Clay Minerals (2020), 55, 1–11

doi:10.1180/clm.2020.10

Review Article

Clay minerals in drilling fluids: functions and challenges

Jun Rui Zhang1,2,3, Meng Dan Xu1, Georgios E. Christidis4 and Chun Hui Zhou2,3*
1
Zhijiang College, Zhejiang University of Technology, Hangzhou 310014, China; 2Research Group for Advanced Materials and Sustainable Catalysis (AMSC), State Key
Laboratory Breeding Base of Green Chemistry – Synthesis Technology, Institute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of
Technology, Hangzhou 310032, China; 3Qing Yang Institute for Industrial Minerals, You Hua, Qing Yang, Chi Zhou 242804, China and 4School of Mineral Resources
Engineering, Technical University of Crete, 73100 Chania, Greece

Abstract
The addition of clay minerals in drilling fluids modifies the dispersion’s viscosity. In this article, scientific advances related to the use of
clays and clay minerals (bentonite, palygorskite, sepiolite and mixtures of clay minerals) in drilling fluids are summarized and discussed
based on their specific structure, rheological properties, applications, prevailing challenges and future directions. The rheological prop-
erties of drilling fluids are affected by the temperature, type of electrolytes, pH and concentration of clay minerals. Bentonites are smect-
ite-rich clays often used in drilling fluids, and their composition varies from deposit to deposit. Such variations significantly affect the
behaviour of bentonite-based drilling fluids. Palygorskite is suitable for use in oil-based drilling fluids, but the gelation and gel structures
of palygorskite-added drilling fluids have not received much attention. Sepiolite is often used in water-based drilling fluids as a rheo-
logical additive. Dispersions containing mixtures of clays including bentonite, kaolin, palygorskite and sepiolite are used in drilling fluids
requiring specific features such as high-density drilling fluids or those used in impermeable slurry walls. In these cases, the surface chem-
istry–microstructure–property relationships of mixed-clay dispersions need to be understood fully. The prevailing challenges and future
directions in drilling fluids research include safety, ‘green’ processes and high-temperature and high-pressure-resistant clay minerals.

Keywords: bentonite, drilling fluids, palygorskite, sepiolite

(Received 12 August 2019; revised 1 April 2020; Accepted Manuscript online: 8 April 2020; Associate Editor: Laurent Michot)

Human survival, economic activities and the exploitation and agents. The additives are usually inorganic, organic or polymer
utilization of mineral resources all depend on the supply of compounds (Ma et al., 2014).
energy. Currently, the primary energy production requirements Clay minerals are the basic constituents of the drilling fluids.
are met using hydrocarbon resources, with crude oil still domin- They can build up and maintain a suitable viscosity at low solid
ating global energy production. Because of the increase in con- levels and control the fluid loss throughout the drilling process
sumption, the demand for fossil fuels is increasing (Omole et al., 2013; Benslimane et al., 2016). For successful dril-
continuously. Drilling in unconventional reservoirs can help to ling, the selection and quantity of clay minerals are critical factors
meet the world’s energy demand. for achieving the required fluid properties (Al-Zubaidi et al.,
Drilling fluids, also known as drilling muds, are generally 2016). The clays used in drilling fluids are mainly divided into
recognized as the ‘blood’ in oil and gas well-drilling engineering two types. The first type is bentonite, which consists mainly of
and architectural engineering (Ma et al., 2014). Drilling fluids montmorillonite (Mt). Sodium-bentonite contains 70–90 wt.%
are mainly composed of a liquid phase, a solid phase and addi- sodium-Mt and it has a high swelling capacity. Potassium ions
tives (Fig. 1). The liquid phase is usually water (fresh water, are often used in these types of drilling formulations owing to
brine), oil (crude oil, diesel oil) or emulsion (mixed-oil emulsion, their roles as swelling inhibitors (Li et al., 2015; Barast et al.,
reverse-phase emulsion). Drilling fluids with water as a continu- 2017). The second type is the sepiolite/palygorskite (Pal) group
ous phase are called water-based muds (WBMs), and those with (Wang & Wang, 2016).
oil as a continuous phase are called oil-based muds (OBMs). In The properties of drilling fluids, namely the plastic viscosity,
most drilling processes, WBMs are used, owing to the simplicity apparent viscosity, yield point, mud density, fluid loss, pH and
of their preparation low cost, environmental friendliness, cutting- gel strength, have been studied extensively. Rheological character-
based removal and fast formation/breaking-down rate. Oil-based ization is of great importance for clay minerals in drilling fluids,
muds are used in specific cases, such as high-temperature deep as they are often used in a variety of changing environmental con-
wells, high-angle directional wells and horizontal wells. The ditions, such as changing pressure and temperature, and inflow
solid phase mainly includes clay minerals, cuttings and weighting through various geometrical shapes of a conduit (e.g. in pipes
and strange annuli for oil and gas wells and in rivers and hills).
Therefore, most studies focus on the rheological properties of the
*Email: clay@zjut.edu.cn
Cite this article: Zhang JR, Xu MD, Christidis GE, Zhou CH (2020). Clay minerals in
drilling fluids. The temperature, types of electrolytes, pH and con-
drilling fluids: functions and challenges. Clay Minerals 55, 1–11. https://doi.org/ centration of clay minerals are important factors influencing the
10.1180/clm.2020.10 rheological properties of the drilling fluids (Afolabi et al., 2017).
© The Mineralogical Society of Great Britain and Ireland, 2020
2 Jun Rui Zhang et al.

owing to shear thinning or pseudo-plastic behaviour. In addition,

the shear thinning will increase as n approaches 0. When n > 1,
the apparent viscosity increases as the shear rate increases; this
is caused by shear-thickening or dilatant behaviour.
The Bingham model is described by Eq. (2):

t = t0 + hD (2)

where τ is the shear stress (Pa), τ0 is the yield stress (Pa), η is the
plastic viscosity (Pa) and D is the shear rate (s–1).
The Bingham model also shows the yield stress (i.e. the
amount of shear stress required to initiate flow); the value is simi-
Fig. 1. Main components of drilling fluids.
lar to that in the Herschel–Bulkley model. It also provides the
plastic viscosity, which is the viscosity of a material after yielding
(Ko & Kang, 2015). Baravian et al. (2003) effectively assessed the
This work reviews comprehensively the factors that influence viscosity of these dispersions through the definition of an effective
the rheological properties of drilling fluids containing clay miner- volume fraction. Using such an approach, they transformed the
als. It summarizes the application and research progress on the relationship between the viscosity and volume fraction (ηr = f
clay minerals used in drilling fluids and discusses the future pro- (ϕ)) into a relationship that links the viscosity with both the
spects regarding the use of clay minerals in drilling fluids. flow and volume fraction (ηr = f(ϕ, Pe)) (Baravian et al., 2003).
Some modes have been proposed for interactions between clay
particles in drilling fluids. Van Olphen (1951, 1956) suggested the
Bentonite-based drilling fluids
formation of a three-dimensional ‘house of cards’ network,
Bentonite is a type of clay consisting predominantly of Mt. including three possible modes for associations of the Mt particles
The general structural formula of Mt in bentonite clays is in aqueous bentonite dispersions: face-to-face (F–F), edge-to-edge
(1/2Ca, Na)x(Al2–x, Mgx)(Si4O10)(OH)2nH2O (Afolabi et al., (E–E) and edge-to-face (E–F). The E–F interactions are induced
2017; Zhuang et al., 2017c). Owing to their exceptional rheological by electrostatic attractions between the opposite charges of the
properties, bentonite-based clays are usually the main solid com- edges (+) and faces (–) of the particles and should dominate
ponents of drilling fluids, and they also function as viscosifiers under acidic conditions. This has been confirmed by various
for reducing water losses (Falode et al., 2008). rheological measurements (Ramos-Tejada et al., 2001).
A good-quality bentonite for drilling fluids should contain However, it has also been clearly demonstrated that the system
mainly Mt. Nevertheless, in practice, bentonites often contain is repulsive, and that the house of cards model could not account
other clay minerals (illite and kaolinite) and non-clay minerals for the behaviour of clay gels at low ionic strength. As the gel
such as quartz and feldspars, which have an adverse effect on ben- structure could be stabilized by the repulsive forces between the
tonite quality (swelling capacity) (Abdou et al., 2013). The main interacting electrical double layers of the platelets, a completely
types of bentonite are Na-bentonite, which has a high swelling cap- different view was proposed supported by measurements of inter-
acity that contains sodium-Mt at 70–90 wt.%, and Ca-bentonite, particle forces and rheological properties (Norrish, 1954). Fractal
which will quickly generate colloids in water and is considered to or cluster associations have also been suggested as possible
be a non-swelling clay (Dill, 2016; Yan et al., 2016). mechanisms for explaining the macroscopic structure of the gel
based on various scattering (light, X-ray and neutron) and nuclear
magnetic resonance experiments (Shalkevich et al., 2007;
Rheological models
Benna-Zayani et al., 2009; Paineau et al., 2011a).
Rheological models are important tools for investigating the rheo- The first mode (F–F) results in thicker and larger particles in
logical properties of dispersions. Previous works have studied the bentonite dispersions, and the E–E and E–F associations form a
rheological behaviour (plastic viscosity, apparent viscosity, gel three-dimensional network similar to a house of cards structure
strength and yield stress) of bentonite-based drilling fluids. Two (Benna et al., 1999). Two possible mechanisms account for the
models are commonly used to explain the rheological behaviour gel formation of Mt: (1) the strong electrostatic attraction between
of a clay dispersion: the Herschel–Bulkley model and the the negatively charged faces and the positively charged edges
Bingham model. (Heller & Keren, 2001); and (2) the E–E and F–F interactions
The Herschel–Bulkley model is described in Eq. (1): via long-range electrostatic double-layer repulsion (Callaghan &
Ottewill, 1974). These associations may account for the customiz-
t = t0 + kgn (1) ing of the rheological properties of bentonite dispersions, and
they are affected significantly by the temperature, types of electro-
where τ is the shear stress (Pa), τ0 is the yield stress (Pa) and repre- lytes, pH and smectite content in the bentonite. Finally, the rheo-
sents the magnitude of the shear stress needed to initiate flow, k is logical properties of bentonite dispersions also seem to depend on
the consistency index (Pa) and represents the viscosity of a mater- the magnitude and localization of the layer charges of smectites.
ial at one reciprocal second, γ is the shear rate (s–1) and n is the Smectites with a high-layer charge and/or abundant tetrahedral
flow index and represents the degree to which a material exhibits charges (e.g. beidellites or nontronites) tend to form dispersions
non-Newtonian flow behaviour. with inferior rheological properties, as compared to their counter-
In the Herschel–Bulkley model, n < 1 indicates that the appar- parts with low-layer charges located in octahedral sites (Christidis
ent viscosity of the material decreases as the shear rate increases et al., 2006).
Clay Minerals 3

Table 1. Research on the effects of temperature on the rheological behaviour of bentonite dispersions.

Formula Temperature Main results Reference

4 mass% bentonite dispersions Up to 176°C For 4 mass% bentonite dispersions in the presence of electrolytes: (1) both Hiller (1963)
plastic viscosity and yield stress decreased with increasing temperature
(up to 176°C) at low electrolyte concentrations and increased slightly
with pressure (up to 550 bar) at low electrolyte concentrations; and
(2) increased yield stress and decreased plastic viscosity with increasing
temperature at high electrolyte concentrations
7–10 mass% water-based bentonite dispersions Up to 140°C The yield stress increased significantly with temperature while the plastic Briscoe et al.
viscosity decreased significantly at temperatures up to 140°C for 7–10 (1994)
mass% water-based bentonite dispersions
The yield stress increased with temperature because of thermally induced Rossi et al.
swelling (1999)
Water-based high-temperature drilling fluid systems 25–180°C A small decrease of apparent viscosity up to temperatures between 80°C Santoyo et al.
that were formulated from Mexican commercial and 120°C and a drastic increase at temperatures ≥125°C and up to 175°C (2001)
materials
5, 10, 15 and 20 mass% water-based bentonite 3°C and 25°C The yield stress of dispersions increased with temperature for commercial Lin et al.
dispersions kaolinite and commercial bentonite water dispersions at 3°C (close to (2016)
sea-bed temperature) and at 25°C
7 mass% water-based bentonite dispersions 25–80°C Greater temperature increased the shear stresses at low shear rates, while Vryzas et al.
the effect was much smaller at higher shear rates. A standard (2017)
methodology to complement API standards that may give very consistent
results was proposed

The role of temperature

conditions and reported that the yield stress increased with tem-
Temperature has a significant influence on the rheological behav- perature, which was caused by the thermally induced swelling.
iour of bentonite suspensions through various mechanisms Santoyo et al. (2001) evaluated the rheological behaviour of drilling
(Darley & Gray, 1980): (1) physically, as an increase in tempera- fluids of four different (mainly sodium-Mt) bentonites. A small
ture will decrease the viscosity of the liquid phase; (2) chemically, decrease in apparent viscosity was observed at temperatures up
as hydroxides such as sodium hydroxide, calcium hydroxide or to 80–120°C and a drastic increase was observed at temperatures
other additives may react with clay minerals above 90°C (although of 125–175°C (Santoyo et al., 2001).
this has little influence on the rheological properties at low alka- In drilling activities in deep-sea beds, where the ambient tem-
linity, it may be important at high alkalinity); and (3) electro- perature is significantly lower than at the sea surface (i.e. only a
chemically, as an increase in temperature will increase both the few degrees centigrade), it is necessary to study the effects of tem-
ionic activity of the electrolyte and the solubility of any partially perature on the behaviour of clay suspensions. The yield stresses
soluble salts present in the suspension. The resulting changes and dynamic moduli of commercial bentonite water suspensions
will substantially affect the degree of aggregation and/or the sus- at 3°C and 25°C were reported to increase with temperature, and
pension of the bentonite particles in the medium. Most studies on the temperature-dependent behaviour became more evident as
the rheology of bentonite suspensions have been performed at the concentration of clay increased (Lin et al., 2016).
room temperature. However, there also exists a limited number As temperature is known to adversely affect the rheology of
of studies that have investigated the effects of temperature on water-based bentonite suspensions, several additives are used to
the rheological properties of bentonite suspensions. These studies counteract these adverse effects. However, the exact mechanism
are important to the drilling industry because of the extreme con- by which higher temperatures lead to enhanced flocculation of
ditions that exist in environments such as high-temperature reser- Mt platelets is unclear. Vryzas et al. (2017) performed a system-
voirs and deep wells in which drilling fluids are used. Moreover, atic study of the rheological properties of 7 mass% bentonite sus-
they contribute to our understanding of the behaviour of drilling pensions at temperatures of 25–80°C under atmospheric pressure.
fluids that undergo temperature changes during geothermal well- As the temperature increased, the shear stresses at low shear rates
drilling operations and provide a database for improving the increased. The effect of temperature was much smaller at higher
development of numerical wellbore simulators (Table 1). shear rates, and the Herschel–Bulkley rheological model fitted
Hiller (1963) examined the rheological behaviour of 4 mass% all of the data well. A standard methodology was proposed to
Na-bentonite dispersions (using Wyoming bentonite converted complement the American Petroleum Institute (API) standards,
to Na-bentonite as a raw material) at high temperatures and and it provided consistent results (Vryzas et al., 2017).
observed that both the plastic viscosity and yield stress decreased The properties of drilling fluids that use bentonite for rheology
with increasing temperature (up to 176°C) at low electrolyte con- control and water as the fluid are greatly and adversely influenced
centrations. In addition, an increase in yield stress and a decrease by temperature, and the degree of influence should be known with
in plastic viscosity were reported with increasing temperature at accuracy. However, as several variables are involved, the rheo-
high electrolyte concentrations. Briscoe et al. (1994) observed logical behaviour of bentonite suspensions is unpredictable and
that the yield stress significantly increased with temperature, but incompletely understood at elevated temperatures. Most studies
the plastic viscosity decreased significantly at temperature up to in the past used oil as the main liquid phase, as it was more stable
140°C for 7–10 mass% water-based Na-bentonite dispersions. at high temperatures. However, in view of the emerging need for
Rossi et al. (1999) investigated the effect of temperature on the rhe- environmental protection, and because of logistics and cost con-
ology of sodium-Mt dispersions under various electrolyte siderations, the best choices for deep-drilling applications are
4 Jun Rui Zhang et al.

high-temperature-resistant WBMs. The conventional approach is Numerous studies have shown that the isoelectric point of the
to use additives to counteract the adverse effects of temperature edges of Mt-based drilling fluids is in the range of 5.0–8.0
on the rheological properties of the bentonite suspensions. The (Kelessidis et al., 2007). According to Heath & Tadros (1983), the iso-
commonly used additives are anionic polyelectrolytes, which are electric point was estimated to be at a pH value of ∼7, at which the
bound on the surfaces of bentonite particles, thereby prohibiting system exhibited a minimum yield value and the residual viscosity
the agglomeration of the clay particles and keeping the suspen- was determined (Heath & Tadros, 1983). Benna et al. (1999) studied
sions stable. Such anionic polyelectrolytes are lignosulfonate com- the effect of pH on the rheological behaviour of Na-bentonite suspen-
plexes with various types of metals, tannins, humic acids, lignites sions. The yield stress decreased at a natural pH and it reached a min-
and synthetic polymers (Zhang & Yin, 2002; Luo et al., 2018). imum in a basic medium, whereas it increased and reached a
However, the aforementioned additives have inherent shortcom- maximum when the pH decreased (Benna et al., 1999).
ings, as they can undergo thermal degradation at high tempera- Although the effects of pH on the rheological behaviour of
tures (Wan et al., 2011; Oyewole et al., 2013; Dias et al., 2015). bentonite suspensions is of prime interest and many studies
Ionic liquids (ILs) are liquid organic salts at room temperature have been conducted thereon, a complete understanding of the
composed of positive and negative ions. They are considered to be effects of pH on the particle association and macroscopic struc-
‘green chemicals’ because of their diversity, high thermal stability, ture of these suspensions is still elusive, especially for concen-
selective dissolution and other advantages. They have attracted trated suspensions. Kelessidis et al. (2007) investigated the
interest owing to their excellent properties, such as high thermal influence of pH values in the range of 7.5–10.5 for 5.00% and
stability, ‘zero’ vapour pressure and compatibility with many 6.42% aqueous Wyoming bentonite suspensions, and they
types of materials (André et al., 2009; Macfarlane et al., 2014; reported that the pH affected the type of Mt particle association.
Singh et al., 2014). Some studies have used ILs to improve the Moreover, the maximum yield stress, flow consistency index and
thermal stability of Mt-based drilling fluids, and the early studies apparent viscosity were determined at the natural pH of the sus-
mainly addressed the practical applications of IL-modified Mt pensions. The shear stress showed an increasing trend with
(Kim et al., 2006; Takahashi et al., 2012). Luo et al. (2017) thor- increasing pH values up to 9.1, and then decreased at higher
oughly investigated the influence of a water-soluble IL on the pH values (Kelessidis et al., 2007). Choo & Bai (2015) also studied
rheological and filtration properties of water-based drilling fluids the effects of solution pH on the rheological properties and long-
under various experimental conditions. The rheological behaviour term stability of bentonite suspensions (Fig. 2). The absolute value
of the water-based drilling fluids was improved at high tempera- of the ζ-potential decreased, and an initial stress value was
tures (up to 240°C) and low concentrations of IL (as low as 0.05 observed at the initial shear rate value as an amount of 1 M
mass%). Moreover, the filtration volume at high temperatures and HCl was added to the fresh suspension. However, the pH
high pressures was reduced by as much as 52%. This demon- increased and the viscosity decreased after the suspensions were
strated that the excellent rheological and filtration properties of stored for 72 h with large amounts of added acid. The shear stress
water-based drilling fluids at high temperatures are caused by increased with the addition of up to 5 mL 1 M HCl (pH 7.3) and
the high thermal stability and cation-exchange capacity of the decreased with the addition of greater amounts of 1 M HCl (Choo
ILs (Luo et al., 2017). Ofei et al. (2017) studied the effects of a & Bai, 2015). Huang et al. (2016) evaluated the effects of pH on a
1-butyl-3-methylimidazolium chloride IL (BMIM-Cl) on the mixed bentonite suspension consisting of 40.4% sodium-Mt and
rheological and filtration properties of a WBM system in the tem- 16.0% sepiolite. The gel displayed very low or no yield stress at
perature range of 25–200°C at a pressure of 1000 psi. The viscos- a pH value of 5.2 and a maximum yield stress at a pH value of
ity, solid suspension capacity and filtration behaviour of the 8.5. The ageing and/or structural recovery behaviours of the gels
drilling fluid were remarkably stabilized in the presence of were most pronounced at high pH values (Huang et al., 2016).
BMIM-Cl, even at temperatures up to 180°C (Ofei et al., 2017). In the aforementioned studies, the effects of pH on Mt particle
The inherent superior performances of ILs render them ideal association and the resulting macroscopic structure that causes
for use as additives to drilling mud. However, additional insights the rheological behaviour of these dispersions remain elusive for
regarding the detailed mechanisms thereof are necessary to better concentrated suspensions, which are the suspensions that meet
understand the influence of ILs on drilling muds. industrial requirements. The view has been that, as long as the
pH value of the mud is stabilized over a considerable range, the
role of pH has not needed much attention; there has been a
lack of in-depth research as a result.
The role of pH
Montmorillonite particles, which are the major components of
The role of electrolytes
bentonite, have negatively charged faces and edges, with the latter
generally corresponding to <5% of the total surface area. The The edges of Mt particles are usually irregular (Keren et al., 1988;
edges are positively charged at pH values below the isoelectric Zou & Pierre, 1992). The particles may remain isolated or form
point and negatively charged at pH values above the isoelectric thin packets and may fail to agglomerate in a dilute clay dispersion
point of the edges (Delgado et al., 1986). The isoelectric point owing to the interaction of diffuse double layers (Bergaya & Lagaly,
of the smectite particles in the drilling fluids is the pH at which 2013). Nevertheless, they may flocculate in the presence of electro-
the smectite particles have zero charge (van Olphen, 1977). The lytes. Hence, the influence of electrolytes on the association of Mt
pH of the drilling fluids determines the type of Mt particle asso- particles has also been a critical topic of research in drilling fluids.
ciations, endowing the system with viscosity and yield stress The addition of inorganic salts (especially NaCl) may strongly
(Lagaly et al., 2003). Therefore, the effects of pH on the rheo- affect the rheological properties of bentonite-based drilling fluids.
logical behaviour of drilling fluids is a topic of considerable inter- Numerous studies have evaluated the effects of the concentration
est (Duran et al., 2000; Ramos-Tejada et al., 2001; Tombácz & of NaCl on the rheological behaviour of bentonite dispersions
Szekeres, 2004; Laribi et al., 2006). (M’bodj et al., 2004; Tombácz & Szekeres, 2004; Duman &
Clay Minerals 5

Fig. 2. Flow curves of the bentonite dispersions in HCl solutions

(reprinted with permission from Choo et al. (2015), copyright
Elsevier B.V.).

Tunç, 2009; Liang et al., 2010). In this respect, E–F hetero- the monovalent cation salts (Fig. 4) (Abu-Jdayil, 2011). Duman &
coagulation might occur in NaCl solutions with concentrations Tunç (2009) investigated the electrokinetic and rheological proper-
>25 mM at a pH of 4, where a screening electric double layer ties of Na-bentonite dispersions in the presence of various electrolyte
of positively charged edges may emerge. A greater concentration solutions, including LiCl, NaCl, KCl, NH4Cl, NaClO4, CH3COONa,
of salt (∼50 mM of NaCl) will induce E–F interactions between NaNO3, Na2SO4, Na3PO4, CuCl2, MnCl2, CaCl2, BaCl2, NiCl2 and
poorly charged edges and negatively charged faces around the AlCl3. The divalent cations (Cu2+, Mn2+, Ca2+, Ba2+ and Ni2+) and
point of zero charge of the edges (pH value of ∼6.5). A transient trivalent cation (Al3+) controlled the surface potential of the smec-
coagulation of F–F homotype interactions appears after adding tites in the Na-bentonite dispersions. Trivalent cations such as Al3
≥0.1 M NaCl (Tombácz & Szekeres, 2004). Thus, the addition +
changed the surface charge of the Na-bentonite from negative to
of NaCl salts affects concentrated bentonite dispersions. The positive (Duman & Tunç, 2009). Recent research has confirmed
yield stress, flow consistency index and apparent viscosity were that the charge location might have a significant impact on the
reported to decrease monotonously with increasing salt concen- phase behaviour of swelling clay minerals. Paineau et al. (2011a)
trations (up to 1.0 M) (Fig. 3) (Kelessidis et al., 2007). investigated the structures of clay platelet dispersions with various
Miyahara et al. (1998) examined the maximum sedimentation charge locations at various ionic strengths using small-angle X-ray
rate as a function of the volume fraction of solids at a pH value of scattering experiments and transmission electron microscopy
10, with NaCl concentrations ranging from 0.5 to 1.5 M. The (TEM), and they proposed that stronger electrostatic repulsions
equivalent hydrodynamic diameter of the floc (df ) and increment might improve the liquid-like positional local order. These authors
ratio of the effective volume fraction of the particles (α) increased also conducted a comprehensive investigation of the rheology behav-
with the salt concentration, and the value of α agreed qualitatively iour of various natural colloidal clay minerals in aqueous dispersions
with the values obtained from the rheological data (Batchelor, under both dynamic and steady-state conditions. The viscoelastic
1977; Miyahara et al., 1998). The observed increase in df was properties were closely related to repulsive electrostatic interactions
ascribed to F–F association, as the vicinal platelets approach between the platelets and the charge localization of the clay structures
and form flocs with more irregular shapes with increasing salt in such systems. In addition, new insights were provided on sol–gel
concentrations (Miyahara et al., 2001). transitions, which depend on the size of clays (Paineau et al., 2011b).
The influence of other types of electrolytes (BaCl2, CaCl2, KCl The effects of salt concentrations on the sedimentation behav-
and Na2SO4) on bentonite dispersions has not received the same iour of Mt dispersions is still not well understood. Wu & Adachi
amount of attention as the influence of NaCl. Mpofu et al. (2005) (2016) studied the sedimentation behaviour of semi-dilute disper-
investigated the influence of hydrolysable metal ions, Mn(II) and sions of Mt in a flocculation regime as a function of ionic strength
Ca(II), on the interfacial chemistry, particle interactions and dewa- at pH values of 4.0 and 9.5. The maximum velocity of the bound-
tering behaviour of Mt clay dispersions in the pH range of 3–12, ary between the supernatant and sediment and the ultimate sedi-
and they observed that the metal ions had a profound influence on ment height were strongly affected by the salt concentration (Wu
the colloid stability, rheology and dewatering behaviour of unfloccu- & Adachi, 2016). In addition, a few authors have analysed the
lated and flocculated Mt dispersions (Mpofu et al., 2005). The add- morphological aspects of Mt through various techniques (scatter-
ition of 0.02–0.2 M of electrolytes reduced the apparent viscosity of ing, cryo-TEM, X-ray microscopy and others). Hence, Ahmad
the bentonite dispersions and modified their rheological behaviour et al. (2018) studied the effect of an electrolyte (0.1 M NaCl)
from shear thinning to Newtonian and shear thickening on the rheological and morphological properties of a bentonite dis-
(Abu-Jdayil, 2011). The divalent cation salts were more effective at persion and noted that electrolyte-treated bentonite dispersions have
reducing the apparent viscosity and yield stress of dispersions than inferior rheological properties as compared to the base bentonite
6 Jun Rui Zhang et al.

Fig. 3. Flow curves of 6.42 wt.% Wyoming bentonite dispersions

in electrolyte solutions (reprinted with permission from
Kelessidis et al. (2007), Elsevier B.V.).

Fig. 4. (a) Effect of NaCl concentration on the flow curves of bentonite. (b) Comparison between the effects of monovalent and divalent electrolytes on the flow
curves of bentonite (reprinted from Abu-Jdayil (2011), Elsevier B.V.).

dispersion. Moreover, the particle morphology was dominated by The bentonite content affects the rheology of drilling fluids in
the aggregation of Mt platelets (Ahmad et al., 2018). HTHP conditions; the greater the bentonite content, the more
inferior the rheological properties of the drilling fluids, although
the bentonite content does not affect the shear rate and shear
The effect of bentonite concentration
stress (Shi et al., 2008). Abu-Jdayil (2011) investigated the rheo-
The fact that the bentonite concentration is important is evident logical behaviour of three types of bentonites at various bentonite
from a rheological standpoint. Starting with the Einstein equation, concentrations. The bentonite concentration and bentonite type
it has long been known that the volume fraction affects viscosity. had significant impacts on the Newtonian, Bingham plastic and
A high clay concentration would slowly lead to the formation of a shear thinning behaviour of bentonite dispersions (Abu-Jdayil,
continuous gel structure as the suspended particles orientate 2011). In a similar study, the viscosity and shear stress of benton-
towards the positions of minimum free energy according to ite dispersions increased with increasing bentonite concentration,
Brownian motion. Large clay contents in water-based drilling and a considerable initial stress was observed at the initial shear
fluids may be detrimental to drilling operations, leading to pro- rate as the storage time increased (Choo & Bai, 2015).
blems such as a reduction of the drill bit penetration rate, precipi- The aforementioned studies refer to the rheological behaviour of
tation of a thick filter cake, differential pipe sticking and bentonite-based drilling fluids at various temperatures, pH values,
formation damage. Therefore, the clay concentration is an electrolytes and concentrations. In contrast, there have been rela-
important factor that may influence the length of time required tively few studies addressing the rheological behaviour of locally for-
for the gel to reach maximum strength (Luckham & Rossi, 1999). mulated bentonite-based drilling fluids in challenging environments,
Clay Minerals 7

Fig. 5. (a) The structure and (b) an SEM image of palygorskite (Pal) (reprinted with permission from Zhang et al. (2017), Elsevier B.V.).

such as in deep offshore drilling and under HTHP conditions. In inhibiting agent for circulation loss in oil-well drilling fluids
addition, the thermal stability of these clays after beneficiation has (Darley & Gray, 1988).
not been well documented; this is a major concern regarding clays The use of Pal in water-based drilling fluids and its gel structures
used in drilling fluids. Previous studies have focused on the upgrad- and properties in aqueous systems have been studied. Neaman &
ing of Ca-bentonite, usually with chemical treatment by Na2CO3. A Singer (2000) investigated the rheology of aqueous suspensions of
limited number of studies has been performed on the rheological Pal with various particle morphologies as a function of clay concen-
properties of Ca-bentonite dispersions at various pH levels, salt con- tration, adsorbed ions, pH and electrolyte concentration using a
tents and in the presence/absence of polymeric additives (Karagüzel rotary viscometer. The rheological parameters (plastic viscosity,
et al., 2010). Bingham yield value and apparent viscosity) of Pal suspensions
The structure of the clay (particle size and shape) is crucial for depend on the aspect ratio (length:width) of the Pal fibres, with
a correct understanding of the rheological features. Some studies the plastic viscosity increasing linearly with the clay concentration
have attempted to determine the links between the structure of up to 5% w/v (Neaman & Singer, 2000). Both the morphology and
the clay and the rheological properties of drilling fluids. The rheo- the surface charge of the particles have major effects on the suitabil-
logical behaviours of pure mineral-colloid systems, the clay sizes ity of a drilling fluid; a rounded shape and a ζ-potential close to the
and shapes of which changed systematically, were studied by isoelectric point favour particle aggregation, resulting in low-
ten Brinke et al. (2007) and they provided a physical model for viscosity dispersions (Baltar et al., 2009). In addition, with an
describing the observed behaviours. In another study, the rheo- increasing concentration of the dispersed phase in the Pal suspen-
logical modifications in mixed anisometric colloid systems were sions, the areas in the flow curves near the critical concentration
investigated and the mixtures displayed a complex “yield space” (ϕcr; which indicate the onset of the rearrangement of the disper-
transition (ten Brinke et al., 2008). The physicochemical factors sion structure) are identified, and a sharp change occurs in the
of the transition were discussed and a simple qualitative model character of their flow in the immediate vicinity of ϕcr (Khil’Ko
was described. This study provided a quantitative model-system & Titov, 2002). Finally, the rheological properties of Pal dispersions
baseline for mixed colloidal dispersions (ten Brinke et al., are not affected by the presence of electrolytes, in contrast to ben-
2008). Philippe et al. (2013) investigated the rheological evolution tonites (Christidis et al., 2010)
of size-selected natural swelling clay minerals from isotropic With the increasing importance of environmental protection
liquids to weak nematic gels. An effective approach to assessing and the development of petroleum exploration research, oil-based
the viscosity of the dispersions was used, and the relationship drilling fluids have attracted significant research and application
between the viscosity and volume fraction (ηr = f(ϕ)) was trans- interest owing to their excellent temperature resistance, good lubri-
formed into a relationship that linked the viscosity with the cation, shale inhibition, high reservoir protection and environmen-
flow and volume fraction (ηr = f(ϕ, Pe)) (Philippe et al., 2013). tal friendliness. Organo-clay minerals may reduce the filtration loss
and increase the viscosity and shear stress of drilling fluids, and
their performance directly affects the rheology and filtration prop-
Palygorskite-based drilling fluids
erties of drilling fluids. Hence, organo-clay minerals are important
Palygorskite is a hydrated magnesium aluminium silicate clay additives to oil-based drilling fluids. Organo-Mt is subject to ther-
mineral with the theoretical formula of Si8Mg8O20(OH)2 mal degradation and thermal thinning, permanently destroying its
(H2O)4⋅4H2O (Giustetto & Chiari, 2004). It has fibrous habit capacity to develop viscosity. Therefore, Pal has gained significant
with fibre lengths of 0.2–2.0 mm, widths of 10–30 nm and attention with regards to its use in oil-based drilling fluids owing
thicknesses of 5–10 nm (Fig. 5) (Zhuang et al., 2017c). Palygorskite to its high thermal stability and salt resistance (Farrow et al.,
has excellent colloidal properties, including high-temperature 2003; Dino & Thompson, 2013; Mainye & Teutsch, 2015).
resistance, salt and alkali endurance and high adsorbing capa- Organo-Pal has exhibited excellent rheological properties and
bilities (Galan & Singer, 2011). Therefore, Pal is often used as a thermal stability in oil-based drilling fluids. The microstructures
thixotropic agent and viscosity controller, and it may act as an and properties of Pal in OBMs are influenced by the surface
8 Jun Rui Zhang et al.

Fig. 6. The structure of sepiolite and the possible posi-

tions of organic surfactants; OSep = organo-sepiolite
(reprinted with permission from Zhuang et al.
(2018a), Elsevier, Inc.).

properties and organization of Pal. In addition, both Mt and Pal are based drilling fluids were studied using X-ray diffraction, scanning
suitable for use in oil-based drilling fluids, with the former providing electron microscopy, Fourier-transform infrared spectroscopy, ther-
excellent rheological properties and the latter providing good ther- mal analysis and surface contact-angle analysis (Weng et al., 2018;
mal stability (Zhuang et al., 2017a, 2017b, 2017c). However, the Zhuang et al., 2018a, 2018b). A sepiolite modified with surfactants
gel structure and gel formation of organic Pal in oil-based drilling had high thermal stability and exhibited excellent rheological prop-
fluids have not been studied extensively. It is suggested that investi- erties in oil-based drilling fluids (Fig. 6). These studies strongly
gating these issues may promote the application of Pal in oil-based suggest that organo-sepiolite is a potential rheological additive in
drilling fluids and consequently improve drilling engineering. oil-based drilling fluids, with excellent rheological properties.

Sepiolite-based drilling fluids Composite clay minerals in drilling fluids

Sepiolite is a nanofibrous hydrous magnesium silicate, with an All bentonite clays may develop a high-yield-stress gel at a low con-
ideal unit-cell formula of Si12Mg8O30(OH)4(OH2)4(H2O)8 centration (∼5 wt.% solids), irrespective of the source. Nevertheless,
(Suárez & García-Romero, 2011). Owing to its fibrous morph- bentonite-based drilling fluids (in Na or Li form) have limitations
ology, intra-crystalline channels and small particle size, sepiolite because of flocculation and instability problems at HTHP condi-
has the largest specific surface area (up to 900 m2 g–1) among tions. In this regard, Pal has excellent colloidal properties, such as
clay minerals. Moreover, its unique microporous channels high-temperature endurance, salt and alkali resistance and high
(0.30–1.06 nm) lead to it having the strongest adsorption capacity adsorbing capacity (Lagaly, 1989). In contrast, kaolin clays have a
among clay minerals. Therefore, sepiolite has been used fre- low swelling capacity, and their suspensions display significant
quently as a drug and catalyst carrier (Núñez et al., 2014), adsorb- yield stresses, and viscosity only at high concentrations (>40 wt.%
ent (Rytwo et al., 2011; Duman et al., 2015) and inorganic fibre, solids; Teh et al., 2009; Shanker et al., 2010). Hence, the mixing
among other applications (Zheng et al., 2011; Xu et al., 2013). It is of the clay minerals may control and tailor the rheological properties
stable up to 260°C and in a saturated saline-water phase owing to for given applications, such as for use in high-density drilling muds
its structure (Altun & Serpen, 2005). Sepiolite is also used in dril- or in impermeable slurry walls. Bailey et al. (2015) summarized the
ling fluids as a rheological additive, as it exhibits great thermal current status of research in the area of mixed suspensions of clays,
stability, excellent salt resistance and excellent rheological proper- focusing on phase behaviour and rheological properties.
ties in water-based drilling fluids (Abdo et al., 2016). The addition of small amounts of bentonite to kaolin clay dis-
Similar to Pal, organo-sepiolite may potentially develop excellent persions might drastically modify their rheological properties.
rheological properties in oil-based drilling fluids. Hence, the prepar- Indeed, in the Hanford River Protection Program, bentonite
ation of organo-sepiolite has been reported and has attracted signifi- was used to tailor the kaolin clay rheology to achieve a specific
cant attention; however, the interest has mainly been focused on yield stress and plastic viscosity (Daniel & Eibling, 2005). The
the preparation of sepiolite–polymer nanocomposites (Tartaglione mixed bentonite–kaolin drilling fluid had a greater viscosity at a
et al., 2008; Garcia-Lopez et al., 2013; Fernandez-Barranco et al., pH value of 4 than at a pH value of 7 owing to positive–negative
2016), which do not meet the requirements of drilling fluids. charge interactions between the various clay particles (Keren,
Recently, the structures and properties of organo-sepiolite in oil- 1989). Kaolin clay may also be added to bentonite-based drilling
Clay Minerals 9

fluids to increase the slurry density and control the rheological drilling fluid film efficiencies, etc.). With the development of deep
behaviour. Increasing the kaolin content reduces the slurry viscos- wells, complex wells, special technology wells and special reservoirs,
ity and increases its density (Adebayo & Ajayi, 2011). as well as with the attention now being paid to environmental pro-
Unfortunately, the pH of the slurries, which is expected to be tection, the requirements for drilling fluids are increasing.
important, was not measured in the aforementioned studies, Therefore, high-temperature resistance, high-pressure resistance,
and the microstructures formed in these mixed slurries that are complex formations in deep wells and reservoir protection are
responsible for the viscosity properties remain unclear. still important research directions for drilling-fluid technology.
Moreover, the bentonite content determined the magnitude of
Financial support. This research was supported by the Zhejiang Provincial
the yield stress of the kaolin–bentonite composite dispersions,
Natural Science Foundation of China (LQ18E030014, LQ18E030013 and
whereas the kaolin clay determined the pH value of the maximum
LQ19F050004), the Zhejiang Provincial College Student Science and
yield stress (Au & Leong, 2013). Technology Innovation Activity Plan (Xinmiao Talent Plan), the National
The properties of mixed Mt–Pal dispersions have also been Natural Science Foundation of China (41672033), the open fund from the
studied. A significant improvement in rheology was observed Key Laboratory of Clay Minerals of the Ministry of Land and Resources of
when using Pal as an additive in small amounts with Mt and the People’s Republic of China and the Engineering Research Center of
water. Palygorskite may tailor the properties of drilling fluids by Non-metallic Minerals of Zhejiang Province, Zhejiang Institute of Geology
reducing the particle size of the solid phase. Moreover, the addition and Mineral Resource, China (ZD2018K04).
of small amounts of Pal may impart to the drilling fluid consider-
able stability under HTHP conditions (Abdo & Haneef, 2013).
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