2.1.

3 Electrolyte

The solution of sodium chloride (NaCl) in deionized water was used as electrolyte. The sodium
chloride (99.5% purity) was supplied by Merck.

2.1.4 Carbonate Rock Sample The carbonate rock sample was received from Aligoodarz Mine located
in south west of Iran. The main constituent of the rock sample was calcite and its purity was known
to be as high as approximately 99%.26 The X-ray Diffraction (XRD) pattern of the rock sample, shown
in Figure 2, was demonstrated to be in accordance with the pure calcite pattern.

2.2 Methods

Figure 3 shows a schematic of the methodology applied in this study. The details of the procedures
are described in the following sections.

2.2.1 Nano-fluid Preparation

SNP suspensions were made by adding the desired amount of NP powder to deionized water.
Magnetic stirring followed by the sonication process were utilized to prepare a homogenous and
uniform colloidal suspensions. If only magnetic stirring was applied, the NP settled down in couple of
seconds because it was not able to break the SNP aggregations and reduce their size in an efficient
manner. Thus, the sonication process must be used thereafter. As a preliminary step four nano-fluids
at different sonication times of 5, 10, 20 and 40 min were prepared. Then, the stability of
suspensions were studied (see next section) to find an efficient time for sonication. Analysis revealed
that the stability of nano-fluids was improved by increasing the sonication time. However, no
significant difference was observed between the 20 and 40 min. Therefore, for confidence in the
process, the efficient sonication time was selected to be 40 min. A stock solution of 2500 mg/L was
made and then diluted with deionized water or electrolyte to the designed concentrations. The stock
solution was used within an hour to ensure the stability. However, the results of stability analysis
revealed that it can be stable for much more time (see section 3.1). Furthermore, to provide a
homogeneous distribution in the prepared samples, magnetic stirring was used during the dilution
process.

2.2.2 Nano-fluid Stability Analysis

To ensure that the properties of SNP suspensions have not been changed during the tests, the
stability of the prepared nano-fluids was studied through two different methods: (i) visual
observation, (ii) optical absorbance analysis using an ultraviolet-visible (UV-Vis) spectrophotometer.
The effect of SNP concentration, ionic strength and time were investigated. These methods were also
utilized by other researchers.

2.2.3 Surface Modification of Calcite

In the first step, a number of substrates were prepared from the calcite sample. The unmodified
calcite surfaces were water-wet. To render the substrates to oil-wet state, they were aged in the
model oil for 24 h at the room temperature. Before that, the substrates were wetted with deionized
water for improving the adsorption of SA from the model oil.

Having aged the substrates, they were washed with n-heptane and deionized water and then dried.

2.2.4 Wettability Alteration Using Nano-fluids

To testify the efficiency of SNP for alteration the wettability of calcite, the oil-wet substrates were
aged in the nano-fluids and then the contact angles were measured. For this purpose, two methods
of equilibrium and transient analysis were applied. In the equilibrium tests, the substrates were
immersed in beakers containing different concentrations (250-2000 mg/L) of SNP for about 50 h. To
investigate the effect of salinity, the equilibrium tests were conducted

for ionic strength of 0.05 M NaCl. In a distinct scenario, the equilibrium experiments designed for 250
and 500 mg/L were also repeated in the ionic strength range of 0-0.2 M. Transient analysis was
performed in the concentrations of 500 and 1000 mg/L. To do so, six oil-wet substrates were
immersed in nano-fluids. Then, at suitable time intervals a substrate was pulled out for analysis. To
see the effect of salinity, the transient tests were also conducted in concentration of 1000 mg/L and
0.05 M. All the tests were performed at the ambient condition. The intervals of the different
properties such as salinity and nano-fluid concentrations were selected based on the experience
provided by our pervious reported work investigating the adsorption behavior of SNP onto calcite
surface.

2.2.5 Contact Angle Measurement

Contact angle measurement was utilized to evaluate the potential of SNP suspensions for wettability
alteration of calcite. The following procedure was used: (a) the oil-wet substrates were aged in the
nano-fluids. Then, they were pulled out and washed with deionized water. (b) Substrates were then
placed in a horizontal position and submerged in a water filled container. (c) An oil droplet was
released from a needle and captured below the substrate. (d) The image of the droplet was captured
using a high-resolution camera and thereafter the contact angle was estimated using drop-shape
image analysis. The difference between left and right contact angles; measured at the both sides of
the drops; was less 0.1 degree. The contact angle measurements were double checked and the
maximum change in the second sets of experiments was less than ±2.5 degrees. 2.2.6 Scanning
Electron Microscopy The surface modification processes were visualized by scanning electron
microscopy (SEM). The characterization was performed using a field emission scanning electron
microscope (FESEM; S-4160 Hitachi instrument).

3. RESULTS AND DISCUSSIONS

3.1 Nano-fluids Stability

The effectiveness of nano-fluids is directly related to their stability because in an unstable condition
the NP interact to form agglomerations with aggregate size in the range of severalmicrons and even
larger. Having lost their nano-sized feature, NP advantages are dramatically reduced. Thus, in this
work, a preliminary step was design to check the stability of nano-fluids prior to main wettability
alteration tests. The time dependent stability tests were carried out for three SNP concentrations of
500, 1000 and 2500 mg/L at five different levels of ionic strength, i.e. 0.086, 0.172, 0.346, 0.522,
0.699 M (corresponding to 0.5, 1, 2, 3, 4 wt% respectively). Figure 4 illustrates the direct visualization
of nano-fluids stability over 6 days. No detectable particle agglomeration and sedimentation was
seen for 500 mg/L SNP suspensions over the tested range of ionic strength. However, in the case of
1000 mg/L nano-fluids, a small amount of sedimentation was observed for ionic strength of 0.699 M
after 6 days. The instability was enhanced for 2500 mg/L suspensions. The first evidence of visual
destabilization was seen for 0.699 M in the 4th day. After 6 days, the suspensions at ionic strength of
0.086 and 0.172 M were still stable. Although the visual observation gives some insight about the
stability, the aggregation of NP may occur in the nano-sized scale which cannot be visually seen.
Thus, beside this technique, the optical absorbance measurements using an UV-Vis
spectrophotometer were utilized. Using light absorption analysis of nano-fluids, one can accurately
detect the particle agglomeration at early stage of instability. Figure 5 shows the resulted absorbance
profile for different nano-fluids over the time (the absorption was conducted at the wavelength of
400 nm as used by Metin et al.27). The stability of 500 mg/L nano-fluids was confirmed for all ionic
strengths as there was no significant change in the light absorption (Figure 5 (a)). However, Figure 5
(b) illustrates that the critical value of salt concentration for instability of 1000 mg/L suspensions
(determine at the point of sharp increase in absorbance) does reduce with time. This value
decreased to 0.522 M in the 3rd day and reached to 0.172 M after 6 days. Figure 5 (c) shows the
variation of critical salt concentration for 2500 mg/L. As expected, the critical value decreased at
smaller time intervals. This value was reduced to 0.172 M and 0.086 M after 2 and 3 days
respectively. The intensified instability of nano- fluids with the increase in salt concentration was
attributed to the compression of the double layer. At the higher ionic strengths, the extent of
repulsive electrostatic interaction reduces and the energy barrier is lowered. Thus, some particles
that have enough kinetic energy can overcome the barrier and aggregate. Among different types of
NP used for EOR, SNP suspensions were reported to be more stable even without addition of any
dispersant agents while the other types of untreated nano-fluids (e.g. titanium and aluminum oxides)
were stable only for a few hours. 24 The results of this analysis prove the stability of SNP suspensions
used for subsequent experiments in the utilized range of NP concentration, ionic strength and time.