A series
of gemini surfactants were synthesized to examine their
adsorption properties. The properties of gemini surfactants, including
critical micelle concentration, electrostatic potential distributions,
charge, occupied volume, lowest unoccupied molecular orbital (LUMO),
and highest occupied molecular orbital (HOMO), were evaluated using
conductivity and density functional theory (DFT) calculations. The
calculation results indicated that the electrostatic potential distributions
were similar among the four gemini surfactants. Moreover, surfactants
with longer carbon chains are more likely to be oblique on the rock
surface according to the energy gap between the HOMO of the surfactants
and the LUMO of the calcite surface. Experimental tests and molecular
dynamics (MD) simulations were conducted to analyze the calcite–surfactant
interactions. Combined with the free energy (ΔG) based on the contact angle and adsorption energy (E) based on MD simulation, the adsorption ability increases as the
carbon chain length decreases. MD simulation is used to understand
the form of surfactant molecules on the calcite at an atomic scale
at different times. An obvious aggregation of gemini surfactants was
found with an increase in the carbon chain length, which reduces the
adsorption density and covered area of the surfactant. The adsorption
behavior of the gemini surfactant is beneficial for isolating H+ transfer and retarding the acid reaction with the rock. The
retarding ability and etching morphology were studied by acid etching.
The acid-rock reaction rate showed that 12-4-12 had the best inhibition
performance. Meanwhile, the uneven surface pattern following 12-4-12
etching is beneficial for maintaining the acid fracturing conductivity.