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Journal of Petroleum Science and Engineering 67 (2009) 8490

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Journal of Petroleum Science and Engineering

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p e t r o l

Rheological properties of biopolymers drilling uids

Samira Baba Hamed , Mansour Belhadri 1
Laboratory of Rheology, Transport and Treatment of the Complex Fluids, University of Sciences and Technology-Mohamed Boudiaf, Boite Postale 1505, El M'Naour, Oran-31 000, Algeria

a r t i c l e

i n f o

Article history:
Received 16 May 2007
Accepted 14 April 2009
drilling mud

a b s t r a c t
Drilling muds are complex uids, generally used to clean the well, maintain hole integrity, transport the rock
cuttings, lubricate the drill bit and control formation pressures. Two basic types of drilling uids are used,
water based muds (WBM) and oil based muds (OBM). OBM are very effective but polluting, and environmental regulations continue to restrict the use of oil based muds in many areas of the world. In order to
reduce the mud toxicity, we developed water based mud systems using two biopolymers, which are xanthan
gum and scleroglucan, generally proposed for high permeability reservoirs or for complex geometries such as
horizontal wells. In this study, we evaluated the rheological behaviour of different samples and we determined the effect of components such as clay, calcium carbonate and potassium chloride. This formulations
exhibit non-Newtonian rheological behaviour which can be described well by the tree parameter in
HerschelBulkley rheological model.
2009 Elsevier B.V. All rights reserved.

1. Introduction
During the last few years, petroleum industry has developed new
drilling techniques such as horizontal and directional well. In order to
increase well productivity, directional drilling must reach rock reservoir i.e. high permeability and unconsolidated formation. In these
formations, drilling mud requires specic properties. The literature
reports that the most effective drilling uids are based on oil, crude or
synthetic, but their impact on environment pollution is very important. If horizontal and inclined drillings are also productive, it is
thanks to their passage in the reservoir. In these formations, the
drilling uid responsible of cutting ascent and good cleaning of the
hole must have specic properties. Horizontal wells are normally
selected for their ability to deliver high production rates and large
reserve volumes (Butler et al., 2000). Simulation studies indicate that
horizontal wells in thermal projects can increase recovery efciency
due to better area sweep, accelerate production which improves the
oil-steam ratio (OSR), shorten project life, and increase project
protability (Carpenter and Dazet, 1992). The role of drilling uid is
to pass through formations with high porosity while keeping all its
rheological properties and without causing damage to the crossed
formations. To reduce the mud toxicity, the water based mud was
developed. The studies carried out used a drilling uid containing
water, a natural or synthetic polymer and additives. Only the type
of polymer is different considering its molecular conguration, its
behaviour in aqueous medium as well as the viscosiers properties,

Corresponding author. Tel./fax: +213 41 56 03 23.

E-mail addresses: (S. Baba Hamed), (M. Belhadri).
Tel./fax: +213 41 56 03 23.
0920-4105/$ see front matter 2009 Elsevier B.V. All rights reserved.

which it confers on mud. The polymers currently used in the oil industry are cellulosics, guar gum, xanthan gum, polyacrylates, polyacrylamides and maleic anhydride derivatives. Control of drilling uid
properties is essential when encountering unconsolidated formations in complex geometries. These properties include uid density,
rheological parameters (viscosity and yield stress).
This paper describes a study of water based mud used in complex
geometries, including both polysaccharide xanthan gum and scleroglucan. Among hydrophilic polymers, polysaccharides are the choice
material due to their no toxicity and acceptance by regulating authorities
(Bonferoni et al., 1993). Comparisons were made between xanthan
formulations and scleroglucan formulation at different concentrations.
The systems used in this study comply to API standards. The similar
formulations were studied for high temperature zone and/or high
permeability reservoirs (Sanchez et al., 2003). Other studies show that
the reservoir must be drilled with specic drilling uid because these
formations created some difculty and additives give precise properties
to the mud which help to control uid loss. Horizontal sections are
drilled with specialised reservoir drilling uid (RDF) that contains
primary polymers for viscosity, bridging agents like sized calcium
carbonate (CaCO3) or sodium chloride (NaCl) salt and additives (usually
starch or another polymer) tailored to control uid loss (Houwen et al.,
The system is composed of a biopolymer viscosier, a starch loss
agent and a bactericide calcium carbonate is needed to develop density. The clay High Mod Prima (HMP) is the solid added to WBM
system. Alkalinity is controlled with potassium hydroxide. The goal of
this work is to determine a water based drilling uid containing
biopolymer and additives which is not polluting for the environment
or with acceptable toxicity, and also to carry out a comparative study
between biopolymers in order to decide which product is the best. To

S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490


Table 1
Products used.

Commercial name

Biopolymere 1 scleroglucan
Biopolymere 2 Xanthan gum
Weight material
Potassium chloride



Chemical composition


Al4 Si4O10 (OH)8

Vary the load factor

Viscosier, easily biodegradable
Viscosier, easily biodegradable
Lost circulation material, acid soluble
Potassium salt for inhibition and density
Protect the starches and polymers against the parasites

Degussa (ex skw polymers)



Potassium hydroxide

Gifrer Barbezat


achieve this goal, we tested two biopolymers xanthan gum and

scleroglucan. The tests carried out in sedimentation pushed us to
supplement this study by a rheological characterization.
In rst step, we varied the clay concentration by maintaining xed
the potassium chloride concentration for studying the effect of clays on
the uid. Then we xed a clay value and varied the calcium carbonate
which is used as a weighting agent, with different concentrations. The
functions of weighting materials are to increase the density of mud,
balancing formation pressure and preventing a blowout. Salinity is a
very important parameter in drilling uids; the last study was made
with different concentrations of potassium chloride. The rheological
properties on the water drilling mud systems were tested using a
modular rheometer the RS600 of ThermoHaake with a temperature of
25 C 1 C.
2. Materials and experimental methods
The model used in this study is water-based mud with different
formulations. The generalized composition of drilling uid is shown in
Table 1. The biopolymer powder was dissolved in distilled water to a
concentration of 5.75 g/l, we added 11.5 g/l of starch and 1.72 g/l of
bactericide. The constants of this experimentation are biopolymer,
starch and the bactericide. Other materials as clay, calcium carbonate
and potassium chloride varied with different concentrations.

C6 H10 o

Control pH to 8.59.0

2.1. Biopolymers
Both biopolymers used are polysaccharides, the xanthan gum and
the scleroglucan which have high properties viscosiers with low
Scleroglucan also known as schizophyllan (Van der Valk et al., 1977)
or lentinan depending on biological source) is a fungal polysaccharide
with immunostimulatory properties (Jong and Donovic 1989; Pretus
et al., 1991). This polymer is an exopolysaccharide chosen because of its
usefulness in enhanced oil recovery, food and pharmaceutical application (Sandford, 1979).
The biopolymers tested in this study were provided by the Degussa
and Schlumberger companies, they have different conformations and
present specic properties in aqueous medium. Scleroglucan, industrial name BIOVIS is produced by the Degussa society. BIOVIS is a nonionic, readily water-soluble biopolymer produced through fermentation of a carbohydrate by a fungus. BIOVIS solutions exhibit exceptional
shear thinning rheology and suspending ability. The advantages of
BIOVIS in comparison to other biopolymers are higher thermal stability, pH stability and tolerance of divalent and trivalent cations such as
Ca2+, Mg2+ and Fe3+. In an aqueous solution, BIOVIS molecules adopt
a triple-helical conformation and can be described as rigid rods. Under
static conditions, these rods form a web-like 3D structure. The resulting gel provides an excellent carrying capacity (Biovis, 2003). Its

Fig. 1. Diffraction of X-rays: behaviour of the clay after different treatment.


S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490

molar mass is 5.106 Da. The xanthan gum of industrial name Idvis
was provided by the Schlumberger Company. Xanthan is used frequently in drilling uids, either in combination with the traditional
thickener, bentonite clay, or alone in clear muds (Linton et al., 1991). It
is reported, with respect to suspending ability, that xanthan gum
surpasses that of any other polymer currently used in drilling uid (Shah
and Ashtaputre, 1999). But Xanthan gum has a limited temperature
stability (Caenn and Chillingar, 1996).
Xanthan gum is a high molecular weight polysaccharide that can give
interesting properties to the drilling uids. It is used as a rheology
control agent in aqueous systems and as a stabilizer for emulsions and
suspensions. Its numerous areas of applications cover a broad spectrum
and range from the food industry to oil recovery (M'bodj et al., 2004).
Xanthan gum is a nonionic biopolymer. The molecule conforms in the
form of simple, double or triples helix which interacts with other
molecules of polymer to form a complex network. In dilute solution,
aggregates formatted with weak connections which could be dissociated by mechanical action as a shearing. Its molar mass is 2.106 Da.

Fig. 3. Flow curve in plate-plate system for two different values gaps.

2.2. Additives
The additives used are: clay High Mod Prima (HMP), the calcium
carbonate and the potassium chloride. Drilling muds containing the
biopolymers usually are treated with biocides to inhibit microbial
degradation of the polysaccharides. The bactericide used in this study
is paraformaldehyde. Starch is used for control of uid loss to permeable formations High Mod Prima (HMP) was added in some of the
formulations to simulate drilled solids. The microscopic structure of
HMP clay is analyzed using X-ray diffraction (XRD). The diagram of
XRD of Fig. 1 shows four spectrums of various forms: the spectrum A
represents raw clay i.e. untreated. In the spectrum B, clay was heated to
550 C after a 4 h transit by the drying oven. The spectrum C indicates
the clay treated with ethylene glycol during 24 h. The last spectrum D
represents the clay treated under the normal conditions, that is to say
under free air drying for 24 h duration. After different treatment,
diffraction of X rays represented in Fig. 1 showed that the clay was
primarily composed of kaolinite, illite and quartz. Kaolinite, Al2Si2O5
(OH)4, is a layered aluminosilicate with a dioctahedral 1:1 layer structure consisting of tetrahedral silicate sheets and octahedral aluminium
hydroxide sheets (Bailey, 1980). Sized calcium carbonate particles
(D50 ~ 40 m) are added to increase the uid density up 1.01 g/cm3.
Calcium carbonate particles, associated to biopolymers, control uid
loss in drilling muds. Scleroglucan and xanthan gum were considered
as viscosiers and uid-loss additives, while calcium carbonate
particles were considered to be the best bridging (JPT, 2003).

Potassium ion is used in drilling uids to aid in the stabilization of

shales and to control swelling clays. Inhibition is obtained with KCl in
two ways. The Chloride ion (Cl) prevents water from entering the
clay matrix by what is called Mass action. This is true whether the
salt is KCl, Sodium Chloride (NaCl) or Calcium Chloride (CaCl2).
Potassium works as an inhibitor by exchanging with the Na+ or Ca+
found in native clays. The potassium ion is small and powerful, tting
ideally into and shrinking the space where water can be drawn into
the clay, reducing swelling. (GEO Drilling Fluids, Inc., 2001). To control
the alkalinity, the pH was adjusted to 8.59 using caustic potash
(KOH). The density of the samples varies between 1.01 g/cm3 and
1.18 g/cm3.
For the preparation of the samples, we needed a great agitation to
dissolve polymers. The dissolution of paraformaldehyde was obtained
at a temperature of 60 C by adding some potash drops to dissociate
the crystals. The temperature was maintained constant with 25 1 C
using a constant-temperature water-bath, the DC30 In this study, a
series of measurements was carried out on drilling mud formulations
for both biopolymers tested. In rst step, we varied the clay
concentration by maintaining xed the potassium chloride concentration in order to study the effect of clays on the uid. Then we
xed a clay value and varied the calcium carbonate, which is weighting
material, with different concentrations. Salinity is a very important
parameter in drilling uids; the last study was made with different
concentrations of potassium chloride. The samples were tested with a
modular rheometer, the Rheostress 600 of ThermoHaake. It is equipped
with the coneplate and coaxial cylinder geometries. Measurements
were made using the conguration of the coneplate combinations
having the following characteristics: diameter 60.00 mm, angle 3,
distance 0.105 mm, sample volume 2.00 cm3. We also used coaxial
cylinder system: gap 1.7 mm and sample volume 65.4 cm3.
Fig. 2 demonstrates that the difference between the two systems
does not exceed the 10% The results show the absence of the apparent
slip in Fig. 3. To avoid the problems of sedimentation, we limited the
experiment time to 60 s. Flow curves (Pa), (s-1) were obtained
with a stress controlled rheometer RS600 We tested samples in
sweeping of shear stress from 0 to 20 Pa.
3. Results and discussion

Fig. 2. Comparison between cylinder and coneplate sensor system.

Although the biopolymers used in the samples of drilling uid were

with weak concentrations, all the solutions had a marked non
Newtonian behaviour, which is with the very high molar mass polysaccharides and with the load in solid particles. The desirable properties
of polymers for polymer ooding and oil drilling uids are:(i) high
viscosity at low concentration; (ii) pseudoplastic ow behavior,

S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490


Table 2
Fluid based biopolymers with various clay HMP concentrations measured at 25 C.
Xanthan gum









Fig. 4. Inuence of high mod prima on xanthan gum. Flow curve in permanent regime.

enabling easy injection; and (iii) stability of the polymer viscosity to

salinity, temperature, and alkaline conditions (McWilliams et al., 1973).
The formulations used are complex and there properties depend
on the system's rheology. Drilling mud exhibit non-Newtonian behaviour, conventional rheological models in widespread use for the past
half century in the oil industry include the Bingham plastic, Powerlaw, and Newtonian models. The Power-law model provides more
information in the low-shear-rate condition but still has a weakness at
high shear rates (Lauzon and Reid, 1979). More recently, the Herschel
Bulkley model has seen increased usage because it accommodates the
existence of a yield point (Bingham plastic) as well as the nonlinearity
of the relationship of shear stress to shear rate (Power-law) (Power
and Zamora, 2003).
In the range of the rate of shearing considered, the totality of the
samples presented a shear-thinning well represented by the model of
= S + k

shear stress
shear yield stress
shear rate

k and n parameters characteristic of the equation such as k represents

consistency and n the index of ow. The parameters of HershelBulkley
estimated starting from the curves of ow presented coefcients of
correlation of 0.99.
The HerschelBulkley equation is preferred to Power Law or Bingham
plastic relationships because it results in more accurate models of rheological behaviour when adequate experimental data are available
(Hemphill et al., 1993).
This study made it possible to highlight the variation of the
rheological properties for various kinds of mud, and to see the effect of

biopolymers on the concentrations in products and the inuence of

the addition of additives. In the following paragraphs, we will show
the inuence of the clay rate, the rate of weighing materials and
salinity on the various rheological parameters (s, , and k) on the
addition of clay HMP, weighing materials calcium carbonate and salts
potassium chloride, in the presence of one or the other biopolymer.
3.1. Effect of clays on the parameters of HerschelBulkley for both
In this experiment, we varied clay HMP concentrations of 2.83%, 6%,
10%,15% and 20% of both biopolymers. Others components are constants.
From the rheograms presented in Figs. 4 and 5 above, as well as from the
values of the rheological parameters listed in Table 2, the results show
that the typical behaviour of these formulations is well represented by
HerschelBulkley model. The three rheological HerschelBulkley parameters were derived according to standard methodology, non linear
regression with an appropriate numerical package. These values are
given in Table 2, yield stress, index ow value and consistency.
The results show low values of yield stress for all the studied samples.
For xanthane formulations, the values of yield stress increase with HMP
concentration, whereas for the scleroglucan uids, yield stress values
does not vary much, they lie between 2 Pa and 3 Pa. A previous study of
interactions of clays with neutral polysaccharides has shown that
scleroglucan induces the formation of water-stable aggregates with
kaolinite (Chenu et al., 1987). Index ow of xanthan formulations is
weak, with an average of 0.35, compared to scleroglucan based mud
where index ow decrease when HMP concentration decrease. The
increase of consistency in suspensions where HMP clay had been added was more marked in xanthan uids than in those containing
scleroglucan. Xanthan gum's major application in low-solid drilling mud
is that of a suspending agent to impart cuttings carry capacity' to the
drilling mud. (Shah and Ashtaputre, 1999).
For index ow and consistency, the difference between the two
biopolymers is noticeable at weak concentrations, but with high
concentrations this variation decreases. It is possible that with high
concentrations the two curves meet, thus making it possible to dene
a value where the type of biopolymer used is important only by the
proportioning of the additives used.
It is possible that with the addition of the biopolymers, the yield
stress is low like specied in others studies. The addition of polymers
to drilling mud, for example CMC (CarboxyMethylCellulose) even
with very small quantity allows to obtain an increase in viscosity and
very often, a reduction in the yield stress (Wanko and Bekkour, 2003).
3.2. Effect of calcium carbonate on the parameters of HershelBulkley for
both biopolymers

Fig. 5. Inuence of high mod prima on scleroglucan. Flow curve in permanent regime.

The ow curves in permanent regime of the tested uids, containing a different voluminal fraction in calcium carbonate are represented in Fig. 6.


S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490

Fig. 6. Inuence of calcium carbonate on xanthan gum. Flow curve in permanent


In this case, we maintained xed the proportioning of all products,

only the calcium carbonate concentration varies from 09%, to 15%, 20%,
25% and 30%. The results are shown in Table 3.
Concerning the addition of calcium carbonate which is a weighting
material, the yield stress for all formulations containing xanthan or
scleroglucan are practically constant. Their values vary between 2 and
3 Pas.
The consistency k is higher for xanthan gum formulations, ow
index n is constant. For scleroglucan samples, consistency k is low
initially and increases with the concentration, contrary to the formulations containing xanthan where k is almost equal to 2. The ow index of
xanthan gum formulations is xed, compared to scleroglucan drill in
uid, where ow index n decreases for a concentration of 20%. It is
probable that this concentration is the best for maximal value and it is
possible that above this value, the CaCO3 becomes less effective as a
weighting material and appeared to have no signicant effect on the
rheology. This can be attributed to the interaction of CaCO3 with various
components of the drilling mud. CaCo3 is weak mechanically but its
advantage is acid-soluble and can be dissolved with hydrochloric acid. If
higher densities are required, it is preferable to use other weighting
agent like barite or hematite.
Barite (barium sulfate: BaSO4) is a soft, dense (4.14.5 g/cm3) natural
mineral used as a weighting agent in drilling muds of all types (National
Research Council, 1983; Neff et al., 2000) or Hematite (iron oxide: Fe2O3)
occasionally is used instead of barite to prepare a high-density water
based mud or oil based for use in deep drilling (Chnard, 1984).

Fig. 7. Inuence of potassium chloride on xanthane gum. Flow curve in permanent


values are represented in Table 4 as well. In the tested biopolymer

uids, the addition of potassium chloride does not have a notable
inuence on yield stress. Fig. 9 shows that consistency for scleroglucan
uids is constant for all concentrations tested. For xanthan uids,
consistency increase between two concentrations 1.5% and 2.0% and
became relatively constant for other concentrations. Fig. 10 shows that
ow index for sclerolucan and xanthan formulations vary same manner
with different values. Many polysaccharides need some salt to be
present in solution to stabilize their structures, and will denature when
no salt is present. The contour length of the biopolymers decreased
when salt was added, probably because the macromolecules could adopt
a more coiled conformation (Nehal, 2003). Xanthan chains transformed
from isolated extended rods to coils and sometimes aggregates when
KCl was added to solution (Camesano and Wilkinson, 2001).
To summarize, we can deduce that the consistency is higher for uids
containing xanthan than for those containing scleroglucan for the
various concentrations of clay HMP, calcium carbonate and potassium
chloride. The yield stress in all samples is low, the solids proportion in
the drilling uids is considered as being the main factor which affects
the rheology of a mud. A low yield stress is often regarded as being
the criterion of a good drilling mud considering the easiness of uid
The xanthan gum and scleroglucan have similar rheological
properties(Bryant, 1987). The presence of salt can inuence on the
structure of the biopolymer and condition its rheological behavior.
However, some polysaccharides are much rigid, such as xanthan

3.3. Effect of potassium chloride on the parameters of HerschelBulkley

for both biopolymers
In these samples, the potassium chloride concentration varies from
1.5%, 2.0%, 2.5% to 3.0%; the rheograms are shown in Figs. 7 and 8, and the
Table 3
Fluid based biopolymers with various calcium carbonate CaCo3 concentrations
measured at 25 C.
Xanthan gum









Fig. 8. Inuence of potassium chloride on scleroglucan. Flow curve in permanent


S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490


Table 4
Fluid based biopolymers with various potassium chloride Kcl concentrations measured
at 25 C.
Xanthan gum









(Camesano and Wilkinson, 2001) (segment length Lp can be hundred

of nm, depending on whether salt was present) and scleroglucan
(Lp = 80 10 nm) (Stokke and Brant, 1990 Vuppu et al., 1997). But the
presence of additives which chemically react in the aqueous medium
can moderate the rheological variations of mud. By having precise
information on the geological formations, it is possible to choose the
most appropriate biopolymer to each case. The same components
were used in off shore South East Sumatra, in the Indonesian Java, this
eld was drilled using a water based Drill-In Fluid (DIF) composed of
KCl Brine, Xanthan Gum as the primary viscosier, starch for ltration
control and secondary viscosier, and sized calcium carbonate
(CaCo3) as bridging and weighting agent (Saldungaray et al., 2001).
The rheological properties of the biopolymers do not vary in the
presence of potassium chloride in the range of concentrations studied,
particularly for the scleroglucan. This results from its molecular conformation. Other studies conrmed it, the rigidity of the macromolecular chain of scleroglucan when is at aquose solution produce stable
solutions and their rheological properties are independents from the
salinity of the medium (D'Angelo et al., 2001).
The other possibility is the presence of the illites in clay, with illites
the potassium replaces any exchangeable cation impurities in the structure and exposes the entire shale to an environment composed of the
same cation as is binding the illite fractions together (O'Brien and
Chenevert,1973). Scleroglucan was thus proposed as a better alternative
to xanthan gum for drilling uid compositions (Gallino et al., 1996).
The results show that the scleroglucan has a good stability with
salinity compared to the xanthan gum. Biopolymers are therefore being
considered as alternatives and although xanthan gum is currently an
agent used for this purpose, it is not ideal as its temperature and salt
sensitivity are not as low as desired (Parker, 1983). More recently,
properties of such scleroglucan based formulations were investigated to
optimise formulations in terms of minimum uid losses (Cobianco et al.,

Fig. 9. Inuence of the potassium chloride on the consistency.

Fig. 10. Inuence of the potassium chloride on ow index.

The choice of the biopolymer is according to the applications on

drilling, each biopolymer has a specicity and particular application in
elds like the nature of geological formations. Scleroglucan, a nonionic
polymer, can be used to viscosify all types of brines containing monovalent or/and divalents cations, but the uid pH must be kept lower than
12.5. At higher pH values, the polymer completely and irreversibly loses
its rheological properties because the polymer backbone chains strats to
collapse. Xanthan gum contains anionic groups that make it chemically
incompatible with brines containing divalent ions such as calcium
chloride (CaCl2), but xanthan gum can be used to viscosity brines with a
pH higher than 12.5 (JPT, 2003).
4. Conclusion
The present study has claried the effect of additives on water based
mud containing both biopolymers. All the studied systems present a
shear thinning behaviour with a low yield stress; it was shown that the
HerschelBulkley rheological model described all formulations. There is
a good balance between the ingredients' toxicity of these drilling muds
and their interesting properties for high permeability reservoirs or for
complex geometries indeed this formulations present a low toxicity, the
majority of the products are biodegradable thus the environmental
restrictions are respected.
Biopolymers used to viscosify the mud must be chosen carefully,
considering reservoir information and the nature of geological
formations. Chemical compatibility of the various components must
be determined to optimise rheological properties. It is apparent that
the scleroglucan is more effective in the presence of salt than the
The use of this formulations particularly this biopolymers may
limit the mud toxicity and will allow to access to high permeability
reservoir without causing damage. From these concentrations in
biopolymers, it is possible to have drilling mud in conformity with the
API standards and the project will be economic for these values
considering the very high molar mass of these polysaccharides. More
investigations will be favourable to understand better chemical action
of these drilling mud systems.
American Petroleum Institute
concentration (%)
consistency (Pa.s)n
ow index
High Mod Prima

shear rate (1/s)

shear stress (Pa)

shear yield stress (Pa)


S. Baba Hamed, M. Belhadri / Journal of Petroleum Science and Engineering 67 (2009) 8490

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