AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS

Technical Publication No. 1401

(CLASS G, PETROLEUM DIVISION, No. lSI)
DISCUSSION OF THIS PAPER IS INVITED. Discussion in writing (2 copies) may be sent to the
Secretary, American Institute of Mining and Metallurgical Engineers, 29 West 39th Street, New York, N. Y.
Unless special arrangement is made. discussion of this paper will close Dec. 31. 1941. Any discussion offered
thereafter should preferably be in the form of a new paper.

Chemical Treatment of Bentonitic Suspensions and the

Relationship to the Heaving-shale Problem
By H. H. POWER,· MEMBER A.I.M.E., AND CHARLES R. HOUSSIERE, JR. t
(Dallas Meeting, October 1941)
THE development of effective and depend- methods for drilling through these trouble-
able methods for drilling through the so-called some beds is believed to comprise a major
"hea ving-shale" horizons, particularly in the contribution to drilling technology, and
Gulf Coast area, is believed to comprise a
to the task of finding and developing our
major contribution to drilling technology,
undiscovered oil pools.
and to the task of finding and developing our
undiscovered oil pools. Many mechanical Since the attack on the heaving-shale
remedies have been proposed and are in use in problem by mechanical means was princi-
troublesome areas for combating heaving shale, pally a matter of field investigation, it was
However, in conducting a research program it concluded that a research program should
was concluded that the physical and chemical be concerned with the physical and chemi-
properties of shales should be investigated, and , cal properties of heaving shales, and the
the effect of added chemicals on such properties effect of added chemicals on such proper-
determined. As a preliminary step, the effect ties. It was realized that a study of shales
of chemicals on bentonitic suspensions was
required an advanced knowledge of the
determined in accordance with recent contribu-
tions in the field of ceramics. The most plausible behavior of the individual clay minerals.
theoretical explanations for the behavior of the A thorough review of the literature led
clay minerals involved are offered in the paper the authors to the conclusion that very
that follows. It is hoped that subsequent recent contributions 2 ,3 in the field of
investigation of actual shale from troublesome ceramics furnished the most plausible
wells will be aided by the initial work done on theoretical explanations for the behavior of
bentonitic suspensions of known composition. clay minerals. Accordingly, these funda-
mental ideas will be used in an attempt to
INTRODUCTION explain the behavior of more complex
systems whose composition and replaceable
Formations variously designated as ions are known.
"heaving shale," "sloughing shale" and In order to obtain comparable results
"caving shale" impede and may even it was deemed important to select an
preclude drilling of oil wells, particularly easily procurable clay of uniform charac-
in certain parts of the Gulf Coast. In a teristics. Accordingly, Wyoming bentonite,
previous paperl it has been stated that the which is marketed under the name of
development of effective and dependable "Volclay,"· was used for the preliminary
investigations. The chemical analysis re-
Manuscript received at the office of the Institute ported by the distribution is given as
Sept. 2. 194I.
* Professor of Petroleum Engineering, The Uni- follows:
versity of Texas. Austin, Texas.
t Research Assistant, Bureau of Engineering
Research, The University of Texas. * American Colloid Co., Chicago, Ill., bulletin:
1 References are at the end of the paper. Data No. 203.
Copyright. 1941, by the American Institute of Mining and Metallurgical Engineers, Inc.
PETII.OLEUM TECHNOLOGY, November 1941. Printed in U. S. A.
2 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS
Per Per
CENT CENT
Si02........... 64.3 2 FeO ........... 0·46
AltOa .......... 20·74 T i 0 2.......... 0.14
CaO .......... 0·52 P 20& .......... 0.01
MgO ..........
2.30 SOs ........... 0·35
Fe20 a......... 3. 03 H 20 (+rroC) .. 5· IS
NatO ......... 2·59 H 20 (-rroC) .. 0.00
KIO ........... 0·39
DETERMINATIONS
Ion Determination and Base Exchange
Capacity
The ions adsorbed on the clay particles
were determined in order to predict their
behavior. A simple electrodialysis cell 4 was
set up. A 2 per cent Volclay mixture was
placed in the middle compartment and
subjected to constant stirring. A con-
trolled potential of IIO volts and current
of 0.1 amp. were imposed upon the system.
The exchangeable ions were reported on
the basis of the milliequivalents of metal
per 100 grams of clay. This apparatus was
used in determining the base exchange
capacities of both the unfractionated and
fractionated clays.
The following ions were identified by
electrodialysis in order to determine base
exchange capacity:
Exchangeable Metallic Bases, M illiequiva-
lents per 100 Grams
Calcium... . . . . . . . . . . . . .. 1.8
Magnesium.............. 4.5
Sodium .................. 77.0
Potassium............... 0.5
Sulphate ................. 10.2
94. 0
It is probable that the sulphates are
present as soluble calcium or magnesium
sulphates together with adsorbed metals. s
Preparation of Suspensions
The suspensions were made up to the
required concentrations by adding incre-
ments of the clay to a container filled with
distilled water and stirred constantly, a
procedure that hastened the dispersion
of the clay. The mixture was stirred for
6 hr. at high speed and permitted to stand
for one month. The suspension was then
agitated for 3 hr. The un dispersed coarser
particles, such as sand, were removed
after settling for 12 hr. The supernatant
liquid was separated for subsequent ex-
amination. In centrifugal separation a
slight amount of "Daxad"* was added in
order to ensure sufficient peptization.
Fractionation and Determination of Particle
Size
Centrifugal procedure described in previ-
ous investigations6 was used for fractiona-
tion into the various ranges of particle
sizes desired. The average diameter of
particles was more precisely determined by
means of the slit-ultramicroscope. t
In order to facilitate the separation of
the coarser particles from the original
suspension, a 10,000-r.p.m. Sharples cen-
trifuge, with a 4-in. diameter bowl was
utilized. This permitted the initial removal
of particles down to 200 mu. A regular
high-speed laboratory model Sharples su-
percentrifuge of smaller diameter was used
for the removal of particles in the range
200 to 25 mu. It was possible to remove
particles varying in diameter from I micron
to 25 millimicrons. This allowed detailed
classification of particle-size ranges. The
flow diagram in Fig. I gives recovery in
minimum time.
Determination of Viscosity
Since the suspensions necessarily were
dilute, viscosity measurements provided
the best means for comparing the resistance
to shear under the various physical and
chemical conditions arbitrarily imposed
in the investigation. Accordingly, a stand-
ard Stormer viscosimeter was used and the
data were reported in grams required to
maintain 600 r.p.m. for the drum. The
* A proprietary compound of the Dewey-Almy
Chemical Co .. Cambridge. Mass. i a name for various
polymerized organic salts of sulphonic acid.
t Bausch and Lomb Optical Co .. Rochester, N. Y.
 r---------' f---------' f-------' r--------..

-
r r
....
0
-1
. -z
----;r.-
'E_..
z
-1
.
0

l
...
.. " !
~ ..~
~
6
~

Xl
l _l
L _________ _
1
L __________ _

CLAY SOLUTIO", RAPIDL.Y AFTER 30 DAYS SETTLlfIIGS DISCARDED

AGtTAT£D AGAlfli AGITATED Q. 1700 .C.C.'IIII'N Q. 1000 C..C.'MIN. Q. eoo c. CJ NUl·
. . I. 10,000 R.PM .. I 10.000 H.P. N. " • 10,000 II.RII .

<iIIIl------------. r-----------"'! r-----------t r----------l

t t -1
T.. n-
I

T 1 1 T
.. .
~
• 2
N
E ...
~ ... '"
., :i

1* ~l J
iii
1 1
E ~.

i
!
N

l
I\Z

~
L_ _ _ _ _ J
----------
, _________ .. .J

Q. M) C.t./MIN 0_100 C·c"/MIN. Q: 2001 II. H. 0'100,,,.,11. Q.200/MIN Q

'
400'IIU"
WI 150.000 H.P.... ... 35.000 H.P,... 1.11 1 35,000 R.PM ... 10,000 H.P. ... ".IOpOORP.M. .. IIOPOO H.P....

FIG. I.-PATH OF FLOW OF COLLOIDAL DISPERSION.

Optimum conditions of operation to obtain maximum recovery of material in the least time.
This diagram assures accurate recovery of the following particle-size ranges in the least required time: 500-425, 425-350, 350-275,
275-200,200-125,125-75,75-50,50-25.
 4 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS
same method of testing was used for all
fractionated and unfractionated systems.
Hydrogen-ion Concentration
The determination of the hydrogen-ion
concentration is important. The instru-
ment consists of a combination quinhy-
drone-calomel cell, and affords accurate
determinations for suspensions of below
9 pH. The galvanometer used was the
Leeds-Northrup type.
Filtration Studies
Throughout the investigation it was
deemed important to determine the rate
of loss of water due to the permeability
of the plastic bentonitic mass or "cake."
In order to investigate the behavior of
the clay systems under varied conditions, a
battery of four" Baroid" filtrate testers was
used. * No. 50 (or No. 52) Whatman's
filter paper was used throughout the tests.
Four hundred cubic centimeters of the
clay suspension were placed in the cell,
and submitted to a pressure of 100 lb. per
sq. in. The rate of efflux during the initial
30-min. period was then determined.
Gel-strength Determination
The determination of gel strength is an
arbitrary procedure. Although more re-
fined apparatus is available for absolute
o 0
measurements, the method used involved
the determination of the least number of
grams required to cause incipient move-
o 20°C.
ment of the drum on the rotor of the
Stormer viscosimeter. This gave an indica-
tionof the force required to shear the gel
structure.
EXPERIMENTAL PROCEDURE
The investigation has been directed to
show the effect of the monovalent, divalent
and trivalent ions of the diatomic and
triatomic easily ionizable salts, acids and
• Baroid Sale. Inc .• ,Los Angeles. Calif. (See H. B.
Weiser: Colloid Chemfstry. 149. Fig. 36. New York.
1939. John Wiley and Sons.)
bases on the bentonitic suspensions. This
will be followed by an investigation of the
more complex phosphate salts, and the
salts of organic acids.
The first investigations were conducted
to show the effect of the monovalent ions
on the bentonitic suspensions added singly
and in combination with each other.
The following chemical reagents were
employed: potassium chloride, sodium
chloride, hydrochloric acid, sodium sul-
phate, and sodium hydroxide. The concen-
trations of the chemicals were 2N, IN,
ando·5 N .
Since the experimental data are more
easily presented in graphical than in tabular
form, the discussion will be developed
accordingly. All data are not included
in the graphs, since the higher concentra-
tions of certain reagents resulted in
complete coagulation 'of the bentonitic
suspensions.
Where combinations of two salts were
used, the mixture consisted of 50 per cent
each of the total milliequivalents. For
example, a mixture of IN NaCl and IN
KCI included the same number of equiva-
lents as IN N aCl.
All suspensions were made up to 4 per
cent by weight of solids, and. allowed to
stand 24 hr. after violent stirring. After
standing, they were again stirred, immedi-
ately preceding the determination of their
various properties.
The investigations were conducted at
It was found that the particles present
below 500 mu showed no essential differ-
ence in exchange capacity per gram.
This is in agreement with the statement
that" the exchange capacity of all particle-
size fractions of hydrogen bentonite are
identical within the limit of experimental
error."7
EXPERIMENTAL RESULTS
Considering first the addition of the
sodium hydroxide, Fig. 2 shows that the
 H. H. POWER AND CHARLES R. HOUSSIERE 5
viscosity of the system increases with of the electrolyte causes a reduction in
the concentration of the base. The initial the thickness of the lyosphere. Since
reduction caused by the addition of small "swelling" is related to the size of the
amounts of reagent is explained by the lyosphere, it becomes obvious that excess

-
ao·c.

VISCOSITY
rlLTRATE -------

~Or-----2~----~4-----te----~~--~IO~--~,2r---~~r---~O
c.C.S. OF REAGENT ADDlD TO 200 CC 5 OF' 4'% BENTONITE
FIG. 2.-VISCOSITIES AND FILTRATE RATES OF BENTONITE SUSPENSION TREATED WITH NaOH.

saturation of the particles by the negative electrolyte causes a decrease in "swelling."

ions. The sodium ions of this reagent act
as counter ions. These are present in the
lyosphere. If more electrolyte is added, a
reduction in the charge of the particle
occurs. This may be explained by the fact
that" increased concentration of the elec-
trolyte in the dispersion medium" (p.
201 of ref. 3) changes the conditions of
equilibrium, which results in the accumula-
tion of additional sodium counter charges
in the solvated hull. This change results
in neutralization of the effect of the ad-
sorbed ion. In other words, the repulsion
forces are decreased.
It has been mentioneds that an excess
Decreased swelling and decreased repulsive
forces contribute to a greater mechanical
energy required for shear. The viscosity
curve flattens out at concentrations of
8 C.c. of IN NaOH and beyond. This is
due to maximum decrease in repulsive
forces and swelling. 9 The explanation for
the more gradual increase of viscosity with
the o.SN NaOH over the entire range is
obvious.
The effect of the reagent on filtrate rate,
as shown by Fig. 2, is more difficult to
explain. In the lower ranges it iss probable
that the lowering of viscosity is accom-
panied by improved orientation of the
6 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS

particles, which results in a filter cake of o.SN reagent appear to have a slightly
minimum packing and permeability. Al- higher permeability and filtrate rate. When
though the curves for the IN and o.SN equal amounts of ions from reagents of
sodium hydroxide show little divergence different concentration are added, the
80

80 !L..-
.9
""

1
20·C.

/ ~
I;;
.0
ifVI SCOSIT .

/
FILTRATE -------- L.----
20 1'1 ",Cl..
~.--

~
IE j ~
"'~ /
W

/
I I

/ / / ~-...
:;
IE
W

!.~
~~

~ ~~ ---
~ . ~"'~ . '
~
~

40
80
>:s;2
'\
I'---...

.- - .. -- ~~.::~ -·W.:ct;'t
"'-, ..........
;:~:... ---
.......... -_ .. _

\
--- ........
...
:::;;:.~"
;c.C.\..
- ~
.. ......
b::::::
--...... 1~ ~£~.:!'-~'" HCl
---..........

20 0

°c • C c.s or
8 10
REAGENT ADDED TO 200 C.C.S
BENTONITE.
or
I. 14 leO

FIG. 3.-EFFECT OF IN REAGENTS 'ON BENTONITIC SUSPENSIONS.

up to 4 c.c. of reagent added, a maximum behavior of the systems should be identical

divergence is shown at the 8-c.c. point. as long as dilution effects do not occur.
This is followed by convergence at the As the amount of o.SN NaOH is increased,
I6-c.c. point. The curve for the o.SN the number of ions adsorbed approaches
reagent is principally responsible for the the number adsorbed from IN NaOH.
divergence noted. The trend of the curve It is probable that after 8 C.c. of IN NaOH
for the o~SN reagent at the 8-c.c. point is added the amount of sodium ions forced
indicates decreased hydration. Approxi- into the lyosphere is small.
mately 4 c.c. of the IN NaOH reagent Fig. 3 shows the effects of the addition
should give the same result to substantiate of potassium chloride, sodium chloride and
this premise. It is seen that the viscosity hydrochloric acid reagents.
increases rapi?ly and thereby promotes It is noted that the viscosity reduction is
nonpermeability to water. Probably this is decreased considerably more by the IN
due to enmeshmen t as a result of clusters.1° KCI than by the IN NaCl. Although the
Thus, the agglomerates resulting from the chloride ion probably has the same effect

j
 H. H. POWER AND CHARLES R. HOUSSIERE
in each case, it is reasonable to assume that
the highly hydrated sodium ion increases
the thickness of the lyosphere and thereby
partly overcomes the tendency of the
7
indicated by the upward trend of the
viscosity curves.
The curve for the mixture of IN KCl and
IN NaCl differs from those of the single

- ao·e.
(TOi'

VISCOSITY
/
FILTRATE
--r- /

.
I
A, ~& INN CL

V
:I
II:

100

i \. -- .........
II:
'"~ ~ ~IN IIIA2 Sq{ ..... '

..:...-- ;::.--- ~
,
...........-
.....g r--- -'
f
& 1111 NAC L .....
_....... _/

.... - .
~
80
! \, '
NN~~

:>-- --.- ,- ....-

>
..... ....-'
~."1', \ \
ii
Q

g
..... \
.. ~.-.-
, ....
~. IN NA2~ & IN NACI.
80
:I
<[
II: '." ~.........

"
40

zo

0 0
0 2 4 6 10 12 14 \I
C.C.S OF REAGENT 'AOOEO TO 200 cCS OF (4"") BENTONITE
FIG. 4.-EFFECT OF IN REAGENTS ON BENTONITIC SUSPENSIONS,

electrolyte to reduce the viscosity of the
suspension. The final viscosity increase due
to the addition of IN KCl is lower than that
due to IN NaCl. This difference may be
related to the difference in hydration of the
Na and K ions. The less the hydration
of the ions, the less the thickness of the
lyosphere. This explains the lower initial
decrease in viscosity caused by the potas-
sium chloride. Further addition of elec-
trolyte causes a reduction in the thkkness
of the lyosphere as well as in repulsion
forces, as explained previously. This is
reagents in that the viscosity is not lowered
initially. This curve is similar to Fig. 5
beyond the 4-C.C. point showing the effect
of 2N NaCl. The IN mixture affects
viscosity in the same degree as does the
2NNaCl.
It may be observed that the relative
effects of sodium chloride and sodium
hydroxide are sometimes confusing. Con-
sidering the same concentrations and the
same volumes of each reagent added,
the suspension treated with NaOH gels
rapidly with a resulting low water loss,
8 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS

and that treated with N aCI fails to gel
perceptibly and experiences a viscosity
increase similar to that shown in Fig. 5.
The difference in the effect of the hydro-
gen and the potassium ions is shown by a
It is concluded that the agglomerates
formed by potassium chloride are smaller
and do not enmesh the water as do those
formed by hydrochloric acid. The increase
in quantity of potassium chloride used is

.<I'c
I

VISCOSITY
FILTRATE ----- -
~ .----
I 120

... I
IE
£. V 2111 NACL & 2N N"2~
I00

~ ~ ?N N:2SC1$ f-.-:::c.;-'-'-'
'" F-<' f--.-._-

I - k------
.-.~ .
2N NACL & 2111 NA2SCk
80

e
'" ~~
i
.I /
/ 2-·-
2N NAZS04 '- -' '-.
.
!
- -'
.....
....... / 80
y
" ,'\ /'-. .,/
1--
P"-~::::: ._._.- ...... -.- .~-'
././

'" ~'<.-.-
2N NACL
40

0 0
o 2 4 8 8
C.C.S. OF REAGl:NT ADDED TO 200 c.cs. OF (4""
10 12
BENTONITE
14 18

FIG. 5.-EFFECT OF 2N REAGENTS ON BENTONITIC SUSPENSIONS.

comparison of the curves for IN KCI with accompanied by a corresponding increase

the behavior caused by IN HCI (Fig. 3). in permeability, as shown by Fig. 3.
When IN KCI is added, the viscosity is Again, from Fig. 3, no initial reduction
reduced initially, but gradually recovers. of viscosity is shown when a mixture of IN
When IN HCI is used, immediate gelation NaCI and IN HCI is added to the suspen-
results. The gel or coagulum formed by sion. This indicates that the hydrogen is
the addition of 4 C.c. of the reagent changes adsorbed preferentially, as would be
the gel color to white and probably is expected. Any repulsive forces that might
caused 10 by large inclusions of water. The exist are immediately neutralized. The
water is not forced out, even by submitting same reasoning for the addition of excess
the filter cake to pressure in the perform- reagent may be applied for the range of
ance tester. sudden rise in viscosity.
 H. H. POWER AND CHARLES R. HOUSSIERE
A comparison of the curve of IN NaCI
plus IN KCl with the curve for either
I~ KCl or IN NaCI (Fig. 3) shows an
interesting behavior. No initial reduction
in viscosity is observed for the combination
curve. A large increase followed by a flat-
tening of the curve corresponds somewhat
to that of the curve for IN KCI. The final
increase in viscosity appears to be a com-
bination of the effects shown by the IN
NaCI and IN KCl curves. It is difficult to
explain why the viscosity increase for the
combination curve is so much more rapid
than for the curves of the individual re-
agents. A hint is offered by observing the
curve of filtrate loss for the reagent mix-
ture, where minimum water loss is obtained
in a region corresponding to the middle
region of modified viscosity increase. If
corresponding points of the abscissa of the
filtrate and viscosity curves are compared,
it may be inferred that the combination of
the sodium and potassium ions may cause
the formation of a loose agglomerate, which
thereby enmeshes a quantity of water. The
middle range may indicate the point where
the existing agglomerates adhere together
with minimum additional agglomeration.
The viscosity curve finally follows the
normal tendency. This is due to the addi-
tion of excess electrolyte, which forces more
cations into the lyosphere, decreasing its
thickness and the charge on the particle.
The reagents containing potassium cause a
final increase in filtrate rate and viscosity.
However, those containing hydrogen in-
stead of potassium show opposite trends.
This may be a reflection of the difference
in structure built up by the two type
cations.
Considering the 2N KCl curve (Fig. 3),
the structure varies greatly as the quantity
of the reagent is increased. The middle
region indicates the presence of loose
agglomerates with enmeshed water. The
region toward the end of the curve indicates
that the agglomerates form effectively
larger particles, which result in higher
9
permeability. Reliable filtrate-rate curves
give some indication concerning the type
of structure occurring in the system.
Considering a mixture of IN Na 2S04
and IN NaCl, Fig. 4 shows that the vis-
cosity reduction of a bentonitic suspension
is initially the same for IN Na 2S04 and
the combination of reagents. Further addi-
tion of the single reagent results in a vis-
cosity increase and leveling off, while for
the combination reagents the viscosity
continues to increase. The curve for the
IN Na 2S04 indicates that a few of the
hydroxyl ions formed by the hydrolysis of
Na 2S04 have a slight initial effect on the
increase of repulsive forces. Further addi-
tion of electrolyte results in the formation
of water by the hydroxyl and hydrogen
ions. The viscosity increase may be said
to be due to the forcing of more sodium
ions into the lyosphere.
A study of the curve for the combination
reagents mentioned reveals a more gradual
increase in viscosity beyond the minimum
point. With the same volume of the IN
Na 2S04 plus IN NaCI as used for the
sodium sulphate alone, the number of
divalent anions in the former is less. This
lends further support to the theory pro-
posed for the mixture of reagents. Con-
sidering the mixture, a slightly higher
viscosity increase may be attributed to the
greater number of different ions present,
possibly forming ionic clusters having the
same effect as would an increase in solid
particles for the system. This theory is
supported by the investigations of Hauser
and Hirshon 11 with particular respect to
the initial work of Wolfgang Ostwald.'2
Referring to the filtration curves (Fig. 4),
the region of low viscosity for the IN
Na 2S04 is also reflected in the filtration
rate. "Under sufficient peptization the par-
ticles may orient themselves so as to pack
more closely when pressure is applied,
thereby causing decreased permeability
and filtration rates. Minimum filtrate rate
results from maximum peptization. This
10 CHEMICAL· TREATMENT OF BENTONITIC SUSPENSIONS
effect appears to be limited by a definite
minimum p:uticle size. Where more reagent
is added beyond the point of maximum
peptization repulsive charges apparently
are decreased to a point where agglomer-
ation takes place. The gradually increasing
filtrate rate reflects the degree of agglomer-
ation with an increase in permeability
resulting from increase in "particle size."
Considering the curves for the com-
bination reagents, however, an immediate
rapid increase in filtrate rate is followed by
a rapid decline. This irregularity is not
reflected in the forepart of the correspond-
ing viscosity curve, and is difficult to
explain. At points beyon.d 6 c.c., the filtrate
rate shown by the IN Na 2S04 curve is
greater than for corresponding points of
the other curves.
Two sodium atoms are present for each
sulphate radical in sodium sulphate, and
one sodium atom for each chlorine atom in
sodium chloride. If a liter of IN NaCl is
mixed with a liter of IN Na2S04, there will
be 12.12 X 1023 atoms of CI + 3.03 X 1023
S04 radicals. Therefore, the ratio of poten-
tial positive ions to potential negative ions
is 4 to 3. The ratio of potential positive to
potential negative ions for sodium sulphate
iS2 to I. The amount of sulphate ions avail-
able in IN Na 2S04 is 3.03 X 1023 per liter.
Four times as many sodium ions as sulphate
ions are available in the IN Na 2S04. For
the mixture, eight times as many sodium
ions as sulphate ions exist. However, the
effect of divalence still must be considered.
Theoretically, although sodium ions num-
ber eight times the sulphate ions available,
the' sulphate ions remain significant. The
viscosity does not change appreciably after
8 c.c. has been added. However,the filtrate
rate changes considerably.
Comparing an equal number of equiva-
lents, a greater number of sulphate ions
exists in the sodium sulphate reagent than
in the combined reagents. The maximum .
charge is reached more quickly, indicating
an earlier decrease of charge byconcentra-
tion 13 in the lyosphere. However, it appears
that. the sulphate ion prevents material
increase in viscosity. This situation is illus-
trated clearly in Fig. 4. Figs. 4 and 5 show
that the viscosity and filtrate behaviors
are somewhat reversed for the IN as com-
pared to the 2N reagents. A gradual in-
crease in viscosity is shown by the curve
for 2N NaCl. For equal amounts of 2N
NaCl and 2N Na 2S04 the viscosity increase
is rapid, followed by marked flattening of
the curve. It is probable that the excess
reagent causes a reduction in particle
charge while decreasing the thickness of
the lyosphere. The sulphate ion apparently
overcomes the discharge effect of the
sodium in the 2N N a 2S04. If residual posi-
tive valences exist on the particles, they
may become effective when the residual
negative valences are satisfied by the
sodium. These residual positive valences
may attract the divalent sulphate and
decelerate the rate of charge decrease.
Thus, the sulphate ion may partly oppose
viscosity increase, and promote repulsive
forces not capable of existing with the
chloride ion. It is not believed that the
chloride ion exerts any appreciable effect.
The ·sulphate ion apparently neutralizes
the effect of the hydrated sodium in the
sodium sulphate reagent, with little in-
crease in viscosity.
It is difficult to explain the behavior of
the curves for filtration rate shown in
Fig. 5. A maximum filtrate rate apparently
exists in connection with the 2N NaCl
curve. A minimum filtrate rate accom-
panies the 2N Na2S04 curve. A complete
reversal of behavior continues upon the
addition of the above reagents. The effect
on filtrate rates is reflected only slightly
by the viscosity behaviors for the corre-
sponding reagents. No explanation is
offered for the filtrate behavior caused by
2N Na 2S04. Possibly the further addition
of sodium ions decreases permeability due
to water enmeshment and to hydration of
the sodium ion. A constant increase of
 H. H. POWER AND CHARLES R. HOUSSIERE ·11

viscosity is shown by the curve for sodium
chloride. This corresponds to a maximum
filtrate rate, followed successively by a
minimum, and then a final increase. The
700
troIs viscosity increase, but in this instance
does not reduce the viscosity. Although
the lyosphere thickness is decrcased, the
presence of the sulphate ion closer to the

8OO1----+---+-----+---1--+_ ••.•. -t--+--f----+-----1-----l

so
..
2
Ii ·_~2N.KCL
§
..,
It
II
It
g
en
..,
/
~\
> "\
__ ~-- ~--~~-1Cl

___ -r
DO
0 \" /"" IN.KCI..
g \ I. . 1-.__ . / ___ ~---- ~ _-1c)O.~N IICL

..'"
II
It
~~-.- --:~ :..::---~--- ~~~
llCLlB

" ~ _______ _________ IN.IICL (8)

- -. ... - --------:-. . O.~N.IICL 181
~~~ ~~~~ :~--~--~~,~=~- :---:-:::~:;:. ~:--. ---.--
. . 21it1.a... (AI 0.51 rN:L (A)I.t.RcL (A
OOI_~~~--~(~--~-----7----~----~----~----;----7.
::- 2 4 8 8 10 12 14 18 Ie
c..c.S. OF' REAGENT ADDED TO aDO c..c.s. OF 4'" BENTONITE
FIG. 6.-VISCOSITIES OF SUSPENSIONS OF SEVERAL PARTICLE SIZES TREATED WITH VARIOUS
NORMALITIES OF KCl.

sodium ion probably promotes increase of
viscosity due to agglomeration with the
resulting increase in permeability pre-
viously noted. The viscosity increase con-
tinues, since the sodium ion decreases the
charge by suppression of the ion atmos-
phere. The ion density may be sufficient
to cause increased viscosity and less uni-
form packing of the filter cake in the tester.
Hence, the decrease in permeability is not
so pronounced.
Referring again to Fig. 5, an optimum
effect on viscosity is noted for the combined
2N Na 2S04 and 2N NaCI reagents. The
curve follows the same trend as does that
·for the :iN Na 2SO, alone. Apparently, the
sulphate ion exerts a certain viscosity
control, which is subject to further investi-
. gation. Ordinarily, the sulphate ion con-
particle may oppose the decrease of charge
on the particle. The effect of the substi-
tutions of equal equivalents of chloride
ions for the sulphate ions is shown. The
sulphate ion in the sodium sulphate reagent
causes early minimum filtrate rate, fol-
lowed successively by rapid increase and
decrease. However, the combined reagents
apparently decrease the sulphate-ion effect
shown by the single reagent, which results
in less peptization up to the 4 c.c. point.
Apparently, the sodium ion then becomes
important and predominates to a point
where agglomeration is controlled more
effectively. Hence, as a result of this slower
orientation, water is not enmeshed, but
forced through the filter cake. It is an odd
characteristic that the higher concentra-
tions of the mixed reagents give a much
12 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS
higher filtrate rate than the zN NaCI or
zN Na 2S04 reagents singly, although the
viscosity resulting from the mixed reagents
is below that shown for the zN aCI reagent
alone. Again, this is thought to indicate the
type of structure within the suspension.
Effect of Particle Size
The effect of potassium chloride reagent
on fractionated bentonitic suspensions
grouped into particle-size ranges of (A)
500 mu and Icoarser, (B) 200 to 140 mu,
and (C) 130 to 90 mu, is shown in Fig. 6.
It"is observed immediately that the
smaller volumes of the reagent result in
the greatest viscosity reduction. The rate
of viscosity increase becomes greater with
decreasing particle size, or, obviously, with
increasing surface forces resulting from
comminution of particles. By inference,
addition of reagent increases the thickness
of the lyosphere and causes minimum
viscosity. The addition of excess reagent
causes more ions to be forced into the
lyosphere, decreasing its thickness and the
charge on the particle, which results in
reduced repulsive forces, and viscosity
increase. Although the initial viscosity for
the particle-size B suspensions and par-
ticle-size C suspension is almost identical,
the latter, by calculation, has slightly over
172 times as much surface area as the
former. Since the number of particles varies
inversely as the cube of the diameter, there
areapproprimately 3.7 times as many
particles present in C as in B.
The foregoing shows that fewer ions are
required for the suspensions of decreased
particle size for the same viscosity increase.
For the same number of cubic centimeters
of reagent there is a greater viscosity in-
crease for the smaller particle-size range.
For a larger number of particles there
should be a greater viscosity. In addition,
the lyospheres 14 around the smaller par-
ticles probably have a relatively larger
thickness than those around the larger
particles. The increased effective diameter
of particles is accompanied by viscosity
increase of the suspension. The greater
the amount of chemical added, the less the
repulsive forces. The smaller particles,
having less kinetic energy and less" mean
distance" between them, would be ex-
pected to be more easily influenced by the
reagent. If enmeshment of water were to
take place, this too would contribute to a
higher viscosity for the small particles.
Ion orientation mp.y be further accentu-
ated as particle size decreases. A greater
tendency for suppression of the ionic layer
may possibly be for the small particle sizes
and concentrated reagents. Because of the
greater number of exposed, unsatisfied
surface bonds, a larger attractive or repul-
sive effect may be exerted by the particles
on the ions present in the suspension.
When the suspension is treated with
highly concentrated reagents, an orienta-
tion of ions may take place,11 resulting in
the formation of ion clusters. In the finer
range the particle dimensions considered
approach those of the coarser molecules.
Clusters of such ions may interfere with
particle movement. Observations made
through the ultramicroscope indicate areas
void of particles. Apparently, oriented par-
ticle groups are held apart by a phe-
nomenon that possibly may be explained
by cluster formation.
In Figs. 7 and 8 an optimum particle
size is indicated below which filtration
properties are poor. Assuming that par-
ticle size affects permeability only, it is
obvious that bridging must precede filtra-
tion. In the absence of bridging, the smaller
particles pass through the filter cake with
the filtrate.
From Fig. 7,' for particle-size range A
(500 mu and coarser) it is observed that the
filtrate rate increases slightly with the
concentration of potassium chloride, which
probably is due to slight decrease in disper-
sion of the particles.
For particle-size range B (200 to 140 mu),
the filtrate rate drops about 30 per cent for
 H. H. POWER AND CHARLES R. HOUSSIERE 13

the higher concentration of electrolyte. Ori- appears. From observation, some of the
entation of particles probably accounts for finer colloids pass through the filter. Upon
the early portion of the filtrate curve. This the addition of further reagent, the entire
is reflected by the successive increase, suspension is forced through the filter
~
zo·c.
I
A - ABOVE 500 WI'- V
(el

B - 200- 140 " /

e- 130- 90 ,../
"

1 /'"
V
I
VISCOSITY /
:I
Q;
a:
rlLTRATE -------
/
§
\
/ 100

\ / (9)

~~
---.--.~, ~WENT CO ....LETEL THRU
----- ----
-----
:::!
«
a:
"I
1\ / AS A CEILl
...-
___
_ _ ..... a ........ •
(AI
......... .....

V /
~-
-------_.
----_ ....... - en
~ ............. - .... .- .. ---_.
---_ .. .... ---
.. .... - (B) o
o

----
I
,
~. -'. .... _- .. ------- ---------- ...
I

~7 ~ lAl i
.d
0
0 12 14 16
CC.S. ~F 2N. ~CL ~OOED TO 8200 C.C.S. OF 4% BENTONITE
10
o 2
FIG. 7.-EFFECT OF PARTICLE SIZE ON VISCOSITY AND FILTRATION CHARACTERISTICS.

decrease, and final prolonged increase in
filtration rate. However, this curve is lower
than that for the coarser particles con·
sidered previously. This may be explained
on the basis that upon compaction the
intermediate particles form a filter cake
having less permeability than that formed
by the coarser particles.
For particle-size range C (X30 to 90 mu),
a definitely higher filtration rate results
from low concentrations of the potassium
chloride reagent. Although bridging is still
evidenced, little initial resistance to flow
paper. It appears that increased defloccu-
lation facilitates a better orientation of
particles to permit closer packing. How-
ever, further increase in repulsive forces,
coupled with increase in hydration, allows
the particles to slip, one past the other.
Accordingly a very stable gel may be
forced through the performance tester. By
test, the gel under pressure passes through
the filter as a fluid and immediately sets
up again as a gel.
The filtration rate, therefore, is not negli-
gible for thixotropic systems and must be
14 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS

defined. In systems forming gels two as- much more slowly, which probably is due
sumptions are made: (r) the particles touch to greater adsorption onto the particles by
one another; (2) the particles do not touch reason of the increased surface. This is re-
but are held in equilibrium by surface flected in Fig. 8, which shows that as

/~ VISCOSITY . . - / (B)

~v '~"_TE-=-_:;:_/=-_::..=_::.._
-+V-:;::;:~--:::"-I (e)

i32Clf""l-\----?t--T--\-t-v~\,V"~--+--+--.J.------IIOO
j
~
e iV;/\ -- './
a:2~~-1~~~~---~~~t-------~------~------~---------~------4-------~
,(C) .............
'. . . . -1----- - - . - - - - - ._'- - (s)
80 ~
S
14; i "I' '- ~
~ i " ---------- ---------- ---------- --------- ---------- ------------ (A) 60g
13e i ..,/ (e) ~
12~ 1..,.. _.-- ==.-•.,.~:::- .::::::::.--: ::::-::-:::: :::::::::---- -::::::-::~:-~ (B) ~
~. __ .~ •• _- 400
,
II 18(1-.-,.;..:'-.. . :. . .__ ._. ____ ._
(!) / .. - ..... ~::?'""
~
=i = .:i" / - - --_. ----.- (A) -
10 90
,-.£.. - ..... '
~~
~

9 'III~

8 ~.~~==;:~~~::::=t==::=t====~~====t=====~=====1(~A~)___-J
"0 4 6 8 I 12
C.C.S. OF O.SM No OH ACO£O TO 200 C.C,S. OF .BENTONITE
14
(4'1&) 16 18
0

FIG. 8.-VISCOSITIES, pH VALUES, AND FILTRATE RATES OF SUSPENSIONS OF VARIOUS PARTICLE

SIZES TREATED WITH o.SN NaOH.

forces. According to the last assumption, viscosity decreases, pH increases gradu-

the individual particles are separated and ally. Where there is no viscosity change for
surrounded by lyospheres. The smaller the the coarse particles, a rapid increase in pH
particle, the larger the comparative size is evidenced, indicating nonadsorption of
of the lyosphere and the greater the tend- electrolyte from the suspension. At this
ency for certain particles to slide over the point, the pH of the suspension approaches
others. that of the reagent.
The effect of o.SN NaOH on viscosities,
Also, it is evident that for the same
filtration rates, and pH of the suspensions
amount of reagent the average reduction of
made up of the three particle sizes noted is
viscosity is less for the suspensions of smal·
shown in Fig. 8.
Fig. 8 shows also that the pH values for ler particle size and, further, that addition
the suspensions containing particle-size A of the reagent causes a suppression of the
increases initially and then flattens out over lyosphere, as evidenced by the curve. This
the remaining portion of the curve. The is followed by increase in viscosity, which
curve for the finer particle sizes increases may be caused by the formation of ion
 H. H. POWER AND CHARLES R. HOUSSIERE'
orientations, or by the suppression of the
ion atmosphere, resulting in a gel.
In the correlation of filtrate rates and
viscosity, fairly general relationsarenoted.
For the coarse particles. the amount of
reagent added has comparatively little
effect on the viscosity and amount of
filtrate. This is reasonable since the surface
forces of the large particles exert little
effect as compared with other factors.
Hence, permeability is changed but little
with increase of the pH value.
However, where sufficient electrolyte is
added to lower the viscosity of the suspen-
sions of finer particle size, the filtrate rate
is correspondingly low. When the viscosity
builds up, the permeability increases as a
result of the agglomerated condition of the
particles. After this the viscosity is lowered
with a correspondingly lower filtrate rate.
However, if more electrolyte is added,
the filtrate rate remains about the same.
At the point corresponding to 8 C.c. of the
reagent, the system is still viscous. Further
addition of ions, instead of affecting the
distance between particles, may- form
ionic clusters, which cause added resistance
to shear but no definite effect on the filtrate
rate.
Comparative gel-strength values are
considered only briefly because partial
coagulation results from the addition of
reagents of particular concentration. Vis-
cosity curves indicate, to a large extent,
the relative gel strengths. Their significance
so far is not important, since the dispersive
properties of the ions selected for investi-
gation are of more immediate concern.
CONCLUSIONS
I. It is again generally observed that
effective positive ion adsorption is in the
order; Na, K, H.
2. Enmeshment of water apparently
results from treatment with sodium hy-
droxide. Treatment with sodium chloride
does not indicate this behavior.
3. The viscosities and filtrate rates
IS
resulting from the combined IN KClcIN
HCI do not in any way correspond to the
effects of each reagent alone.
4. The greater effect of the hydrogf'n
ion is indicated when hydrochloric acid is
substituted for potassium chloride.
5. In some instances, it appears that
the assumption of the presence of ionic
structures may furnish a partial explana-
tion for viscosity changes when the filtrate
rates remain constant.
6. A relation apparently exists between
the degree of peptization and orientation
of particles. This relation is evidenced by
the parallel variations in viscosity and
permeability.
7. In a comparison of the two systems
IN NaCI-IN Na 2S04 and 2N NaCI-2N
Na 2S04, the viscosity and filtrate relation-
ships are somewhat reversed.
8. Using salts, it appears that the
reduction of viscosity is due tothe number
and kinds of ions present. When ions are
added in aqueous form, the dilution. effect
is small, provided the concentration of
ions in the aqueous solution is reasonably
high.
9. The viscosity varies in inverse pro-
portion to particle size. Viscosity decrease
at low concentrations of reagent is directly
proportional to particle-size decrease to a
lower limit of approximately 130 mu.
10. In a study of filtration characteris-
tics, "bridging" of particles is shown to be
important. Particle-size distribution rather
than high viscosities apparently accounts
for low filtrate rates.
I I. The charge of pH is retarded as
particle sizes are decreased. If viscosity
change is due primarily to adsorption of
ions from the solution, a variation in pH
results. Thus, the degree of the viscosity
change is reflected in the change of pH.
This is not always the case, since viscosity
changes are not always due to adsorption
of ions alone.
12. Although these conclusions are tena-
ble for the lower concentrations used, the
16 CHEMICAL TREATMENT OF BENTONITIC SUSPENSIONS
behavior is not postulated for higher
concentrations of reagents. Possibilities
exist for further suppression of the ionic
atmosphere and the formation of ionic
structures.
ACKNOWLEDGMENT
The authors are indebted to the Bureau
of Engineering Research of the University
of Texas, which graciously extended them
its sponsorship and facilities for carrying
on this work.
Acknowledgment is also made to Dr.
E. A. Hauser, of the Massachusetts
Institute of Technology, and to Dr.
James Coull, of the C niversity of Pitts-
burgh, for their most helpful guidance in
the graduate programs of the authors.
REFERENCES
I. H. H. Power and C. R. Houssiere. Jr.: Prelimi-
nary Survey of Heaving Shale Problem. Paper
presented before the American Petro lnst ..
Shreveport meeting. Feb. 28. 1941. Reprinted
Oil Weekly (March 3. 1941).
2. E. A. Hauser: Colloid Chemistry in Ceramics.
Jnl. Amer. Ceramic Soc. (1941) 24(6). 179-
189.
3. A. L. Johnson and F. H. Norton: Fundamental
Study of Clay-II. Mechanism of Defloccu-
lation in the Clay-Water System. Jnl. Amer.
Ceramic Soc. (1941) 24(6). 189-203.
4. E. A. Hauser and J. E. Lj'nn: Experiments in
Colloid Chemistry. New York. 1940. McGraw-
Hill Book Co.
5. R. P. Graham and J. D. Sullivan: Critical Study
of Methods of Determining Exchan~eable
Bases in Clays. Jnl. Amer. Ceramic Soc. (1938)
21(5). 181.
6. E. A. Hauser and H. K. Schachman: Particle
Size Determination of Colloidal Systems by the
Supercentrifuge. Jnl. Phys. Chern. (1940) 44.
58 4-591.
7. E. A. Hauser and C. E.' Reed: Studies in Thixo-
8. S. ti"fPM!lts~~' [::.~. ~ls~iI (C';II~ia''s~1~vior:
Forms and Functions of Water. Soil Sci. (1932)
33(4). 301-323.
9. L. D. Baver: Soil Sci. (1930) 22(4). 298.
10. A. Demolon and G. Barbier: Contribution Ii
l'etude de l'argile colloidale. A 1111. Sci. A grail.
(1927) 44. 341-375.
II. E. A. Hauser and S. Hirshon: The Behavior of
Colloidal Suspensions with Electrolytes. Jnl.
Phys. Chern. (1939) 43(8). 1027.
12. W. Ostwald: Electrolyte Coagulation and Coeffi-
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(1938) 42(8). 981-1000.
13. E. A. Hauser: Colloidal Phenomena. 97. Fig. 40.
curve 2.
14. E. A. Hauser and D. S. Le Beau: Studies in Col-
loidal Clays. Phys. Chern. ('938) 42(8). 1041.