Effects of imidazolium- and ammonium-based ionic liquids on clay swelling: experimental and simulation approach

Water-based fracturing fluids without an inhibitor promote clay swelling, which eventually creates wellbore instability. Several ionic liquids (ILs) have been studied as swelling inhibitors in recent years. The cations of the ILs are crucial to the inhibitory mechanisms that take place during hydraulic fracturing. Individual studies were carried out on several ILs with various cations, with the most frequently found being ammonium and imidazolium cations. As a result, the goal of this study is to compare these two cations to find an effective swelling inhibitor. A comparison and evaluation of the clay swelling inhibitory properties of tetramethylammonium chloride (TMACl) and 1-ethyl-3-methylimidazolium chloride (EMIMCl) were conducted in this work. Their results were also compared to a conventional inhibitor, potassium chloride (KCl), to see which performed better. The linear swelling test and the rheology test were used to determine the inhibitory performance of these compounds. Zeta potential measurements, Fourier-transform infrared spectroscopy, and contact angle measurements were carried out to experimentally explain the inhibitory mechanisms. In addition, the COSMO-RS simulation was conducted to explain the inhibitory processes and provide support for the experimental findings. The findings of the linear swelling test revealed that the swelling was reduced by 23.40% and 15.66%, respectively, after the application of TMACl and EMIMCl. The adsorption of ILs on the negatively charged clay surfaces, neutralizing the charges, as well as the lowering of the surface hydrophilicity, aided in the improvement of the swelling inhibition performance.

Cation Hydration Energy and Surface Hydration Have Crucial Role On Thermodynamics of Clay Swelling

The swelling capacity and stability of clay play a crucial role in various areas ranging from cosmetics to oil extraction; hence change in their swelling behavior after cation exchange with the surrounding medium is important for their efficient utilization. Here we focus on understanding the role of different hydration properties of cation on the thermodynamics of clay swelling by water adsorption. We have used mica as the reference clay, Na+, Li+, and H+ ions as the interstitial cations, and performed grand canonical Monte Carlo simulations of water adsorption in mica pores (of widths d = 4−40 Å). We found that water adsorption in Na-, Li- and H-mica pores is qualitatively similar; however significant quantitative differences are observed, especially at smaller d. Higher water density in H-mica pores (ρH) was expected due to the smaller size of H+ ions having higher hydration energy. However, a counter-intuitive trend of ρLi > ρNa > ρb (bulk density) > ρH was observed due to adsorption energy where the contribution of mica framework atoms was also found to be significant. The disjoining pressure (Π), swelling free energy (∆Ωex), and several structural properties of confined water and ions were calculated to perform thermodynamic analysis of the system. Our detailed calculations have captured the structural evolution of ions and water, especially the transitions from mono- to bi- and multilayer as a function of d. Oscillatory behavior in the Π and ∆Ωex profiles with diminishing to zero for d ≥ 11 Å is observed in all three mica systems. A shift in the location of global minima of ∆Ωex towards the higher d values and ∆Ωex becoming more repulsive is observed in the increasing order of hydration energy of Na+, Li+, and H + ions. The ∆Ωex for Na-mica is characterized by global minima at d = 6 Å corresponding to crystalline swelling, a significant barrier for crystalline swelling from d = 6 to 9 Å and lower for crystalline (d = 9 Å) to osmotic swelling (d > 12 Å). For Li-mica, the energy barrier for crystalline to osmotic swelling is lesser compared to the Na-mica system, whereas for H-mica the ∆Ωex > 0 for all d thus favoring osmotic swelling. We found that the hydration of cations by surface atoms plays a key role in the thermodynamics of clay swelling. The Na+ ions hydrate more number of surface oxygens, act as anchors, and hold the mica pore at d = 6 Å by sharing hydrating water with ions of opposite sides forming an electrostatically connected bridge of mica Na-water-Na-mica. The Li+ ions do hydrate surface oxygen atoms, albeit lesser number and sharing of hydration shell with nearby Li+ ions is also minimum. Both, surface hydration and water sharing, is minimum in the H+ ion case, as they are mostly present in the center of the pore as diffusive ions; thus exerting a consistent osmotic pressure on the mica frameworks, favoring swelling.

Petrophysical Properties of Limestones - Influence On Behaviour Under Different Environmental Conditions And Applications

Limestones have wide variety, namely by differences in the process of formation, mineralogical composition, grain size and texture. Such variability leads to differences in weathering characteristics and behaviour under different environmental conditions and applications. Therefore, detailed studies are mandatory to assess the main factors controlling the physical-mechanical properties and the durability to propose the best applications for the limestones. This study presents the petrographic and petrophysical data of eleven selected Portuguese limestones. Texture, mineralogy and porosity were identified as key parameters for the durability of limestones. Two main groups were identified regarding the texture/petrography and weathering resistance; the compact micritic limestones and with the sparitic grainstones. For the first time an outstanding bowing behaviour was identified in a limestone, probably related with clay swelling minerals and iron oxides present in the micrite groundmass around or in the stylolitic planes.

Degradation of ancient Maya carved tuff stone at Copan and its bacterial bioconservation

Much stone sculptural and architectural heritage is crumbling, especially in intense tropical environments. This is exemplified by significant losses on carvings made of tuff stone at the Classic Maya site of Copan. Here we demonstrate that Copan stone primarily decays due to stress generated by humidity-related clay swelling resulting in spalling and material loss, a damaging process that appears to be facilitated by the microbial bioweathering of the tuff stone minerals (particularly feldspars). Such a weathering process is not prevented by traditional polymer- and alkoxysilane-based consolidants applied in the past. As an alternative to such unsuccessful conservation treatments, we prove the effectiveness of a bioconservation treatment based on the application of a sterile nutritional solution that selectively activates the stone´s indigenous bacteria able to produce CaCO3 biocement. The treatment generates a bond with the original matrix to significantly strengthen areas of loss, while unexpectedly, bacterial exopolymeric substances (EPS) impart hydrophobicity and reduce clay swelling. This environmentally-friendly bioconservation treatment is able to effectively and safely preserve fragile stones in tropical conditions, opening the possibility for its widespread application in the Maya area, and elsewhere.

Imidazole-Based Ionic Liquids with BF4 as the Counterion Perform Outstanding Abilities in Both Inhibiting Clay Swelling and Lowing Water Cluster Size

Promoting fluid transportation in porous media has important applications in energy, pedology, bioscience, etc. For this purpose, one effective way is to prevent swelling through surface modification; however, it is far from enough in real cases, such as ultra-low permeability reservoirs and tight oils. In this study, we considered the comprehensive effects of inhibiting clay swelling, flocculation performance, reducing water clusters and interfacial tension and developed a series of imidazole-based tetrafluoroborate ionic liquids (ILs) with different lengths of alkyl chains. Through measurements of anti-swelling rates, XRD, SEM, 17O NMR, molecular dynamics simulation, zeta potential, flocculation evaluation, interfacial tension and a core flooding experiment based on ultra-low permeability reservoirs, the relationships between the molecular structure and physicochemical properties of ILs have been revealed. Interestingly, one of the selected ILs, imidazole-based tetrafluoroborate ILs (C8-OMImBF4), shows excellent performance, which is helpful to design an effective strategy in promoting fluid transportation in narrow spaces.

Modification and Application of Waste Shaddock Peel as a Green Additive for Water-Based Drilling Fluid

To develop an eco-friendly drilling fluid additive, shaddock peel was modified and was used in water-based drilling fluid in this work. The shaddock peel has obvious effects on rheological properties, filtration, and wall formation of drilling fluid. It also displays the inhibition of clay swelling, while the shaddock peel slurry is easy to ferment, mildew and so on. The performance of the shaddock peel slurry and moldy/fermented shaddock peel slurry in water-based drilling fluid were compared, which shows that the efficiency, such as the AV and PV, decrease obviously by more than 50%. The swelling rate of bentonite in the water extraction of moldy/fermented shaddock peel in 90 min is about 62%, which is obviously higher than the swelling rate of the non-mildew/fermented shaddock peel water extract, 46%. Then preservative was evaluated in shaddock peel slurry modified drilling fluid. The result indicates that the effect of moldy/fermentation on the viscosity and the inhibition of shaddock peel was obviously inhibited by the preservative. The combined sodium benzoate and formaldehyde can protect the shaddock peel slurry from mildew and fermentation, which can keep the performance of shaddock peel slurry in the drilling fluid.