-smectite 25; mica 1 26 0.18 4.5 - 1.60
16 Quartz-dolerite 1.6 Chlorite-smectite 10: 51 0.18 1.8 - 0.90
'Swelling' chlorite 40, mica 1 0.05 2.013-8
17 Quartz-diorite 2.7 'Swelling' chlorite 25 25 0.05 1.2 - 1.30
18 Quartz-diorite - Chlorite-smectite 25: mica 1 26 0.18 4.5 0.57 1.10
19 Quartr-diorite 1.6 Chlorite-smectite 22 22 0.18 4.0 0.57 1.05
20 Quartz-diorite -
Chlorite-smectite 30 30 0.18 5.4 0.92 1.35
21 Quartz-diorite 3.0 Chlorite-smectite 30; mica 1 31 0.18 5.4 - 1.25
22 Quartz-dolerite 1.5 Chlorite-smectite 35; mica I" 36 0.lR 6.3 - 1.25
23 Quartz-dolerite 1.1 Chlorite-smectite 25" 25 0.18 4.5 - 145
24 Quartz-dolerite 1.9 Chlorite-smectite 35; mica 2 37 0.18 6.3 - 0.95
25 Olivine-basalt 0.7 Smectite (saponite) 5 5 0.38 I .9 0.32 0.55
26 Olivine-basalt - Smectite (saponite) 15 15 0.38 5.7 1 .no 1.35
27 Olivine-basalt - Smectite (saponitej 20 20 0 38 7.6 1.30 2.25
28 Kaolinised eranite - Kaolinite 25: mica 20 (45)b
I ,
no on - I .40
"Also examined in thin-section.
bParentheses indicate less accurate estimate of percentage concentration.
'Test curtailed on reaching this value.
dSarnple not analysed by X-ray diffraction.
Table 3. Materials wed in the methylene blue test

Methylene blue
The methylene blue was supplied by BDH Chemicals Ltd.
Thcrc were two grades:
A Standard stain methylene blue: For microscopical staining and reagent for molybdate.
Product No 34048 48.
B Oxidation-reduction indicatoi- methylene blue: Kedox indicator for biological work. E'o at pH 7.0+0.01 I
Product N o 20064 3%
(Note: This product is more expensive than A).
Filter paper
The filter paper was Whatman No 40,
with the following specification LCPC draft specification
Weight 96gm * 95 g m-'
Per cent ash 0.01 mas less than 0.01
Retention 0.008 mm 0.008 mm
Filtration speed 75 s 75 s
Thickness 0.2 mm 0.2 mm
2.3. Techniques used to investigate the mineralogy and petrographic texture

The mineralogical composition of each sample was investigated using X-ray diffraction
techniques-with the exception of the limestone filler (sample 14).
As a means of calibrating the X-ray diffraction traces, five rock specimens of basalts and
dolerites (samples 1, 4, 11, 22 and 23) were examined in thin-section. This enabled the volume
nm
12 15 2 0 2 9
0 32 0 35 0 4 0.7 0.8 09101 I I 3 I 7 2 5
:-s
Non-swelling C-S
--
I I I I I
I I 1
I I
I 1 1 1 I I I I
28 27 26 25 24 23 22 21 20 13 12 I I 10 9 8 7 6 5 4 3
Degrees 28
nm
1.2 1.5 2.0 2.9
0.32 0-35 0.4 0.7 0.8 0-91.01.1 1-3 1.7 2.5
I I I I I I I I I
:I F
F F Q
I 1
1
_-
1 1 1 1 1 1 1 I I I l l 1 I I I I
28 27 26 25 24 23 22 21 20 13 12 I 1 10 9 8 7 6 5 4 3
Degrees 28
Figure 1 . X-ray diflraction traces for (a) sample 4 and (b) samplc 22. Q, quartz: F, feldspar; A . amphibole: M, mica; C-S,
chlorite-to-smectite series of minerals; Glycol, glycolated peak for expansive minerals.
percentage of each of the minerals to be determined accurately by point-counting, and their

petrographic texture to be observed in detail. Calibration was further improved by comparing the
traces for the samples with those for artificial mixtures of measured amounts (by mass) of similar
constituents.
Particular attention was paid to those layer-lattice minerals (smectite, chlorite, kaolinite, mica
and illite) which would have the most effect on the blue value. Chlorite, illite and mica
commonly form the cement or matrix of gritstones. Members of the chlorite, ‘swelling’ chlorite,
chlorite-smectite, smectite series commonly occur as ‘secondary’ minerals in basic igneous rocks.
Under certain conditions, kaolinite replaces feldspar in granites.
The estimated quantities are given in Table 2. The accuracy of these percentages is generally as
follows: at the 5% level, k2; at the 20% level, ?5; and at the 45% level, +lo. However, for the
gritstones and acid igneous rocks (samples 9, 12, 13 and 28), which were not examined in thin-
section, the inaccuracy is probably greater.
The powdered samples were scanned in the air-dry condition in a Philips PW 1050 X-ray
diffractometer, using copper K-alpha radiation, at a rate of 1 degree change in 28 per minute.
To investigate the swelling properties of the clay minerals, subsamples were treated with
ethylene glycol and scanned using the same machine settings. Glycolation3 expands the structure
of swelling clays, producing a new set of basal reflections which may then be compared with
those for the mineral in the air-dry condition.
The amount of expansion on glycolation depends to some extent on the ion-saturation of the
mineral and is about equal to the expansion due to water adsorption. The expansion reflects the
degree of mixed-layering in the mineral structure, and hence the position of the mineral within
the chlorite-to-smectite series referred to above. Examples of the X-ray diffraction chart recorder
traces are reproduced in Figure 1.
2.4. Water absorption determinations
For the samples consisting of suitably sized material, a water absorption test was carried out
according to BS 812: Part 2: 1975. For samples 4, 11 and 21, the water absorption of single rock
specimens (each weighing about 200 g) was determined. The values obtained would be expected
to be lower than if a crushed sample of the material were tested.
Water absorption values were of interest because they are an accepted and simple way of
indicating the soundness of aggregates. For basic igneous rocks, water absorption is a measure of
the water contained within clay minerals as well as the permeability of the rock. For sedimentary
rocks, such as gritstones, water absorption measures porosity, and in this case a high value might
be tolerable-even though the strength were reduced.
3. Experimental results and discussion

Some preliminary methylene blue tests were carried out on eight of the samples, with the
test-samples passing the 0.425 mm sieve, to see if the grade of the methylene blue reagent had
any effect on the results. Two grades were used: grade A was a standard stain, and grade B was a
more expensive oxidation-reduction indicator. For the limited results shown in Table 4, statistical
analysis has shown that, for a particular sample of aggregate, there was no significant difference
in blue value between a pair of tests, one using grade A and the other grade B. The standard
stain was therefore used for all the test results reported in Table 2.
To investigate the effect on the blue value of the particle size of the sample, tests were carried
out (in 13 cases) both on test-samples ground to passing the 0.425 mm sieve and on test-samples
ground to passing the 0.075 mm sieve. The blue values for each size are plotted against each
other in Figure 2. There is a linear relationship, and the blue value for the coarser test-samples is
about 60% that of the finer ones. This not unexpected result makes it clear that, when a ground
specimen is to be tested, the particle size of the test-sample should be specified.
The blue value of a ground test-sample is arbitrary unless the particle size is so small that all
the clay present is accessible to the blue dye. The critical size for complete accessibility has not
Table 4. The effect on thc blue value of the grade of

methylene blue (All the test-samples were passing
0.425 mm)
1 2" 36 4'
Blue value
Grade of methylene hluc A A B
Sample ref no
5 0.30 0.30 0 25
6 0 85 0 85 0 80
9 0.20 - 0.25
10 0.45 - 0.45
19 0.60 0.55 0.55
20 0.95 0.Y0 0.85
25 0.35 0.30 0.35
26 1.05 0.95 0.95
"First determination using methyiene blue A (standard
stain).
bDuplicate determination using methylene blue A .
'Determination using methylene blue B (oxidation-
reduction indicator).
been determined. In the discussion below, the blue values considered are those for the finer
test-samples, passing 0.075 mm.
The results of the X-ray diffraction analyses are given in Table 2 . The type and percentage of
the layer-lattice minerals are shown, and the total percentage is given in the adjacent column.
The blue values are plotted against these total percentages of layer-lattice minerals in Figure 3 .
The points in the graph show considerable scatter. However, whether or not the blue value is
sensitive to the percentage of layer-lattice minerals depends on the nature of these minerals. As
shown in Figure 3, the graph may be divided into three sectors: the top sector corresponding to
smectite; the middle to mixed-layer minerals; and the bottom to chlorite.
1.5 -
1.0 -
a,
a
t,
-
x
f
i
Methylene blue value (passing 0.075rnrn)
Figure 2. The effect of the particle size of the test-sample on the methylene blue value. Blue value for passing 0.425 mm
against blue value for passing 0.075 mm
12
3.0 /
/
//
/
/
2.5 /
1
/
E /
E 270 /
LD
Ic /
g
m
2.0 Smecti te
/
/ Mixed loyer
c /
._
fn / r Kaolinised
0
a
v
a, 1.5
-
2
a,
-
D
: 1.0
-
0)
L
5.
+
a, loo
z /
0.5 - 2500/,
5/,
0 13 \ F;Z
t;h
14. /// 9
. Chlorite dolerites
/
.I
1 I I I I I
0
0 10 20 30 40 50 60
Percentage of loyer- lattice minera Is
Figure 3. Blue value against percentage of layer-lattice minerals
In the smectite sector, the blue values are high for relatively low concentrations of the
expansive clay. The samples include olivine-dolerites and basalts from Scotland and Northern
Ireland. There appears to be a linear relationship between the blue value and the clay content,
with a blue value of 1.0 corresponding to about 10% of clay; and a blue value of 2.0, to 20%.
In the mixed-layer sector, the blue values are fairly high for substantial proportions of the
moderately expansive chlorite-smectite. The shaded area in Figure 3 is that occupied by the
points for the Scottish quartz-dolerites. This area extends into the chlorite sector. The
relationship between the blue value and the mixed-layer clay content is less well defined than is
the case for true smectites: a blue value of between 1.0 and 1.5 is obtained for a clay content
ranging from 20 to 35%.
In the chlorite sector, the blue values are low for relatively high levels of non-swelling or
slightly expansive chlorites. Materials in this sector include a ‘greywacke’ from Northern Ireland
(sample 9), and, from the south of Scotland, a sandstone (sample 12) and an acid igneous rock
(sample 13). The point for the kaolinised granite (sample 28) lies close to the boundary between
the mixed-layer and chlorite sectors and shows that a substantial proportion of kaolinite and/or
mica can give a high blue value. Smaller proportions of mica mixed with either non-swelling
chlorites or chlorite-smectites give some of the lowest blue values.
So far, the blue value has been compared with the percentage of layer-lattice minerals in the
sample. Since the methylene blue value is related to both the quantity and the mineralogical
nature of the clay fraction, it may be argued that it would be better to take into account the
varying capacity for swelling of each mineral, as observed in X-ray diffraction. For example,
chlorite-smectite in a Scottish quartz-dolerite gives an air-dry basal reflection at 1.49 nm which,
on glycolation, expands by 0.18 nm. For a smectite contained in a Scottish olivine-basalt, the
comparable air-dry peak at 1.35 nm expands by 0.38 nm.
The blue value has therefore been compared with the 'swelling index' of the sample. 'Swelling
index' will be defined as the number equal to the percentage of the expansive mineral multiplied
by its measured expansion of basal spacing on glycolation. It should be noted that the swelling
index calculated in this way is a measure of the potential expansion of a sample-that is, the
amount it would swell if it were free to do so. In practice, the potential would not be fully
realised if the sample were a basic igneous rock with a closely interlocked crystalline structure
which offered some resistance to the internal pressure exerted by its clay component when
wetted. Further, such a structure would also impede the movement of moisture.
The calculated values of swelling index are given in Table 2, and are compared with the blue
values in Figure 4. The scatter is considerably reduced compared with Figure 3 and the
relationship obtained by linear regression has a correlation coefficient of 81%.
Improved correlations may be obtained if the graph of blue value against swelling index is
restricted to one type of layer-lattice mineral. Figure 5 shows the results for samples from three
quarries where the clay component was smectite. The correlation coefficient for linear regression
is 93%. Figure 6 shows the data for two quarries where the clay component was chlorite-
smectite. In this case the correlation coefficient is only 66%. This low value may be partly
attributed to the small range of the swelling index.
For the quarries whose data are given in Figures 5 and 6, consideration of the general
characteristics of the best quality road aggregates, and the known and expected performance,
suggests that 4.0 could be taken as a tentative maximum acceptable value for the swelling index.
This corresponds to a blue value of 1.10 where the smectite content is about lo%, and to a blue
value of 1.15 where the chlorite-smectite content is about 20%.
The results for the water absorption test are plotted against the blue value in Figure 7. The
correlation is a poor one. This shows that the blue value (of the powdered rock) is not strongly
3'01
+
I
.I
I I I 1 I J
2 4 6 8 10 12
Swelling index
Figure 4. Blue value against swelling index.

J. F. Hills and G. S. Pettifer
12
I
Figure 5. Smectite: blue value against swelling index. Quarry: 0 . C: Q. G: 0. M

10
I
I
8
Swelling index
r
6
I
4
I
I
I
I
I
I
I
I
I
2
I .
.2
176
177
8
I
Inter mediate
-
7
I
inter locked
interlocked
Crystalline
of igneous
structure
Closely
Poorly
rocks
6
I
Figure 8. Water absorption against swelling index.

0 21
Figure 7. Water absorption against blur value.
2.0
Methylene blue value (passing 0.075mm)
I
5
I
Swelling index
Comparison of clay mineral content and methylene blue values of rocks
23
1.5
4
I
I
3
I
1.0
I
2
I
0.5
I
0 17
-
I
I
0
178 J. F. Hills and G. S. Pettifer
dependent on the water absorption (of the aggregate chippings). For basic igneous rocks, the
water absorption value is a reflection of both the secondary mineral content (particularly
adsorptive clays) and the permeability of the aggregate chippings. In turn, the permeability will
be related to the crystalline structure of the rock, as indicated at the right of Figure 7, and hence
to strength. The presence of microfractures, sometimes infilled with expansive clay, would place
a rock in the ‘poorly interlocked’ category. In extreme cases, rocks of this type have been known
to disintegrate in the stockpile. Thus a poor road performance might be expected from an
aggregate with a high water absorption (even if the blue value were low). On the other hand, an
aggregate with a relatively high blue value might perform satisfactorily because it had a low water
absorption.
Water absorption is plotted against swelling index in Figure 8. The correlation is even worse
than that in Figure 7-the water absorption being virtually independent of the swelling index.
Accepting the validity of water absorption as a guide to the road performance of an aggregate, it
is apparent that the results of methylene blue tests on the powdered aggregate, taken on their
own, might be misleading.
4. Conclusions
1. When the methylene blue test is applied to a finely ground rock sample, the blue value
depends on the particle size of the specimen tested.
2. For basic igneous rocks, the relationship between blue value and clay content is good when
the clay is a smectite, but poor when the clay is a mixed-layer chlorite-smectite.
3. There is a fairly good linear correlation between the blue value of an aggregate and its
‘swelling index’.
4. The methylene blue value for a powdered sample should not be used as the sole criterion
for assessing an aggregate source, because it does not take account of the effect of petrographic
texture on performance.
Acknowledgments
The investigation was supported by Wimpey Asphalt Limited. The detailed procedures for the
methylene blue test described in Appendix B were developed by R. G. Redding and A. J.
McLintock (who carried out the tests). The authors wish to thank their colleagues in Wimpey
Asphalt Limited and Wimpey Laboratories Limited for valuable discussions.
Appendix A
Methylene blue test method published by the Department of the Environment, Northern Ireland.
Addition: Reference circular letter no 2 dated 27 September 1982. Series no. 2700
2723 Methylene blue test
This test is utilised to quantify the amount of clay mineral (smectite group) present in a given
aggregate and hence to indicate the soundness of the aggregate. The test is carried out as
published in L‘essai au Bleu de Methylhe, un Progres dans la Mesure et le Controle de la
PropretC des Granulates (Tran Ngoc Lan), Bulletin de Liaison des Laboratories des Ponts et
Chaussees, 107, Mai-Juin 1980, Ref 2455.
Reagents
Distilled or de-ionised water.
Methylene blue reagent: 0.1 g methylene blue made up to 100 cm3 with distilled water.
Method
A representative sample of the aggregate is finely ground in a suitable grinding machine. A
sample of approximately 1.0 g is accurately weighed out and dispersed in 30 cm3 of distilled
Comparison of clay mineral content and methylene blue values of rucks 179
water. The dispersion is stirred continuously throughout the titration with the methylene blue
reagent. The methylene blue reagent is added stepwise in 0.5 cm3 aliquots allowing 1 to 2 min
between successive additions. At the end of each time period one small drop of the dispersion is
removed and placed on an absorbent paper (filter paper). Initially a circle of dust is formed
surrounded by an outer ring of clear water. The end point is reached when a ‘permanent’ light
blue coloration is observed in this ring of water. The time between successive additions of
methylene blue reagent may be extended as the end point is approached depending on the type
of aggregate.
Calculate the ‘blue value’ (% of methylene blue absorbed by weight) as follows:
TxO.1
Blue value= ~
W
where T = titration value” and W = weight of sample tested (g).
The aggregate should be rejected if the blue value exceeds the values given below when tested
using this procedure: basalt rock 1.O; gritstone 0.7.
Appendix B
Wimpey Laboratories test method: methylene blue test
Introduction
The method described here is an expanded and more detailed version of the one given in the
Northern Ireland DOE ‘Addition, Reference Circular Letter No 2, dated 27 September 1982,
Series No 2700, 2723 Methylene Blue Test’. The test is used to quantify the amount of clay
mineral (smectite group) present in an aggregate and hence to indicate the soundness of the
aggregate.
Apparatus and reagents

25 cm3 burette mounted on a stand; 250 cm3 Erlenmeyer flasks; 100 cm3 volumetric flask and
stopper; 250 cm3 beakers; 50 cm3 graduated cylinder; glass stirring rod; small clock glasses;
sample containers (to take 100 g ground aggregate); spatula; Whatman No 40 filter papers
(12.5 cm diameter); distilled or de-ionised water; B D H ‘standard stain’ methylene blue.
Access to an analytical balance; aggregate crusher; grinding machine; large and small riffle
boxes; scoop; metal trays; an oven.
Principle of the test
The test consists of measuring the adsorption capacity of a test-sample by titration.
Successive equal-volume additions of a solution of methylene blue are made to a suspension of
the test sample in water. The adsorption of methylene blue is checked after each addition by
carrying out a spot test on filter paper.
Method
T o make up the methylene blue solution, weigh out accurately 0.1 g of methylene blue stain and
dissolve it completely in 100cm3 of distilled water. Fill the burette with the solution, ensuring
that the stem below the tap is also filled.
To prepare the test-sample, riffle the sample of aggregate down to a portion of about 1 kg and
crush it in a jaw crusher to passing the 6.3 mm sieve. Then riffle the portion down to about 100 g
and, using the jaw crusher, crush it as finely as possible (say passing 0.425 mm). Follow this by
grinding in a mechanical pestle and mortar until nearly all of it passes the 0.075 mm sieve. The
material retained on the 0.075 mm sieve is ground to passing this sieve using a hand agate pestle
and mortar. Place the sample in an oven at 105°C for about an hour, remove it and allow it to
cool, and place it in a jar with a screw-lid.
“Transcriber’s note: The titration value is the quantity of reagent used to reach the end point (cm’)
The blue test is carried out on a test-sample of 1 g. Mix the sample thoroughly and take a
representative sample, weigh out the test-sample on the analytical balance and place it in the
Erlenmeyer flask. Add about 30 cm3 of distilled water and disperse the sample by shaking.
To perform the titration, add successive volumes of 0.5 cm3 of the methylene blue solution to
the flask. After each addition, agitate the flask for 1 min and remove a drop of the dispersion
with the glass rod and dab it carefully on a sheet of filter paper. Initially, a circle of dust is
formed which is coloured dark blue and has a distinct edge, and is surrounded by a ring of clear
water.
When the edge of the dust circle appears fuzzy andtor is surrounded by a narrow light blue
halo, agitate the flask for 1 more min and do another spot test. If the halo has disappeared, add
more blue. If there is still a halo, agitate the flask for a further 2 min and do another spot test.
Whatever the outcome of this test, add more blue, agitate for 2 min, do a spot test, then agitate
for a further 2 min and do another spot test. This sequence, with a total of 4 min of agitation, is
repeated until there is a definite light blue halo.
To determine the end-point, hold the filter paper up to daylight while it is still damp, and
compare the dust circles made after 4 min of agitation. It should then be possible to see where
the halo first appears and thus where the end-point is.
Result
The ‘blue value’ (per cent mass of methylene blue adsorbed) is calculated as follows:
Blue value = (V x 0.1)lM
Where V = total volume of methylene blue solution added to reach the end-point ( ~ m - ~and
)
M = mass of sample tested (8).
References
I . Tran Ngoc Lan. The Methylcne Blue Test. Bulletin de Liaison des Laboratoires des Ponts er Chaussees, 1980,107, 13&135.
2. Department of the Environment. Northern Ireland. Reference Circular Letter 2. Clause 2723. 1982.
3. Brindley, G. W.; Brown, G. C.’r.ysral Srructure of Clay Mineral> and their X-ray Identification. Mincralugical Society
Monograph No. 5 . 1980.

Hills and Pettifer 1985 - The Clay Mineral Content of Various Rock Types, JCTB

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19351836, 1985, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jctb.5040350404 by Texas A&M University Libraries, Wiley Online Library on [10/02/2023].

The Clay Mineral Content of Various Rock Types

Wimpey Laboratories Limited, Beaconsfield Road, Hayes. Middlesex UBIOLS

2. Materials and methods

Table 1. List of samples tested

'Type 1. 2X-10 mm' refers to the 28-10 m m fraction of material conforming lo

Table 2. Rcsults of X-ray ditfraction analyses and methylene blue tests

Table 3. Materials wed in the methylene blue test

2.3. Techniques used to investigate the mineralogy and petrographic texture

percentage of each of the minerals to be determined accurately by point-counting, and their

3. Experimental results and discussion

Table 4. The effect on thc blue value of the grade of

Methylene blue value (passing 0.075rnrn)

Figure 4. Blue value against swelling index.

Figure 5. Smectite: blue value against swelling index. Quarry: 0 . C: Q. G: 0. M

Figure 8. Water absorption against swelling index.

Apparatus and reagents

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