SPE 94686

Development of a Nanocomposite Gel for Lost Circulation Treatment

E. Lécolier, B. Herzhaft, L. Rousseau, and L. Néau, Inst. Français du Pétrole, and B. Quillien and J. Kieffer, SNF-Floerger

Copyright 2005, Society of Petroleum Engineers jobs. Lost circulation or lost returns is defined as partial or
This paper was prepared for presentation at the SPE European Formation Damage total loss of circulating mud within the annulus escaping into
Conference held in Scheveningen, The Netherlands, 25-27 May 2005.
formations.1 Losses can result from either natural or induced
This paper was selected for presentation by an SPE Program Committee following review of causes.2 Natural thief formations could be cavernous, fissured
information contained in a proposal submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to or coarsely permeable layers. Lost circulation is one of the
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
drilling’s biggest expenses in terms of rig time and safety.
SPE meetings are subject to publication review by Editorial Committees of the Society of Moreover, uncontrolled lost circulation can result in a
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers is dangerous pressure control situation and loss of the well. So,
prohibited. Permission to reproduce in print is restricted to a proposal of not more than 300
words; illustrations may not be copied. The proposal must contain conspicuous
in order to save money and to guarantee safe drilling jobs,
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. several operators asked for new efficient solutions to reduce or
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
eliminate lost circulation issues.
Abstract The objective of this project was to develop new solutions
The problems due to lost circulation events may represent a to seal loss zones responsible of severe lost circulations due to,
major source of expenses for drilling operators, even if their for example, naturally fractured formations. In this case, losses
consequences do not have all the same level of gravity. can range from tens of barrels per hour to thousand of barrels
Probably the most problematic situations are the naturally per hours. The developed remedial solutions are settable plugs
fractured formations where the operator may face total loss that are polymer-based fluids that gel to seal off loss zones.
with no mud return in the annular.
The voids or large fractures encountered in this case are
often far too large to be plugged with conventional Lost Background
Circulation Material. For these severe losses, the failure of A lot of remedial products have been developed to cure lost
extreme solutions as cement injection may even lead to loss of returns. 3-5 The required properties of lost circulation pills are
the well. Recently, treatments based on cross-linked pills have numerous:
shown their effectiveness to plug large fractures under • To provide strong plug
downhole conditions of pressure and temperature. • To have no harm effect on mud chemistry
This paper describes the research and development process • To not plug bottom hole assembly or any circulation
to formulate a new cross-linked pill usable to control severe devices
losses: this new pill is a nanocomposite organic/inorganic gel. • To allow permeability recovering of production layers
Formulation strategy, laboratory procedures and experimental
results will be described. The gelation time, the viscosity Various solutions have been used to restore circulation of
before setting, the gel strength formed and the dependence of the drilling muds when lost circulation has occurred. The basic
these parameters with pressure, temperature and physico- method is to add solid materials to the drilling fluid. These
chemical environment are characterized with specific solid materials are generally referred as lost circulation
experimental devices. Particular components of the materials (LCM). The LCM could be fibrous, flaky or granular
formulation give excellent visco-elastic properties to the materials. Two types of plugs can be formed by LCM: either a
nanocomposite gel, enhancing the ability to sustain pressures seal at the wall of wellbore or a seal within the fracture. The
peaks. second type of plugs is preferred because they are difficult to
The typical final formulation, which is easily prepared on be dislodged as a result of pipe movement for example. A
site (dry blend formulation) gives remarkable properties proper sealing of natural fracture is too difficult to achieve
regarding pumping through drill pipes, adjustment of setting with LCM because particle size distribution has to be sized to
time and especially strength of the lost zone sealing. fracture openings. Therefore, it implies to know the widths of
fractures existing in the loss zones to adequatly select LCM. If
LCM particles are too large compared to fracture width, an
external plug is formed and is eroded with time to be finally
Introduction washed out. On the contrary, if LCM particles are too small,
During drilling operations, drilling fluids account for over solids go through cracks and no effective plug can be formed.
25-40% of total costs. Therefore, any mud loss increases the Alternative remedial materials are settable plugs. The term
total cost and contributes to non-productive time of drilling “settable plugs” is used for slurries which gel or solidify in
2 SPE 94686

seal loss zones. Main advantages of the settable fluids are, Rheological measurements have been performed with a
firstly, no risk of bit nozzles plugging, and secondly, the controlled shear stress rheometer (Haake RS 150). The
ability of invading a wide range of fracture widths contrary to rheometer was equipped with a vane geometry allowing us to
conventional Lost Circulation Materials. Some examples of measure rheological properties of fluids containing large
such plugging products are gunks or cross-linked polymers. particles at atmospheric pressure. The vane is made of six
Gunk is a mixture of high concentration of bentonite and blades disposed around a cylindrical shaft. For pressurized
cement with diesel oil. This fluid hydrates when mixed with rheological measurements, a coaxial grooved cylinders
water to form a hard plug. Gunks present some disadvantages. geometry was used in order to avoid slip at the wall. This
First, there is sometimes difficulty in spotting them at the right equipment allowed to characterize visco-elastic behavior of
location. And secondly, the use of diesel oil may not comply nanocomposite gels under a pressure of 5MPa. Temperature
with local environmental regulations which are getting more was controlled thanks to a thermostated bath. All the results
and more stringent. given in this paper have been obtained at 60°C. Temperature
Cross-linked polymer slurries are generally formed by variations during measurements did not exceed 2°C.
adding multivalent ions to a polymer solution. The cross- A classical measurement procedure was as follows:
linking mechanism leads to a soft and deformable rubber-type just after mixing, the fluid was poured into the measuring
solid. The main disadvantage of the cross-linked pills lies in tool. Covering the sample with a low viscosity mineral oil film
the placement of the fluid because the cross-linking reactions prevented evaporation. We verified that the presence of oil
are initiated on surface. Therefore, a premature gelation can film did not influence rheological measurements.
occur far before to penetrate the loss zones. To avoid this
situation, a smart plugging product has been recently We determined the following parameters:
developed.3 The cross-linking reactions are triggered by high • Initial viscosity and gelation kinetics
shear rates encountered downhole. Another drawback of these • Visco-elastic properties (elastic modulus, G’, and viscous
reactive pills like crosslinked polymer gels is that they are modulus, G’’) of the gel
easily extrudable into the fracture under high differential • Yield stress (or shear strength) of the gelled fluid
pressure. Recently, some new remedial solutions have been
proposed to counteract this drawback.5 For all these measurements, applied flow sequence
In order to remedy this problem, IFP and SNF have consisted in imposing, first, a constant shear rate (10 s-1) to the
developed a novel solution using crosslinked polymer gel fluid while recording viscosity. Indeed, it has been shown that
containing swelling polymer particles and colloidal ones. We viscosity is much more sensitive to gelation than elastic
name this material a nanocomposite organic/inorganic gel. The modulus.6 Gelation time is defined as the time when a sharp
new sealing pill intimately associates four components: an increase of the viscosity is observed (see Figure 1). Once
aqueous viscous polymer base, a cross-linking agent, swelling gelation time has been measured, we let the polymer-based
cross-linked grains and colloidal particles. fluid under oscillatory shear stress while monitoring the
development of viscoelastic properties versus time. After some
hours (typically 3 hours after the adding of cross-linkers in the
Experimental fluid mixture), the elastic modulus reaches a pseudo-plateau
Different cross-linkers have been tested in this work. We (see figure 2). Then, we applied a constant shear rate while
present the results obtained with chromium acetate recording the stress evolution versus time. Figure 3 shows a
(CH3CO2)7Cr3(OH)2 purchased from Aldrich. typical curve of shear stress versus time. We can notice, first, a
Polymers were synthesized by SNF-Floerger. SNF- sharp increase of the stress. Then, shear stress presents a peak
Floerger is able to manufacture different grades of before decreasing and stabilizing around an average value.
copolymers. Different molecular weights and hydrolysed The shear stress peak corresponds to the gel strength (also
degrees have been successfully tested. Here we only report the named shear strength in the following). The measure does not
results obtained with a polyacrylamide whose molecular correspond to the optimal shear strength but only to the
weight equals to 500×103 g⋅mol-1 and hydrolysis degree 5%. strength after 3 hours. If we wait a longer time, nanocomposite
gel will develop higher shear strength. It is worth noting that
Preparation of the polymer-based mixtures was performed for the value of shear stress corresponding to the peaks, the gel
by adding adequate amounts of the different powders used in does not experience a shear flow but a mechanical breaking.
the formulations into an aqueous solution. Aqueous solution is The observed curves are typical of soft solids ones.
either deionised water or brine. The composition of the brine We measured the shear strength of nanocomposite gels
is the following: after ageing at high temperature (120°C) to evaluate how
sealing properties of the material evolve at such temperatures.
• KCl: 5 g/L We started the experiment by applying, with the rotating vane
• CaCl2: 5 g/L geometry, a constant shear rate until the viscosity starts to
• NaCl: 40 g/L diverge. Then, cylinder containing sample and measuring tool
were carefully removed from the rheometer and placed in an
The different tested formulations are given in table 1. oven at 120°C. Special attention has been paid to let the vane
perfectly centered within the cylinder in order to get
meaningful measurements. Samples were left under rest for 16
SPE 94686 3

hours. The next step consisted in replacing cylinder containing inorganic particles. The shear strength of cross-linked polymer
sample and measuring tool on the rheometer without is about 1300 Pa. Therefore, the reference nanocomposite gel
disrupting nanocomposite gel structure. Finally, constant shear (Formulation A) exhibits shear strength almost three times
rate was applied while recording the stress evolution. greater than basic cross-linked gel. From application point of
The most efficient nanocomposite organic/inorganic gel view, it means that the nanocomposite organic/inorganic gel
plugs correspond to the formulations with the highest can sustain higher pressure drop (typically of the order of 10
viscoelastic properties (relating to the consistency of the gel) MPa/m for fracture width of 1 millimeter) due to, for instance
and shear strengths. to surge and swab events, without any failure.
Let us now consider the flow of a Bingham fluid between
two plates in order to simulate the invasion of a fracture by
sealing fluid. We can show that the shear stress is maximum at Influence of cross-linked polymer grains
the walls. The equation relating the shear stress at the wall, concentrations
τwall, the pressure drop by fracture length unit and the fracture Sealing pills exhibiting swelling behavior is seeked because it
width, w is: ensures a very strong bridge within the loss zone. To obtain
swelling sealing treatments, we incorporated cross-linked
w ∂P polymer grains in the composition of the nanocomposite
τ wall = organic/inorganic gel. The mean diameters of the grains are of
2 ∂x some hundred of microns. In contact with water, they easily
swell. As observed on Figure 4, the cross-linked polymer
Therefore, to ensure an efficient plugging, the shear stress at grains concentration has a strong effect on the gel strength.
the wall must not exceed the yield stress. The higher the yield Multiplying the concentration of cross-linked polymer grains
stress, the higher the value of pressure drop that can be by two increases the shear strength by almost the same factor.
sustained by the gel. Then, in case of high differential pressures are expected,
In this project, we formulated sealing pills with optimized gel increasing the amount of cross-linked polymer grains can
strength with a swelling behavior. reinforce strength of nanocomposite gels. Moreover, thanks to
the swelling of these grains within the fracture, a strong bridge
can be achieved even for large widths.
Results
As already mentioned above, the new sealing fluid developed Influence of water salinity
in this project is a four-components material mixing both The effect of brine salinity on properties of nanocomposite
inorganic and organic components in order to enhance organic/inorganic gel was studied only for the reference
intrinsic properties of cross-linked polymer gels. We name this composition (Formulation A). Same amounts of the
sealing fluid a nanocomposite organic/inorganic gel. We recall components were dispersed in brine to obtain Formulation C.
the four components of the nanocomposite organic/inorganic Then, we evaluated the same properties than those measured
gel: a viscous polymeric base, cross-linkers, colloidal particles on composition prepared with deionised water. Interestingly
and cross-linked polymer grains. enough, the gelation kinetics is not delayed due to the increase
The first task of the study consisted in determining the of salinity contrary to what is observed with cross-linked
optimal range of concentrations of the four components polymer.6 The gelation times for Formulations A and C are
participating to the nanocomposite gel. A reference equal to 15 minutes. As illustrated in Figure 5, the strength of
formulation composition is given in table 1. The figure 1 the nanocomposite gel is not lowered by shifting from
shows the gelation kinetics of this benchmark formulation. deionised water to brine. One can notice on Figure 5 that the
The measurements have been carried out at 60°C and gel strength is around 3000 Pa for both formulations.
atmospheric pressure. At this temperature, the gelation time Therefore, nanocomposite gels can be prepared with fresh
equals to 15 minutes. As one can notice on Figure 1, the water or seawater without degrading properties. It is worth
gelation kinetics is quite reproducible (comparison between noting that the viscosity before gelation is lowered by 20% for
blue curve with squares and red curve with circles). This Formulation C. This can be explained by the screening of the
gelation time is short. Gelation can be delayed by use of electrostatic repulsions between negative charges carried by
adequate retarders (like sodium lactate). The measured polymer chains due to the presence of electrolytes. The short
apparent viscosity of the Formulation A is about 800 mPa⋅s. range of electrostatic interactions in electrolytes solutions
This viscosity is high compared to drilling fluids but it is the leads to a lower level of polymer chains interpenetration and
necessary counterpart for efficient sealing properties. This thus a lower viscosity. Formulating the nanocomposite gel
viscosity greater than drilling fluids one permits a very good with brine is therefore beneficial for the application: same
mud displacement within fractures and then to obtain a non shear strength than with deionised water and lower viscosity
polluted sealing gels. At the moment, new developments are before gelation.
underway to reduce the viscosity of composite gels before
gelation. From Figure 3, one can deduce the gel strength (or
shear strength) of the reference formulation. Shear strength Influence of pressure on gelation kinetics
equals to 3000±120 Pa. This value is far greater than the value It is well known that temperature is the parameter that most
obtained from the same cross-linked gel without organic and strongly affects the gelation kinetics of cross-linked polymers.
4 SPE 94686

But it is interesting to know how pressure can impact the blending all the components and then stored and delivered in
gelation time of such materials. Thanks to a pressurized cell, big bags. On the rig, the dry blend can be directly mixed with
we measured the gelation time of Formulation A without on-site water to prepare the sealing fluid. Moreover, it is
cross-linked polymer grains (Formulation D, see Table 1) at interesting to point out that no degradation of properties was
the same temperature (60°C) but under 5 MPa. The gelation observed for nanocomposite gels aged at 120°C for 16 hours.
time of the Formulation D at atmospheric pressure is 12 As indicated by the formation damage tests, the nancomposite
minutes. We measured exactly the same gelation time under gels are very effective to reduce permeability of very
50 MPa. One can estimate that the chemistry of cross-linking permeable formations. Tests are now conducted to evaluate
mechanisms is not influenced by pressure. Nonetheless, in nanocomposite organic/inorganic gels for resistance to break
nanocomposite gels developed during this project, numerous down or failure in large fracture widths (of some millimeters).
types of complex interactions can exist between the different For this, a special experimental set-up (see Figure 8) has been
components of the material. For instance, replacing fibrous designed in order to reproduce on-site sequences (filtration of
clay by bentonite clay increases the gelation time of 40% drilling mud into fracture, pumping the sealing pills, pressure
indicating that pressure can impact gelation processes taking test to evaluate break-down resistance of the plug).
place in nanocomposite gels. Besides, IFP and SNF-Floerger are continuing to develop new
polymers to design gel-based treatments, which allow both
lower viscosities before gelation and high gel strengths.
Temperature ageing of nanocomposite Evaluations of different solutions to carefully control gelation
organic/inorganic gel times at bottom-hole conditions and to trigger cross-linking
Once in place, the question of how long the nanocomposite gel down-hole are currently investigated.
can maintain its sealing properties is crucial. We evaluated the
shear strength of gels aged for 16 hours at 120°C. We repeated
the measurements three times with samples prepared with Acknowledgements
similar compositions. We found a very good reproducibility. This project had been funded by Réseau de Recherche sur les
Figure 6 depicts the measurements of the gel strength for both Technologies Pétrolières et Gazières (RTPG). The authors
temperature-aged gel (blue curve with squares) and unaged gel thank the management of both IFP and SNF for permission to
(red curve with circles). For the sake of clarity, only one result publish this paper.
of aged nancomposite gel is presented in Figure 6. After this
temperature ageing, the strength is reduced by only 20%.
Therefore, the nanocomposite gel is stable at high temperature References
at least for middle term.
1. Chilingarian, V.G., Vorabutr, P.: “Drilling and drilling
fluids”, Elsevier Scientific company, 1983.
Evaluation of formation damage of nanocomposite
organic/inorganic gel 2. Messenger, J.U.: “Lost circulation”, PennWell Publishing
In order to characterise damaging effects of developed Company (Tulsa), 112 pages, 1981.
nanocomposite gels, we carried out formation damage
experiments with a dynamic filtre-press. We used a very 3. Quinn, D., Sunde, E., Baret, J.F.: “Mechanism of a novel
permeable rock core sample. The oil permeability of the core shear-sensitive plugging fluid to cure lost circulation”, paper
sample was 555 mD. After filtration of the nanocomposite gel, SPE 50722 presented at the International symposium on
the permeability reached a very low value, 1 mD. This shows oilfield chemistry, Houston, 16-19 February 1999.
the great sealing properties of the developed plugging pills.
Nonetheless, the nanocomposite gels can be destroyed thanks 4. Sweatman, R.E., Kessler C.W., Hillier J.M.: “New solutions
to conventional acidic treatments or hydrogen peroxide (see to remedy lost circulation, crossflows and underground
figure 7). Picture A on figure 7 shows the nancomposite gel blowouts”, paper SPE 37671 presented at the SPE/IADC
after 3 hours gelation and Picture B, the same gel after a Drilling conference, Amsterdam, 4-6 March 1997.
contact time of 10 hours with hydrogen peroxide.
5. Ivan, C.D., Bruton, J.R., Thiercelin, M., Bedel J.-P.:
“Making a case for rethinking lost circulation treatments in
induced fractures”, paper SPE presented at the SPE Annual
Conclusion Technical Conference and Exhibition, San Antonio, 29
During this project, we have developed a new type of September - 2 October 2002.
polymer-based materials to cure lost circulation: this new type
is a nanocomposite organic/inorganic gel that ensures high gel 6. Broseta, D., Marquer, O., Blin, N., Zaitoun, A.,:
strength aiming at plugging highly permeable layers. The “Rheological screening of low-molecular-weight
nancomposite gels can be pumped in naturally fractured polyacrylamide/chromium(III) acetate water shutoff gels”,
formations in order to seal a wide range of width cracks. paper SPE 59319 presented at the 2000 SPE/DOE Improved
The nanocomposite gels developed in this study present oil recovery Symposium, Tulsa, 3-5 April 2000.
some specific advantages. First, they are environmentally
friendly. Secondly, the product can be prepared by dry
 Cross-linked
Copolymer Cross-linker
Water polymer grains Fibrous clay (g/L)
content (g/L) (g/L)
(g/L)
Formulation A deionised 50 5 5 50

Formulation B deionised 50 5 10 50

Formulation C brine 50 5 5 50

Formulation D deionised 50 5 0 50

Table 1: Formulations tested in the study

6000

5000

4000
Viscosity (mPa.s)

3000

2000

1000

0
0 5 10 15 20

Time (mn)
Figure 1: Viscosity evolution for Formulation A - 60°C and atmospheric pressure
6 SPE 94686

4
10

G' (Pa)
G'' (Pa)
3
10
G' (Pa), G'' (Pa)

2
10

1
10

0
10
0 500 1000 1500 2000 2500 3000 3500 4000

Time (s)

Figure 2: Evolution of elastic and viscous moduli for Formulation A - 60°C and atmospheric pressure

3500

3000

2500
Shear Stress (Pa)

2000

1500

1000

500

0
-100 0 100 200 300 400 500

Time (s)

Figure 3: Yield stress (or shear strength or gel strength) measurements for Formulation A - 60°C and
atmospheric pressure
SPE 94686 7

6000

5000

Concentration of cross-linked polymer grains = 10 g/L

Shear Stress (Pa)

4000

Concentration of cross-linked polymer grains = 5 g/L

3000

2000

1000

0
0 20 40 60 80 100

Time (s)

Figure 4: Comparison of shear strength between Formulation A (squares) and Formulation B (circles) -
60°C and atmospheric pressure

3500

Deionised water
3000 Brine

2500
Shear Stress (Pa)

2000

1500

1000

500

0
0 20 40 60 80 100

Time (s)
Figure 5: Influence of the salinity on shear strength: Formulation A (circles) and Formulation C
(squares) - 60°C and atmospheric pressure
8 SPE 94686

3500

Gel strength
3000 Gel strength after ageing at 120°C for 16 hours

2500
Shear Stress (Pa)

2000

1500

1000

500

0
0 50 100 150 200

Time (s)

Figure 6: Comparison of shear strength between Formulation A and Formulation D after a 16-hours
ageing at 120°C and 10 bar

Picture A Picture B

Figure 7: Nanocomposite gel before hydrogen peroxide treatment (Picture A - Left) and after 16 hours of
hydrogen peroxide treatement (Picture B - Right)
SPE 94686 9

Figure 8: Experimental set-up dedicated the evaluation of sealing pills for lost circulation (maximum
temperature: 100°C, maximum pressure 100 bar)