Clay Minerals (1973) 10, 41.

ACTIVATION

OF NON-SWELLING

BENTONITE

R. L. BLEIFUSS
Mineral Resources Research Centre, University of Minneapolis, Minnesota 554 55, U.S.A.

(Received 4 July 1972; revised 12 December 1972)

A B S T R A C T : Examination of field samples shows that the alteration of the bentonite beds of Wyoming and Montana near the surface to produce high-quality, highswelling, commercial bentonites is analogous to pedocal soil development. The near
surface bentonite has undergone extensive calcification, and in some zones it is so
heavily altered as to diminish its swelling properties. These low-swelling bentonites
can be activated by conventional soda-ash additions. The naturally high-swelling
materials have undergone only partial calcification and do not require soda-ash modification. The relatively unaltered 'grey' or 'blue' bentonites have undergone little or no
calcification. The latter have the highest Na to Ca ratios, are non-swelling, and do not
respond markedly to soda-ash additions. Such low-swelling materials will respond to
calcium-activation with markedly improved physical quality parameters of flocculation
as measured by Marsh Funnel and Fann viscosimeter. The study indicates that vast
reserves of low-swelling bentonites in Montana-Wyoming may be susceptible to controlled calcium activation and expanded commercial utilization.
INTRODUCTION
This p a p e r is directed p r i m a r i l y t o w a r d t h e m o d i f i c a t i o n of b e n t o n i t e s to m e e t the
needs of the iron o r e industry. B e n t o n i t e is an a d d i t i v e w h i c h is necessary f o r the
successful b a l l i n g a n d pelletizing of finely g r o u n d i r o n - o r e concentrates. E i g h t y
m i l l i o n tons of pellets a r e p r o d u c e d a n n u a l l y on the N o r t h A m e r i c a n continent
requiring some 800,000 tons of bentonite, of which a b o u t 400,000 tons p e r y e a r are
shipped to M i n n e s o t a operators.
T h e feed m a t e r i a l in the pelletizing process is finely g r o u n d i r o n - o r e concentrate
which is a b o u t 9 0 % ~ 3 2 5 mesh a n d contains a b o u t 10% moisture. A b o u t 1 % o r
some 20 l b / t o n of b e n t o n i t e is m i x e d into the fine concentrate. T h e m i x e d m a t e r i a l
is transferred into a b a l l i n g d r u m where the concentrate a n d a d m i x e d b e n t o n i t e is
rolled into 'green' balls a b o u t 0"5 in. in diameter. These green balls then m o v e t h r o u g h
a h e a t - h a r d e n i n g step where they are h e a t e d r a p i d l y f r o m r o o m t e m p e r a t u r e to
1300~ in less t h a n 20 rain.
Bentonite is considered to have a m a j o r role at three critical points in t h e
pelletizing process. T h e first is in the green b a l l stage where the b e n t o n i t e contributes to the strength of the balls a n d p e r m i t s t h e m to stand u p u n d e r m u l t i p l e
screening a n d transfer steps on their w a y to the i n d u r a t i n g machines. G r e e n balls

42

R. L. Bleifuss

without bentonite cannot survive these handling steps without excessive breakage.
The second point is in the drying stage where the green balls are heated rapidly
from room temperature to 250~ The bentonite seems to act as a buffer during this
stage, moderating the release of moisture from the ball. Green balls of taconite
concentrates with no binder often explode because of the internal steam pressure.
The third point is in the preheating stage as the dry halls are brought from 250~
to about 900~ The dry ball is weakest in this range and the bentonite provides
sufficient cementation to prevent breakage. Without the admixture of bentonite the
balls are subject to both breakage in handling and to severe wind erosion and dusting
commonly resulting in major operating problems. Bentonites, particularly the
sodium-type bentonites, have been found to be uniquely suited to fulfilling the three
critical roles mentioned.
Taconite companies in Minnesota have been using western bentonites for some
20 years, yet despite this no common bentonite specifications have been established.
The companies specify a Wyoming-type or Na-type bentonite because there is clear
evidence that they are superior to a Ca-type bentonite. Some taconite companies
place minimum N a 2 0 specifications, or set maximum CaO contents, or specify
N a 2 0 : C a O ratios, but specifications vary from company to company. Companies
usually specify a minimum Marsh Funnel value, which is a relative measure of the
viscosity of a bentonite slurry at 5% solids, or sometimes a range of gel strengths.
In addition, moisture, particle size, and the percentage of ~ 3 2 5 mesh material (grit)
are controlled.
Preliminary mineralogical analyses of commercial bentonites supplied to Minnesota pelletizing plants show that although they are dominantly Na-montmorillonites they also contain a substantial percentage of mixed-layer clay components.
This is somewhat surprising in view of the high sodium:calcium ratios specified in
most of the contracts. Therefore, the Mineral Resources Research Center undertook
a mineralogy-oriented study of both the commercial bentonites supplied to the
taconite companies and field samples collected from bentonite producers in Montana
and Wyoming in an effort to determine some of the characteristics which make a
particular bentonite satisfactory as a pelletizing clay. During the summer of 1970
some 100 field samples of bentonite were collected with the cooperation of most of
the bentonite suppliers.
Samples were collected from all of the bentonite layers being mined at each
company's pit. Most samples collected represent material from active mine areas and
are considered typical of each company's normal production.
MINERALOGICAL

STUDY

Field samples were run through conventional physical and mineralogical tests including Marsh Funnel, gel strength, X-ray diffraction, differential thermal analyses,
partial chemical analyses, grit determinations, and moisture content. A five-fold
classification of the samples was made on the basis of the field occurrence and the
X R D patterns of the clay-size fraction.

Activation of non-swelling bentonite

43

The five divisions are: (1) calcium bentonite--oxidized, near surface, and calcium
saturated; (2) grey bentonite--sodium saturated, some random mixed-layer components; (3) sodium bentonite--no random mixed-layer components, oxidized yellowgreen material; (4) sodium bentonite--some random mixed-layer components,
oxidized yellow-green material; (5) sodium bentonite--moderate random mixed-layer
components, oxidized yellow-green material.
The relationship between the viscosity as determined by Marsh Funnel tests and
the various sample groups is shown in Fig. 1. The first group, Ca-bentonites, in
this case consisting only of oxidized yellow-green bentonites, shows very low viscosity
with Marsh Funnel values distributed over a narrow range from 17 to 22 sec. The
second group, the grey bentonite samples that show little evidence of surficial alteration, are also low viscosity with an average value of 25 sec. The third group, Nabentonites with no mixed-layer components, has Marsh Funnel values that are also
low and in the same range as those of the grey bentonites with the exception of three
samples which gave values of + 50. The diffraction patterns for this group show
sharp symmetrical peaks at 12.6 .K at 5 0 ~ humidity. The fourth group, Nabentonites with some mixed-layer components, shows a wide range of viscosities and
a substantial number of samples with very high viscosities. The fifth group, containing moderate to substantial mixed-layer components, has a range of viscosities
essentially equivalent to group four.
The mineralogical studies show that bentonite groups four and five, which for
the most part have relatively high viscosities, are characterized by mixed-layer components in these samples. The first order Na-montmorillonite X-ray peak is clearly
asymmetrical toward the low-angle range at 50~ humidity. Glycolation and heating
studies show that the asymmetry is not due to illite or chlorite mixed-layer
components.
CHEMICAL ANALYSIS
Partial chemical analyses for Na20 and CaO were run on forty-five representative
samples of the five groups. These data, Table 1, show that each group has a
characteristic chemistry and Na~O:CaO ratio. The highest NazO:CaO ratios are
associated with the grey bentonites which have relatively low Marsh Funnel values,
average 25 sec, whereas a moderate increase in CaO is correlative with improved
physical properties of flocculation as indicated by higher Marsh Funnel readings.
The Ca-bentonites (Group 1) contain excess Ca and typically give low Marsh Funnel
values.
These data show that both high-Na-bentonites and high-Ca-bentonites are
characterized by low Marsh Funnel values. This trend is in keeping with the prior
observations of Williams, Elsley & Weintritt (1954) reported in Grim (1962) where
they showed that the viscosity of the clay slurries reached a maximum with 40~/o
of the Na replaced by Ca. Their earlier work (Williams, Neznayko & Weintritt, 1953)
on field samples showed that the exchangeable cations present as Ca + Mg was
35-67~'o of the total exchange capacity. Chemical analyses presented in this paper

44

R. L.

Bleifuss

Group I
Ca-bentonites

0L

I '~

Group 2
Grey bentonites

I0

Group 5
-~- I01--

No-bentonites
No mixed layering

"5

0u

ll

Group 4
No-bentonites
Slight mixed layering

I~I

5~0
~

1F

ill

ll

it

Group 5
Na-bentonites

010

20

50

40

50

+50

Marsh Funnel value (sec)

FIG. |. Distribution of Marsh Funnel values for each group of bentonite samples.
show substantially higher N a 2 0 : C a O ratios (total Na20, CaO) present in the crude
blue bentonites which gave low Marsh Funnel values. These would seem to be
susceptible to activation by addition of calcium.
FIELD

RELATIONSHIPS

The materials collected for this study represent a random sampling of the bentonites

Activation of non-swelling bentonite

45

TABLE 1. Partial chemical analyses of Bentonites for Na20 and CaO

Sample No.

Na20

CaO

Sample No.

Average

1"00
1-33
1-19
1"12
0.69
0.49
0"27
0'53

1-20
1"18
0.88
1'50
1'25
1' 12
0.81
0.98

0"82

1" 12
(R=0.73)

Group 3. Sodium bentonite,

no mixed layer components
09
89
19
83
44
81
01
42
93
79
Average

2"02
1-43
1-75
2"14
2"45
1.69
2"70
2"41
2-39
2"16

0'45
0-74
0.77
0.78
0.80
0"42
0.42
0.67
0.56
0.63

2" 11

0.62
(R=3.40)

Group 5. Sodium bentonite,

moderate mixed layer components
46
18
62
03
53
40
37
35
50
56
58
Average

1 "46
1.44
1.75
1-43
1"09
1"12
1"35
1"21
1"87
1"42
0"94

2.92
1.90
1-16
0.77
1.48
1"19
0'99
0"90
2"27
1"15
0'85

1"37

1.42
(R=0"96)

CaO

Group 2. Grey bentonite

Group 1. Calcium bentonite

66
49
08
92
34
034
12
65

Na20

55
52
64
14
09
61
16
51
25
00

1"35
1.52
1-71
2.06
2-53
2"60
2"20
2'01
1"75
2-49

1"19
0-83
1-30
1-12
0"81
0"95
0' 90
0"70
0-83
0-56

Average

2-02

0-92
(R=2-20)

41"
80*

2.31
2.71

0.39
0.36

Average

2"51

0"37
(R = 6-78)

Group 4. Sodium bentonite,

some mixed layer components
91
72
30
24
29
84
26
36
48
97
75
Average

* No mixed layer components.

1-39
1-71
1-62
2"29
2"26
2.04
1-58
2"16
2-14
2"16
1"86
1"93

1"08
1-60
0"95
1-28
1"14
0"70
1"30
2"01
0-42
0"59
1"22
1-12
(R = 1"72)

46

R. L. Bleifuss

of Montana and Wyoming currently under commercial exploitation. The samples

were taken with the purpose of obtaining all types of materials that might be included
in the shipments of pelletizing plants, but not with the purpose of establishing a
weathering or alteration profile. It was therefore encouraging to find that the sample
groups established on the basis of clay mineralogy and field description do fit into
a geological and geochemical pattern compatible with the climatic conditions of the
region.
The five sample groups are related to a hypothetical weathering or alteration
profile as shown in Fig. 2. The average Na~O and CaO analyses of each group and
the range of analyses are indicated graphically. The surficial material commonly
is composed of highly weathered yellow-green bentonite. It may be gypsum bearing
and the montmorillonite is Ca saturated. The clay is difficult to disperse in water in
its natural state, but will commonly respond to soda-ash modification. The yellowgreen bentonites that contain moderate amounts of mixed-layer components represent
somewhat less altered material that is characteristically high yield. The next layer
beneath is very similar in physical qualities, but has a lower mixed-layer clay component. Materials from both layers commonly respond satisfactorily to soda-ash
addition. The upper three layers show a significant increase from top to bottom in
the total Na20 content from 0"82-1-93yo, more than a two-fold increase. At greater
depth, layer four, the bentonites are oxidized, but do not contain mixed-layer components and the average NazO content becomes greater whereas the CaO content
is substantially lower. The least altered material, represented by the grey bentonites,
shown as layer five, has a slightly higher Na20 and CaO content. These last two
layers characterized by low yields, seem to be sodium saturated and generally do
not respond to the addition of soda ash.
The assumption made in this composite profile is that the chemical and
mineralogical changes we observe going from top to bottom are the effects of
decreasing alteration, i.e. weathering. The upper oxidized sections show calcification
and replacement of sodium.
The bentonite beds occur within the Cretaceous Mowry shale as described by
Slaughter & Early (1965) and it may be that part of the calcium is being introduced
into the bentonite beds in solution from the overlying shale units. Calcium progressively replaces sodium from the clay, putting sodium into solution. It is assumed
that sodium then migrates out of the formation. However, some of the sodium will
migrate ahead of the calcification front which might account for the somewhat
higher sodium values in the oxidized bentonites of the fourth layer where no mixedlayer components are found. The low CaO values in this group also support this
hypothesis. The grey bentonites beneath the latter oxidized layer contain mixed-layer
components and are believed to represent the least altered material in the section.
The bottom group is represented by only two samples of grey bentonite that contain no mixed-layer components. Only two such samples were collected and consequently they were not included as part of the hypothetical weathering sequence;
however, they might represent an intermediate phase between the oxidized normal
Na-montmorillonites and the mixed-layer grey bentonites. Under this scheme sodium

Activation of non-swelling bentonite

47

Hypothetical
relationships
i
2
3
4
2

7O

Surficial material
Gypsum common
Ca2+ saturated
Low yield (Group I)

j\

I Yellow bentonite
2 Mixed layer components moderately
developed
5 High yield (Group 5)
! Yellow bentonite
2 Mixed layer components slightly
deve{oped
3 High yield (Group 4)
', Yellow oxidized
bentonite
2 No mixed layer
components
3 Low yield (Group 5)

./

I Grey bentonite
2 Layer components
moderately developed
3 Low yield (Group 2)
I Grey bentonite
2 No mixed layer
components
3 Low yield (Group 2)

--am
;'0

20
NO20 %

3"0

t
{'0

I
2"0
CoO %

I
3'0

FIG. 2. Hypothetical relationships showing each bentonite group in its relative position
in the postulated weathering profile.
or calcium additions and alteration of the bentonites is not necessarily coincident
with oxidation. Though the alteration effects described for the composite section are
considered to have been achieved over a long period of semi-arid climatic conditions
in the area, the process is thought to parallel some of the transformations in pedocal
soil formation under present day semi-arid conditions.
BENTONITE

ACTIVATION

Measurements show that the maximum viscosity values are observed in montmorillonites in which calcium occupies about 40~/o of the exchangeable cation sites
(Williams et al., 1954). The foregoing discussion suggests that many of the grey or
blue bentonites and the oxidized yellow bentonites that normally do not respond
to sodium activation are in fact calcium deficient. These bentonites are on the sodiumrich side and therefore show no better dispersion characteristics than the Ca-saturated
bentonites and should respond to Ca additions. The effect of adding Ca to the
bentonites was first investigated by running conventional Marsh Funnel tests. The
test data obtained from seven representative samples are shown in Fig. 3. The tests
show that grey bentonites respond markedly to Ca additions with increased Marsh
Funnel values. Oxidized bentonites that do not respond to soda-ash treatment also

R. L. Bleifuss

48

respond to Ca additions. One of the high-sodium grey bentonites that contains no

mixed-layer component reacted to a limited extent. Calcium-saturated bentonites,
as illustrated by one sample, do not respond to further calcium activation. The effect
of adding 1-5~/o soda-ash to these samples is also shown in Fig. 3; with the exception
of one sample sodium did not affect Marsh Funnel data.
+6

IC

0
I
0

0-5

0-6
I
I0

0-9
J .2
Ca (0H)2%
, ] .....
20
( I b / l o n g ton)

~'-5

3'0

I-8

,,

1.5
No2C03%
[
40

,,.

FIG. 3. Marsh Funnel values obtained on bentonites with progressively larger Ca(OH)z
additions compared with data obtained with Na2CO3. A, Grey bentonite; A , grey
bentonite; O , grey bentonite; O, grey bentonite; x , grey bentonite; [], oxidized
bentonite Group 3 ; II, Ca bentonite.

Marsh Funnnel data indicate that with no additives the grey bentonites are in a
nondispersed state, i.e. they contain a relatively small percentage of clay-size particles.
With the progressive addition of calcium, dispersion into clay-size particles is increased and we observe a gradual increase in viscosity. The calcium-dispersed clays
are then reflocculated at higher lime levels as indicated by the very high Marsh
Funnel values. The lime addition can be kept low enough to accomplish dispersion
without causing massive flocculation; flocculation may be undesirable in some applications, although not necessarily deleterious to a pelletizing operation.
CoIIoid* determinations were run on selected samples of bentonite at various
levels of lime addition to demonstrate that activation with lime hydrate promotes
* The percent colloids was determined by dispersing I0 g of clay in 500 ml of distilled water and
determining the percentage still in suspension after 24 hr.

Activation of non-swelling bentonite

49

complete dispersion of the clay. The graphs in Fig. 4 indicate the change in percentage
of colloids as a function of percentage of calcium hydroxide addition and of equivalent soda-ash additions. These graphs illustrate the significant increase in the percentage of colloids with increasing calcium activation. The influence of soda ash on these
samples is negligible, as indicated--there is no appreciable increase in the measured
colloid content. Samples No. 00 and No. 14 are grey bentonites, the third, No. 93,
is an oxidized bentonite that shows no mixed layering, and No. 24 is a yellow-green
bentonite that shows slight mixed-layer components, but did not respond to soda-ash
treatment.

"0.. .... 00.80

Sample no. O0

Grey bentonite
Group 2
400

1-0

2-0

4-0

lOG

40

60

6O
I
I "0

4C

2-0

,,I
4.0

,0 7 -

8O

I-0

I
2-0

I
4-0

40

Sample no. 14
Grey bentonite
Group 2
I
I-0

2-0

4-0

S lOOt-

......

'~176
F

Sample no. 93
Oxidized yellow
bentonite

60

60

Group 3
40

I"0

2"0

I001-

4-0
.....

40

I "0

I
2"0

,I
4-0

IOOF

Sample no. 24
8 0 ~ 0
60

80f
60

Oxidized yellow
bentonite

Group 4
40

I "0

2"0

Ca (OH) 2 %

4"0

40

I-0

2.0
NozC03%

4-0

FIG. 4. Percentage of colloids as a function of the progressive addition of Ca(OH)2 or

Na2CO3.
D

50

R. L. Bleifuss
SUMMARY

The samples collected in the field seem to fit into a hypothetical weathering pattern
that is compatible with their chemistry, mineralogy and geological environment. The
data show that the grey or blue bentonites, and many of the oxidized bentonites that
are low-yield materials in their natural state and of restricted commercial application
at present are calcium deficient. Addition of calcium progressively increases their
dispersion as measured by the percentage of colloids. The addition of excess calcium
above that required for dispersion results in concomitant flocculation. The high dispersion and sequential flocculation attainable by calcium activation of grey bentonites
seem to be uniquely suited to the bailing and pelletizing of taconite concentrates. It
seems logical that calcium activation might be equally suited to some of the other
common commercial bentonite uses.
ACKNOWLEDGMENTS
The supporting funds for this study were provided primarily through a grant by the American Iron
and Steel Institute. Further support was provided by funds made available by the Mineral Resources
Research Center of the University of Minnesota.
REFERENCES
G ~ R.W. (1962) Applied Clay Mineralogy, McGraw Hill, New York.
SLAUGHTERM. & EARLYJ.W. (1965) Spec. Pap. geol. Soe. Am. 83, pp. 95.
WILLIAMSF.J., ELSLI~YB.C. & WEISTPOTT,D.J. (1954) The variations of Wyoming Bentonite as a
function of the overburden. In Clays and Clay Minerals (A. Swineford and N. V. Plummet,
editors). Natl. Research Council Publ. 327, 141.
WrLLIAMSF.J., NEZNAYKOM. & W~INrParr D.J. (1953) J. phys. Chem. 57, 6.