3.1. Interaction under static conditions
The graph in
Figure 1 shows the time for which was observed total loss of physical integrity of the pellet, in seconds, for each of the saline solutions analyzed at different saturations.
In an oil field, the displacement of the pellets inside the well takes approximately 120 minutes. Thus, the same time was estimated for the duration of this test. However, for all saline solutions analyzed, regardless of saturation, the maximum disintegration time was 180 seconds (3 minutes).
The physical appearance of the bentonite pellets, before contact with any type of fluid, is shown in
Figure 2,
Figure 3 and
Figure 4 shows the appearance observed at the end of the test for the samples that presented the shortest and longest disintegration time for each brine, respectively.
As seen in
Figure 3 and
Figure 4, there was a significant physical change on the pellets in contact with saline solutions, compromising their integrity. This may occur due to changes in the microstructure of compacted bentonite promoted by exposure to saline solutions, once the concentrated saline media promotes an osmotic suction, which can act as an internal compaction tension, causing the particles to approach each other [
18]. Associated with this mechanism, there is a minimization of the repulsion of the double layer, caused by the presence of the high content of cations in the solution, resulting in an increase in the attraction between the lamellae and consequent aggregation of the clay particles. Furthermore, the formation of aggregated structures by the clay particles becomes even more significant when the cations in the saline solution have a greater number of electrons in the valence layer, exerting greater compaction of the double layer. This effect is observed in
Figure 4.
In the images presented in
Figure 4, it was also observed that pellets exposed to higher saline saturations, presented a less expressive disintegration when compared to that presented by the pellets exposed to saline solutions with saturations varying between 10% and 20% (
Figure 3), indicating a correlation between the mechanical properties of clay and brine saturation. Zhang et al. (2016) observed a decrease in plastic compressibility of compacted clays with increasing saline concentration [
14]. This behavior would also be related to the osmotic suction, which is proportional to the salt concentration, resulting in the induction of the formation of aggregates and inter-aggregates in the pores, also contributing to the decrease in deformability [
14,
19]. Destabilization of bentonite particles may occur when in contact with saline solutions of NaCl and CaCl
2 at concentrations even lower than those used in this study [
20]. It was observed that in concentrations in the order of 10-5 to 10-3 mol/L there is flocculation of the bentonite and, consequently, the sedimentation of its particles.
Although saline solutions (especially KCl solution) are commonly used in drilling fluids, during the well drilling, when reactive formations are encountered [
21], this practice should not be extended to the abandonment of wells, since the physical integrity of the pellets is compromised when in contact with NaCl, CaCl
2 and KCl solutions, regardless of their concentration.
For the evaluated organic compounds, i.e. diesel, olefin and glycerin, the immersion of the pellets resulted in the physical aspects recorded in the images presented in
Figure 5,
Figure 6 and
Figure 7, respectively.
Through the images presented in
Figure 5 and
Figure 6, it is observed that physical integrity of pellets immersed in diesel and olefin is preserved. However, the presence of small clay fragments was observed, deposited at the bottom of the container, when the pellets were immersed in glycerin (
Figure 7), indicating disintegration of the pellets when immersed in this organic medium.
Natural bentonite clays have a hydrophilic surface and, therefore, do not adsorb hydrophobic liquids, such as diesel and olefin, since these clays contain exchangeable inorganic cations that are highly hydratable only in aqueous media [
22]. Therefore, the occurrence of disintegration into glycerin, although in low proportion, may be associated with the intermolecular interaction between glycerol, the main component of this compound, due to its hydrophilicity, presenting chemical affinity with the clay surface [
23]. However, this chemical affinity does not constitute a possibility for the occurrence of premature swelling of the pellets in this medium, once glycerin seems to have a limited invasion radius in bentonite specimens [
24].
The physical appearance of a bentonite pellet after immersion in deionized water for times of 60 and 120 minutes can be visualized through the images shown in
Figure 8. It was observed that there are no significant differences in pellet swelling after times of 30 and of 60 minutes, proving that almost total hydration and swelling occur in the first 60 minutes of contact with deionized water. This time is greater than expected for pulverized particles of bentonite, which is in order of minutes [
25].
3.2. Physical integrity under dynamic conditions
In view of the results obtained under static conditions, the organic compounds, diesel, glycerin and olefin, showed a better tendency to maintain the cohesion of the pellets, with total physical preservation when the organic medium was diesel and olefin, and partial preservation when glycerin was used. In this sense, the integrity of the pellets in contact with these fluids was also investigated through tests conducted under dynamic conditions, which are close to the turbulent conditions in which the pellets are transported into the well.
Figure 9 presents images of the organic fluid media (diesel (a), olefin (b) and glycerin (c)) filtered after the tests to evaluate the physical integrity of the pellets under dynamic conditions.
The dynamic test significantly enhanced the disintegration of the pellets in glycerin (
Figure 9(c)), which was also observed, in a lesser extent, under static conditions. This behavior can be clearly noted by the significant volume of fragments visualized at the bottom of the beaker containing the filtered glycerin after the test, and is probably due to the combined action of shear with the longer exposure time of the test, when compared to the test carried out under static conditions. In contrast, no fragments were observed in the filtered material when diesel and olefin were used (
Figure 9(a) and (b)).
Table 1 presents the initial mass of the pellets, the residual mass obtained at the end of the test (final mass), and the disintegration rate for each of the analyzed organic compounds.
The results obtained demonstrate a greater disintegration for the pellets immersed in glycerin, calculated at 14.35%. The disintegration rates calculated for diesel and olefin were 10.10% and 12.55%, respectively. These values are higher than expected, since the filtrate obtained after the tests are clear, with no visible evidence of pellet fragments (
Figure 9).
Thus, in order to understand and elucidate the results obtained, additional tests were carried out with the aim of obtaining the average mass reduction by loss of moisture in the pellets under the same test conditions, without prior contact with any organic compound. In addition, specific measurements of the interaction between the pellets and the liquids were carried out, with the pellets being immersed in the media for 2 hours before submitting them to the dispersibility test, excluding the loss of mass resulting from the disintegration of the pellets.
Table 2 and
Table 3 present the results obtained in these additional tests.
The results obtained show an average mass reduction due to moisture loss of the pellets without prior immersion of 13.90% (
Table 2). This value is significantly close to the disintegration rate obtained for the test carried out under dynamic conditions for the previously immersed samples in diesel and in olefin, which are 10.10% and 12.55% (
Table 3). Similarly, the mass variations obtained when performing the static immersion of the pellet in diesel and olefin, once again represent losses similar to those obtained in the other tests, calculated at 10.70% and 12.25%. Thus, the water physically attached to the edges and external surfaces of the pellets is removed during drying and considered in the calculations to obtain disintegration. As this amount of water removed does not compromise the physical cohesion of the pellets, a correction considering the moisture loss is required in order to obtain the actual rate of disintegration.
Although the temperature at which the pellets were exposed during drying (60°C) is lower than that at which water boils, the moisture loss verified is consistent with thermogravimetric tests conducted with the clay mineral montmorillonite, the main component of bentonites, which demonstrate that the thermal transitions associated with the elimination of adsorbed water can occur at temperatures below 100°C [
26,
27].
It was also possible to observe that, both for the disintegration test and for the test in which there was static immersion in diesel and olefin, the values of lost mass (
Table 1 and
Table 3) are lower than the values of mass reduction due to loss of moisture presented in
Table 2. This behavior is probably related to the disposition of organic compounds on the surface of the pellets, even in small amounts, given the increase in mass registered after immersion, as shown in
Table 3. This result demonstrated that, although the affinity between the organic compounds and the pellets is not expressive, this contact might form a physical barrier capable of hindering, even in a minor way, the elimination of water molecules during drying.
For the pellets immersed in glycerin, it was observed absorption of this fluid as a result of the interaction in the first two hours of the test in static condition, resulting in a mass of 26.06g. This mass increase is expressively significant, which represents a percentage of about 30.30% in relation to the mass of the dry sample (
Table 3) and is attributed to the strong intermolecular interactions between glycerin, which has a hydrophilic nature, and the surfaces of the clay mineral [
23].
This behavior, combined with the high boiling temperature of glycerin, which is 290°C, inhibited the elimination of organic molecules adsorbed under the test conditions. Thus, the increase in mass verified after drying, of approximately 17.60%, corresponds to the compensation between the absorption of organic molecules, which remain in the system and are responsible for the moistened appearance of the sample, and the elimination of water molecules, which corresponds to 13.90% (
Table 2). Thus, the physical disintegration value of 14.36%, presented in
Table 1, must be corrected, adding the mass gain resulting from the interaction between the pellets and glycerin (17.60%), so that the actual physical disintegration rate obtained is approximately 32%.
Table 4 presents the corrected values for the physical disintegration of the bentonite pellets in organic compounds, exclusively considering the loss of structural integrity provided by contact with these fluids. These results are based on observations during the performance of the test and on the interpretation of the results obtained for the additional tests performed targeting the calculation of moisture content of the pellets.
For diesel and olefin, the corrected results showed that there was no relevant quantitative disintegration of the pellets, which is demonstrated by the visual appearance of these fluids, in which no disintegrated particles were observed. Furthermore, the negative value obtained for the disintegration rate of the pellets in diesel suggests that the mass of the sample immersed in this fluid, after drying, was greater than the initial mass of the sample without immersion, also after drying. Once there is no chemical interaction between the pellets and the diesel, it is inferred, therefore, that only the physical adsorption of the medium to the surface of the pellets occurs and this mass increase is attributed to the thin oily layer adhered to the surface of the pellets. For glycerin, in turn, an even higher disintegration rate was observed after correction, attributed to the strong intermolecular interactions between glycerin and the pellet surface [
23].
3.3. Linear swelling
Percentage linear swelling measured for the pellets, initially immersed in the organic compounds for 1 hour and then immersed in deionized water for 24 hours, is shown in the graph in
Figure 10.
During the first hour of test the bentonite pellets were in contact with the organic media and different behavior was observed. The samples immersed in diesel and olefin did not show swelling, while the sample immersed in glycerin showed swelling from the beginning of the test, accounting for a total swelling close to 7% in 1 hour.
As discussed previously, the interaction between organic compounds and bentonite might be attributed to the chemical properties of these substances. Glycerol, the main component of glycerin, has a hydrophilic nature [
28], and when in contact with a mineral that is also hydrophilic, such as bentonite clay, develops interactions with the surfaces of particles that are electrically active [
29], promoting an increase in the basal interplanar distance and, consequently, its swelling. In contrast, diesel and olefin are hydrophobic substances [
30] and, therefore, do not develop interactions when in contact with a hydrophilic material [
31].
After replacing diesel, olefin and glycerin with deionized water, a similar behavior was observed, regardless of the initial organic fluid: continuous swelling was recorded until the end of the 24 hours of testing. For tests carried out with samples previously immersed in diesel and olefin, linear swelling values of approximately 78% were obtained. For the test carried out with the sample previously immersed in glycerin, the linear swelling obtained was 92%. Comparing these values, there is a 14% greater linear swelling when glycerin was previously used. As already discussed, this greater swelling is most likely due to interactions between glycerol and clay particles that promoted an initial expansion between the clay layers. This first interaction made the layers more loosely bound, favoring the hydration mechanisms as well as the hydration rate of the clay particles.
The linear swelling obtained for the samples that had previous contact with the diesel and the olefin evidenced that the immersion of the samples for a period of 1 hour promoted the formation of a membrane on the surface of the tablets and this, in turn, prevented the hydration and total swelling capacity of the samples. It is evidenced by the lower total linear swelling of the samples previously immersed in diesel and olefin, which was approximately 78%, while the swelling of pellets only immersed in water (blue curve in the graph in
Figure 10) was 101% at the end of 25 hours.
Although the linear swelling test, carried out in the LSM equipment, registers the percentage of swelling of the sample vertically, it is possible to observe the swelling of the material radially through the metallic screen in which the sample is contained. This swelling was recorded and is shown in the images in
Figure 11.
Figure 11 (a) and (b) exhibit a similarity in the radial swelling of the tablets that were previously immersed in diesel and olefin. The material has a uniform and cohesive appearance, although small openings are observed. For the tablets previously immersed in glycerin (
Figure 11(c)), many openings are observed, larger than that noted in tablets immersed in diesel and olefin, suggesting absence of cohesion between the particles.
The visual inspection of the pellets after 25 hours of testing in the LSM, together with the other tests carried out and the analysis of the results, showed that the contact of bentonite pellets with the glycerin favors the dispersion of the clay particles, compromising its physical integrity. On the other hand, diesel and olefin do not interact with the clay particles, do not interfere in the physical integrity of the pellets and, finally, do not affect their swelling, suggesting that these are promising fluid to be used on the displacement of bentonite pellets in offshore wells.