Investigation of Changes in the Structure
of Clays During Hydrothermal Study
of Drilling Fluids
Leroy L. Carney, SPE, Texas Tech U. and Concentrated Mud Chemicals Inc.
Necip Guven, Texas Tech U.
Abstract
The need for a drilling fluid that will exhibit its basic
requirements at temperature levels high enough to be
used for geothermal drilling has prompted studies of
various systems. I The temperature range of some of
these studies has been between ambient temperature
and 700°F (370°C). A system was developed that
exhibited the desirable properties of a good drilling
fluid system at elevated temperatures and pressures.
A fluid that exhibited these desirable properties after
being subjected to high temperature and pressure was
unusual as compared with presently used fluids.
Therefore, investigation into why these fluids were
capable of exhibiting good rheology and fluid-loss
control was conducted. It was found that certain
mineralogical components of the drilling fluid un-
dergo transformation after being subjected to high
temperatures and pressures. The conversion is
temperature dependent but also is affected by the
presence of various salts as well as the presence of
silica and calcium.
The fluids under investigation contained the
mineral sepiolite as the basic ingredient. The changes
in the sepiolite are reported in this paper.
Introduction
A drilling fluid (350 mL) containing sepiolite (15 g),
Wyoming bentonite (5 g), NaOH (0.5 g), and organic
polymers (2.5 g) was heated at 700°F (370°C) for 16
hours in a cement consistometer. In this system, after
the same hydrothermal treatment, almost all the
sepiolite was destroyed along with the carbonates and
the 12.3- A Na-montmorillonite was converted to
13.3- A montmorillonite. A new crystalline phase
was formed, constituting about 10 to 15070 of the
0197·752018010010·7896$00.25
Copyright 1980 Society of Petroleum Engineers
OCTOBER 1980
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solids in the drilling fluid. This new phase occurs as
laths elongation along the b axis, with lengths of 2 to
3 microns (2 to 3 j-tm) and widths of 0.1 to 0.7
microns (0.1 to 0.7 j-tm). The laths generally form
regular aggregates similar to cordwood. In many of
these stacks, individual laths are arranged in a
regular manner into single crystals or into
polysynthetic twins; some of them exhibit a perfect
morphology with 60° interfacial angles. The selected
area electron diffraction patterns of the new
crystalline phase displays an A-centered lattice with
the unit-cell parameters: b = 7.17 ± 0.05 A, c =
14.6 ± 0.1 A, and ex = 90° 10' ± 10'. These lattice
parameters and the morphological features of the
new crystalline phase are similar to those of
xonotlite, a hydrated cement mineral.
After these tests were completed, further studies
were conducted using sepiolite alone in water and
sepiolite with various salts added under controlled
conditions. The usefulness of sepiolite in drilling
fluids under extreme conditions of temperature,
pressure, and pH during deep-well drilling now is
recognized.
Commonly, these drilling fluids are contaminated
with salts of Na, Ca, and Mg from the formation.
Sometimes the salts or hydroxides are added pur-
posely to the drilling fluids. Therefore, it is im-
portant to evaluate the effects of these salts and
hydroxides on the sepiolite under hydrothermal
conditions.
Methodology
Evaluation is based on the formulation of 100 mL of
fluids, containing 4 g sepiolite and 1 g salt (or hy-
droxide), subjected to hydrothermal treatments in a
high-temperature, high-pressure autoclave at tem-
peratures ranging from 300 to 600°F (150 to 316°C)
385
 TABLE 1 - CONVERSION RATE OF SEPIOLITE TO SMECTITE IN VARIOUS
SYSTEMS AND UNDER DIFFERENT TEMPERATURES AND PRESSURES
(all at 24 hours)
Amounts of
Smectite
Formed
Temperature/Pressure in Reaction
Systems (OF/psi) (C/bars) (wt%)
Sepiolite/H 2O 300/475 149/33
300/10,000 149/690 5
400/500 204/35 20
500/1,000 260/69 40
600/20,000 316/1,379 80
Sepiolite/NaCI 300/475 149/33
300/10,000 149/690
400/1,000 204/69 60

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500/1,000 260/69 70
600/20,000 316/1,379 80
Sepiolite/NaOH '300/200 149/14
400/500 204/35 20
500/1,000 260/69 70
Sepiolite/CaCl 2 300/475 149/33
300/10,000 149/690
400/1,000 204/69 20
500/1,000 260/69 50
600/20,000 316/1,379 80
Sepiolite/Ca(OHb 300/200 149/14
400/500 204/35 10
500/1,000 260/69 30
Sepiolite/MgCl 2 300/475 149/33
300/10,000 149/690
400/1,000 204/69 5
500/1,000 260/69 40
600/20,000 316/1,379 60
Sepiolite/Mg(OH)2 300/200 149/14
400/500 204/35 10
400/1,000 260/69 70
'Not detectable with X-ray powder diffraction.
··Present but at a level below 5%.

for 24 hours under pressures ranging from 200 to
20,000 psi (13.79 to l379 bar). After the
hydrothermal runs, these samples were washed with
water, centrifuged, and then dialyzed to remove the
excess salts. Subsequently, oriented clay films were
prepared. These oriented slides were X-rayed after
having been air-dried at room temperature and at a
relative humidity of 40 to SOUTo. The same slides then
were saturated with ethylene glycol and X-rayed
again. On the X-ray diffraction patterns of the air-
dried slides, the 011 reflection of sepiolite (about 12
A) and the 011 reflection of smectite (12 to 15 A)
superimpose. This superposition leads to the ap-
pearance of a very strong composite reflection. Upon
glycol saturation of the sample, this composite
reflection resolves into the distinct reflections of
sepiolite and smectite.
The quantitative X-ray diffraction analysis of the
reaction products was performed by comparing the
intensity of the 17- A smectite (glycolated) reflection
with the intensity of the 12- A sepiolite reflection.
Mixtures of the sepiolite (used in these experiments)
and Cheto smectite (from Arizona) were prepared at
10% intervals. The Cheto smectite was chosen
because of its morphological similarity with me
smectite formed in these experiments. Both the
synthetic mixtures (sepiolite/Cheto smectite) and the
products of the hydrothermal runs were examined by
a Philips Norelco X-ray diffractometer. Oriented
clay films were air-dried at room temperature and
40% relative humidity. They then were saturated
with ethylene glycol for 24 hours.
The conversion rate of sepiolite to smectite in
various systems and under different temperatures
and pressures is shown in Table 1. Some examples of
the conversion as determined by X-ray diffraction
are shown in Fig. 1.2 These data were supported by
observations using an electron microscope, where the
needle-like structure of sepiolite can be seen con-
verting to the flaky particles of smectite. 2
Electron-microscope grids (coated with Formvar)
also were prepared from the sample, which was
washed and dialyzed. These grids subsequently were
coated with gold and carbon. A lEM-7 electron
microscope was operated at 80 kV. The results of
these mineralogical studies are discussed in the
following.
Reactions of Sepiolite in the Presence
of Salts and Hydroxides
Sepiolite and NaCI Systems
Hydrothermal treatment at 300°F (149°C) under
pressure of 475 psi (33 bar) does not seem to cause

386 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 12.111". 12.2s1
12.011.~

12.24"&';
149"C 149·
33 BARS 33 BARS
12.141

,12.IIA

149·C
690 BARS
12.0IA:

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316"C
1319 BARS 316·C _
1379 BARS i

12· 10· ~ •• 4· 28 12" 10· e· 6· 4· 28 12" 10" e· e· 4· 28 12· 10· e· 6· 4· 28

SEPIOLITE / WATER SEPIOLITE / NaCI SEPIOLITE / CaCl z SEPIOLITE / MgCl z

Fig. 1 - X·ray diffraction data.

any changes in sepiolite. The X-ray diffraction
pattern after this treatment displays a 12.11- A
reflection for the air-dried sample. This 12.11- A
reflection (sepiolite 011) shows a slight expansion to
12.38 A upon glycol saturation. No smectite is
formed under these conditions. When the pressure is
increased to 10,000 psi (690 bar) at 300°F (149°C), a
few (about 5070) smectite-like layers seem to develop.
This is indicated on the X-ray diffraction pattern in
the form of a broad but weak reflection at 18.4 A.
On the same pattern, the sepiolite displays its 011
reflection at 12.11 A, which expands slightly to
about 12.3 A upon glycolation. Thus, the increase in
the pressure from 475 to 10,000 psi (33 to 690 bar)
has only a small effect in promoting sepiolite-to-
smectite conversion. Sepiolite occurs in fibers or in
bundles of fibers after these hydrothermal reactions.
They do not seem to have been affected in their
morphology by the above hydrothermal conditions in
the sepiolite/NaCI system.
Major changes in sepiolite take place when the
temperature is raised to 400°F (204°C). Large
amounts of smectite (about 70%) form at this
temperature and under a pressure of 1,000 psi (69
bar). The X-ray diffraction pattern of the glycol-
saturated sample reveals a very strong 17.4- A
reflection of smectite and a 12.28-A reflection of
OCTOBER 1980
sepiolite. Before the glycolation, the 011 reflection of
smectite and the 011 reflection of sepiolite
superimpose and form a strong reflection at 14.05 A.
Similar reactions take place in the system at 500°F
(260°C) and under a pressure of 1,000 psi (69 bar) in
24 hours. Smectite makes up about 70% of the
sample after the hydrothermal reaction at 500°F
(260°C). The X-ray diffraction pattern of the sample
after glycol saturation shows a strong 17.1- A
reflection of smectite and a distinct reflection at 12.7
A (Fig. 1). Electron-microscopic examination of the
samples after 400 and 500°F (204 and 260°C)
treatments show the common sepiolite fibers and
smectite particles. These smectites display the
transition of fibrous units into flakes with an
irregular outline. In parts of these flakes the original
fibers are still visible. 2
When the temperature is raised to 600°F (316°C)
and the pressure is increased to 20,000 psi (1,379
bar), smectite makes up about 80% of the sample in
24 hours. The X-ray diffraction pattern of the glycol-
saturated samples after this treatment shows distinct
12.34- A reflection of sepiolite and 17.0- A reflection
of smectite.
Sepiolite and NaOH Systems
Reactions in the system of sepiolite and NaOH were
387
carried out at 300, 400, and 500°F (149, 204, and
260°C). At 300°F (149°C) and 200 psi (13.79 bar) no
changes were observed in sepiolite when the sample
was examined subsequently with an electron
microscope. At 4()O°F (204°C), about 20070 smectite
was formed. At 500°F (260°C) and 1,000 psi (69
bar), more smectite develops at the cost of sepiolite.
The sample after the treatment consists of about 70070
smectite. An intermediate phase (sepiolite/smectite
mixed layering) is revealed by a distinct 12.83-A
reflection for the glycol-saturated sample. This
intermediate phase is about 30070 of the sample.
Sepiolite and CaCI 2 Systems
The hydrothermal treatment at 300°F (149°C) and
475 psi (33 bar) does not cause any visible changes in
sepiolite's morphology or in its structure. The X-ray
diffraction pattern of the sample after treatment
gives 12.0-A spacing for sepiolite's 011 in the air-
dried state. This 011 spacing shows a slight expansion
to 12.28 A upon glycol saturation. When the
pressure is increased to 10,000 psi (690 bar) at 300°F
(149°C), similar results are obtained as the lower-
pressure runs; the only difference is the appearance
of small quantities (5070) of smectite. This smectite is
revealed by a broad but weak reflection at 17.0 A
upon glycolation of the sample. No discrete smectite
particle is observed, but a few of the fibrous sepiolite
aggregates show flaky transitional patches. Most of
the sepiolite maintains its fibrous morphology at this
point. At 400°F (204°C) and 1,000 psi (69 bar),
smectite develops and is about 20070 of the sample.
This smectite has a broad reflection, with a peak
position at 17.3 A for the glycolated sample. The rest
of the sample (80070) consists of sepiolite, which does
not seem to be affected by this treatment. The X-ray
pattern displays a strong 12.11- A reflection for
sepiolite in the air-dried state after this treatment.
The 12.11- A reflection of sepiolite expands slightly
to 12.24 A upon glycol saturation.
After the hydrothermal treatment at 500°F
(260°C) and 1,000 psi (69 bar) for 24 hours, the
sa,mple consists of 50070 sepiolite and 50070. smectite.
Upon glycolation, the X-ray diffraction pattern of
the sample displays two distinct reflections at 12.28
A sepiolite and 17.1 A for smectite. Before the
glycol saturation, there appears only one reflection at
12.03 A, which represents the superposition of
sepiolite's 011 and smectite's 011 reflections. Similar
results are obtained in this system when the pressure
is raised to 20,000 psi (1,379 bar) and the temperature
is kept at 500°F (260°C). This again shows that the
pressure has minor influence in converting sepiolite
to smectite in these hydrothermal systems.
When the temperature is raised to 600°F (316°C),
most of the sepiolite converts into smectite. The X-
ray pattern displays a broad reflection, with peaks at
14.4 and 13.0 A for the air-dried sample. Upon
glycol saturation, this broad reflection resolves into a
strong 16.9-A reflection of smectite and a distinct
12.81-A reflection of a mixed-layer phase between
sepiolite and smectite (Fig. 1). The smectite particles
occur in the form of irregular, flaky aggregates in
388
which the inherent fibrous texture is almost disap-
pearing. Only a little unaltered sepiolite is observed
during the electron-microscope examination.
Sepiolite and Ca(OH)2 Systems
During hydrothermal treatments at 300 and 400°F
(149 and 204°C), sepiolite undergoes reactions
similar to those of the previous system with CaCl 2 at
the same temperatures. After the treatment at 300°F
(149°C) and 200 psi (13.79 bar) for 24 hours,
sepiolite displays a strong 12.01- A reflection in the
air-dried state. This reflection expands slightly to
12.28- A upon glycolation. No smectite is developed,
but small quantities of newly formed calcite (5070) are
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observed. Appreciable amounts of smectite (about
30070) develop in this system when the temperature is
raised to 500°F (260°C). At this temperature, a
sepiolite/smectite mixed layer with a 12.77-A
reflection makes up the rest of the sample. Electron-
microscopic examination shows that sepiolite fibers
and their bundles, with no visible alteration, are
about 50070 of the sample. Other sepiolite aggregates
show alterations to a flaky phase.
Sepiolite and MgCI2 Systems
At 300°F (149°C) and 475 psi (33 bar), sepiolite does
not seem to alter to smectite in 24 hours. The X-ray
diffraction pattern of the sample after this treatment
displays the strong 12.14- A reflection of sepiolite in
the air-dried state. This reflection shifts slightly upon
glycol saturation to 12.28 A. Almost identical results
are obtained when the pressure is increased to 10,000
psi (690 bar), but the temperature is kept at 300°F
(149°C). Smectite seems to develop first at 400°F
(204°C) in this system. Appreciable quantities of
smectite (about 40070) are formed at 500°F (260°C).
The X-ray pattern of the glycol-saturated sample in
Fig. 1 displays strong reflections at 12.28 A for
sepiolite and 17.6 A for smectite. Before the glycol
saturation, these two phases form a composite
reflection at 12.04 A in the air-dried state. After the
hydrothermal treatment at 600°F (316°C) and 20,000
psi (1379 bar) for 24 hours, the sample consists of
about 60070 smectite and 40070 sepiolite. After this
treatment, the X-ray patterns of glycol-saturated
samples display strong reflections at 12.27 A for
sepiolite and 18.4 A for the smectite-like phase. The
18.4- A basal spacing is unusually large for a glycol-
saturated smectite (Fig. 1).
Sepiolite and Mg(OH)2 Systems
Reactions in this system at 300 and 400°F (149 and
204°C) are very similar to those in the previous
MgCl 2 system. Some differences are observed
between these two systems at 500°F (260°C). The
presence of Mg(OHh instead of MgCl 2 seems to be
more favorable for the formation of smectite. About
70070 smectite is observed after the hydrothermal run
at 500°F (260°C) [1,000 psi (69 bar) for 24 hours] in
the presence of Mg(OHh. The smectite, is charac-
terized by a strong reflection of 16.6- A for the
glycol-saturated sample. The rest of the sample
(about 30070) is made up of a sepiolite/smectite mixed
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 TABLE 2 - PERFORMANCE OF A SEPIOLITE SLURRY ON
THE ULTRAHIGH·TEMPERATURE, HIGH·PRESSURE THICKENING TIME TESTER
Test slurry: 24lbm/bbl (68.4 kg/m3) sepiolite in fresh water.
Time Viscosity Temperature Pressure
(minutes) (units of consistency) (OF) rC) (psi) (bar)
0 2 80 27 500 35
30 2 190 88 2,500 172
40 1 235 115 2,500 172
60 1 330 165 5,000 345
80 2 440 225 7,500 516
100 1 490 255 10,000 690
120 5 550 287 12,500 861
140 4 638 335 15,000 1,034
150 4 685 365 17,500 1,205
160 7 730 388 20,000 1,379
166 7 750 400 20,000 1,379

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188 7 750 400 20,000 1,379
200 6 750 400 20,000 1,379

layering with a 12.6-;\ interplanar spacing in the

glycol-saturated sample. Smectites occur as irregular
flaky aggregates in which the inherent fiber texture is
still visible. TABLE3 - PROPERTIES OF A SEPIOLITE SLURRY
An example of the rheology and fluid-loss BEFORE AND AFTER AGING AT 750°F(400°C)
properties as measured by a high-temperature, high- Test slurry: 24Ibm/bbl(68.4 kg/m3) sepiolite in fresh water.
pressure consistometer and high-temperature, high-
pressure fluid-loss apparatus is shown in Tables 2 Initial Aged"
through 5. Apparent viscosity, cp (mPa.s) 37.5 (37.5) 65.5 (65.5)
Tables 2 and 3 show a sepiolite in freshwater slurry 600 reading 55 131
heated to 750°F (400°C) and up to 20,000 psi (1,379 300 reading 50 89
Plastic viscosity, cp (mPa.s) 5 (5) 42 (42)
bar). The units of consistency (Table 2) show an Yield point, Ibf/100 sq ft (Pa) 45 (21.5) 47 (22.5)
initial temperature thinning and then an increase in 200 reading 49 70
viscosity at about 550°F (287°C), which holds fairly 100 reading 44 46
level through 750°F (400°C) and 20,000 psi (1,379 6 reading 30 15
3 reading 20 12
bar).
'Sample taken from the ultrahigh-temperature, high-pressure thickening tester
The Fann data (Table 3) show an increase in after being heated to 750'F (400'C)_
viscosity after heat aging, but not unreasonable for
good mud rheology. The yield point has little change.
Tables 4 and 5 show a high-temperature mud
formula and its rheology and fluid loss after being
subjected to various temperatures at 10,000 psi (690
bar).
These data show good mud rheology and fluid-loss TABLE 4 - TYPICAL ULTRAHIGH·TEMPERATURE MUD
control through high-temperature treatments. The FORMULATION USING SEPIOLITE IN CONJUNCTION
conversion of sepiolite to smectite explains the ability WITH VARIOUS FLUID·LOSS CONTROL ADDITIVES
of the system to exhibit good rheology and fluid-loss 15 Ibm/bbl (42.75 kg/m 3 ) sepiolite
control. 5 Ibm/bbl (14.25 kg/m 3 ) Wyoming bentonite
2 Ibm/bbl (5.7 kg/m 3 ) Polymer A
Conclusions 0.5 Ibm/bbl (1.4 kg/m 3 ) Polymer B
0.5 Ibm/bbl (1.4 kg/m 3 ) NaOH
In systems where sepiolite is the only clay mineral, it
is converted to stevensite (a smectite) under
hydrothermal conditions.
1. The effect of pressure is rather negligible in the
conversion of sepiolite to stevensite. This was
demonstrated by the results at 300°F (149°C) for all
the systems, and by the hydrothermal runs at 500°F
(260°C) for the sepiolite/CaCl 2 system.
2. Temperature is the major factor in sepiolite-to-
stevensite conversion. Appreciable amounts of
smectite (i.e., more than 10%) first develop at 400°F
(204 °C) within 24 hours.
3. Chlorides of sodium and calcium are more
effective than hydroxides in converting sepiolite to
smectite in the temperature range up to 500°F
OCTOBER 1980 389
 TABLE 5 - EFFECT OF STATIC AGING AT VARIOUS TEMPERATURES ON THE MUD FORMULATION IN TABLE 4
Test slurry: formulation outlined in Table 4.
Aging viscosity, cp (mPaos) 350 (175) 400 (204) 450 (235) 500 (260) 560 (295)
Aging time, hours 24 24 24 24 24
----
Plastic viscosity, cp (mPaos) 12 (12) 13 (13) 13 (13) 13 (13) 10 (10) 9 (9)
Yield point, Ibf/100 sq ft (Pa) 3 (1.4) 7 (3.4) 5 (2.4) 4 (1.9) 5 (2.4) 3 (1.4)
pH 11.8 9.5 9.3 9.2 8.6 9.2
API fluid loss, mL (cm 3 ) 8.2 (8.2) 8.5 (8.5) 8.8 (8.8) 8.7 (8.7) 8.4 (8.4) 12.7 (12.7)
High·temperature fluid·loss, mL (cm 3 )
300' F (149'C) at 500 psi (35 bar) 32 (32) 36 (36) 37.4 (37.4) 36.2 (36.2) 33.0 (33.0) 34.0 (34.0)
400' F (204 'c) at 500 psi (35 bar) 29.8 33.2
450'F (235'C) at 500 psi (35 bar) 31.6 37.4

(260°C). However, Mg(OHh promotes the con- supported by Sandia Laboratories of Albuquerque,

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version more than MgCI 2 . NaCI is the most efficient NM, under Contract No. 13-5104 and by the Center
agent in this conversion up to 500°F (260°C). for Energy Research of Texas Tech U.
4. In fresh water, sepiolite converts to smectite up
to 500°F (260°C) as easily as in the presence of References
calcium. 1. Carney, Leroy L. and Meyer, Robert L.: "A New Approach to
5. When the temperature is raised to 600°F High-Temperature Drilling Fluids," paper SPE 6025 presented
(316 ° C), most of the sepiolite converts to smectite, at the SPE 51st Annual Technical Conference and Exhibition,
regardless of whether salts are present. This again New Orleans, Oct. 3-6, 1976.
2. Carney, Leroy L. and Guven, Necip: "The Hydrothermal
shows the paramount importance of temperature in Transformation of Sepiolite to Stevensite and the Effect of
this conversion. Added Chlorides and Hydroxides," Clays and Clay Minerals,
In the systems containing additional silica and/or Clay Minerals Society (1979) 27, NO.4.
calcium, the conversion of smectite to cement
crystals was observed. These conversions can be of SI Metric Conversion Factors
paramount importance in drilling and cementing A x 1.0* E-Ol nm
wells, regardless of the primary purpose of the well. OF CF-32)/1.8 °C
Further studies should reveal how present practices
of drilling and cementing wellbores may be im- psi x 6.894 757 E - 02 == bar
proved. wt% x 1.0* E-02 kg/kg
·Conversion factor is exact.
Acknowledgments SPEJ
We express our appreciation to Texas Tech U. for
Original manuscript received in Society of Petroleum Engineers office Dec.
granting permission to publish this paper. Also 27, 1978. Paper accepted for publication April 14, 1980. Revised manuscript
gratefully acknowledged is the permission of the Clay received July 21, 1980. Paper (SPE 7896) first presented at the SPE 1979 In·
ternational Symposium on Oilfield and Geothermal Chemistry, held in Houston,
Minerals Society to reproduce Fig. 1. 2 This work was Jan. 22·24.

390 SOCIETY OF PETROLEUM ENGINEERS JOURNAL