SOCIETY OF PETROLEUM ENGINEERS OF AIME SPE 540

6300 North Central Expressway

Dallas 6, Texas

THIS IS A PRE PRINT - SUBJECT TO CORRECTION

CLAY CHEMISTRY AND DRILLING FLUIDS

By

w. C. Browning, Member AIME

and A. C. Perricone, Junior Member AIME
Milwhite Mud Sales Company
Houston, Texas

Publication Rights Reserved

This paper was presented at the First University of Texas Conference on Drilling and Rock Mechanics !n
Austin on January 23 and 24, 1963, and is considered the property of the Society of Petroleum Engineers. Permission
to publish is hereby restricted to an abstract of not more than 300 words, with no illustrations, unless the paper is
specifically released to the press by the Editor of the Journal of Petroleum Technology or the Executive Secretary.
Such abstract should contain conspicuous acknowledgment of where ~d by whom the paper is presented. Publication
elsewhere after publication in Journal of Petroleum Technology or Society of Petroleum Engineers Journal is granted
on request, providing proper credit is given that publication and the original presentation of the paper.

INTRODUCTION It is believed that the study of clay-water chemistry

The drilling of oil and gas wells demands ingenious
engineering, utilizing the best mechanical and chemical
principles. It is obvious that many aspects of the so-
called borehole stabilization problem are mechanical and
can best be dealt with by mechanical means. 1 Some as-
pects of borehole stabilization problems are primarily
chemical, however, and may be alleviated by proper atten-
tion to the chemical factors involved. It should be clear if
any feasible chemical means can be employed to make
drilling more efficient, or to facilitate coping with the
mechanical problems of well drilling, full advantage should
be taken of such chemical means. By so doing, it is pos-
sible to continue to increase the efficiency and minimize
the cost of oil well drilling.
The subject matter of this paper is concerned with
the relationship of the colloid chemistry of clays to dril-
ling fluid design when water is the continuous phase. It
is also concerned with the promotion of more efficient
drilling techniques by utilization of principles derived
from increased knowledge of the colloid chemistry of
clays.
The data given in this paper emphasize certain as-
pects of clay chemistry pertinent to drilling technology
that are not dealt with or are inadequately dealt with in
earlier literature. The subject matter of this paper is spe-
cific and deliberately limited in scope. It does not purport
to be a comprehensive treatment of drilling technology
and clay science.
References and illustrations at end of paper.
with r~spect to drilling fluids is of value at the present
and will continue to be so in the future, although some re-
cent trade literature implies that oil phase drilling fluids
solve all our drilling problems.
It should be noted that oil phase drilling fluids are
not new to drilling technology. Oil muds began to be used
in the middle 1930's even before the use of starch in wa-
ter base muds. The non-swelling of Wyoming bentonite in
oil makes anyone concerned with drilling technology con-
sider the use of oil as a drilling fluid.
It was soon found, however, that the mere presence
of a continuous oil phase did not necessarily eliminate
all borehole problems. Farrand and Clark 2 reported in
1944 that some shales were found to slough in the pres-
ence of oil base fluids. Recent experience indicates that
borehole problems continue even into the present with the
newest oil phase fluids.
The foregoing comment is not to be construed as an
argument that water base muds are better than oil base
muds for drilling and, therefore, has to be supported in
this paper by rigorous experimental evidence. The point
of digression is this: the use of oil as a continuous phase
in a drilling fluid is not new to drilling technology. The
use of oil does not automatically eliminate downhole
problems, but it is automatically more expensive than
water.
Irregardless of interest in oil phase drilling fluids
the fact remains, however, that water base fluids can be
further improved. Research effort should, therefore, be
2 CLAY CHEMISTRY AND DRILLING FLUIDS
continued to accomplish this because the basic economic
factors resulting from such improvements would benefit
the industry.
Improvements have been made in water base drilling
fluids during the past few years. It is generally conceded
that we now have drilling fluids significantly improved
over any mud type discussed by Rogers 3 in the 1953 edi-
tion of his book. In fact, a new mud system concept was
introduced to drilling technology as a practical opera-
tional technique in 1960. 4 This system has since become
generically designated as "lignosulfonate mud".
The techniques introduced in 1960 have proved of
considerable economic benefit to drilling production.
Stock and CookS have discussed the practical impact of
these new techniques upon California drilling operations.
Significant improvement of caliper logs over other mud
systems, including calcium sulfate muds, was noted by
these authors. In one particular well in the Los Angeles
Basin, the caliper log was better than any previous log
ever run in this field. In addition, production from this
well was higher than anticipated. Essentially gauge
holes have been drilled with lignosulfonate muds in
many areas where normally troublesome shales were en-
countered.
By paying attention to the principles of clay chemis-
try and utilizing drilling mud conditioning agents designed
to function in harmony with these principles, muds rou-
tinely cared for have performed exactly as desired in
wells in which temperatures exceeded 400 o F. For exam-
ple, the Chapman No. 1 Well in Waller County, Texas was
drilled to 20,800' and the bottom. hole temperatures
reached 450 0 F or more. 6 No gelation problems were en-
countered in this mud which contained a normal load of
clay solids. In drilling this hole only $112,000 was spent
on the mud to drill to T.D. and only 158 days elapsed be-
tween spud-in and reaching total depth of 20,800'. During
this run, a total of 3,127' of core was cut between 17,189'
and 20,800' with five diamond bits. All coring below
18,414' was done with 21 runs of 100' core barrel. Rig
time costs were reduced because not one hour was spent
conditioning mud during the entire operation.
Samples, obtained from this well, of mud that had
circulated for days at bottom h~le temperatures in excess
of 400 0 F gave essentially Newtonian flow curves at
150 of when tested with a recording Fann Viscometer.
The faster than usual penetration rate is interesting
because low filtration rates were maintained throughout
the drilling. It may be noted by referring to Table 1 that
at 18,500' the API filtrate was 1.8 ml. Furthermore, the
350 0 F high temperature, high pressure filtrate was 9.0 ml.
At 19,500' the API filtrate was 2.3; at 20,800' the API
filtrate was 1.4 ml. It does appear, therefore, that a prop-
erly maintained lignosulfonate mud can achieve excellent
penetration rate performance.
SPE 540
The results obtained with the lignosulfonate mud sys-
tems require that accepted advantages of other mud sys-
tems be re-evaluated. It is improper to place these ligno-
sulfonate muds in the same category as the older "fresh
water muds"or"sodium muds" for the purpose of predicting
their performance characteristics. These so-called "ligno-
sulfonate muds" first introduced in 1960 7 are not to be
advocated or regarded as the ultimate drilling fluid. It is
important, however, that the principles of clay chemistry
upon which they are based be carefully considered. It is
most probable that if further study and research is given
to the subject of clay chemistry, further improvement in
the technology and economics of drilling production will
result. On the basis of the evidence thus far amassed
concerning the field performance of lignosulfonate muds,
it appears that another milestone in drilling technology
has been passed. It is important to remember that the suc-
cess of these muds does not depend upon some magic
quality of the organic agents used to condition them, but
rather upon engineering and well-designed mud programs
that give full regard to the principles of formation clay
chemistry. These principles are vitally important as evi-
denced by the fact that if they are ignored, hole condi-
tions deteriorate and chemical costs go up. It is obvious
that the quality and performance characteristics of the
particular lignosulfonates used to condition these muds
will affect performance and cost characteristics. Even
the best of the lignosulfonates, however, will not com-
pensate for ignoring the facts of formation clay chemis·
try or the ,mechanical aspects of drilling a well.
Because of the technological impact of the "ligno-
sulfonate muds" upon drilling production, it is
appropriate that the principles of clay chemistry upon
which these muds are based be discussed.
1'0 place the clay chemistry of the lignosulfonate
muds in perspective, however, it may be well to first re-
view briefly some of the salient points of the concepts of
clay chemistry upon which sodium muds and calcium muds
were based.
CLAY CHEMISTRY OF SODIUM MUDS
We may define "sodium muds" as those muds that
have their properties adjusted by treatment with phos-
phates, sodium tannatE~s, gallates, or lignites.
The sodium mud concept may be regarded as repre-
senting the thinking of mud technologists between 1922
and 1947 with an anachronistic penetration into the
present.
It is characteristic of the sodium mud era that most
of the thinking revolved around the properties of bento-
nite. Drilling mud additives were evaluated in terms of
their ability to reduce the viscosity of hydrated bento-
nite suspensions. This thinking was carried into the API
SPE 540 W. C. Browning and A. C. Perricone
"Suggested Procedures for Laboratory Evaluation of Dril-
ling Mud Materials". There, in Appendix A of API RP 29,
Section A-39, it is recommended that thinners be evalua-
ted in hydrated bentonite suspensions or in mixtures of
bentonites and sub-bentonites with or without contamina-
tion by salt and/or gypsum.
In the May, 1957 edition of API RP 29, no mention is
made that it might be desirable to limit pH values to a
maximum of 9.5 whenever possible. Instead, it is suggest-
ed that caustic be added in whatever concentration is
needed to obtain the pH nece ssary to develop the maximum
thinning efficiency of the organic agent being tested as a
thinner.
In all of Appendix A of RP 29 there is no indication
that organic agents, such as the lignosulfonates, may be
utilized to minimize incorporation of formation clays into
drilling muds. Lignosulfonates, as well as plant tannins
and lignites, are defined explicitly as "materials that re-
duce viscosity and gel strength of muds by means other
than dilution or precipitation."
With respect to morphology, clay particles of the so-
dium mud era were conventionally depicted as neat little
hexagon platelets. Reed 8 pointed out in 1938 that gelation
of bentonites could be explained by the essentially me-
chanical theory of Lewis, Squires, and Thompson. 9 This
theory focused attention upon the plate-like shape of the
par ticles and assumed a mechanical network being formed
as a result of the clay particles' edge on collision. This
network finally resulted in the immobilization of the clay'
particles and formation of a gel structure - the familiar
"house-of-cards" arrangement.
Broughton and Hand, 1 0 in 1938, reported studies con-
cerning the flow properties of clay suspensions. These
authors felt that the particle interference theory advoca-
ted by Lewis, S quires, and Thompson gave the best ac-
count of observed properties, although they noted some
difficulties in correlating the difference between large and
small particles. Hydration of clay as a factor significantly
affecting the flow properties of suspensions is discounted
by these authors. Reed also considered it unlikely that
hydration was responsible for the high viscosity values
of bentonite suspensions.
Rogers 11 reflects the thinking of this period when he
pointed out that with clays of the kaoli~ type there are no
replaceable cations, no planar charges from ionization,
and no hydration properties. Broken-edge unsatisfied va-
lencies are regarded to be present, however, and these
forces act to cement particles together either by extending
the lattice structure or by edge-wise cementation. Thus,
for non-bentonitic clays the contribution to high viscosity
and gel strength is made only by virtue of unsatisfied
edge valencies.
One of the better presentations of clay chemistry made
3.
in the sodium mud era was by A. B. Garrison in 1938. 12
Garrison drew freely from previous workers in the field of
clay chemistry for his theoretical background. The previ-
ous workers that particularly influenced his point of view
include, among others, Bradfield, 13 Pauling, 14 Jenny and
Reitemeier, 15 and Kelly, Jenny, and Brown. 16
Garrison, in this 1938 paper, made some very perspi-
cacious observations which, if pursued diligently by other
workers at that time, should have greatly increased the
pace of the development of mud technology. He noted, for
example, that marine shale, when exposed to fresh water,
deflocculated easily and caused drilling difficulties
particularly at high pH. Unfortunately, he attributed this
difficulty entirely to the conversion of calcium formation
clays to the sodium form.
Garrison 1 7 also noted that sodium hydroxide acted
to increase the gelling rate of sodium bentonite, but he
believed that this resulted from the formation of a sodium
clay which thereby facilitated the cleavage of stacked
polar clay crystallites creating more surface area.
Although Garrison noted time and again in this and
in succeeding papers that there was something critical
occurring at pH values greater than 9.0, he never did con-
sider this as a special hydroxyl effect, but only as a point
at which conversion of calcium clays to sodium clays was
accelerated.
Garrison and ten Brink, 18 in studying some phases of
chemical control in clay suspensions, conducted experi-
ments showing that barium clay is less hydrated than
sodium clay. This was explained on the basis that the
barium ion was less hydrated than the sodium ion. The
morphology of clay dispersion as conceived by Garrison
and co-workers persists to the present day and is repeated
in essence in the 11th edition of Principles of Drilling
Mud Control published in 1962.
The rheological effects of bentonite suspensions in
water are explained by these workers on the basis that
the bentonite particles are very small and each individual
particle is surrounded by a layer of sorbed water. The
thickness of this sorbed layer is dependent upon the de-
gree of hydration of the base exchange ion present on the
bentonite.
Norton 1 9 discussed the deflocculation of clay sus-
pensions or thinning of muds in the sodium mud era as
being a chi eve d by the for mat ion of a double-layer
electrical charge effect about the individual clay particles.
Deflocculation could be achieved by treating clay sus-
pensions with phosphate or tannates which would create
a double-layer charge or satisfy broken valence bonds.
Divalent ions such as calcium were supposed to bind clay
particles together, hence, clays could be deflocculated by
sequestering calcium ions. The mud chemistry of this
period was greatly concerned with various means to treat-
4. CLAY CHEMISTRY AND DRILLING FLUIDS
out contamination incurred by drilling through anhydrite
stringers or cement.
CLAY CHEMISTRY OF CALCIUM TREATED MUDS
By the clay chemistry concepts presented by Garrison
and ten Brink, 2 0 the "hydration" of bentonite would be
decreased if the bentonite were converted from a sodium
clay to a calcium clay by a base exchange reaction. If
this were done, the viscosity of the clay suspension or
drilling mud would be reduced because of the reduction
in total hydrodynamic volume. Garrison emphasized that
increased colloidal dispersion increased the effective
volume of the suspended solids by virtue of the fact that
the increase in surface area of the clay caused an enor-
mous inc rea s e in bound or sorbed water due to the
hydration of the clay particles. He then showed that this
hydration could be reduced by satisfying the base ex-
change capacity of the bentonite with barium which he
regarded as being less hydrated than sodium. He pointed
out, however, that alkaline earth hydroxides caused floc-
culation of the clay par tic I e s, and there by acted to
increase the structural viscosity of the suspension.
It was disclosed by Barnes 21 in 1947 that a calcium
lignosulfonate, prepared in a certain way to obtain a
specific molecular weight range, was very effective in
preventing the flocculating effect of alkaline earth hy-
droxides upon clays. Barnes, therefore, found it possible
to control the viscosity and gel values of a drilling mud
by, "treating the mud with a calcium lignosulfonate and
also treating it with an alkaline earth metal compound to
convert the clay present in the mud from the usual sodium
form into an alkaline earth metal clay, such as calcium
clay, by base exchange reactions."
Determination of actual lattice spacing of calcium
and sodium bentonites by x-ray techniques in the 1940's
began to confuse Garrison's "hydration" picture. The
sodium ion was found to be less hydrated than the calcium
ion. Lattice spacings of sodium bentonites in a moisture
vapor atmosphere gave a single water layer resulting in
an (001) spacing of 12.4 A and an asymmetry value of 1.
Calcium bentonite, on the other hand, was found to give o
a "double water layer" and an (001) spacing of 15.4 A
with an asymmetry of 1.
This evidence of greater h y d rat ion of calcium
bentonite concerned Battle and Chaney, 22 who pointed
out that although hydration and swelling had long been
used synonymously, each property probably should be re-
garded separately. These authors leaned to the concept
of Grim regarding swelling mechanism of clays. Grim 23
states: "It is a well-known fact that sodium montmoril-
lonite expands greatly in the presence of abundant water;
whereas, under similar conditions calcium montmorillonite
SPE 540
expands very little. According to this concept the great
swelling of the sodium montmorillonite is due not to the
hydration of the sodium ion serving as a wedge to force
the layers apart, but to the absence of a strong bridge
because 0 f the univalent character of the sodium ion; and
perhaps also because of its small size enabling it to fit
well in the hole of a silicate sheet. The calcium montmo-
rillonite does not expand greatly, not because of the
slight hydration of the calcium ion, but because the di-
valent ion holds the layers together so that a thick series
of water sheets cannot form between them."
Unfortunately, this concept begins to get a little com-
plicated when it is also considered that sodium bentonites
do not swell greatly in sat u rat e d sod i u m chloride
solutions.
Lime muds enjoyed great popularity for a period of
time by providing a mud resistant to electrolyte contami-
nation and more resistant to temperature than had previ-
ously been available. With deeper drilling, however,
temperatures in excess of 250 0 F became more common
and high temperature stability problems began to be en-
countered with the lime muds. It was realized that expo-
sure to high temperatures of clay suspensions treated
with high concentrations of sodium hydroxide would
result in the formation of aluminates and amorphous
silica. It was also realized that silica and lime would
react to form tri-calcium silicates and other cementatious
materials. This reaction is the basis of the old "Silica-
Lime" brick industry. To attempt to combat this chain of
events, muds were proposed that contained less and less
lime, less and less caustic, and less and less organic
thinner until eventually such muds became quite sensitive
and difficult to maintain in the field.
This s tat e of a ff air s was sum mar i zed by
T. E. Watkins 24 as follows: "A base exchange process
may be utilized to inhibit excessive mud-making by
bentonitic shales; however, the mud should preferably
not contain undissolved lime or appreciable concentrations
of electrolyte. Alkalinity should be kept as low as possi-
ble in order to maintain high resistivity and minimize
hazards from bodily contact. A maximum pH value of 12.0
should usually satisfy these latter requirements."
Calcium sulfate to supply.calcium ions has long been
used in the Mid-Continent. Gyp-ferrochrome lignosulfonate
muds made their debut in 1956 and became popular in the
weighted "hot-hole" conditions of Gulf Coast drilling.
The calcium sulfate muds apparently removed the fear of
high temperature solidification that many people associa-
ted with lime muds. Clay chemistry concepts of the gyp
muds were, however, still identical with those of the
earlier lime muds. The use of calcium sulfate to supply
calCium to control the swelling of bentonite was advocated
by ;youngblood 25 in 1960 and by Simpson 26 in 1961.
SPE 540 w. C. Browning and A. C. Perricone
It was recognized by Monaghan and Gidley 2 7 that
base exchange and swelling reactions were different and
to control adequately the swelling of bentonite, concen-
trations of calcium ions in the order of several thousand
ppm were necessary; far more than the 300 ppm of calcium
ions that are sufficient to secure clay base exchange
reactions in the lime muds. These authors stated that the
"use of a mud in which bentonite clays do not swell
should result in other benefits in addition to reduction of
formation damage. Mud viscosity build-up caused by dis-
persion of drilled cuttings should be reduced and borehole
enlargement should be decreased." To achieve these
benefits, a concentration of 3,000 to 4,000 ppm of soluble
calcium is required. This level of calcium ions may be
supplied by adding calcium chloride to the mud.
These high calcium muds did not become very popular
due to difficulties encountered during logging, difficulties
in controlling filtration rate, and the fact that in some in-
stances, sloughing shales ~re still encountered.
The problems resulting with calcium muds, including
those encountered with the high calcium systems, indica-
ted to the authors of this paper that perhaps an approach
to the controlling of shale reactions other than that first
proposed by Garrison might possibly have merit and gave
impetus to studies that resulted in the concept of
lignosulfonate muds.
The clay chemistry upon which the lignosulfonate
muds are based differs in several subtle aspects from the
views held for over a decade by mud technologists. These
differences are best understood by relating them to the
colloid chemistry of lignosulfonate muds.
COLLOID CHEMISTRY OF LIGNOSULFONATE MUDS
The thesis of lignosulfonate mud research could well
have been taken from a statement by Garrison: 28 "What-
ever the nature of the formations being drilled, a know-
ledge of the colloid chemistry of the clays and shales
involvea will make it possible to adopt an intelligent and
consistent policy of prevention rather than cure. Such a
policy will consider the entire drilling program and will
make i n v est men t s in chemical control that will pay
dividends in reduced maintenance costs, lessened delays
and fewer difficulties."
The distinguishing characteristic of lignosulfonate
muds is that they are designed to provide a liquid phase
that has minimum reaction with formation clays. This mud
concept is distinguished from the calcium-treated muds
which were designed to promote reaction with formation
clays, or "sodium muds" that sought to "treat out" cal-
cium. Clay chemistry, when discussed in connection with
drilling fluids, commonly revolves around the flow proper-
ties of clay suspensions. Discussions relative to drilling
muds have been concerned primarily with problems related
5.
to controlling viscosity and gel values and improving fil-
tration rate control. Lignosulfonate muds differ from most
previous mud systems in that they did not originate as a
treatment for thinning a bentonite suspension, or for that
matter, any other clay suspension. They were designed as
·a drilling fluid system that would act to maintain the
status quo of formations being drilled. Within the frame-
work of this non-reactive or inert liquid environment, the
lignosulfonate mud was designed to provide flow property
control, filtration rate control, high temperature stability,
and all of the other desirable attributes of a circulating
drilling fluid.
Because the expanding lattice minerals, if pr~sent
in the formations being drilled, can be exceedingly
troublesome, it is well to consider the nature of bentonite
swelling, and its relation to the properties of lignosulfo-
nate muds.
Swelling of Bentonite
The expanding lattice minerals, of which bentonite
is a member, have the distinguishing characteristic of
expanding or swelling greatly when they are placed in
water as dry powders. It is this quality of swelling that
gives the expanding lattice minerals their unique col-
loidal properties. It should be remembered that all natural
clays are hydrophilic and hydrate or sorb water when in
aqueous suspensions. Kaolins, illites, and the like,. all
adsorb water on their surfaces, contrary to the ideas of
early workers in the field of drilling mud chemistry.
Bentonites not only adsorb water on their surfaces in
some sort of structure, but are also capable of expanding
or swelling by retaining the water in a fixed manner be-
tween the silicate layers - a sort of triple or multi-layer
"sandwich". It is important from the colloidal point of
view that in most industrial suspensions and in most dril-
ling muds, the swollen bentonite sandwich remains as a
colloidal unit. Only in near infinite dilution in a well-
deflocculated suspension do the in d i v i d u a I silicate
platelets tend to separate distinctly from one another in
the manner suggested by Garrison,29 or by Gill and
Carnicam. 3 0 Norrish 31 has shown by x-ray diffraction
techniques that hydrated bentonite in water suspensions
remains in packets rather than dispersing to individual
platelets. Recently Van Olphen 3 2 has discussed work of
his own and work of Norrish's regarding bentonite packet
formation due to long range equilibrium spacings between
unit layers in swollen flakes of expanding montmorillonite
clay in water and in salt solutions.
It is frequently overlooked that the rheological prop-
erties of ben ton it e suspensions are very. complex
because they are related to the ability of bentonite to
exist as particles composed of assemblages of stacked
platelets in various states of expansion, as well as
6. CLAY CHEMISTRY AND DRILLING FLUIDS
simultaneously in various states of flocculation or de floc-
culation.
This complexity is apparently not considered, for
example, in the API bentonite yield tests, nor is it dis-
cussed in the 1962 11th edition of Principles of Drilling
Mud Control. This important and complex relationship is
not discussed in RP 29 of May, 1957.
The chemistry related to the flow properties of
suspensions has previously been discussed, 33 but it
should be remembered that the addition of calcium ions
never thins a suspension of clays of the non-expanding
lattice type. Such clay suspensions, however, may be
treated with deflocculants to give essentially Newtonian
flow characteristics. Suspensions composed of non-
expanding or non-swelling particles may, therefore, be
examined rheologically to ascertain their state of defloc-
culation, as illustrated in Figures 1 and 2.
However, with suspensions composed of a dispersed
phase that is capable of swelling or de-swelling, the
rheological properties do not accurately indicate their
state of deflocculation. This is shown in Figure 3 where
a bentonite suspension deflocculated with phosphates has
a considerably higher viscosity than has a suspension
treated with calcium ion to convert the bentonite packets
into an unexpanded but highly flocculated state.
The difficulty of evaluating the colloidal properties
of bentonites by examining their flow properties is shown
in Figures 4 and 5. In Figure 4 are curves obtained from
a recording viscometer of the flow properties of bentonites
prepared according to API procedures to determine yield.
In Figure 4 it appears that three quite different bentonites
are being evaluated - one having an API yield of 92, an-
other a yield of 86, and a third with an API yield of 64. If
these same suspensions treated with an optimum ainount
of deflocculant such as a complex phosphate are ex-
amined, it is found that the two bentonites showing 92
and 86 API yield have essentially the same flow curve,
one having a calculated plastic viscosity of 11, the other
having a plastic viscosity of 10. The third, a low yield
Texas bentonite, has a plastic viscosity of 7. These data
indicate that the actual rheological volumes or degree of
hydration or swelling of the two Wyoming bentonites are
actually almost identical, as shown in Figure 5. The
Texas bentonite shows a rate of shear curve indicative
of a low hydrodynamic volume.
Although the true lignosulfonate muds were not de-
signed to shrink swollen bentonite structures, but rather
to maintain the status quo of borehole formation clays, it
is well to consider what is involved in the mechanism of
bentonite swelling. It is not enough to state, as has been
done: "Swelling is due to the penetration of water along
the silicate surfaces of the mineral, thereby increasing
the cleavage spacing bet wee n adjacent sheets of
bentonite. "
SPE 540
The volume increase or swelling of bentonite in
water is best explained by regarding the clay as a col-
loidal electrolyte.
This concept of bentonite swelling developed by
Foster 34 and others considers the crystallite of bentonite
composed of two silica layers bonded together by an
aluminum layer as an inorganic polyelectrolyte anion. The
sheet-like three layer crystallites of the bentonite mineral
are bound together in stacked arrangement by Van der
Waals-like forces. When dry, such bentonite packets will
have their three layer crystallite sheets separated by only
the diameters of the base exchange ions on the planar
surfaces. In moisture vapor atmospheres these interplanar
• 0
spacings will amount to about 12.4 A for sodium bentonite
o
and 15.4 A for bentonites that have their base exchange
capacity saturated with calcium.
Upon contacting such a packet of bentonite with
liquid water, the water will penetrate between the crystal-
lites by a capillary process induced by hydrogen bonding
between the silica surface and the water. When sufficient
water penetrates between the crystallites the base ex-
change cations will begin to electrolytically dissociate
from the silica surface. The degree of dissociation is
characteristic of the cation - high for sodium, low for
calcium. The like-charges of the dissociating cations
exert a repulsive force between each other and, con-
sequently, between the silica surfaces of the adjacent
crystallites. As this repulsive force is exerted, more
water will enter between the crystallites permitting the
dissociating cations to 0 b t a in their e qui lib r i u m
dissociation.
For sodium bentonite in 7 per cent suspension, this
interlayer spacing could be approximately 300 A. If the
base exchange cations are calcium, however, they will
not freely dis soc i ate from the silica surface of the
bentonite crystallites; consequently, they will exert little
repulsive force between the bentonite particles, and very
little swelling will occur.
The voluminosity, or degree of swelling of bentonite
packets in water solution can, therefore, be controlled
by two means: (1) add sufficient cations in the surrounding
water phase to repress the dissociation of the base ex-
change cation from the silica surface; (2) effect a base
exchange reaction to convert all of the base exchange
cations of the bentonite to calcium, barium, iron,
chromium, etc., if a low degree of dissociation or swelling
is desired, or convert the bentonite to a sodium form if a
high degree of swelling is desired.
Base Exchange
Careful experiments made with a highly purified and
dialyzed lignosulfonate have failed to show by x-ray
techniques any penetration of the lignosulfonate into. the
SPE 540 W. C. Browning and A. C. Perricone
bentonite packet occurring in bentonite suspensions con-
taining the equivalent of 3.0 ppb of lignosulfonate
concentrations. On the other hand, infra-red absorption
t~chniques have shown that the lignosulfonates are highly
adsorbed upon the basal planes of the clay minerals.
As previously stated, lignosulfonate muds differ
from the calcium muds ill that the base exchange mechan-
ism is not deliberately used to control swelling as in the
case with calcium treated muds. Since formations being
drilled are most always in a hydrated condition and
montmorillonite clays, if present, are in a state of partial
expansion, lignosulfonate mud experience has shown that
the greatest over-all good is accomplished if base ex-
change reactions are avoided. This is not to be interpre-
ted as meaning that effort is expended in trying to "treat
out" sodium or calcium ions; it simply means that
soluble sodium or calcium salts are not deliberately
added in large amounts to the mud as part of the chemi-
cal treatment program. It should be noted that lignosulfo-
nates are highly dissociating polyelectrolytes, and in
sufficient solution strength will achieve the same
inhibiting effects on bentonites as will strong solutions
of sodium chloride or any other highly dissociating
electrolyte.
The mechanism of lignosulfonate action upon a clay
packet is shown in Figure 6. The multi-layer adsorption
of the lignosulfonate polyelectrolyte about a clay packet
surrounds this packet with a swarm of cations dissociated
from the sulfonic groups of the adsorbed lignosulfonates.
These cations may repress the swelling of bentonite by
limiting the dissociation of the base exchange cations
of the expanding lattice minerals. The degree of swelling
inhibition by lignosulfonates by this mechanism will
depend upon the particular structural characteristics of
the lignosulfonate in question as well as the dissociation
characteristics of the clay colloidal electrolyte. In addi-
tion, the adsorbed lignosulfonate in higher concentration
does definitely have a clogging and blocking effect that
tends to minimize base exchange reaction, thus acting to
keep formation clay in a status quo condition.
This effect may be shown by referring to Figures 7
and 8. In Figure 7 the effects of electrolyte treatment of
the flow properties of a 7 per cent Wyoming bentonite
suspension are shown. Treatment of the bentonite sus-
pension with phosphate lowers the value of the stress-
strain intercept or rheological yield because of defloccu-
lation. This suspension has a lower resistance to shear
at 600 rpm than does the sample with no phosphate
treatment. In Figure 7 the flow curve of the no-treatment
sample shows some slight degree of inherent flocculation
whereas the phosphate-treated sam pie ish i g hi y
deflocculated.
If, on the other hand, another sample of the bentonite
is treated with calcium sulfate and hot-rolled for a suffi-
7.
cient time to permit base exchange reactions to occur,
microscopic examination will show the bentonite to be in
a highly flocculated state. Nevertheless, the lessened
expansion of the calcium bentonite packet lowers the
hydrodynamic volume of this suspension so that its
resistance to shear is very much lower than a well-
deflocculated phosphate treated suspension containing
expanded packets. The fact that the gyp-treated suspen-
sion is flocculated is indicated by its relatively higher
yield value. With a slight lowering in actual solids,
however, the Fann instrument would give a flow curve
of so low a slope that it would appear by commonly
accepted rheological criteria to be highly deflocculated,
i.e., the sample exhibits no appreciable yield point.
Obviously, apparent viscosities or apparent thinning of
bentonite suspensions must be treated with caution in
interpreting the results as being due to flocculation or
deflocculation when evaluating thinners.
An interesting series of experiments is illustrated
in Figure 8. Here it is shown that a bentonite suspension
treated with a chrome modified sodium ammonium ligno-
sulfonate and calcium sulfate causes some lowering of
viscosity and a decided lowering of rheological yield
value over the untreated sample. On the other hand, the
flow curve obtained with treatment by the lignosulfonate
alone practically coincides with the calcium sulfate-
lignosulfonate curve indicating that no appreciable
decrease in packet volume occurred due to the gyp. If,
however, a sample is prepared by adding calcium sulfate,
hot-rolling for approximately half an hour, then treating
with a lignosulfonate, it is found that the resistance to
shear is substantially decreased. This is interpreted as
being due to the fact that the prior treatment of the cal-
cium sulfate causes some base exchange reaction to
occur with a consequent decrease in the hydrodynamic
volume before the lignosulfonate addition arrests the base
exchange reaction. If a sample is prepared by treating
with calcium sulfate, hot-rol~ed overnight to maximize
the conversion of the sodium bentonite to calcium bento-
nite and then by treating the sample with a chrome
modified sodium ammonium lignosulfonate, it is found in
Figure 8 that a low-viscosity, nearly Newtonian stress-
strain flow curve results.
These tests indicate that the lignosulfonate in ques-
tion minimizes base exchange reactions involving the
conversion of a sodium clay to a calcium clay by calcium
sulfate treatment. These results also show that in usual
suspensions the base ex chan ge re act io n is not
instantaneous, for the longer period of time that the
bentonite is exposed to the calcium sulfate, the greater
is the degree of base exchange and the lower is the
hydrodynamic volume of the bentonite packets. Micro-
scopic examination of the lignosulfonate gyp treated
bentonite suspension shows the samples to be highly
8. CLAY CHEMISTRY AND DRILLING FLUIDS
deflocculated, whereas, with gyp alone, the bentonite is
in a state of flocculation. Study of the curves of Figure 8
clearly shows that considerable care must be taken when
treating bentonite suspensions with thinners if a compari-
son of thinner efficiency is being sought.
It is not by accident that the particular lignosulfo-
nate compound shown in this data has the property of
minimizing base exchange reactions. Lignosulfonate
compounds may be made that will not minimize base
exchange reaction. In fact, some lignosulfonates may be
made that will actually promote base exchange reactions.
For example, the iron of a particular ferrochrome ligno-
sulfonate has been shown to be capable of base exchang-
ing with sodium bentonite. 36
The particular sodium ammonium lignosulfonate
indicated in Figure 8 was developed after extensive field
tests in which it was found for the areas of concern that
the best operating properties and lowest cost of drilling
occurred when the lignosulfonate mud conditioner had the
ability to minimize base exchange reactions. Another
aspect of the minimization of base exchange reaction is
shown in Figure 9. In the series of experiments here
represented, bentonite suspensions were prepared, some
of which were untreated, some were treated with sodium
hydroxide, and some were treated with a chrome modified
sodium ammonium lignosulfonate.
The bentonite suspensions were filtered un d e r
conditions so that all would have the same cake thick-
ness and solids content. After completion of the filtra-
tion, the excess suspension was carefully decanted from
the filter cake and then the filtration cells filled with the
solution to be evaluated, i.e., distilled water, calcium
chloride solution, or sodium chloride solutions. The cells
were reassembled and filtration continued at 100 pounds
pressure. The volume of filtrate obtained was plotted
against time in minutes. Examination of Figure 9 reveals
that sodium bentonite filter cakes contacted with calcium
chloride show a steadily increasing rate of filtration as
base exchange reactions occur converting the sodil!m
bentonite to calcium bentonite. Sodium chloride in con-
trast has a much slower rate of change effect but after a
time its rate too begins to accelerate, corresponding with
the shrinkage of the expanded bentonite packets in con-
tact with an inhibiting concentration of sodium ions.
Pre-treatment of the bentonite suspensions with sodium
hydroxide caused some flocculation to occur as indicated
by the change in rheology. This sample consequently
shows a higher rate of filtration to occur because of the
flocculated state of the sodium bentonite. Base exchange
reaction in this sample is retarded by the "stuffing" of
the sodium ion in the innerlayers of the packet which
tends to greatly retard base exchange reactions. A consi-
derably longer period of time is therefore required with
this sample before the filtration rate begins to increase
SPE 540
due to conversion of the sodium bentonite to c a I c i u m
bentonite.
On the other hand, the sodium bentonite suspensions
prepared with sodium ammonium lignosulfonate gave
filter cakes which, when contacted with sodium or cal-
cium chloride, resulted in filtration rates much lower than
the untreated bentonite filtering distilled water. The fact
that the rate of filtration does not increase with time
shows that under these conditions of test, the bas e
exchange of the filter cake from sodium bentonite to cal-
cium bentonite is minimized by the presence of the ligno-
sulfonate. This protection of bentonites from base ex-
change reaction by the multi-layer sorption of the ligno-
sulfonate has a remarkable effect in maintaining filter
rate control in field muds and lowering over-all drilling
costs.
There is, of course, more to the control of filtration
than flocculation or deflocculation of a clay suspension.
It may be noted that filtration control with bentonite is at
its best when the packets are expanded, thereby giving a
distribution of particles that have an ability to distort
and, hence, closely pack in a filter cake. If these bento-
nite particles are shrunk or converted to the calcium form
so that they do not expand, a particle is thereby created
with less distortibility which results in higher filtration
rates. This may be illustrated by the fact that a highly
deflocculated calcium bentonite, as evidenced by ultra-
microscopic observation, will still have a high filtration
rate.
It may be noted that the rheological evidence of
Figure 8 and the filtration behavior of Figure 9 mutually
confirm each other with respect to interpretations regard-
ing their colloidal behavior.
As previously stated, the lignosulfonate muds were
designed to minimize base exchange reactions, particu-
larly with the formation clays. This is in line with the
premise that the most stable borehole is the one that has
not been chemically altered. The shift in emphasis from
flow properties of mud to the effect of mud upon the bore-
hole formation is important. This shift in emphasis leads
to the interesting conclusion that the "best looking" mud
in the pit might not be the best mud to drill with.
Figures 8 and 9 also emphasize the fact that the
lignosulfonate muds cannot be regarded as fresh water
sodium muds because every attempt is made to minimize
treatment with compounds supplying sodium ions. Further-
more, it is regarded as critical that the lignosulfonate
muds never be in such a condition that they facilitate
base exchange reactions converting formation clays into
sodium clays by virtue of deliberate additions of exces-
sive amounts of sodium ion containing compounds.
SPE 540 w. C. Browning and A. C. Perricone
The Hydroxyl Effect
The preoccupation with base exchange reactions
. during the decade of the 1950's tended to obscure the fact
that some of the most troublesome shales to drill through
were non-bentonitic and had low base exchange capacity.
For example, the Atoka shale of Oklahoma and the St. John
shale of Alberta have no montmorillonites present and
have base exchange capacities of a p pro x i mat ely
9 meq/100 g of clay. 37
One of the distinct facets of the lignosulfonate mud
concept has been emphasis placed upon maintaining as
Iowa pH or hydroxyl concentration .as is practical in the
circulating mud system, i.e., not in excess of 9.5 pH.
This is done to minimize the effect of hydroxyl ion upon
increasing clay surface area by promoting cleavage of
clay aggregates. This maintenance of low pH is not done,
as some have alleged because the lignosulfonate used to
condition the mud does not function at the higher pH
ranges. There is only one reason why the pH of the ligno-
sulfonate muds is kept low, and that is to minimize clay
cleavage reactions. Actually, the lignosulfonates used
function more effectively as deflocculants at pH values
greater than 9.5.
The effect of hydroxyl or sodium hydroxide content
upon increasing clay surface is illustrated in Figure 10.
I
/ There it is shown that if formation clays are maintained
at 9.5 pH for days there is little increase in surface area
as indicated by the viscosity curve. As pH values in-
crease from 10.5 to 11.0 pH in the absence of defloc-
culants the resistance to shear of the system rapidly
increases with increasing time, indicating increase in
surface area of the clay suspension. Obviously, use 0 f
deflocculant is increased in systems being maintained
at higher pH values because they literally have more work
to do. Furthermore, such systems can be anticipated to
give greater hole enlargement if there is opportunity for
clay hydroxyl reactions to occur.
Stability at high temperature is also promoted by the
use of low alkalinity muds. It may be noted in Figure 11
that if we make up two clay suspensions, one at lOA pH
and the other at 7.3 pH, that after being aged for 16 hours
at 32s o F the lOA pH sample will have had its pH revert
to 7.5, whereas, the sample starting at 7.3 remains at
7.3 pH through the high temperature aging period. Ob-
viously, clay reactions occur at high t e m per a t u res
consuming available hydroxyl. It is, therefore, indicated
that the lower the hydroxyl concentration, the more stable
the clay system will be to time and temperature. It may
\
; also be noted on this figure, by the differences in re-
sistance to shear of the suspensions, that the increase
in surface area of the clay is dis tin c t I y less in the
sample that had not been adjusted to lOA pH prior to
high temperature aging.
9.
Solvation Cleavage
Not all troublesome non-bentonitic shales are mud
making. Some, like the St. John shale become mechanically
weak because of liquid penetration along bedding planes
or micro-fractures. 38 Once weakened, such shales fracture
easily, large chunks may break off into the mud stream,
and stuck pipe may result. Sealing of the exposed forma-
tion in the borehole to prevent structural weakening is,
therefore, most important in such conditions. The ability
of the lignosulfonates to form adsorption multi-layers,
thus providing a membrane that has a low diffusion rate,
acts to minimize liquid penetration into such shales.
The importance of this sealing effect (it can hardly
be called filtration control) is shown in Figure 12. Here a
crude experiment illustrates the principles previously
discussed. A non-bentonitic shale core was obtained and
kept from drying out by being placed in a plastic bag. A
section was cut from the interior of this core and formed
into small blocklets. These small blocks were then ex-
posed to different drilling fluid media. The sample in
contact with 11.0 pH water exhibited great structural
weakening occasioned by water moving by capillary
action through fracture planes. A lignosulfonate mud with
low filter rate characteristics did not penetrate the core
in the same period of time to any appreciable degree. The
penetration of any liquid phase into a formation clay is
potentially hazardous. Although the diesel oil in the time
period did not create the expansion cracks exhibited by
the sample in contact with alkaline water, it did migrate
very rapidly through the shale sample. Therefore, if any
structural planes of weakness occur in the formations
being drilled, the lubrication by the oil phase could cause
a sloughing condition as has occurred in a number of in-
stances when drilling with oil phase fluids.
The multi-layer adsorption film of the lignosulfonates
that surrounds clay particles forms a semi-permeable
membrane which acts to retard fluid in vas ion, thus
minimizing clay particle disintegration when penetrating
soft dispersible formations. Here again should be noted
the distinct difference between a properly prepared ligno-
sulfonate mud and a conventional fresh water sodium
mud; the protective multi-layer adsorption film is not
developed in the sodium muds.
The basic clay concepts embodied in the ligno-
sulfonate muds are illustrated in diagrams of Figures 13
and 14. In Figure 13, we have represented dispersion
effects upon clays of the non-expanding lattice type. This
diagram is reminiscent of the Garrison diagram represent-
ing bentonite reactions. Included in this diagram is the
illustration of the weakening of massive shale bodies by
the penetration of water along bedding planes or cleavage
planes. In Figure 14, the complex reactions of clays of
the expanding lattice type are shown. It will be noted that
10. CLAY CHEMISTRY AND DRILLING FLUIDS
the diagram of Figure 14 differs considerably from the
Garrison diagram. In these diagrams the various clay
factors discussed above are illustrated.
SUMMARY
The past and continuing study of clay formation
chemistry is enabling drilling fluids to be designed to
minimize objectionable clay reactions in the drilling of
oil and gas wells. The more recent studies have resulted
in the development of a distinct drilling mud type referred
to in a general way as "lignosulfonate muds", although
it should be carefully noted here that not all lignosul-
fonates perform in the same manner.
These lignosulfonate muds were first designed and
introduced to fulfill objectives indicated by knowledge
derived by basic studies of formation clay chemistry.
These clay studies indicated an approach in drilling mud
design that was at variance with established ideas in
drilling mud technology. This approach was based upon
premises new to drilling mud technology: (1) Lignosul-
fonates of the proper kind may be used to inhibit the
swelling of bentonite and control the swelling of bentonite
in water media as well as reducedisintegration of cuttings
and protect the borehole. (2) Lignosulfonates alone, with-
out concomitant additions of various electrolytes can
provide a drilling fluid having inertness or non-reactivity
with formation clays, as well as minimize base exchange
reactions. (3) The drilling mud should be conditioned in
a way to avoid unnecessary treatment with compounds
providing sodium or calcium ions, thereby attempting to
lessen reactions that weaken formation clays. These
concepts are diametrically opposite to the calcium mud
philosophy of promoting chemical clay reactions which
dominated drilling mud chemistry from 1948 to 1960. The
general success, however, of the techniques embodied in
the lignosulfonate muds first introduced in the spring of
1960 indicate that continued study of clay chemistry is
indeed worthwhile to the advancement of drilling mud
technology .
SPE 540
REFERENCES
1. Thomeer, J .H.M.A., and Bottema, J .A.: "Increasing
Occurrence of Abnormally High Reservoir Pressures
in Boreholes, and Drilling Problems Res u It i n g
Therefrom" , The Bull e tin of the Am eric an
Association of Petroleum Geologists, Vol. 45, No.
10, October, 1961.
2. Farrand, W.H., and Clark, W.A:: "Drilling Fluid for
the Completion of Shallow Wells", API, Pacific
Coast, Central Committee on Drilling and Production,
March 23; 1944; Petroleum Engineer (Reference Ann-
ual) 15 (10) 60 (1944).
3. Rogers, Walter F.: Composition and Properties of
Oil Well Drilling Fluids, 1953.
4. & 7. Jung, R.A.: "New Mud Organic", The Oil and
Gas Journal, Vol. 58, No. 43, pp 129-130, 132,
October 24, 1960.
5. Stock, J., and Scott, R.V.': "Use of the Complex
Metal Lignosulfonate Drilling Fluids in California",
801-38J, API, Pacific Coast, Division of Production,
May, 1962.
6. McGhee, Ed: "Shell's Deep Coring is Fast, Sure,
Cheap", The Oil and Gas Journal, Vol. 60, No. 30,
p. 1%, March 26, 1962.
8. Reed, Charles E.: "Recent Advances in Knowledge
of the Colloidal Properties of Clay Suspensions and
Gels", Transactions A/ME (1937) 871. 53.
9. Lewis, W.K., Squires, L., and Thompson, W.I.:
Transactions A/ME (1936) 118, 1.
10. Broughton, G., and Hand, R.S.: "Viscosity Charac-
teristics of Clays in Connection with Drilling Muds",
Transactions A/ME (1938) 1002, 69.
11. Rogers, Walter F.: Composition and Properties of
Oil Well Drilling Fluids, Gulf Publishing Company,
p. 282, 1953.
12., 17., & 28. Garrison, A.D.: "Surface Chemistry of
Clays and Shales", Transactions A/ME (1938) 1027,
74.
13. Bradfield: Journal of Physical Chemistry (1924) 28,
170; Soil Science (1924) 17, 411, (1927) 24, 365.
14. Pauling, L: Proc. Nat. A cad. Sci. (1930) 16, 123.
15. Jenny and Reitemeiet: Journal of Physical Chemistry
(1935) 39, 593.
16. Kelly, Jenny, and Brown:: Soil Science (1936) 41, 259.
18. & 20. Garrison, A.D., and ten Brink, K.C.: "A Study
of Some Phases of Chemical Control in Clay Suspen-
sions", Transactions A/ME (1939) 1124, 1.
19. Norton, F.H.: Journal of American Ceramic Society
(1938) 21, 33.
21. Barnes, 'W.E:: U.S. Patent No. 2,491,436.
22. Battle, Jack L. and Chaney, P.E:: "Lime Base
Muds", Dri lling and Production Practice, API, 1950,
pp 99-108.
23. Grim, Ralph E.': "Modern Concepts of Clay Material",
Journal of Geology, 50 (30) 272, April-May (1942).
24. Watkins, T.E.: Drilling and Production Practice,API
(1953) pp 7-13.
SPE 540 w. C. Brownina and A. C. Perricone 11.

25. Youngblood, James F.: "How to Get the Most from
your Gyp-Spersene Muds", Drilling, J un e 1960,
pp 52-53.
26. Simpson, Jay P., and Sanchez, H.V.: "Inhibited Dril-
ling Fluids - Evaluation and Utilization", Transac-
tions API (1961) 801-37C.
27. Monaghan, P.H., and Gidley, J.L.: "A High-Calcium
Drilling Fluid", Transactions API (1959) 926-4-L.
29. Garrison, A.D., ten Brink, K.C. and Elkin, P.B.:
"Dispersion of Clays and Shales by Fluid Motion",
Transactions AIME (1939) 1125.
30. Gill, J.A., and Camicam, W.M:: "New Calcium-
Treated Muds Slash South Louisiana Drilling Costs",
The Oil and Gas Journal (1959) 57, 28.
31. Norrish, K:: "The Swelling of Montmorillonite",
Discussions, Faraday Soc. No. 18, 120-134 (1954).
32. Van Olphen, H '. "Unit Layer Interaction in Hydrous
Montmorillonite Systems", Journal of Colloid Science
17, 660-667 (1962).
33. Browning, W.C.: Paper 557-G (1955) 30th Ann. Fall
Meeting, Petroleum Branch, AIME.
34. Foster, M.D.: Clays and Clay Minerals Nat. Acad.
Sci., National Research Council, Pub. 395, p. 205.
35. Browning, W.C. and Perricone, A.C.: Paper SPE-432,
(1962), 37th Ann. Fall Meet., Petro Branch, AIME.
36. Jessen, F.W. and Johnson, Charles A.: Paper SPE-
492 (1963) First Conference on Drilling and Rock
Mechanics, Co-sponsored by Petro Branch, AIME.
37. & 38. Perricone, A.C. and Browning, W.C.: Paper
SPE-433 (1962), 37th Annual Fall Meeting, Petroleum
Branch, AIME.

Table l-Drilling-mud properties

Viscosity
r A , Yield Gel strength, lb.
Weight, API point, lb. per 100 sq. ft.
Depth, lb. per funnel, Apparent, Plastic, per 100 r A
,
ft. gal. sec. cpo cpo sq. ft. Initial 10-min.
13,308 10.4 50 27 21 10 4 4
15,900 12.1 55 38 34 8 0 5
16,500 12.0 57 42 34 16 0 6
17,650 12.7 60 26 28 8 0 4
18,500 12.7 63 42 40 5 0 2
19,500 12.8 58 37 33 9 0 3
20,800 12.4 67 47 39 17 0 3

0/0 by vol ume Hi-temp.,

r A
, API hi-press.
Depth, Oil Solids filtrate, filtrate, *
ft. content content ml. ml.
13,308 6.0 18 3.5 5.6
15,900 5.0 21 3.0 11.6
16,500 5.5 21 2.2 7.8
17,650 5.0 25 2.3 8.6
18,500 8.0 21 1.8 9.0
19,500 10.5 22 2.3 9.6
20,800 8.0 2.4 1..4
 FLOCCULATED CLAY

z
z
~
o

RPM

FIGURE 1

DEFLOCCULATED CLAY

z
z
~
o

RPM

FIGURE 2
FLOW CURVES OF A 7% BENTONITE SUSPENSION

RPM

FIGURE 3

RHEOGRAM OF 25 ppb BENTONITE SUSPENSIONS

50

40

30
z
z
~
o
20

100 200 300 400 500 600

RPM

FIGURE 4
 RHEOGRAM OF 25ppb BENTONITE SUSPENSIONS
(DEFLOCCULATED)
50

40

30
z
z
o
li':
20

10

MODEL ILLUSTRA TING POL YMOLECULAR ADSORPTION

RPM OF LIGNOSULFONATES ON CLAY PAR TICLES

FIGURE 5

FIGURE 6

EFFECT OF COLLOIDAL STATE ON THE

FLOW PROPERTIES OF BENTONITE
75
SUSPENSION: 7"10
WYOMING BENTONITE
60

z 45
z
o
rt
30

15

100 200 300 400 500 600

RPM

FIGURE 7

EFFECT OF BASE EXCHANGE ON RHEOLOGY OF

7% BENTONITE SUSPENSIONS
200
/ ~,'? ,
••- cJ:J-{ ,-';,;o1J
z
160
~tY
"'~.
"./
",~.'
~ 120
u.
o
..-
7 ~,."
A~
"
,. """
.-:
.-:
A NaNH 4 LS03 - 6 ppb
"" GYP -5 ppb

200 300 400 500 600

RPM

FIGURE 8
 FACTORS AFFECTING FILTER CAKE EFFECT OF TIME AND pH UPON YIELD
BEHAVIOR OF BENTONITE SUSPENSIONS OF
25 200
(B) (C),/ /(A) ./(F) ~ FORMATION CLAYS II PLASTIC
'/ /. ~. (E)

" /' / .. / ...

"'1
/ 160
20
. .
"I /' / . ..<-..
:lE
,/ Q.
a:

) ,/ Y ..
0 120
/ /.'- .. fil
.

-
r-
,,%~.:/. (A) NeOH TREATED CAKE + CeCI2
/ " 10.5 pH.....-o
.. 80
z ,. / --r;' 0
z
,," "..-1-'. .
0-0-
(B) UNTREATED CAKE + CeCI2
~
/ /.~. (C) UNTREATEDCAKE+ NaCI o 0 ___ - - 0

5 I /~.. •• (D) LS03 TREATED CAKE + NaCI

I • (E) LS03 TREATED CAKE + CaCI2 C~~-- _ 9.5 pH
(F) UNTREATED CAKE + DIST. H20 L_---=-:::~=--=:::-=-'::-=-~l!=--~.1l~-=-=-=--=-=-:!I-=-::!=-=:=:!!:.::~:-:'=-.5pH
20 40 60 80 100 120 140 160 2 3 4 5 6 7 8 9 10 II 12 13 14
TlME,min. DAYS

FIGURE 9 FIGURE 10

EFFECT OF pH ON HIGH TEMPERATURE STABILITY

OF CLAY SUSPENSIONS
125

f\~~L p'I-U;.5- - - - - --
---
100 ~ \0 4 ------
S1~R1~<!2----
z .-------
~ 751----~
~
°50~7.3
F\~AL p~ 7.3 -
25
SUSPENSION: 39'-. FORMATION
SOLIDS AGED 16hrs. AT 325°F

100 200 300 400 500 600

RPM

FIGURE 11

PENETRATION OF FORMATION SHALE BY

VARIOUS LIQUIDS

SALT WATER LS0 3 MUD IlpH WATER

DIESEL OIL INVERT MUD

FIGURE 12
 MORPHOLOGY OF CLAY SUSPENSIONS
NON-EXPANDING LATTICE CLAY

(ILLITE, KAOLINITE)

FORMATION CLAY

- -
- -
-
---s=- / 7
-~---- /--....,;:;:=--:::::::-)=...::fi~7:~ 7
HYD~ATION r-,:---- ~--= 7
DRILLED CHIP HYDRATION FRACTURES

FLOCCULATED DEFLOCCULATED

• FLOC
DEFLOC
~ ~IIII
@ II@.Y
FLOCCULATED
CLEAVAGE

• DEFLOC • (J) ~
FLOC <2 j)
DEFLOCCULATED

FIGURE 13
 MORPHOLOGY OF CLAY SUSPENSIONS
EXPANDING LATTICE CLAY
(MONTMORIL LON I T ES)

I
•
DRILLED CHIP DRILLED CHIP

~ flOC @
~ O-E-Fl-O-C ~ ~~d'~
{((
~~(~
.~ ~

FIGURE 14