nanomaterials
Article
Effect of Silica Nanoparticles in Xanthan Gum Solutions:
Evolution of Viscosity over Time
Dayan L. Buitrago-Rincon 1,2 , Véronique Sadtler 2 , Ronald A. Mercado 1 , Thibault Roques-Carmes 2 ,
Lazhar Benyahia 3 , Alain Durand 4 , Khalid Ferji 4 , Philippe Marchal 2 , Julio A. Pedraza-Avella 1, *
and Cécile Lemaitre 2, *
Citation: Buitrago-Rincon, D.L.;
Sadtler, V.; Mercado, R.A.;
Roques-Carmes, T.; Benyahia, L.;
Durand, A.; Ferji, K.; Marchal,
P.;
Pedraza-Avella, J.A.; Lemaitre, C.
Effect of Silica Nanoparticles in
Xanthan Gum Solutions: Evolution of
Viscosity over Time. Nanomaterials
2022, 12, 1906. https://doi.org/
10.3390/nano12111906
Academic Editors: Francesca
Lionetto and Ana María
Díez-Pascual
Received: 24 March 2022
Accepted: 17 May 2022
Published: 2 June 2022
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Attribution (CC BY) license (https://
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4.0/).
Nanomaterials 2022, 12, 1906. https://doi.org/10.3390/nano12111906
1
Grupo de Investigación en Fenómenos Interfaciales, Reología y Simulación de Transporte (FIRST),
Universidad Industrial de Santander, Bucaramanga 680002, Colombia;
dayan.buitrago-rincon@univ-lorraine.fr (D.L.B.-R.); ramerca@uis.edu.co (R.A.M.)
2
Laboratoire Réactions et Génie des Procédés, Université de Lorraine, CNRS, F-54000 Nancy, France;
veronique.sadtler@univ-lorraine.fr (V.S.); thibault.roques-carmes@univ-lorraine.fr (T.R.-C.);
philippe.marchal@univ-lorraine.fr (P.M.)
3
Institut des Molécules et Matériaux du Mans, Le Mans Université, CNRS, F-72085 Le Mans, France;
lazhar.benyahia@univ-lemans.fr
4
Laboratoire de Chimie-Physique Macromoléculaire, Université de Lorraine, CNRS, F-54000 Nancy, France;
alain.durand@univ-lorraine.fr (A.D.); khalid.ferji@univ-lorraine.fr (K.F.)
* Correspondence: apedraza@uis.edu.co (J.A.P.-A.); cecile.lemaitre@univ-lorraine.fr (C.L.)
Abstract: The effect of silica nanoparticles (NP-SiO2 ) in xanthan gum (XG) solutions was
investigated through the analysis of viscosity profiles. First, hydrocolloid XG solutions and
hydrophilic NP-SiO2 suspensions were characterized individually through rheological
measurements, with and without salt (NaCl). Then, nanofluids composed of XG and NP-SiO2
dispersed in water and brine were studied through two different aging tests. The addition of
nanoparticles was shown to produce a slight effect on the viscosity of the fresh fluids (initial time),
while a more remarkable effect was observed over time. In particular, it appears that the presence
of NP-SiO2 stabilizes the polymer solution by maintaining its viscosity level in time, due to a delay
in the movement of the molecule.
Finally, characterization techniques such as confocal microscopy, capillary rheometry, and Zeta
potential were implemented to analyze the XG/NP-SiO2 interaction. Intrinsic viscosity and relative
viscosity were calculated to understand the molecular interactions. The presence of NP-SiO2
increases
the hydrodynamic radius of the polymer, indicating attractive forces between these two
components. Furthermore, dispersion of the nanoparticles in the polymeric solutions leads to
aggregates of an average size smaller than 300 nm with a good colloidal stability due to the
electrostatic attraction between XG and NP-SIO2 . This study proves the existence of interactions
between XG and NP-SiO2 in solution.
Keywords: xanthan gum; silica nanoparticles; colloidal dispersions; rheology; aging tests
1. Introduction
Due to their practical significance, natural polymers, such as xanthan gum (XG)
continue to attract the attention of researchers. Xanthan gum has been widely used for
many applications in the food, pharmaceutical and petroleum industries among others. In
particular, XG is of great interest for Enhanced Oil Recovery (EOR) processes used in the
petroleum industry.
Water-soluble polymers, such as XG, are used in EOR to increase the viscosity of the
water that is injected into the reservoirs in order to extract the oil. Indeed, this viscosity
increase enhances the mobility ratio between the crude oil and the polymer solution, which
impeaches viscous fingering and leads to a greater oil recovery [1–4]. Polymers such as
xanthan gum induce high viscosities in aqueous solutions, even at low concentration.
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2021, 11, x 2 of
1

Nanomaterials 2022, 12, 1906 such as xanthan gum induce high viscosities in aqueous solutions, even at lo2wof c1o4
ncentra
tion. However, EOR not only requires formulations of high viscosity, but also that thi
property remains stable in time against temperature conditions, ionic forces, and shea
H[5o,w6]e. ver, EOR not only requires formulations of high viscosity, but also that this property
remain s s t a b le in t i
X a nt h a n gum icroorganis
iasgainnsatnteiomnpicerahteutreerocopnodliytsioancsc,hioanriidc efoprcreosd,
a n d sh ea r [ 5, 6] .
u c ed b y t h e m
Xanthan gum
Xanthomonas is an anionic
campestris. heteropolysaccharide
The primary structure ofproduced
xanthan bygumtheismicroorganism
a linear, linked β-D-
glu
Xanthomonas campestris.
c o s e b ac k b o nThe e wprimary structure of xanthan gum is a linear, linked i thβ-Da
g l u c os e b ac k b o n e
t ri s a c c h a r i d e si d e ch a in o n e v e r y o t h e r g l u c ose wat C-3 ith
a t r is a c c h a r id e s id e ch a in o n e v e r y o t h e r g l u c
T h e polyme
T h e

pcohlayimnecrocnhasinstcsoonfsiastDs o-gf aluDc-ugrlouncuicroanciicdacuidniut nbiet

tbweteweenentwtwooDD-mmannosseeuunnitist.sO. Onen-he-ahlfalf of th otferthmeitnearml
Din-aml Dan-mnoasnenousneiut ncoitnctoanintasinas pa ypryurvuivcicaaccidid rreesidue
lliinnkkeeddvviaiakekteotgoroguroputop to the tahned4 6anpdo6siptioosnitsio
nwsi,twh iathn aunnuknnkonwown ndidsitsrtirbibuutitoionn.. TThhee D-
maannnnoosseelilninkekdedtotothtehme m
a in ain chai
cchoanintacionnst annsaacnetayclegtyrlogurpouapt patopsoitsiiotinonOO–6–6(F(Figiguurree
11)) [7
7].

FFiigguurere1.1C. Chehmemicaicl astlrsutcrtuucretuorfexoanf txhaannthguanm.gum.

In a q u eo u s so l u t io n s , t h e a d d it io n o f p o ly m e r
In a q u e o us s o l u ti o n s , t h e a d d it io n o f p o ly m
ca u s e s a n in c r ea s e o f t h e v i sc o s i ty ,
e r c a u s e s a n i n c r a s e o f t h e v i s c o sity, du
due to inter- and intramolecular forces within the polymer and with the surrounding
to inter- and intramolecular forces within the polymer and with the surrounding solven
solvent molecules. Furthermore, the presence of charged functional groups in its side chain
m o le c u le s . F u rt h e rm or e , th e p
( ca rb o x yl g ro u p s ( -C O OH ) ) m ak e s
r e s en ce o f c h a rg e d f u n c ti o n a l g r o u p s i n i t s i d e ch
i t a n an io ni c p o ly sa c ch a r id e [ 8 ]. T h e s e p o ly m e r so l u t ion
ain (car
s
e xohxibyilt agrsohueaprs-th(-iCnnOinOgHrh)e) omloagkiceasl
b
ibteahnavaionrio(tnhiecvpisocloyssitayccdhecarreiadsees[8w].itTh hinecsreeapsoinlyg msheer
arsolution
reaxteh)i.bit a shear-thinning rheological behavior (the viscosity decreases with
increasin
sheaXrarnatthea)n. macromolecules may exhibit two different conformational structures: an
ordereXdaanntdh a dimsoarcdreoremdo(lheecluiclaels) cmonafyoremxhatiiboint t[w9–
o11d].ifTfehreeXnGt cuonndfeorrgmoeasticoonfol rsmtrauticotnuarles: an o
cdhearnegdesanindaaqudeiosoursdseorleudtio(nhselwichael)nceoxnpfoosremd attoiotenm[9
p–e1ra1t]u. rTeh, seaXlinGituy,nadnedrgdoeefosrcmoantfionmationa
s t re s s [1 1 ]. As a re s u lt , t h e m o le c ul
c h a n g e s in a qu e o u s s o lu t io n s w
ro t ates its c o nfo rm a tio n a n d t h e
h en xp os e d to te m p e r a tu r e ,
i n t e r m o l ec u l ar an d intramolecular bonds existing in the system, tend to
s al in
weaken andittheny , break,
a n dcausing
d efa ormatio
stress [11]. As a result, the molecule rotates its conformation and the intermolecular an
viscosity loss and/or polymer precipitation [2].
intra m o l e c u l a r b o n d s e x is t in g i n t h e sy s te m,
In r e c e n t y e a rs , si li ca n a n o p ar t icl e s (N P -S iO )
t e n d to w ea k en a n d t h e n 2 b r k , c ausing
h a v e b ee n u se d as a n in n o v at iv e t ec h -
v i s c os i ty lo s
n i q u e t o ad d r es s d is a n d /
foferrepnotlyinmdeurstpriraelccihpaitlaletniognes[2[1].2–14]. Nanoparticles in
general, and
especiIanllyreNcePn-tSiyOe2a,rds,isspilliacya enxacnepotpioanrtailclperso(pNerPti-
e s ow i n t o th ei r s m a ll s iz e an d loavrgaetive tech
S iO 2 ) h av e b e n u se d a s a n in n
snuirqfaucee taoreaad. dTrheesssudriffafceereonf tNinPd
SuiOst2riaallocwhsalalenningteesra[1ct2i–o1n4w].iNthatnhoe p(-aOrHtic/lHes)
ifnungcetnioenrall, and es
gpreocuipasllpyrNesPen-St iiOn 2t,hde ixsapnltahyanexsctreupcttiuornea
lepadroinpgerthtieespolwyminegr ctohatihnesitroslminaklwl sitizhethaenNd Pla- rge sur
SfiaOc2e. aRreecae.nTt hsteusduiersfahcaevoefsNugPg-eSsitOed
a l w s a n in t e r a ct i o n wainthcotnhfeo(r-mOaHtio/Hna)l fturanncstiitoionnal
a lim it a ti on o f t h e x a n th
group 2 d u e t o t he ad d iti on o f N P-
p r s e n t in th e x an t h an
Si O [1 5 ] . I n th e s e n a n ofl u i d s , t h e in t e r a cti on o f th e
s tr u2ct u r e , l ea d i n g t h e p o l y m e r c h a i n s t li n k w
p o ly m er with the NP-SiO allows new cross-linked structures, which delay the
it h t he NP-SiO
conformational
Recent studies have suggested a limitation of the xanthan conformational transition du
transition,
t o t h eimproving
a d d itthe
i o properties
n o f Nof PXG - solutions [11,16]. However, xanthan gum-silica
n a n o p ar t ic le i n t era c ti on s
S iO 2 [1 5] . I n t h e se n a n o f l ui d s , t h e in t e raction of the
in d ilu te s o lu ti o n s ha v e b e e n l itt l e s tu d ie d .
polymer wit
the NInPa-pSirOev2ioaullsowosrkn,etwhe cproolsysm-leinrikceddilustiounctcuurrevse, owf
h ic h d el a y th e c o n f o rm
x a n th an g u m w a s e la b o rat e d b y
a t io n al trans
steioctno,riizminpgrothveinreggtihonesporfodpielurttieeds zoofnXe Gansdolsuemtioi-
ndsilu[1t1ed,16zo].nHe oanwdedviefrfe, rxeannt tmhaenthgodusmto-silica na
pnroepaarretitchlee ninanteorflaucitdio(nXsGinanddilNuPte- [17]. This work
SsioOl2uitniownastheraovrebbreineen) lwitetrle esvtualduiaetded.
is exteInndaedphreevreio, tuosdwesocrrkib, eththeepeovloylmutieornicodf
i l u ti o n cu r ve o f x a n t h a ns ganudmthweaesffecat boof rated b
t h e v i sco si ty of n a n o fl u i d
NsePc-tSoiOri2zionvgertthime er.eTghioenosbjoefctdivieluotfetdhezporneeseannt
e ff e c t
d s e m i -d il u t e d z o n e a n d d study
stu d y i s to i n v e sti g asolutions
te a n andunto d
d ifefrethe
srtainteractions
endt mtheinthods
this
t p r e p
aorfeNtPh-eSinOa2noonflxuaidnth(XanGgaunmd NP-SiO2 in water or brine) were
evaluated [17]. This wor system. Rheological and aging measurements are employed to
characterize
is extendedthe viscosity
here, to describe the evolution of the viscosity of nanofluids and the effect o
NP-SiO2 over time. The objective of the present study is to investigate and understand
th
effect of NP-SiO2 on xanthan gum solutions and to study the interactions in this colloida
Nanomaterials 2022, 12, 3 of

and the stability of the fluids in time. Intrinsic and relative viscosity, Zeta potential, and
confocal microscopy measurements are used to characterize the synergistic interactions
between the polymer and the nanoparticles.

2. Materials and Methods

2.1. Materials
The xanthan gum was purchased from Sukin Industries. The silica nanoparticles
were fumed Aerosil 300 amorphous hydrophilic (300 ± 30 m2 /g) from Evonik Industries.
Sodium chloride was supplied by Sigma-Aldrich 99.5% (58.44 g/mol). Deionized water
was used as solvent and glutaraldehyde, provided by Sigma-Aldrich (50 wt.% in H2 O),
was added as a bactericidal agent.

2.2. Preparation of Xanthan Gum Solutions and Nanoparticles Suspensions

The polymer solutions were prepared with two different solvents. The first solvent was
deionized water, in which polymer powder was incorporated at different concentrations
(150, 300, 600, 1200, 2400 and 4800 ppm). The second solvent was brine, previously
prepared with different concentrations of NaCl (0.5, 1 and 3wt%), in which the polymer
powder was incorporated at a concentration of 600 ppm, to evaluate the influence of
ionic forces on the viscous behavior of the fluid. All solutions were left under magnetic
stirring at room temperature, and bactericide was added to the solvent at a fixed
concentration (80 ppm) before incorporating the polymer. In order to ensure that the
polymer was fully hydrated, two different hydration times were tested: 24 and 48 h. The
viscosity profiles after these two durations were compared.
Similarly, nanoparticle suspensions were prepared with the same two solvents,
before their rheology was characterized. On the one hand, nanoparticles were
dispersed at different concentrations (100, 200, and 300 ppm) in deionized water. On the
other hand, NaCl brines were prepared with different concentrations (0.5, 1, and 3wt
%), and then, the nanoparticles were added at a concentration of 300 ppm, so that the
variability of the viscosity of the nanosuspensions under different ionic charges was
evaluated. All the suspensions were left under magnetic stirring for 1 h at room
temperature.

2.3. Influence of Temperature during Nanofluids Preparation

In previous work, various preparation methods of these nanofluids were evalu-
ated [17]. The protocols differed in the polymer hydration time, the order of addition
of the components, the sonication time applied to the NP-SiO2 suspensions, and the inter-
action time between the components. The method yielding the highest viscosity profile
(30.1% higher than the XG solution without NP-SiO2 ) with a minimum number of steps
was retained. It consists in incorporating the XG and the NP-SiO 2 at the same time in the
solvent and to leave the resulting mixture under magnetic stirring during 24 h. In the
same study, the concentration regimes for XG solutions were determined: the dilute
regime corresponds to 0–600 ppm XG, and the semi-dilute regime to 600–4800 ppm XG
[17].
In the present work, the effect of temperature applied during nanofluid preparation
was evaluated. Using the previously selected preparation method, the operating tempera-
ture was set successively to 20 ◦ C, 40 ◦ C, 60 ◦ C, and 80 ◦ C. The formulations were prepared
with fixed components concentrations (XG: 600 ppm; NP-SiO2 : 300 ppm and 3wt% NaCl)
and at constant pressure.

2.4. Rheological Characterization

Two different apparatuses were used to measure the viscosity of the different fluids
considered in this study: a rheometer and a capillary viscometer.
A strain-imposed Rheometric Scientific RFS II rheometer was used, equipped with a
rheoreactor geometry. This geometry consists of a rotating helical ribbon of 17.95 mm
radius rotating in a tank of 27.5 mm internal radius and 42 mm inner height. It is adapted
to low viscosity fluids since it generates higher torques than classical geometry, like
plate/plate
Nanomaterials 2022, 12, 4 of

cells. Furthermore, the ribbon agitator ensures the homogeneity of the mixture. The
accuracy of this system has been proven by previous studies [18]. The tests were executed
at constant temperature of 25 ◦ C or 60 ◦ C. The shear rate was varied between 0.1 and 100
s−1 , with sensitivities of 1 Pa·s for the viscosity and 0.002 N·m for the torque. Finally, the
effect of NP-SiO2 on the stability of the viscous profile of the formulations under aging
conditions was evaluated. All measurements were repeated at least twice for each
formulation to confirm reproducibility. The particular shear rate of 7.3 s−1 was used to
compare some results since it is a representative rate for the flow profile under well
conditions for EOR applications [19].
Capillary viscometers measure a viscosity from the time it takes for a volume of
polymer solution to flow through a thin capillary.
µs
ts ∼ (1)
ρs
µ
t ∼ (2)
ρ
with ts and t the flow times obtained for the solvent and the considered solution, respec-
tively, ρs and ρ the solvent and solution densities, and µs and µ the solvent and solution
viscosities. Considering equivalent densities (since the solutions are dilute), the relative
viscosity can be obtained through
t
µrel = (3)
st

In order to evaluate the evolution hydrodynamic radius of the polymer in time with
or without nanoparticles, the intrinsic viscosity [µ] of the formulations was determined
from rheological measurements. The intrinsic viscosity of fresh fluids (initial time) was
obtained from capillary viscosimetry, while the evolution of the intrinsic viscosity over
time was calculated from the rheograms obtained with the rheometer at a shear rate of
7.3 s−1 .
Intrinsic viscosity is related to the hydrodynamic volume occupied by isolated indi-
vidual polymer molecules [20]. The relationship between dilute polymer solution
viscosity and concentration can be described by many empirical forms, the most common
being the Huggins equation [21].
µs p 2
= [µ] + k0 [µ] C (4)
C
where k0 is the Huggins constant and C is the polymer concentration. The specific viscosity
µsp is defined as the relative increase of viscosity.

µ − µs
µsp = µs = rel − 1 (5)
µ

with µ and µs , the apparent viscosities of the solution and the solvent, respectively,
and µrel = µ/µs the relative viscosity. The Huggins equation may be simplified by
removing the second-order term for very dilute solutions. Combining the simplified
Equations (4) and (5), the relative viscosity reads [22].

µrel = 1 + [µ]C (6)

In this study, [µ] was determined for all fluids of different ages by measuring the
slope of the relative viscosity as a function of polymer concentration, within the range
1.0 < µrel < 2.0. The obtained intrinsic viscosities were then plotted as a function of aging
time [23].
Nanomaterials 2022, 12, 5 of

2.5. Aging Tests

In the context of EOR applications, it is important to consider the viscosity stability
of XG solutions over time. Indeed, these fluids may remain several months in the
reservoir rock and should keep their efficiency.
In order to study the evolution of the formulation viscosity over time, two aging
tests were performed on the nanofluids. The first test was conducted for an aging time of
1 month. Fluids of different concentrations of NaCl (0% and 3wt%), NP-SiO2 (0 ppm and
300 ppm) and a fixed concentration of 1000 ppm XG (semi-diluted zone) were stored at a
constant aging temperature (60 ◦ C) for this duration.
A second longer test was performed for an aging time of 7 months. The tested fluids
contained NaCl (3wt%), polymer at a dilute (400 ppm XG) or semi-diluted (1000 ppm XG)
concentrations and nanoparticles of different concentrations (0 ppm and 300 ppm NP-
SiO2 ). The viscous profile of the fluids was measured as a function of the shear rate at
different times.

2.6. Confocal Microscopy

Confocal microscopy measurements were performed using a ZEISS LSM800
Confocal Laser Scanning Microscope. The microscope was equipped with four solid-state
lasers, three GaAsP PMT detectors, and one T-PMT detector for transmission light
detection. Images were obtained for nanoparticle suspensions (300 ppm), polymer
solutions (1000 ppm), and nanofluids (XG: 1000 ppm; NP-SiO 2 : 300 ppm) in fresh
conditions (initial time) and aged conditions (1 month). Confocal microscopy enables the
creation of sharp images without any disturbing fluorescent light.

2.7. Zeta-Potential Measurements

Zeta potential measurements of polymer solutions in water and brine (3wt% NaCl),
and nanofluid (400 ppm XG, 300 ppm NP-SiO2 and 3wt% NaCl) were carried out with a
Malvern nanosizer at 25 ◦ C. The Zeta potential reflects the potential difference between
the electric double layer of electrophoretically mobile particles and the layer of dispersant
around them at the slipping plane. It provides an estimation of the surface charge of the
particles.

3. Results and Discussion

3.1. Viscosity Behavior of Xanthan Gum Solutions
The viscosity curves of the polymer solutions were compared for hydration times
of 24 h and 48 h. The viscosities obtained after 24 h of stirring were very close to that
obtained after 48 h. It was thus concluded that a 24 h stirring period is enough to ensure
the complete hydration of the polymer. The polymer solutions show a marked shear-
thinning behavior for concentrations above 600 ppm, Figure 2. For lower concentrations
(150 ppm and 300 ppm XG), shear-thinning is weak, and rheological behavior is close to
Newtonian. As expected, the viscosity increases with polymer concentration.
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eexxtt ee nnddee dd dd uu ee ttoo eel lee cc tt rr oo s stt aa tt iic c rree pp uupll
t e e d d u e to e l e c t r o s t a t ic r e
ussiliosoinnonooffotthfhetehnneeegngaeatgtiivavteeilvlyyeclcyhhaacrrhggaeerddgeaadcc
a ec te yt ly gl
-- e t y l g
g r o u p s [ 2 4 ] . W h e n s a lt is a d d e d , c
r roo u up ps s [[22 4 4] ].. W W hhe en n ssa al ltt iiss aa dd dd ee dd ,, cc h
hhaaarrrgggeeessscccrrreeeenniiinngg ccaauusseess tthe
ssiidee
cchhaaiinnss t tooc co ol l al ap ps se e
t c o ll a p s e
d
d o own t o t h e bbaacckkbboonnee,, hheennccee ggiivviinngg tthhee xxaanntthhaann
t o t h e
molleeccuullee aa rroodd--lliikkee sshhaappee,, morree ccoompaacctt,,
c o r r e s p o
c o r r e s p o n d in g n d i n g
ttoo aa rreedduucceedd hhyyddrrooddyynnaamicc ssiizzee ooff tthhee
molleeccuullee,, lleeaaddiinngg ttoo aa rreedduucceedd vviiss-- viscosity [25,26].
cosity [25,26].
NNNaaannnooommmaaatte 666o

FFFiigigguuurrreee33... VViiissscccoosssiitittyyyooofffpppoololyylmymmeerer srsoosllouulttuiiootin

nossn((s660(06000pp0pppmpXmXGGX)) wGw)iitthwh didtihiffffederriefefnnettrNeNnaatCCNll caco
Connlccceeonnnttrcraaettniiotornnasstiaaossnaasffauusnncac--
ftutiiononcntoiooffntthhoeef stshheeaasrrhreraatree.r.aWteaa. ttWeerra((t□□e)r),,(00 ..55)%,
%0N.N5%aaCCNll (a(●●C)),l, 1(1•%%), NN1%aaCCNll (a(▲Cl)),(, Naann),dda3n3%%d 3NN
%aaCCNlla((C■■)l)..( ).

3..22Viscosity
33.2. .. VViisscBehavior
coossiittyof y BNanoparticle
Beehhaavviioorr ooff Nannooppaarrttiiccllee SSuussppeennssiioonnss
T
TThe h e v
h viscosityi s co s iittyof
o
e v i s cbehavior s yb beehha2asuspensions
NP-SiO vviioorr ooffwasNPanalyzed
--SSiiO22 stosuu ssppeethe
explore nnssdegree
iioonnss
waass aannaallyyzzeedd ttoo eexxpplloorree tthhee ddeeggrreeee
dispersion of the nanoparticles. Indeed, for a smaller agglomerate size or a better dispersion
ofofdispersion
dispersion of the nanoparticles. Indeed, forforaviscous
as smaller
aller agglo erate size
sizeorora abetter dis-
of the NP-SiO2 , ofthethe nanoparticles.
suspensions tend Indeed,
to be more andagglomerate
to adopt a Newtonian better
behavior
persion of the P-Si
persion independent ,
of the NP-SiOof2, thethe suspensions
the shear
suspensions tend to be
tend to be re
more viscous and to adopt a onian
flowviscous
profilesand to adopt a present
2
(viscosity rate). However, the obtained in the
behavior
behavior(viscosity
(viscosityindependent
independentofofthe theshear
shearrate). ver, the
rate). However, theflo
flowprofiles
profilesobtained
obtainedin
Nanomaterials 2022, 12, 7 of

study for three different NP-SiO2 concentrations did not show a significant difference,
see Table 1. Indeed, there was no significant viscosity change between suspensions of 100
ppm to 300 ppm NP-SiO2 . This is possibly due to the low studied concentrations.

Table 1. Viscosity of nanoparticles

suspensions.

Fluid Viscosity (Pa·s) 1

Water 0.001000
100 ppm NP-SiO2 0.001012
200 ppm NP-SiO2 0.001140
300 ppm NP-SiO2 0.001167
1
Viscosity—Newtonian behavior.

The effect of salt on the NP-SiO2 suspensions rheology was then investigated. No
significant difference was observed in water or in brine. The viscosity profiles were not
altered at all. However, since for EOR applications, working brines are estimated to
contain an average concentration of 30,000 ppm (3%) NaCl, this salt concentration is
chosen as a reference in the present study.

3.3. Influence of Temperature during Nanofluids Preparation

After choosing the preparation method from a previous study [17], the effect of
temperature imposed during the preparation of nanofluids was evaluated at 20, 40, 60
and 80 ◦ C. The intermediate concentration of 600 ppm XG, separating the dilute and semi-
dilute regimes, was selected and the NP-SiO2 concentration was fixed to 300 ppm. All
measurements were then performed at the same temperature 60 ◦ C.
The obtained viscosities are shown in Table 2 for a shear rate of 7.3 s−1 , and
compared to the viscosity of the polymer solution without nanoparticles. A viscosity
increase ranging between 15.7 and 21% is obtained for the lower tested temperatures (20
to 60 ◦ C), showing an effect of the presence of the particles. The highest viscosity is
obtained for a preparation temperature of 20 ◦ C. At higher temperatures (80 ◦ C),
however, the measured viscosity is almost that of the polymer solution, which indicates
that the effect of the NP-SiO2 is negligible.

Table 2. Relative viscosity increases due to preparation temperature.

Fluid Preparation Temperature Vicosity Pa·s Visc

Polymer solution ◦ 0.030604 Co
20 C
Nanofluid 20 ◦C 0.037030
Nanofluid 40 ◦C 0.035488
Nanofluid 60 ◦C 0.035959
Nanofluid 80 ◦C 0.031124
1
Viscosity at a shear rate 7.3 s−1 .

This low effect of temperature could be related to the ionic strength. Indeed, the
rheological behavior results from a balance of several factors. Hydrating the polymer at
high preparation temperatures promotes thermal disassociation of the polymer structure. In
aqueous solutions, the backbone of xanthan changes from a disordered (or partly ordered
in the form of a randomly broken helix) to an ordered structure when increasing the
temperature. The conformation of the polymer in the solution mainly affects the viscosity
of the fluid in that a more disordered conformation will achieve a higher viscosity value.
In this case, by increasing the preparation temperature, the molecule is ordered and the
interaction with the nanoparticles is promoted. However, the high ionic strength (3%
NaCl) could inhibit the polymer chain extension/repulsion at high temperature due to
charge screening effects and stabilize the ordered conformation, which leads to a lower
fluid viscosity [10].
 Nanomaterials 2021, 11, x 8 of 14

Nanomaterials 2022, 12, 1906 8 of 14

screening effects and stabilize the ordered conformation, which leads to a lower flu
cosity [10]. id

33.4.4. .AAggininggTTesetss
t—s—SStatabbiliiltiyty
IInnoorrddeerrtotoeevvaaluluaateteththeessttaabbiliiltiytyoofftthheeflfuluididvvisisc
coossitiytyininttiimmee, ,aaggininggtteessttsswweerreeccaarrrrieiedd oouutt. . SShhoorrtt
aaggiinngg tteessttss ((11 mmoonntthh)) wweerreeaapppplliieeddttooppoolylymmeerrssoo
luluttiioonnss((11000000ppppmmXXGG))aanndd
nnaannooflfuluiiddss ((11000000 ppppmm XXGGaanndd330000ppppmmNNPP-S-
SiOiO22)),, eellaabboorraatteedd iinn wwaatteerr oorr bbrriinnee ((33wwtt%%
NNaaCCll)).. The temperature usseedd bbootthhffoorrsstotorraaggeeaannddfofor rththe
evivsicsocsoistyitymmeaesausruermemenetns tws awsa6s0
6°0C◦ (CFi(gFuig
rue r4e).4).

FFigiguurree44. .VVisisccoossitiytyaassaafufunncctitoionnoof ftitmimee.

.VVisicsocosistiiteiseswwereeremmeaesausurerdedataat ashsehaerarartaeteofo7f .73.3s−s−11.
.SSttoorraaggee aannddmmeaesausurermemenetnstps epreforfromremdeadt aTt =𝑇
◦
=606 0C°.CN. aNnoaflnuofidluiind winatwera(t1e0r0(010p0p0mpXpGmaXnGd 3a0n0dp3p0m0
NppPm-SiON2P)- (–S iO).2)P(o–l■y)m. Peorlsyomluetriosonluintiwonatienrw(1a0t0er0 (p1p0m00
XpGpm) (-X-G )).(-N-■an).oNflaunidofilnui3d%inN3a%ClNbarCinleb(r1in00e0(1p0p0m0 pXpGm
aXin
nGd 3a0n0dp3p0m0 pNpPm-SNiOP-)Si(O– 2).(P–●o)ly. Pmoelrymsoelur tsiolnutinio3n
% N3a%CNl barCinl2eb(r•1in0e00(1p0p0m0 pXpGm) (X-G- ) ()-. - ●). •

TThheefoforrmmuulalattioionnssccoonnttaaiinniinnggNNPP--SSiiOO22
pprreesseenntt hhiigghheerr vviissccoossiittiieess tthhaann ppoollyymeerr ssoolluu--
ttioionnsswwiitthhoouutt nnaannooppaarrttiicclleess,, at all times.
FFuurrtthheerrmmoorree, ,ththeevvisisccoosistiytyoof falalllfofromrmuulaltaitoinosnsis
isfofuonudndtotdo edcerecraesaesien itnimtiem, beu, bt
uthtethveisvcoisscitoysiltoyssloi ssliims iltiemditiendthine
pthr espenrecseeonfcne aonfonpaanrotipclaers-. tIicnledsi.stIinlleddiswtialltedr awt
2a0te°rCa, th e b ◦a c k b o ne o f x a n th a n i s d is or d e r e
t 2 0 C , t h e ba c k b o n e o f x a n th a n i s
di(shoerldicearlefdor(mhe),liacnadl fhoirgmhl)y, aenxdtehnidgehdlydeuxetetnodtehde
delueecttroostthaetieclerectpruolsstiaotnics
rferpoumlstihoenschfraormgedthge rcohuaprsgeodn gtrhoeuspids eocnhathines
s[i1d0e]c. hTahiniss d[1is0o].rdTehreisddciosonrfodremreadticoonnofof
rtmheatpioonlyomf etrhecopuolldympreormcouelda pgrroemateortesyangerregaitsetirc
sXynGe/rNgPis-tSiciOX2Gin/tNerPa-cStiiOon2
.inFtoerrmacutiloatni.oFnosrpmreuplaatrieodnsinpraedpiasroerddienreaddciosonrfdoer
mredaticoonnfoofrmthaetpioonl- oyfmtheerp(owlyitmhoeur t(wNiathColu)
tdNisapClal)ydaishpilgahyearhviigshceorsivtyisctohsaintystahlatyn
saltuytisoonlus,tidounes,tdoutehteoftahcet ftahcatt tthhaet
txhaentxhaannthcahnaicnhsaainres amreorme
orereperellpeedllferdomfroemacheaocthhoert.hAer.gAregatreratreerpruelpsiuolnsioinncr
ineacrseasstehse the dhryoddryondaymniacmriacdriuads ioufs
tohfethmeomlecoulelec,uwleh,
wic hitchhentheonccoucpciuespiaeslaarglaergveor lvuomluemweitwhiinthtihne
tfhleuiflduliedadleiandgintog atohaighhiegrhveirscvoisscitoysiotyf tohfethsyesstyemste.
mTh. eTsheerseesureltssuslthsoswhotwhetihnefliuneflnuceenocfe noaf-
nnaonpoapratirctliecsleosnotnhtehceocnofnorfomramtiaotnioonf oXfGX,Gan,
adncdoncosenqsueqenutelnyt, loyn, otnhethveisvciossciotysiotyf pofolpyomlyemr seor-
sloultuiotino,ns, hsohwowinignga agrgeraetaetrerXXGG/N/PN-PS-iOSi2Oin2
tienrtaecrtaicotnio. n.
TThhee eefffeeccttooffththeennaannooppaarrtticiclleess oonn tthhee vvisisccoossiittyy
ooff tthhee flfuluidid isismmoorreerreemmaarrkkaabblelein 1
for ssoolu
in fresh luttiio(time
fluids onnsszero),
wwiitthh
−
waatteerr solvent. AAttaasshheeaarrrarateteoof f7.73.3s−s1 for fresh fluids (time zero), the
vis- vcioscsoitsyitiys is cinrecarseeadsebdyb3y5%35%wiwthitnha napnoarptaicrlteicsliens
winawtear,tecro, mcopmarpeadretod tthoeth20e%20i%ncrineacrseaosbe-
otbatinaiendedininbrbirnien.eT.
hTehevivsicsocsoistiytystsatbabililtiytyoovverertitmimeeisisaallssoo ddiiffffeerreenntt iin
water and iin bbrriinnee.. SSooluluttiioonnss pprreeppaarreedd in
distiilllleed wwaatteerruunnddeergrgooaagrgeraetaetrelrolsoss. sA. fAtefrte3r0
3d0aydsa, yasv, a v i s c o s i ty
i sc o s i t y l o ss los s
f 45 %o f 4i5s
%miesamsueraesdufroerdpfoolrypmoelryimc seorliuc tsiolustiaonnds oannldy o30n%ly
f3o0r%nafnoor fnluaindosfl. uInidbsr.inIen (b3rwint%e (3NwatC%l),NtahCel)e,
t h e ef fe
f f e ct o f n c t aonf onpanarotpicalretsicolens
oflnufliduivdisvcioscsoitsyityisisreredduucceedd: : tthhee viscosity hhaarrddllyy
cchhaannggeedddduurriinngg tthhee enttiire aging periiod..
IInntthheepprreesseenncceeoof fNNaaCCl,lt, hthe epoploylmymeresrtsatbaibliizliezsetso
taonanorodredrerdedcocnofnofromrmatiaotnio. nX.aXnathnathnagnugmumchachinasina
srearmeumchucmhomreoregridigaidndansdtasbtlaebdleuedutoe tthoe
t h e c o ll a p s e o f th e t r is a c c h a rid e sid e c h a i n s o n t o t
c o ll a p s e o f t h e tr is a c c h a r id e si de ch a i n s o n t o t h e
h e m a in b a c k b o n e . T h i s e f fe c t r e d u c e s the mobility of
m a in b ac k b o n e . T h i s e f fe c t r e d u c e s t h e
the molecule and hinders the degradation of the molecular chains with or
without nanoparticles [27].
Nanomaterials 2021, 11, x 9 of 14

Nanomaterials 2022, 12, 1906 9 of 14

mobility of the molecule and hinders the degradation of the molecular chains with or
without nanoparticles [27].
AAsseeccoonnddaaggiinnggtteessttwwaassppeerrffoorrmmeeddffoorraalloonnggeer
rttiimmee((77mmoonntthhss))ttooffuurrtthheerrssttuuddyytthhee
eeffffeecctt oofftthheennaannooppaarrttiicclleess aanndd tthheeiirriinntteerraaccttiioonn w
wiitthh tthhee ppoollyymmeerr iinnssoolluuttiioonnss wwiitthh hhiigghh
iioonniicc ssttrreennggtthh ((33wwtt%
% NNaaCCll,, FFiigguurree55)). . FFoorr tthheessee tteessttss,, ttwwooppoolylymmeerrccoo
nncceennttrraattiioonnss wweerree
ccoonnssiiddeerreedd((ddiilluuttee, ,440000ppppmmXXGGaannddsseemmii--
ddiilluuttee,,11000000ppppmmXXGG))aannddaassiinngglleennaannooppaarrttiiccllee
ccoonncceennttrraattiioonn (300 ppppmmNNPP-S-SiOiO2)2.)T.
T h e s t o r a g e t em p e r a tu
h e s to r a g e t e m p er at u r e o f th e r e o f ftlhueidfls uaindds tahnedtetsht
emteeasst- mureeamsuernetmtemntptermatpuerreatwuererewthereestahme
◦
es,a6m0e°,C6.0 C.

FFiigguurree 55.. Viscosity as a ffunccttiioonn ooff ttiimmeeaattaasshheeaarrrarateteoof

f7.73.3s s .−S1t. oSratogreaagnedanmdeamsuearesmureenmt eant t𝑇a=t
− 1

60 °C . S e m i - d ilu t e n a n o f lu i d ( 1 0 0 0 p p m X G, 3 00
T = 6 0 ◦ C . S e m i- d il u t e n a n o fl u i d ( 1 00 0 p pm X G ,
p p m N P- Si O 2 a nd 3 % N aC l) ( – ■ ) . S e m 2 i- d il u t e p o l-
3 0 0 pp m N P - Si O a n d 3% N a C l ) ( – ) . S e m i - d il u te
y tme na
ilu
p o
e rns oo lu
r flu
ti o n 4 (1
sonial dun(otio 0 n000p(10p0p
m p0Xmpp
G X, 3G 00
a np dp m i (-O-2■).(-D-
3 %NNP a-SCl)
) . ly
D mil ue te fl u i d ( 040NaCl)
0 p pm m XX GG a, n30 d 0 3p%p m
NP-SiO and 3% NaCl) (–N). Semi-dilute polymer solution (400 ppm XG and 3%(-NaCl)
and 3%
2
NaCl) (–▲). Semi-dilute polymer solution (400 ppm XG and 3% NaCl) -▲). (- -N).

AAfftteerr77mmoonntthhss,,aalllltthhee ppoollyymmeerrssoolluuttiioonnsssshhoow
weeddaassttrroonnggddeeccrreeaasseeiinnvviissccoossiittyywwhhiillee
tthheennaannooflfluuiiddssddiissppllaayyeeddaammooddeerraatteevviissccoossiittyylloo
ssss.. TThhee ssaammee bbeehhaavviioorr wwaassoobbsseerrvveeddffoorr
bbootthhddiilluutteeaannddsseemmii--
ddiilluutteeppoollyymmeerrssoolluuttiioonnss. . TThhee sseemmii--
ddiilluutteeppoollyymmeerrssoolluuttiioonnwwiitthhoouutt
nnaannooppaarrtitciclelessuunnddeerwrwenent
ta a727%2%vivsicsocsoistyityrerdeudcuticotnio, nw,
hwilheiltehethseamsaemfoe rfmorumlautiloantiocnonctoanintaining-
ninangonpaanrotpicalertsicelxehs iebxihteibditaedviascvoisitoysidtyrodproopf
on ly 3 4 % . F o r th e d il u te p oolylymmeerriiccssoolluuttiioonn,,
o nl y 3 4 % . F or th e d i lu te p
aa vviissccoossiittyy ddrroopp ooff7733.5.5%
% iinnttimimeewwaassffoouunnddwwitithhoouuttnnaannooppaarrttiicclleess,, wwhhiille
e tthhee ddrroopp wwaass hhaallvveedd((3377%
%))iinntthheepprreesseenncceeooffnnaannooppaarrttiicclleess. .TThheesseelloonnggeerrtte
essttssccoonnfifirrmmtthhaatttthhee pprreesseennccee ooffNNPP--SSiiOO22
p r o mo t e s t h e s t a b i l i t y o f t h e fl u i d , m a i nnttaaiinniinnggtthh
p r o o t e s t h e s t a b i l i t y o f t h e fl u i d , m a i
eevviissccoouusspprroofifliele. .
 TThheesseerhrheoeolologgiciaclarlerseuslutsltcsocuoldulbde
baettraitbturitbeudtteodwtoeawk
epahkyspichaylsaitctarlacattitvreacftoirvceesfobrectewsebeen-
tthwe eceonmtphoenceonmtsp, osuncehntass,
hsuycdhroagsehnybdornodgse.nTbhoensdusr.fTacheeosfusrifliaccaenoafnsoilpicaartnical
nesopexahrtiibciltessseilxahniobl-
gitrsousiplasn(oSli-gOrHou) pwsh(iSlie-OXHG )cwhahiinles
cXoGntcahinaihnys dcroonxtyailngrhoyudprsox(-yOl Hgr)o, uwphsic(h-OmHa)k,
ewsh(i−chOm−aHkδe+s
.(.−.OO−Hδ−δ)+·d··iOpδo-)led–idpioploe–
lediinptoelreaicntitoenrascptiosnssibploe s[s2i8b]l.eH[2o8w].eHveorw,
tehveern,atthuerenoatfutrhee oinf ttehreacintitoenr-
baecttwioenenbextawnethenanxagnutmhaanngdusmilicaandnasniloicpaarntaicnloespaisrtsi
tcill sanisosptiellnaqnuoepsteinonq.uTehstisioans.pTehctiswaislpl becet
dwisicllubseseddisicnutshseedfoilnlotwheinfgolsleocwtiionngs.sections.

33..55.. IInnttrriinnssiicc aanndd RReellaattiivvee VViissccoossiittyy

IInnttrriinnssiicc vviissccoossiitty off xanthan gum
sollutiioonnss aanndd nnaannoofflluuiiddssiisssshhoowwnnininFFigiguurere66aas sa
afufunnctcitoionnoof faaggininggttiimmee. . UUssiinngg tthhee siimplliiffii ed Huggins
equation, EEqquattiions ((44))––((66)) wweerree
aapppplliieeddffoorreeaacchhmmoonntthhaannddccoommppaarreeddtthheessoolluuttiio
onnsswwiitthhoouuttNNPP--SSiiOO22 ((poollyymeerr ssoolluuttiioonnss))
aannddwwiitthhNNPP--SSiiOO22 ((nnaannooflfluuiiddss))..
NNaannoommaateterriaialsls2200221, ,1121, ,1x906
1100ooff1144

50

40

30

[μ] 20

10
1 2 3 4 5 6 7
Months

F i g u r e 6 . I n t r in s i c v is c o s i ty [ 𝜇 ] a s a fu n c t io n o
Ff i gtim o s pit ey r [f µo ] arms a ed
u re.e S6 .toI nrat rg ine sani c dv tise sc ts fu an t ct
𝑇 i=o 6n0o° fC .
tim e. S to ra g e an d te s t s pe r f o r m ed at T = 6 0 ◦ C . Nanofluid (–
■). Polymer solution (–●).
Nanofluid (– ). Polymer solution (–•).

IInn ddiilluuttee ssoolluuttiioonnss,, the polymer chains aarree

sseeppaarraattee,, aannddtthheeinintrtrininssicicvvisicsocosistiytyoof fa
appoloylmymererininsosloultuiotinondedpeepnednsdosnolynloynotnhethheydhryoddry
ondaymnaicmdiicmdeinmseionnssioonfsthoef pthoelypmoelyrm(heyr-
(dhryoddryondaymnaicmvicolvuomluem) [e2)9[]2. 9T]h.
eTihnetriintsriicnvsiicscvoissictoysoitfyXoGf
XsoGlustoioluntsiownisthwaitnhd awndithwouitthoNuPt- NSiPO-S2
i O 2 i s s ho w n in F ig ur e 6 a s a f u n c ti on o f a g in g tiimmee..
i s s h o w n in F ig u re 6 a s a fu n c t io n o f a g in g t
TThhee esttiimated iinttriinssiicc vviissccoossiittyy ((4411.5.522ddLL//g) obtained for tthe
naanoflfluiid iiss muucchh
hhiigghheerr tthhaann tthhaatt oobbttaaiinneedd ffrroommppoollyymmeerr
ssoolluuttiioonn ((37..41
dL/g ). T h e s e r e s u lt s s u g g e s t t h a t the h y dr o d y n acmraic
). Th e s e r e s u l ts s u g g e st t h a t t h e d r o y n a m i
diruasdoiuf sxaonftxhantghuanm
giunmcreianscerseabsesabuesceauosfetohfethneannoapnaorptaicrlteicsl,eas,nadndthtihs isini
cnrceraesaeseoof ftthhee hydrodynamiic vvoolluummee ssuuggggeessttss an efffiicient
iinntteerraaccttiioonnbbeetwtweeennththe epoploylmymerear nadndthethneananpoarptai
crlteic. lFeo. r Fboorthbpotohl- pyomlyemr
esrolsuotliuotniosnasnadndnannaonfolufliudisdsthteheinintrtirninsiscicvvisisccoossitiytydd
eeccrreeaasseess over time. Howeveerr,, tthhee
rreedduuccttioionnoofftthheeppoolylymmeerrddimimeennssioionnssisismmoorreererem
maarkrkaabbleleininththeeaabbsesennceceoof fnnaannooppaartritcilcelse.s.
In order to evaluate the interaction between the xanthan gum and the silica
nanoparti- cles, the relativeµviscosity is plotted as a function of xanthan concentration
(Figure
1.35 7).
As expected, the relative viscosity µrel of polymer solutions and nanofluid was found to
increase
1.30 with polymer concentration. The slope is higher for nanofluids than for polymer
solutions, indicating a higher intrinsic viscosity and thus a higher polymer hydrodynamic
radius1.25
in the presence of nanoparticles. Furthermore, a linear variation was found for the
polymer solutions, which denotes a mass contribution of the xanthan gum without specific
interactions
1.20
[10]. On the contrary, the relative viscosities of the nanofluids did not vary lin-
early, indicating that specific attractive forces were present between the xanthan molecules
and the silica nanoparticles. The non-linear trend is due to another factor than the polymer
μ

1.15
concentration increase. Thus, the hypothesis of intermolecular binding between xanthan
gum and silica nanoparticles is supported by the intrinsic viscosities and relative viscosities
1.10
values obtained for the different formulations.
1.05
1.00
50 100 200 300 400
Xanthan Gum (ppm)
Figure 7. Relative viscosity μrel against xanthan gum concentration. Nanofluid (–■). Polymer solu-
tion (–Δ).

In order to evaluate the interaction between the xanthan gum and the silica
nanopar- ticles, the relative viscosity ��௥௘௟ is plotted as a function of xanthan
concentration (Figure
7). As expected, the relative viscosity ��௥௘௟ of polymer solutions and nanofluid was
found to increase with polymer concentration. The slope is higher for nanofluids than
for poly- mer solutions, indicating a higher intrinsic viscosity and thus a higher polymer
hydrody- namic radius in the presence of nanoparticles. Furthermore, a linear variation
was found for the polymer solutions, which denotes a mass contribution of the xanthan
gum without
 SiO2 is shown in Figure 6 as a function of aging time. The estimated intrinsic viscosity
(41.52 dL/g) obtained for the nanofluid is much higher than that obtained from polymer
solution (37.41 dL/g). These results suggest that the hydrodynamic radius of xanthan gum
increases because of the nanoparticles, and this increase of the hydrodynamic volume
Nanomaterials 2022, 12, 1906
suggests an efficient interaction between the polymer and the nanoparticle. For both pol-
11 of 14
ymer solutions and nanofluids the intrinsic viscosity decreases over time. However, the
reduction of the polymer dimensions is more remarkable in the absence of nanoparticles.

1.35

1.30

1.25

μ 1.20

1.15
Nanomaterials 2021, 11, x 1.10 11 of 14

1.05

specif1ic.00interactions [10]. On the contrary, the relative viscosities of the nanofluids did
not vary linearly, i5n0dicating10t0hat spec2i0f0ic attrac3t0iv0 e force4s0w0 ere present
between the xanthan molecules and the silic a n a n o p ar ti cle s. T h e non-
X a n th a n G u m (p p m )
linear trend is due to another factor than the polymer concentration increase. Thus, the
hypothesis of intermolecular binding be-
tFwFigiegueurnerex77.a.nRtehellaanttiivgeuvmiscaonsditysiμµlri ec l
r e
aaagngaainninsotsptxaxrnatntihcthalenasngiusgmusmucpocpnoconercnteetnrdatrtbiaotynio.tn
l
hN.eaNninoatfnrluionifldsuic(i–dv■(i)–s. cPoo)s.lyitPmieoeslryamsnoedlur -
rseotiloauntiov(–neΔ(v)–.i∆sc).osities values obtained for the
different formulations.

3.6. CoInffocradlleMr tiicocroeosvscaolpuyate the interaction between the xanthan gum and
the silica nanopar-
ticle s ,ht h e r e la ti v e v i sc o t y 𝜇 ௥ f௘௟ is p l o tt e d a s a f u in c
T h e c o ll o id a l d is p e rsi o n o f th e n a n o p a rt ic le s i n
o n o f x a n th a n co n c e n tr a t i o n ( F i g u re 7 ) .
th e b r in e a an d t he p o l y m e r i c s so l u t io n w a s
Aoobsbsseeexrrvpveedcdtethdtrh,ortuohguehgrhecloacntoifvnoecfoavcl iamslciocmsrioitcsy
rcoo𝜇sp௥c௘yo௟ poteyfspttsoe, lssytesme,
eFsriegesuorFleuigt8iu.orAnesll8ai.nmdAaglnleasinmwofaelgureidsunwcaehsraefnoguuen
nd-d
cfoh ran a gll e fd o rf mo ru alla ltifo rm s au f ltaet ri o1n sm ao f nte trhtr
to i n c r e a s e w i p o l y m e r co n c e n
1aatgmioinonng. .tThhTaehgesilnosgep.neTsiihstiehviisgteyhnesoriftfitvohrietyncaonfnoft
fholuceaidclosmntfhiocarcnoaslfcomorpipcerooilsy- -
sacmroepurnesdios3lua0r0tioonunmnsd, eohspyaod
b 3e0 lo0 w n m t h ,i sbse cl oalw e itth i sis n so c ta pl eo si tsii bs rfrtoitchdl
in d i c a t i n g a h i gh e r i n t r i n s c v i
lsencotootsioptbyossaesnribvdleet. hTtuohseoabimsheiarggvheees.roTpfhotehl ey-
yeimnaer
n a m i c r a d i u
nsu asn p oep n asr ito ic nls e ,
s i n t h e p r e s e n c e o f n a n o p a r t le
s Fui gs pu er en s8i ao ,n ss h, oF wi g eud re m 8i ac ,ros hs co ow p eicd am
sg.g F l ou mr t he rea rtm e so r e a,
i cr o sc o p i c ag g
a li e v a r i ti o n w a s f o d
lc ohm i neg rastiez se sr eu apc h toi n2g 0s µi zme s . uAps
e fxop re tch te dp ,o tlhy em p eo rl ys om l ue rti om n os l,e wc uh l iec sh
t o 2 0 μ m . A s e x p e c te d , t h e p o ly m
wedremrneoontleeosct uavlimessiabwslseecoroennntthorietbviumitsiiaobgnleoofontfhtpeh
oxelayinmthaegar nessoglouftpioownlysit,mhsoeur t
sFoigluutrieon8sb,. sOeenFniganuoreflu8bid. sOinmnaagneos,flnuaidnsopimaratgicelse,
angagnroepgaartteisclwe eargegnreogtadteisstiwngerueisnhoatbdleis, tsiene-
F ig u re 8 c . T h is m e a n s t h a t th e ag g r e g a ti o n o f
g u i sh ab l e , s ee F ig u r e 8 c . T 2 h is m e a n s t h a t th e
t h e n a n o p a rt ic le s is a f fe c te d b y t h e p o l y m e r,
a g g re g a t io n o f th e n a n o p a rt ic le s i s a ff e c te d
d ec r e as in g t he s iz e o f t h e N P - Si O a gg r e g a te s fr
b y t h e p o ly m er , d e cr e a s in g t h e s2iz e o f t h e N P -
o m 20 µ m t o s i z es l e ss t h an 300 n m , w h ic h
S iO a gg re g a t e s fr o m 2 0 μm to s iz e s le s s
is the300
than maximum
nm, which resolution of the equipment.
is the maximum resolution of the equipment.
(a) (b) (c)
8 . C o n fo ca l m ic r o s c o p y im ag e s . (a )
Figure 8 . C o n fo c a l m i c r o s c o py im a g e s .
N an o p a r ti c le su sp en si o n : 3 0 0 p p m N P -S iO 22 a n d
( a) N a n o p a r tic le su sp e n s i o n : 3 00 p p m N P - S iO
3% N a C l
an d 3 % in deionized water; (b) polymer solution: 1000 ppm XG and 3% NaCl in
deionized water; (c) NaCl in deionized water; (b) polymer solution: 1000 ppm XG and 3% NaCl
in deionized water;
nanofluid: 1000 ppm XG, 300 ppm NP-SiO2 and 3% NaCl in deionized water.
(c) nanofluid: 1000 ppm XG, 300 ppm NP-SiO2 and 3% NaCl in deionized water.
i c at e s
This indi c a t e s
t h a t a n in te r a c t io n b e tw en x a n t h an g um a nd s il i
t h a t a n in te r a c ti o n b et w een xa n t h a n gu m an d sil ic a
c a n o p a r t ic l e x -
n ano p a rt ic l e s exi s ts ,
ist s , w h ic h le a d s t o t h e b r e ak i n g o f m ic ro n -
w h i c h le a ds t o t h e b r e ak i n g o f m i c ro n - s i z ed
si z e d n a n o p a r ti c le s a gg l o m e rates.
n a n o p a rt i cl e s a g g lo m e r a te s.

3.7. Zeta Potential

Aqueous and saline solutions of xanthan gum, as well as nanofluids containing xan-
than gum and NP-SiO2 in brine, were also characterized by Zeta potential measurements
(Table 3). Xanthan gum is a polyelectrolyte that exhibits a negative surface charge in
aque- ous solution due to its anionic character provided by the carboxyl groups present
in the trisaccharide side chain of its repeat unit [8].
Nanomaterials 2022, 12, 12 of

3.7. Zeta Potential

Aqueous and saline solutions of xanthan gum, as well as nanofluids containing
xanthan gum and NP-SiO2 in brine, were also characterized by Zeta potential
measurements (Table 3). Xanthan gum is a polyelectrolyte that exhibits a negative
surface charge in aqueous solution due to its anionic character provided by the carboxyl
groups present in the trisaccharide side chain of its repeat unit [8].

Table 3. Zeta potential of XG solution in water or brine and nanofluid (XG/NP-SiO2 /NaCl).

Formulation Solvent Zeta P

Xanthan gum (400 ppm) Xanthan gum (400 Water Brine 3%
ppm) NaCl Brine 3% NaCl
Nanofluid: XG (400 ppm) and 300 ppm NP-SiO2
1 Temperature 25 ◦ C.

Measurements show that the addition of nanoparticles in the polymer solution

induces an increase of the zeta potential. The Zeta potential of the nanofluids shows
stronger interaction between the XG and NP-SiO2 , indicating that improved dispersion
stabilization has been achieved [30]. This high negative value for the nanofluids
contributes to explain the stability of the Xantham/NP-SiO2 suspensions over time.
Polymeric solutions of Xanthan gum in distilled water obtained ζ of −19.1 mV, con-
firming the electrostatic repulsion between the polymer chains. By adding the NaCl ions to
the polymer solution, ζ increases to −14.4 mV due to the screening of the Na+ and Cl−
ions on the XG-charged monomer units, resulting in a decrease in the surface charge
density [31]. On the other hand, when NP-SiO 2 is added to xanthan gum solution in
brine, the surface electric charge drops down to −23.0 mV. This decrease is probably
related to the formation of hydrogen bonds between NP-SiO2 and XG, which are
responsible for the formation of stronger networks and structures. As a result of these
physical interactions, the XG repeat units are less exposed to the undesired protective
effects of salt ions.

4. Conclusions
In the present work, the interaction between xanthan gum (XG) macromolecules
and silica nanoparticles (NP-SiO2 ) in water or brine was investigated. Various polymer,
nanoparticle and salt concentrations were considered. Different experimental techniques
were used: rheometry, capillary viscosimetry, confocal microscopy and Zeta potential
measurements. Aging tests were performed, during which the fluids were stored for
several months at 60 ◦ C. Measurements were carried out just after fluid preparation and at
successive aging times.
The individual components were first characterized in water and brine. XG molecules
are satisfyingly dissolved after 24 h and the resulting solutions (without particles)
exhibits a shear-thinning behavior. The addition of salt to these solutions causes a viscosity
decrease while maintaining a shear-thinning behavior. Nanoparticle suspensions (without
polymer) are Newtonian for the considered particle concentrations and their viscosity is
not affected by the addition of salt.
The preparation temperature of the nanofluids (XG and NP-SiO2 in brine) was
varied, and a moderate effect was found on the resulting viscosities.
The rheology of the XG solutions with and without NP-SiO 2 was characterized over
time. The presence of nanoparticles led to higher viscosities. The viscosity of all fluids
decreased in time, but the decrease was limited by the presence of nanoparticles, which
demonstrates the stabilization of xanthan gum solutions by the addition of nanoparticles.
However, these positive effects of NP-SiO2 are attenuated by the presence of salt.
The intrinsic viscosity of the polymer solutions with and without nanoparticles was
calculated from the rheological measurements. The intrinsic viscosity is higher with NP-
SiO2 at every time. This indicates that the hydrodynamics radius of the polymer is larger
 Nanomaterials 2022, 12, 13 of

when nanoparticles are present, which is a sign of polymer/particle interaction. Further-

more, the relative viscosity was found to vary nonlinearly with polymer concentration in
the presence of NP-SiO2 , which is another sign of polymer/particle interaction.
Confocal microscopy images show that the nanoparticles dispersed in water form
large aggregates (20 microns), but that the aggregates are much smaller (under 300 nm)
in the presence of xanthan gum, evidencing an action of polymer on particle dispersion.
It was also shown experimentally that the presence of nanoparticles affects the Zeta
potential of XG solutions.
The nature of the interactions between the XG macromolecules and the silica
nanopar- ticles remains an open question. It is suggested that they may result from weak
interactions by hydrogen bonds.

Author Contributions: Conceptualization, D.L.B.-R.; methodology, V.S. and J.A.P.-A.; confocal mi-
croscopy, L.B.; capillary viscometer, A.D.; zeta potential, K.F.; validation, C.L., P.M. and T.R.-C.;
investigation, D.L.B.-R., C.L. and J.A.P.-A.; resources, P.M., R.A.M. and C.L.; data curation, D.L.B.-
R. and C.L.; writing—original draft preparation D.L.B.-R.; writing—review and editing D.L.B.-R.,
C.L. and J.A.P.-A.; supervision, P.M., T.R.-C. and L.B.; project administration, C.L. and J.A.P.-A.;
funding acquisition, C.L., J.A.P.-A., R.A.M. and P.M. All authors have read and agreed to the
published version of the manuscript.
Funding: This research received no external funding. The reported study was funded by both
research groups: Grupo de Investigación en Fenómenos Interfaciales, Reología y Simulación de
Transporte (FIRST), Universidad Industrial de Santander, Colombia; and Génie Chimique des Milieux
Rhéologiquement Complexes (GEMICO), Laboratoire Réactions et Génie des Procédés (LRGP),
Université de Lorraine, France.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors would like to thank Guillaume Pickaert (Laboratoire de Chimie
Physique Macromoléculaire—LCPM), for infrared spectroscopy tests, which were not successful;
Carole Arnal-Herault (Laboratoire de Chimie Physique Macromoléculaire—LCPM), for her help in
handling the capillary viscometer and in its technique; Frédéric Niepceron (Institut des Molécules et
Matériaux du Mans—IMMM), for his help with the execution and technique of confocal
microscopy.
Conflicts of Interest: The authors declare no conflict of interest.

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