Rheological Properties of Drilling Fluids Prepared

with Nano Sized Polymer Additives

MIHAELA MANEA*
Oil and Gas University of Ploieti, 39 Bucureti Blv., 100680, Ploieti, Romnia

Drilling fluids were prepared as aqueous dispersions using nano sized particles of soluble polymers. These
polymer additives were carboxy methylcellulose, as viscosity controller, and poly-hydroxy ethylmethacrylate,
as fluid loss reducer. The dispersions were characterized from the rheological point of view analyzing the
influence of polymer particle granulometry and the effect of pH. The drilling fluid compositions were
contaminated with electrolytes (NaCl and CaCl2) and with bentonite, both dry and pre-hydrated, in order to
observe the rheology changes. Due to electrolyte coagulation, stability problems were reported. In addition,
it was performed a treatment of density increasing by adding solid particles of calcium carbonate; their
contribution to the system rheology was evaluated. The filtration process was taken into consideration by
measuring the filtrate rheological behavior in order to assess the presence of polymer particles in the filtrate.
Keywords: rheology, polymer additives, drilling fluids, contamination

A major industrial applicability of dispersed systems is

the so-called drilling fluids. They are used in oil industry to
drill crude oil and/or gas wells and must fulfill a series of
technological functions which depend directly on their
properties and composition [1, 2]. One of the most
important functions is linked to the rheological behaviour
of those systems because it influences on the drill bit
advancing rate, the capacity to carry the drilled rocks to
surface and to maintain them in suspension in the case of
stopping circulation [3].
Oil industry is continuously looking for finding new
technologies or to improve the existing ones. Recently, the
promising results of nanotechnology and the emerging of
nanomaterials raised a great interest to the drilling fluid
technology. The merging of both areas is a frontline
research subject of great industrial importance; it created
the novel so-called nanofluids, especially used in HTHP
ultra-deep drilling [4 - 6]. There has been reported the use
of nano particles to improve the rheological properties [7,
8] and the circulation problems of drilling fluids [9], as well
as to enhance oil recovery [10]. In addition, nano particles
have been an innovator application to overcome various
technological issues with smart drilling fluids [11, 12].
This paper is dedicated to aqueous dispersed systems
of soluble polymers of nano size dimension. These kinds
of systems represent the class of water-based drilling fluids
with low solids content, an intensely used and studied type
of fluids due to their technological advantages [13, 14].
They are flexible, use low amounts of materials, are
environmentally friendly and easily support the different
treatments performed during drilling work.
The main focus of the present work was given to the
changes in rheological behaviour of drilling fluids [15, 16]
with nano sized soluble polymers in the case of modifying
the pH of the continuous phase from neutral to medium
alkaline, as it happens in real practice in order to meet the
optimum conditions to cross strata. Even though the
changes in pH are not in a wide range for this kind of
application, there can be significant deviation of flowing
behaviour that can affect the technological performances
of the drilling fluid. This rheological analysis shows the

degree in which the chosen systems can maintain their

stability in this respect.
As any other dispersed system, the drilling fluids are nonNewtonian, usually corresponding to the Bingham model
(natural mud), the Ostwald de Waele model or the Herschel
Bulkley model. The last two models apply to drilling fluids
containing polymers [17, 18].
The chosen polymers for the drilling fluid basic recipe
were carboxy-methyl cellulose (CMC), as viscosity
controller, and poly-hydroxyl-ethyl methacrylate (pHEMA),
as fluid loss reducer [19]. Both polymers are known as
biodegradable; therefore the composition is ecological
[20].
These aqueous dispersed systems were analyzed from
the rheological point of view starting from adding only CMC
in micro dimensional sizes, then in nano dimensional sizes
in order to compare their versatility in different pH media.
The next step consisted in adding pHEMA to the dispersion,
in nano metric sizes, to see how a complete recipe
responds to varying the pH.
Since the water-based polymer drilling fluids have a
density equal to unity, the practical conditions require most
of the cases to use fluids that ensure a head pressure equal
or greater than the pore pressure. Therefore, the density of
drilling fluids must be adapted by adding solid particles
that do not interact chemically with the system. Such
weighting agent is CaCO3. In this study the drilling fluids
were brought to a density of 1200kg/m3 by adding nano
sized CaCO3 and the effect of solid particles presence was
analyzed from the rheological point of view.
After establishing the importance of nano size
granulometry and the contribution of each ingredient with
respect to the drilling fluid flowing behavior, two scenarios
of contamination were taken into consideration. First, it is
possible that clay may enter in these systems during
circulation from the crossed strata. As this plastic mineral
has good hydration and swelling properties [21], it is
expected to have a big impact on the rheology of the
polymer dispersion by dispersing in it. It was evaluated the
influence of nano sized clay presence when it is introduced
both as dry clay and as pre-hydrated clay.

*email: mihaela_manea2002@yahoo.com; Tel.: 0722875759

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REV. CHIM. (Bucharest) 63 No. 11 2012

Secondly, the drilling fluids prepared were contaminated

with electrolytes, namely salts like NaCl and CaCl2. They
may dissolve in the aqueous polymer dispersions coming
from crossing salty strata, commonly present in practice,
or from adding them at the surface as inhibitive agents.
The processes in this case are complex, due to the fact
that electrolytes induce coagulation [22 - 24]. The study
shows how this phenomenon can greatly affect the flowing
properties together with the dispersion stability depending
on the salt cationic valence.
In completion of all the rheological measurements, the
drilling fluids prepared with nano sized polymeric additives
were analyzed by the other standard properties such as
gel formation and filtration, as well as calculating the
rheological parameters, yield point, plastic and apparent
viscosity. It was made a comparison of those properties
when modifying the continuous medium pH value.
Furthermore, the filtration phenomenon was considered
as the flowing behaviour of the filtrate was studied. It is an
innovative research pursuit to perform rheology analysis to
the filtrate in the context of using nano sized additive for
the drilling fluid. Having nano dimensional polymer
particles in the drilling fluid may lead to their entering into
the larger pore of the productive strata during the filtration
process. The interaction of these soluble polymers with
the fluid media inside the strata can have major impact on
the well productivity [25, 26]; therefore it is very important
to assess their presence. One way to detect polymer
presence in the filtrate is to observe if the flowing curves
have a viscous plastic profile.
Experimental part
Materials
The viscosifier used was carboxy methylcellulose of 98%
purity purchased from Tianjin Tailida Chemical & Trade
Co.,Ltd. Poly-hydroxy ethyl methacrylate synthesized by
bulk polymerization to a 100% conversion was the second
soluble polymer added to the aqueous dispersions as fluid
loss reducer. The contaminating salt sodium chloride and
sodium hydroxide, solution 50%, were products of
Chimopar S.A. Romania. The other solid substances: CaCl2,
bentonite and CaCO3 were acquired from Ava Drilling Fluids
& Services S.p.A.
Preparation
The solid particles like bentonite, CMC, pHEMA and
CaCO3 were ground with a Fritsch Pulverisette planetary
mill having an agate bowl and 20 agate ball of 20 mm
diameter.
The drilling fluids were prepared by gradual dispersion
of soluble polymers in water: first the CMC, until forming a
homogenous gel, and secondly the pHEMA under
continuous stirring, using a mechanical agitator mixer type,
MultiLab model VLP-ES.
Characterization
The solid particle size was determined by dynamic light
scattering (DLS) with an equipment Malvern Zetasizer Nano
ZS. The pH value measurements were done with a Techne
pHmeter, model 3505, and the rheology study was carried
on using a Brookfield PVS rheometer having the Rheovision
software to analyze the data. The rheological study involved
the determining of the thixotropic nature in order to assess
the suspension capacity of these systems. It was
performed by the measuring the shear stress when
increasing, as well as when decreasing the shear rate.
Besides this, the rheology was completed by
measurements of a FANN 35A viscosimeter.
REV. CHIM. (Bucharest) 63 No. 11 2012

The filtration process was performed with the standard

Baroid filter press.
Results and discussions
The solid materials were first ground and characterized
from the size point of view. Thus, the carboxy
methylcellulose had an average particle size of 400nm and
the poly-hydroxyl ethyl methacrylate was brought to
200nm particle size. The bentonite used as contaminant
had an average particle diameter of 295nm and the CaCO3
used to increase the density had an average size of 268nm.
First aqueous dispersion was prepared only with un
grounded carboxy methylcellulose, meaning the one
having a micro dimensional size of 937nm. The aim of this
preliminary study was to assess strictly the influence of
pH change. Figure 1 shows the profile of the flowing curves
obtained.

Fig. 1. The flowing curves of micro CMC aqueous dispersions at pH

variation

Fig. 2. The flowing curves of nano CMC aqueous dispersions at pH

variation

Although no significant changes of the shear stress were

observed, it can be seen that at pH 10 the curve decreases;
a greater pH value, 12, favours the viscosity increase. The
analysis continued using the same polymer additive, but in
a nano metric particle size.
Figure 2 presents the evaluation of the flowing behaviour
with pH changes for a dispersion of nano dimensional CMC
in water.
From the representation above it is obvious the system
tendency to lower its shear stress at pH 10 and to enhance
viscosity at a more alkaline pH value. In addition, it can be
seen that at pH 12 there are two distinctive curves forming
a hysteresis. The values of viscosity obtained when gradually
increasing the shear rate are greater than the viscosity
values obtained when the shear rate decreased. This shows
a time dependent viscosity which means that the system
can display suspension capacity.

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Furthermore, the dispersions were all made with nano

sized polymer additives as it was considered to be more
relevant to the rheological changes to pH variation.
In order to achieve dispersions of drilling fluid
composition, besides CMC, the poly-hydroxiethylmethacrylate was introduced as fluid loss reducer.
The working pH values were chosen to be 7, neutral
medium, and 10, as a weak alkaline medium, as used in
drilling practice. A more alkaline medium becomes
corrosive to the metal parts of the drilling equipment. The
rheograms of the water-based drilling fluids prepared with
CMC and pHEMA at two different pH values are given in
figure 3.

values. Therefore, the technological properties are

improved by adding pHEMA.
It can be noticed that the effect of alkaline treatment is
more significant for the dispersions with nano sized
polymer particles. In this respect, when the drilling fluids
work in an alkaline medium, the most convenient systems
are those containing both additives in nano size dimension.
Keeping the idea of following the rheological changes
of the polymer disperse systems made by pH value, certain
contamination scenarios were considered. First, bentonite
contamination was analyzed in two versions: dry bentonite
contamination, in the case when it enters from the strata,
and pre-hydrated bentonite contamination, when the clay
is added at the surface.
Figures 6 and 7 show the flowing curves when bentonite
is added in both manners in a constant amount of 2%wt.

Fig. 3. The influence of pH on the rheograms of drilling fluids with

nano polymer additives
Fig. 6. Rheograms at dry bentonite contamination

Fig. 4. Rheograms of drilling fluids at pH 7

For the same pH value, 7 or 10, two comparisons have

been made between the flowing curves of the aqueous
dispersions prepared: with the two different CMC particle
size dimensions; with and without adding pHEMA. These
are represented in figures 4 and 5.
From both figures 4 and 5 it can be seen that when
adding the fluid loss reducer the dispersed system is
thixotropic because the hysteresis is present at both pH

Fig. 5. Rheograms of drilling fluids at pH 10

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Fig. 7. Rheograms at pre-hydrated bentonite contamination

The results in absolute values for the shear stress

increase greatly due to the hydration properties of the
bentonite. In addition, in the case of pre-hydrated bentonite,
the pH value does not have a remarkable effect. Figures 8
and 9 compare, for the same pH value, the flow curves
variation with and without contaminating bentonite when
it is dry or pre-hydrated.

Fig. 8. Rheograms after bentonite contamination at pH 7

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REV. CHIM. (Bucharest) 63 No. 11 2012

Fig. 9. Rheograms after bentonite contamination at pH 10

Fig. 11. Rheograms after CaCl2 contamination

The increase of rheological parameters is obvious in the

case of bentonite presence, an effect that has to be
quantified when its adding to the drilling fluid is mandatory.
In addition, at neutral pH it is even more apparent the fact
that the pre-hydrated bentonite, meaning already swelled
with water, reacts even more in the sense of increasing
the system shear stress.
The second possibility to contaminate drilling fluids was
considered to be with electrolytes. As sodium chloride is a
salt frequently met and a very soluble one, it was chosen
for study alongside calcium chloride, another soluble salt
which is met both in the strata as well as inhibitive agent.
Figure 10 presents the flowing curves in the case of salt
contamination with NaCl, 5%wt, for two pH values.
Fig. 12. Rheograms at pH 7

Fig. 10. Rheograms after NaCl contamination

Fig. 13. Rheograms at pH 10

It can be noticed that the influence of alkaline pH in this

case is unfavorable to viscosity; at pH 10 the shear stress
visibly decreases.
Next graphic shows the rheograms of the drilling fluids
contaminated with CaCl2, a salt of a bivalent ion, therefore
an ion with a greater coagulation power. At the same
amount of salt, 5%wt, the coagulant effect of calcium ion
already had a destabilizing nature; even at neutral pH, the
flow curve lost its viscoplastic profile. From figure 11 it is
noticeable that the rheograms look more like a straight
line corresponding to a Bingham model rather than like a
curve corresponding to an Ostwald de Waele model.
What is more obvious in the above graphic, figure 11, is
the fall of shear stress at pH 10. In fact, this rheological
behavior coincided with the loss of dispersion stability by
electrolytic coagulation.
Furthermore, figure 12 and 13 make a comparison of
the drilling fluids flowing curves with and without
contamination with NaCl and CaCl2 respectively, at constant
pH values.
Both graphic representations show that the effect of
sodium chloride is in favor of rheological parameter
increase, this salt is synergic to CMC polymer, while the

calcium chloride has a powerful destructive effect on the

structural properties of the dispersion.
Continuing the rheology measurements on aqueous
dispersions of soluble polymers, it was studied the effect
of density increase. This treatment is done by adding
calcium carbonate as chemically inert solid particles.
Again, the influence of the continuous medium pH was
analyzed. Figure 14 presents the rheograms of the drilling
fluids burdened with CaCO3 at a density of 1200kg/m3.

REV. CHIM. (Bucharest) 63 No. 11 2012

Fig. 14. The rheograms of the drilling fluids with CaCO3 of

1200kg/m3 density
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Table 1
THE STANDARD PROPERTIES OF
DRILLING FLUIDS

It is extremely important from the practical point of view

to determine the degree in which the drilling fluid filtrate is
loaded with certain particles in order to predict the way in
which the strata can be affected.

Fig. 15. The rheograms of the filtrates

It can be seen that the shear stress values are relatively

high, a consequence of the extra solid particles presence.
This fact supplementary contributes to the flow behavior
by adding friction forces between particles and between
particles and the continuous medium, water. The influence
of the pH index is significant, though there is a slight
decrease of viscosity at pH 10.
In addition, both drilling fluids brought to a 1200kg/m3
density were analyzed in order to determine other
rheological parameters. These parameters were plastic
viscosity, pl, apparent viscosity, ap, yield point, 0, and gel
strength, , at 1 and 10 min, together with the cumulative
filtration volume, Vf. The results are given in table 1.
As well as for the other fluids previously analyzed, here
is obvious their tendency to lose the flow qualities at pH
values that go towards alkaline medium. The plastic
viscosity and the apparent viscosity decrease, while the
yield point registers a slight increase, probably due to an
intensification of the interactions between calcium
carbonate particles. The gel strength, or the static shear
stress, decreases like the other rheological parameters.
The cumulative filtrate volume at 30 minutes decreases
at pH 10. Therefore, the fluid loss reducer additive, pHEMA,
is favoured in alkaline media.
After performing the filtration measurements, it was
considered important to analyze the obtained filtrate form
the rheological point of view. Though the filtrate is usually
considered to be merely an electrolyte aqueous solution or
even simply water, it was noticed in this case that the filtrate
aspect is similar to polymer dispersion. Considering that
these filtrates come in direct contact with the strata and
certain chemical reactions with the constitutive minerals
may occur, as well as with the reservoir water compounds,
it is vital to determine the chemical nature of these filtrates.
If the analyzed drilling fluid was prepared with nano sized
additives, it is possible that some soluble polymer particles
enter through the pores and get to interact with the fluid
medium there. This is why the flowing behaviour analysis
can provide clear indications whether the filtrate is polymer
dispersion or not. In figure 15 are presented the rheograms
profiles of the filtrate obtained in neutral and in alkali
medium.
The curve aspect of the rheograms clearly shows a
viscoplastic behaviour of the filtrates, both at pH 7, as well
as at pH 10. It means that in the filtrates composition enter
particles of soluble polymers coming from the drilling fluid.
It can also be seen that, contrary to the drilling fluid
tendency, the filtrate at pH 10 is more viscous. It means
that in alkaline medium the polymer particles are more
prone to pass in the filtrate as a consequence of better
polymer solubility at alkaline pH.
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Conclusions
The introduction of nano sized polymer additives in
drilling fluids affects their flowing behaviour, as well as
their filtrate nature.
The dispersions with CMC in nano sized particles have
lower absolute values of the shear stress, though the pH
influence is more significant. For both particle granulometry,
the weak alkaline pH is diminishing the rheological
performances; at a greater pH, the flowing properties are
enhanced.
After adding pHEMA in nano granulometry it can be
noticed that the dispersion becomes fairly stable to the pH
effect and it maintains at intermediary values.
The contamination with nano sized bentonite increases
considerably the shear stress by a synergetic effect of
bentonite, both dry and pre-hydrated. The pH influence is
enhanced in the case of the pre-hydrated bentonite
contamination.
The contamination with sodium chloride increases the
viscosity, while the contamination with calcium chloride
is affecting the system stability. At alkaline pH, the calcium
chloride contaminated drilling fluid looses all stability and
coagulates.
Thus, by using drilling fluids with nano size polymer
additives it can be obtained a reduced filtration which
produces, at the same time, a filtrate with enhanced oil
recovery properties.
The authors recognize financial support from the POSDRU/89/1.5/S/
54785 project: Postdoctoral Program for Advanced Research in the
field of nanomaterials.

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