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DOE OSTI2025

Zeta potential measurements of SiO 2 and TiO 2 particles in anionic and cationic surfactant solutions

Zeta potential measurements can provide valuable insights into colloidal stability and may reflect changes in the electrochemical double layer that influence electrocatalysis. In this study, we used zeta potential measurements to monitor and investigate the adsorption behavior of anionic sodium dodecyl sulfate (SDS), cationic dodecyl trimethyl ammonium bromide (DTAB), and cationic cetyl trimethyl ammonium bromide (CTAB) surfactants on SiO 2 and TiO 2 particles in DI water. The zeta potentials of SiO 2 and TiO 2 particles were measured as a function of particle concentration in 1.0 mM, 5.0 mM, and 10.0 mM surfactant solutions. Results indicate that there is no significant adsorption of DS - ions on SiO 2 particles across all SDS concentrations investigated in this study. The zeta potential of TiO 2 particles shifts from negative to positive as particle concentration increases at 1.0 mM SDS, indicating a decrease in DS - ions adsorption per TiO 2 particle. Adsorption plateaus at 5.0 mM SDS for all TiO 2 concentrations studied. In contrast, DTA + and CTA + ions showed clear adsorption on SiO 2 particles, but DTA + exhibited no apparent adsorption on TiO 2 particles. Interestingly, CTA + adsorption on TiO 2 was only evident at higher surfactant concentrations. This study presents a systematic investigation of zeta potential behavior as a function of particle and surfactant concentration, highlighting adsorption saturation and electrostatic reversal. Unlike prior work that was limited to single particle concentration measurements, our approach reveals how surfactant adsorption per particle decreases with increasing surface area. Despite the structural similarity between DTAB and CTAB, this study captured the different adsorption behaviors of both surfactants on SiO 2 and TiO 2 , emphasizing the role of the overall structure of the surfactant on surfactant adsorption behavior. These insights refine the interpretation of zeta potential data and advance understanding of surfactant adsorption on oxide particles. The insight provided in this study about surfactant adsorption on SiO 2 and TiO 2 particles could have important implications for the design of more effective colloidal and catalytic systems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2020

Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C 18 -Functionalized Silica Surfaces

Mixtures of cationic-anionic surfactants have been demonstrated to spontaneously form ordered monolayers at hydrophobic-hydrophilic boundaries including air-water and oil-water interfaces. Here, confocal Raman microscopy is used to investigate the structure of hybrid-supported surfactant bilayers (HSSBs) formed by deposition of a distal leaflet of mixed cationic-anionic surfactants onto a proximal leaflet of n-alkane (C 18 ) chains on the interior surfaces of chromatographic silica particles. The surface coverage of the two surfactants in a hybrid bilayer was determined from carbon analysis and the relative Raman scattering of their respective head-groups. Within the measurement uncertainty, the stoichiometric ratio of the two surfactants is one-to-one, equivalent to mixed-charge-surfactant monolayers at air-water and oil-water interfaces and consistent with the role of the head-group electrostatic interactions in their formation. When self-assembled on the hydrophobic surface, pairs of oppositely-charged n-alkyl-chain surfactants resemble a phospholipid (phosphati¬dylcholine) molecule, with its zwitterionic head group and two hydrophobic acyl-chain tails. Indeed, the structure of these hybrid-supported surfactant bilayers on C 18 -modified silica surfaces is similar to that of hybrid-supported lipid bilayers (HSLBs) on the same supports, but with denser and more-ordered n-alkyl chains. Hybrid-supported surfactant bilayers exhibit a melting phase transition (gel to liquid-crystalline phase) with structural and energetic characteristics similar to hybrid-supported bilayers prepared from a zwitterionic phospholipid of the same alkyl chain length. These mixed-charge surfactants on n-alkane modified silica are stable in water over time (months), results that suggest the potential use of these hybrid bilayers for generating supported lipid bilayer-like surfaces or for separation applications.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Dissolving Nonionic Surfactants in CO 2 to Improve Oil Recovery in Unconventional Reservoirs via Wettability Alteration

CO 2 injection is a promising method for enhanced oil recovery (EOR) in unconventional shale reservoirs. Here, in this work, we postulate that CO 2 EOR may be improved by the dissolution of surfactants into CO 2 . Although CO 2 is a relatively good solvent for oil, we show that CO 2 and Eagle Ford oil are immiscible at compositions above 70 wt % CO 2 , even at pressures as high as 62 MPa. The presence of a CO 2 –oil interface at reservoir conditions indicates that the addition of a surfactant has the potential to improve oil recovery–via wettability alteration from oil-wet to CO 2 -wet, CO 2 –oil interfacial tension (IFT) reduction, or both. Three nonionic surfactants (branched tridecyl ethoxylate Indorama SURFONIC TDA-9, branched nonylphenol ethoxylate Indorama SURFONIC N-100, and linear dodecyl ethoxylate Indorama SURFONIC L12-6) were evaluated for CO 2 -solubility, shale wettability alteration, effect on CO 2 –oil IFT, ability to generate CO 2 –oil foams, and ability to increase oil extraction from Eagle Ford, Mancos, and Bakken shale cores. Each surfactant dissolved in CO 2 up to 1 wt % at pressures and temperatures commensurate with CO 2 EOR. CO 2 -dissolved surfactants did not significantly affect CO 2 –oil IFT or generate CO2–oil foams, but they did induce a dramatic change in the contact angle of an oil droplet on an oil-aged shale chip in CO 2 from strongly oil-wet (11°) toward intermediate CO 2 –oil wettability (82°) (at 80 °C, 27.6 MPa). The branched tridecyl ethoxylated surfactant, SURFONIC TDA-9, afforded the highest oil recovery in core soaking experiments–75%, compared to 71% by pure CO 2 . Analysis of oil extracts by gas chromatography revealed that heavier oil components were produced when the surfactant was added to CO 2 . These results indicate that CO 2 -dissolved surfactants may increase oil recovery from shale by wettability alteration from oil-wet toward CO 2 -wet.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2021

Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene

We report two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for nonswollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation.

2D nanosheets↗

DOE OSTI2023

Mineral Alteration of Shales by CO 2 and Brine Containing Surfactants

The overall goal of the proposed research was to determine the effect of surfactants on shale mineral reactivity with CO 2 and brine. The specific objectives of the proposed work were to 1) Determine the effect of shale mineralogy and surfactant properties on surfactant adsorption and wettability alteration, 2) Determine the effects of surfactant adsorption and wettability alteration on mineral reactivity with CO 2 and brine for varying hydrodynamic conditions, and 3) Develop a modified mineral reaction model with CO 2 and brine that considers the effects of surfactant adsorption. Four tasks were performed to address the project objectives. These were 1) Select and characterize shale samples, 2) Evaluate the effects of surfactant and reservoir properties on adsorption and mineral reactivity, 3) Determine the effects of surfactant adsorption, wettability alteration, and hydrodynamics on mineral reaction kinetics, and 4) Quantify how surfactant sorption and mineral wettability alteration affect mineral reaction modeling. This final report summarizes results in each of these tasks, as well as associated publications.

58 GEOSCIENCES↗

DOE OSTI2025

A fluctuating hydrodynamics model for nanoscale surfactant-laden interfaces

A multispecies diffuse interface model is formulated in a fluctuating hydrodynamics framework for the purpose of simulating surfactant interfaces at the nanoscale. The model generalizes previous work to ternary mixtures, employing a Cahn-Hilliard free energy density combined with incompressible, isothermal fluctuating hydrodynamics where dissipative fluxes include both deterministic and stochastic terms. The intermolecular parameters in the free energy are chosen such that one species acts as a partially miscible surfactant. From Laplace pressure measurements, we show that in this model the surface tension decreases linearly with surfactant concentration, leading to Marangoni convection for interfaces with concentration gradients. In the capillary wave spectrum for interfaces with and without surfactant, we find that for the former, the spectrum deviates significantly from classical capillary wave theory, presumably due to Gibbs elasticity. In non-equilibrium simulations of the Rayleigh-Plateau instability, deterministic simulations showed that the surfactant delays pinching of a fluid cylinder into droplets. However, stochastic simulations indicate that thermal fluctuations disrupt the surfactant's stabilizing effect. Similarly, the spreading of a patch of surfactant, driven by Marangoni convection, was found to be partially suppressed by thermal fluctuations.

Capillary waves↗

DOE OSTI2024

Understanding the Impact of Fuel on Surfactant Microstructure of Firefighting Foam

Abstract Aqueous film-forming foam is being phased out due to the environmental impacts of fluorinated surfactants contained in the firefighting foams. To develop an environmentally friendly firefighting foam, it is important to understand the factors controlling the firefighting performance of surfactants. Fuel transport through foam has been considered as a dominant mechanism for foam collapse. Therefore, the impact of fuels (heptane, octane and trimethylbenzene (TMB)) on surfactant microstructure was studied for three different types of surfactants (Capstone, Glucopon, and siloxane) that have applications in firefighting foam. Multiple techniques were used to identify the microstructure and interfacial properties of surfactants with and without exposure to liquid fuel. The ignition time of fuel vapor through foam and solubility of fuel through liquid surfactant solution were measured as well. This work shows fuel solubility has an impact on the surfactant microstructure and interfacial properties. In addition, fuel solubility and vapor pressure affect the ignition time of fuel vapors.

Engineering↗

DOE OSTI2024

Surfactant Effects in Porous Electrodes for Microemulsion Redox Flow Batteries

The effect of surfactant additives on electrochemical behavior in porous electrodes was investigated using vanadium redox flow battery half-cells and the dependence of volumetric kinetics and mass transport on electrolyte, surfactant, and electrode type was explored. Without surfactant added, carbon paper electrodes demonstrated greater kinetics and transport compared to carbon felt, for a given electrolyte. Additionally, posolyte kinetics are greater than negolyte kinetics by one to three orders of magnitude, depending on the electrode type. Addition of surfactant increased electrode wettability and possibly electrochemical surface area. However, this was accompanied by a decrease in volumetric mass transport, due to stronger electrolyte-electrode interactions. The presence of sodium dodecyl sulfate (SDS) influenced posolyte and negolyte kinetics differently. Kinetics showed a dependence on electrode type and surfactant. On carbon felt, volumetric kinetics decreased for both posolyte and negolyte with SDS addition. On carbon paper, SDS decreased volumetric kinetics for the posolyte but increased (>2X) kinetics for the negolyte! This kinetic enhancement depends on surfactant chemistry: cetyltrimethylammonium bromide, a cationic surfactant, failed to increase kinetics. Furthermore, SDS did not increase areal specific resistance. Furthermore, these findings show the superior performance of carbon paper compared to carbon felt and suggest SDS as a possible VRFB negolyte additive.

25 ENERGY STORAGE↗

DOE OSTI2021

Biodegradable surfactants and related compositions, methods and systems

Biodegradable surfactants are described, in which an amphiphilic heteroatom containing hydrocarbon optionally comprising at least one counterion (Z), and related compositions, methods and systems. Biodegradable surfactant described herein has an aHLB value in accordance with equation (1): aHLB=20*Gh/(Gh−Gt) (1) wherein Gh is the Group Number of a hydrophilic head portion of the biodegradable surfactant optionally comprising the at least one counterion (Z), and Gt is the Group Number of a hydrophobic tail portion of the biodegradable surfactant. A biodegradable surfactant in the sense of the disclosure can be tuned to a set hydrophilic-lipophilic balance (aHLB) by selectively modifying at least one tuning moiety of the biodegradable surfactants to provide tuned biodegradable surfactants having an increase or decrease in their adjusted hydrophilic-lipophilic balance (aHLB).

Lyman, Mathew Gerald↗

DOE OSTI2020

Improved CO 2 Capture Performance of Electrochemically Mediated Amine Regeneration Processes with Ionic Surfactant Additives

For the effective reduction of global CO 2 emissions, it is essential to develop and deploy efficient and cost-effective technologies for CO 2 capture, especially from large point sources. We recently developed an electrochemically mediated amine regeneration (EMAR) system to replace traditional thermal desorption for the capture of CO 2 from post-combustion flue gases. Despite EMAR effectiveness on a laboratory scale, concerns regarding the high gas-to-liquid ratio in the electrochemical cell and long-term instability of the electrodes need to be addressed before further scale-up of the process to a pilot plant and beyond can be entertained. Accordingly, we investigated the effect of using sodium dodecyl sulfate (SDS) as an anionic surfactant and dodecyltrimethylammonium bromide (DTAB) as a cationic surfactant on the process operation. It was found that it is advantageous to use an anionic surfactant for a system such as EMAR that contains hydrophilic electrodes and a positively charged electrochemically active species. The overall cell resistance was notably reduced when SDS anionic surfactant was used. The precipitation of copper particles observed in the anode outlet when no surfactant was used was effectively avoided when SDS was added to the electrolyte, resulting in electrode stability. In addition, smaller gas bubbles were produced in the presence of the SDS surfactant, which resulted in less blockage of the electrode by the gas with a resultant lower cell potential under constant current conditions, driving more efficient CO 2 desorption. This led to an ~25% reduction in the electrochemical energy requirement, the lowest ever achieved experimentally for the EMAR process. Altogether, the addition of a very low concentration of SDS resulted in the successful circumvention of the important problems faced by the EMAR system regarding further scale-up.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Surfactant-Aided Low-Salinity Waterflooding for Low-Temperature Carbonate Reservoirs

Carbonate reservoirs tend to be oil-wet/mixed-wet and heterogeneous because of mineralogy and diagenesis. The objective of this study is to improve oil recovery in low-temperature dolomite reservoirs using low-salinity and surfactant-aided spontaneous imbibition. The low-salinity brine composition was optimized using ζ-potential measurements, contact-angle (CA) experiments, and a novel wettability-alteration measure. Significant wettability alteration was observed on dolomite rocks at a salinity of 2,500 ppm. We evaluated 37 surfactants by performing CA, interfacial-tension (IFT), and spontaneous-imbibition experiments. Here, three (quaternary ammonium) cationic and one (sulfonate) anionic surfactants showed significant wettability alteration and produced 43–63% of original oil in place (OOIP) by spontaneous imbibition. At a low temperature (35°C), oil recovery by low-salinity effect is small compared with that by wettability-altering surfactants. Coreflood tests were performed with a selected low-salinity cationic surfactant solution. A novel coreflood was proposed that modeled heterogeneity and dynamic imbibition into low-permeability regions. The results of the “heterogeneous” coreflood were consistent with that of spontaneous-imbibition tests. These experiments demonstrated that a combination of low-salinity brine and surfactants can make originally oil-wet dolomite rocks more water-wet and improve oil recovery from regions bypassed by waterflood at a low temperature of 35°C.

02 PETROLEUM↗

DOE OSTI2024

In Situ Monitoring of Non-Thermal Plasma Cleaning of Surfactant Encapsulated Nanoparticles

Surfactants are widely used in the synthesis of nanoparticles, as they have a remarkable ability to direct their growth to obtain well-defined shapes and sizes. However, their post-synthesis removal is a challenge, and the methods used often result in morphological changes that defeat the purpose of the initial controlled growth. Moreover, after the removal of surfactants, the highly active surfaces of nanomaterials may undergo structural reconstruction by exposure to a different environment. Thus, ex situ characterization after air exposure may not reflect the effect of the cleaning methods. Here, combining X-ray photoelectron spectroscopy, in situ infrared reflection absorption spectroscopy, and environmental transmission electron microscopy measurements with CO probe experiments, we investigated different surfactant-removal methods to produce clean metallic Pt nanoparticles from surfactant-encapsulated ones. It was demonstrated that both ultraviolet-ozone (UV-ozone) treatment and room temperature O2 plasma treatment led to the formation of Pt oxides on the surface after the removal of the surfactant. On the other hand, when H2 was used for plasma treatment, both the Pt0 oxidation state and nanoparticle size distribution were preserved. In addition, H2 plasma treatment can reduce Pt oxides after O2-based treatments, resulting in metallic nanoparticles with clean surfaces. These findings provide a better understanding of the various options for surfactant removal from metal nanoparticles and point toward non-thermal plasmas as the best route if the integrity of the nanoparticle needs to be preserved.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Liquid ToF-SIMS revealing the oil, water, and surfactant interface evolution

Bilge water from ships is regarded as a major pollutant in the marine environment. Bilge water exists in a stable oil-in-water (O/W) emulsion form. However, little is known about the O/W liquid–liquid (l–l) interface. Traditional bulk characterization approaches are not capable of capturing the chemical changes at the O/W l–l interface. Although surfactants are deemed essential in droplet formation, their roles in bilge water stabilization have not been fully revealed. We have utilized novel in situ chemical imaging tools including in situ scanning electron microscopy (SEM) and in situ time-of-flight secondary ion mass spectrometry (ToF-SIMS) to study the evolving O/W interface using a NAVY bilge model for the first time. The droplet size distribution (DSD) does not change significantly without the addition of X-100 surfactants under static or rocking conditions. Both the oil components and the water clusters are shown to evolve over time at the O/W droplet interface by in situ liquid SIMS imaging. Of particular interest to droplet stabilization, the contribution of surfactants to the aged bilge droplets becomes more significant as the droplet size increases. The higher mass surfactant component does not appear on the droplet surface immediately while many lower mass surfactants are solvated inside the droplet. We have provided the first three-dimensional images of the evolving O/W interface and demonstrated that in situ surface chemical mapping is powerful enough to reveal the complex and dynamic l–l interface in the liquid state. Our observational insights suggest that surfactants are important in mediating droplet growth and facilitating effective separation of bilge water emulsion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Upcycling of Waste Plastics into Carboxylic Acids for Biodegradable Surfactants

This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.

Biodegradable surfactants↗

DOE OSTI2022

Molecular simulation of the structural and thermodynamic properties of n-alkane/brine interfacial systems with nonionic surfactants

All-atom molecular dynamics (MD) simulations are used to study the structural and thermodynamic properties of water + n-heptane interfacial systems in the presence of salinity (NaCl, NaI, KCl, and KI) and two different nonionic surfactants. Excellent qualitative and quantitative agreement with interfacial tension experimental data is obtained, but this requires applying a charge scaling factor to the ionic species, suggesting the likely role of polarizability effects. Tensoactive behavior is observed for the NaI and KI systems, coinciding with layering of the iodide species near the interface. Further, there are significant interaction differences between the surfactants and the different ionic species, but the structural and thermodynamic behavior of the surfactant molecules is relatively unaffected by the specific salt species. Our analysis suggest that the surfactant-surfactant interactions play a critical role in determining the interfacial behavior, with a much smaller impact associated with the composition of the brine phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Spontaneous emulsification induced by nanoparticle surfactants

Microemulsions, mixtures of oil, water, and surfactant, are thermodynamically stable. Unlike conventional emulsions, microemulsions form spontaneously, have a monodisperse droplet size that can be controlled by adjusting the surfactant concentration, and do not degrade with time. To make microemulsions, a judicious choice of surfactant molecules must be made, which significantly limits their potential use. Nanoparticle surfactants, on the other hand, are a promising alternative because the surface chemistry needed to make them bind to a liquid-liquid interface is both well flexible and understood. Here, we derive a thermodynamic model predicting the conditions in which nanoparticle surfactants drive spontaneous emulsification that agrees quantitatively with experiments using Noria nanoparticles. This new class of microemulsions inherits the mechanical, chemical, and optical properties of the nanoparticles used to form them, leading to novel applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Synthesis of Hydrophilic Derivative Surfactants From Algae-Derived Unsaponifiable Lipids

In the context of decarbonizing the economy, the utilization of biologically sourced feedstocks to produce replacements for petroleum-derived materials is becoming more urgent. Improving renewable biomass production and utilization is imperative for commercializing future biorefineries. Algae-derived biomass is a particularly promising feedstock thanks to its attractive oil content and composition; specifically, the high-value products in the unsaponifiable lipids have not been included in a conversion process. Here we demonstrate surfactant synthesis from a complex oil fraction as the hydrophobic donor moieties, yielding products that are similar to commercially available surfactants such as the linear alkyl benzene sulfonates. Unsaponifiable lipids extracted from algae were derivatized to non-ionic surfactants using a green chemical synthesis route based on a double esterification with succinic acid and polyethylene glycol. The in-depth molecular and structural surfactant characterization is included and indicates that the resulting properties fall between those of pure cholesterol and phytol used as surrogates for the reaction synthesis demonstration. This is the first demonstration of an effective and potentially high-value synthesis of functional surfactants with properties that can be tailored based on the relative composition of the resulting hydrocarbon alcohol components in the mixture. This novel green chemistry synthesis approach provides a route to high-value product synthesis from algae.

09 BIOMASS FUELS↗

DOE OSTI2026

Quantitative SANS and multi-model analysis of spacer-dependent micellization of urea-based gemini surfactants

The micellization behavior of urea-based cationic gemini surfactants was investigated using small-angle neutron scattering (SANS) with multi-model form factor analysis. A homologous series of surfactants with urea group included in the hydrophobic tail and polymethylene spacers consisting of two to ten methylene units was analyzed using three form factor models: a core–shell ellipsoid and two variants of homogeneous ellipsoids. The results from all models show a consistent trend of the micelle structures, confirming that the spacer length critically influences micellar geometry, aggregation number, and hydration. The surfactant with four CH 2 groups in the spacer formed the largest micelles with the highest aggregation number, while longer spacers led to progressively smaller, more compact aggregates. The shell hydration—quantified as the volume fraction of heavy water within the hydrophilic region—decreased systematically with increasing spacer length due to enhanced hydrophobicity of the headgroup-spacer region. Intermicellar interactions, modeled as screened Coulomb interaction using the rescaled mean spherical approximation (RMSA), revealed the strongest electrostatic repulsion for the case of four methylene groups in the spacer, corresponding to the highest micellar charge and largest interparticle spacing. The observed spacer-dependent trends were robust across all modeling approaches, demonstrating that the spacer length serves as a key structural determinant of self-assembly in this type of urea-based gemini systems. These findings provide insight into the design of gemini surfactants with tailored aggregation behavior for applications in drug delivery, nanostructure templating, and solubilization technologies.

Core–shell ellipsoid model↗