Critical Surface Tension Research Articles

Analysis of the Effect of Surfactants on the Performance of Apatite Column Flotation

Given that particle and bubble size, as well as their surface properties, are pivotal in froth flotation, surfactants have been extensively employed due to their impact on bubble size and froth stabilization. This study aimed to investigate the influence of surfactants on the performance of apatite flotation in column. Three different categories of surfactants were examined: anionic, amphoteric, and nonionic, specifically Lupromin, Genagen, and Triton X-100, respectively. The critical coalescence concentration (CCC) and surface tension of each surfactant were determined. The impact of these surfactants on reducing bubble size was quantified, and their subsequent effects on apatite flotation in a column were assessed. The most favorable flotation response for Genagen was achieved at CCC and pH 11, resulting in the highest apatite recovery and the smallest bubble size. For Triton X-100, the best condition was attained at ¼ CCC and pH 11. However, overall, Lupromin was the surfactant that yielded the best flotation results (at ¼ CCC and pH 11). The superior performance of this anionic surfactant was corroborated by chemical adsorption results, as demonstrated by FTIR analyses.

Effect of physicochemical properties on critical sinking and attachment of respirable coal mine dust impacting on a water surface

Respirable coal mine dust (RCMD) inhalation is identified as the main cause of the resurgence of coal worker’s pneumoconiosis (CWP) since the mid-1990s. At present, the predominant dust control technology is the water spray system. However, in practice, the capture efficiency of RCMD by this technology is relatively low. To understand the capturing mechanism and develop improvement strategies, this research is focused on the surface chemistry study of RCMD and its impact on a water surface using a dynamic model. Proximate analysis, chemical, and mineral composition of a run-of-mine (ROM) coal sample from Appalachian region were analyzed using a proximate analyzer, Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and X-ray Diffraction (XRD), respectively. Contact angles were measured by capillary rise test using the Washburn equation. Based on the dynamic model, the effects of particle size, density, contact angle, and surface tension on the critical sinking were investigated. It was pointed out in this work that reducing surface tension, in turn, decreases contact angle, which has been neglected in the literature. Regime maps for different minerals were created and showed that organic matter has the highest critical velocity due to its low density and high contact angle. Reducing water surface tension to the critical solid surface tension of coal around 30 mN/m could maximize the attachment efficiency. Scaling laws, constructed by force balance, led to the criteria of critical sinking: Ucr∼61-cosθ2D+1γlvρlR, i.e., Wecr∼121-cosθ2D+1. A semi-empirical formula for critical velocity was obtained by fitting the simulation data, Ucr=1.0961-cosθ2D+1γlvρlR. Attachment efficiency was defined and formulated as Pa=U02Ucr2=We0Wecr, establishing relationships between attachment efficiency and the physicochemical properties of RCMD and water droplets.

Impact of hydroxyethyl headgroup on long-chain quaternary ammonium cationic surfactants: Solubility, surface activities, self-assembly behaviors, and rheological properties

The incorporation of hydroxy groups into long-chain quaternary ammonium surfactants can enhance their solubility and confer other desirable properties; however, the systematic investigation on the solution properties and the influence of molecular structures was less documented. In this work, two saturated C18-tailed quaternary ammonium surfactants with dual hydroxyethyl moieties, namely N,N-bis(2-hydroxyethyl)-N-methyloctadecan-1-aminium iodide (HEOAI) and N,N-bis(2-hydroxypropyl)-N-methyloctadecan-1-aminium iodide (HPOAI), were designed and synthesized. We investigated and compared their Krafft temperature (Tk), surface activities, self-assembly behaviors, and rheological properties. Our findings demonstrate that the introduction of hydroxyethyl groups dramatically improves the solubility and surface activities. The Tk of HEOAI and HPOAI is approximately 50 °C lower than that of the corresponding surfactant octadecyl trimethylammonium iodide. Both surfactants exhibit lower critical micelle concentration and equilibrium surface tension compared to those of corresponding conventional quaternary ammonium surfactant. This should be ascribed to the formation of hydrogen bonds between hydroxyl groups and water molecules. Moreover, HPOAI shows even better solubility and surface activities than HEOAI does. Additionally, the presence of two more methyl groups for HPOAI enhances its ability to form worm-like micelles in pure water. However, HEOAI shows better salt and temperature resistance for maintaining stability of worm-like micelles. A solution containing 50 mM HEOAI with 10 % NaCl exhibits temperature tolerance up to around 80 °C, indicating potential application as fracturing fluid for shallow and medium oil/gas reservoirs. These findings contribute to designing surfactants with improved solubility and diverse properties.

A modified continuum surface force (M-CSF) model for two-phase flow problems in smoothed particle hydrodynamics

ABSTRACT This work proposes a modified interfacial tension model based on the continuum surface force (M-CSF) in the context of smoothed particle hydrodynamics. This correction aims to enhance computational stability, improve force evaluation precision, and increase symmetry around the interface. Several two-phase flow benchmarks are solved using both the conventional and proposed CSF models, and the results are compared with each other and with the available literature. The results indicate that the modified model can efficiently increase the force evaluation accuracy in the pressure field at the interface. For instance, the relative error in pressure calculation using the proposed and conventional CSF models is 0.05% and 3.5%, respectively, when compared to the analytical solution, with both models having the same particle resolutions for the droplet deformation problem. In predicting the critical surface tension for hydrodynamic instabilities, such as the Rayleigh-Taylor instability, the M-CSF methodology exhibits much better alignment with existing theories, showing less than 5% deviation, while conventionally used CSF models can deviate up to 15% for the same problem. These findings confirm the superiority of the proposed methodology in evaluating interfacial forces, even in complex hydrodynamic instabilities.

Dual function surfactants for pharmaceutical formulations: The case of surface active and antibacterial 1-tolyl alkyl biguanide derivatives

One interesting field of research in the view of developing novel surfactants for pharmaceutical and cosmetic applications is the design of amphiphiles showing further bioactive properties in addition to those commonly displayed by surface-active compounds. We propose here the chemical synthesis, and characterization of 1-o-tolyl alkyl biguanide derivatives, having different lengths of the hydrocarbon chain (C3, C6, and C10), and showing surface active and antibacterial/disinfectant activities toward both Gram-positive and Gram-negative bacteria. Both surface active properties in terms of critical micelle concentration (CMC) and surface tension at CMC (γCMC), as well as the antimicrobial activity in terms of minimum inhibitory concentrations (MICs), were strongly dependent on the length of the hydrocarbon chain. Particularly, the C6 and C10 derivatives have a good ability to decrease surface tension (γCMC <40 mN/m) at low concentrations (CMC < 12 mM) and a satisfactory antibacterial effect (MIC values between 0.230 and 0.012 mM against S. aureus strains and between 0.910 and 0.190 against P.aeruginosa strains). Interestingly, these compounds showed a disinfectant activity at the tested concentrations that was comparable to that of the reference compound chlorhexidine digluconate. All these results support the possible use of these amphiphilic compounds as antibacterial agents and disinfectants in pharmaceutical or cosmetic formulations.

Studies on the properties and molecular dynamics simulations of nonionic surfactants based on succinic acid derivatives

AbstractNonionic surfactants have proven useful in various applications such as wastewater treatment, enhanced oil recovery, dyeing, and cosmetics. Novel nonionic surfactants such as PEMP, BEMP, HEMP and BEEP were synthesized based on succinic acid derivatives and using L‐isoleucine as the linking group and four polyether alcohols as the hydrophilic group. First, the structures of the four nonionic surfactants were studied using Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectra. Then the critical micelle concentration (CMC) and surface tension at CMC (γCMC) of the four nonionic surfactants in aqueous solution were tested. γ‐lg c curves determined the relationships of their surface properties as BEEP &gt; PEMP &gt; BEMP &gt; HEMP. In order to expand the range of applications for nonionic surfactants, we evaluated the salt‐resistant properties of four such surfactants. Our findings demonstrated that this class of surfactants indeed has superior salt‐resistant properties. Molecular dynamics (MD) simulations were used to study how surfactant molecules aggregate in the interfacial film. The study investigated the trend of solvent accessible surface area (SASA) over time. Results showed that the surfactant molecules interacted well with solvent molecules in the equilibrium state. This study investigates the performance differences among four types of surfactants using the electrostatic potential (ESP) distribution of their molecules. The study employed both experimental and computational simulations to provide a more comprehensive understanding of surfactant properties. The results offer insights into the theoretical research and application extension of this class of surfactants.

Adsorption and Aggregation Behaviors of Oleyl Alcohol-Based Extended Surfactant and Its Mixtures.

An oleyl alcohol-based extended surfactant, sodium oleyl polyethylene oxide-polypropylene oxide sulfate (OE3P3S), was synthesized and identified using FT-IR and 1H NMR. The adsorption and aggregation behaviors of OE3P3S and its mixture with cationic surfactant alkyltrimethylammoniumbromide (ATAB) were investigated under different molar ratios. The static surface tension analysis indicated that the critical micellization concentration (cmc) and the critical surface tension (γcmc) of OE3P3S were 0.72 mmol/L, and 36.16 mN/m, respectively. The cmc and γcmc values of the binary system were much lower than that of the individual component. And the cmc values of OE3P3S/ATAB = 6:4 mixtures decreased with an increase in the chain length of the cationic surfactant in the binary system. It was found from the dynamic surface tension that there was a slower diffusion rate in the binary system compared to the pure surfactant, and the adsorption processes for OE3P3S/ATAB = 6:4 were mixed diffusion-kinetic adsorption mechanisms. With a combination of DLS data and TEM measurements, formations of vesicles in OE3P3S/ATAB = 6:4 solutions appeared to occur at a concentration of 0.05 mmol/L. By studying the formation of liquid crystal structures in an emulsion prepared with OE3P3S as the surfactant, it was found that the oil-in-water emulsion is birefringent with a Maltese cross texture, and the rheological properties revealed its predominant viscoelastic behavior and shear thinning properties.

Transit Time Theory for a Droplet Passing through a Slit in Pressure-Driven Low Reynolds Number Flows.

Soft objects squeezing through small apertures are crucial for many in vivo and in vitro processes. Red blood cell transit time through splenic inter-endothelial slits (IESs) plays a crucial role in blood filtration and disease progression, while droplet velocity through constrictions in microfluidic devices is important for effective manipulation and separation processes. As these transit phenomena are not well understood, we sought to establish analytical and numerical solutions of viscous droplet transit through a rectangular slit. This study extends from our former theory of a circular pore because a rectangular slit is more realistic in many physiological and engineering applications. Here, we derived the ordinary differential equations (ODEs) of a droplet passing through a slit by combining planar Poiseuille flow, the Young-Laplace equations, and modifying them to consider the lubrication layer between the droplet and the slit wall. Compared to the pore case, we used the Roscoe solution instead of the Sampson one to account for the flow entering and exiting a rectangular slit. When the surface tension and lubrication layer were negligible, we derived the closed-form solutions of transit time. When the surface tension and lubrication layer were finite, the ODEs were solved numerically to study the impact of various parameters on the transit time. With our solutions, we identified the impact of prescribed pressure drop, slit dimensions, and droplet parameters such as surface tension, viscosity, and volume on transit time. In addition, we also considered the effect of pressure drop and surface tension near critical values. For this study, critical surface tension for a given pressure drop describes the threshold droplet surface tension that prevents transit, and critical pressure for a given surface tension describes the threshold pressure drop that prevents transit. Our solutions demonstrate that there is a linear relationship between pressure and the reciprocal of the transit time (referred to as inverse transit time), as well as a linear relationship between viscosity and transit time. Additionally, when the droplet size increases with respect to the slit dimensions, there is a corresponding increase in transit time. Most notably, we emphasize the initial antagonistic effect of surface tension which resists droplet passage but at the same time decreases the lubrication layer, thus facilitating passage. Our results provide quantitative calculations for understanding cells passing through slit-like constrictions and designing droplet microfluidic experiments.

Investigating the effect of the fluid properties on bubble dynamics and heat transfer in a tapered microgap with multiphase flow modeling

Nucleation and bubble dynamics on a heater surface contribute to high heat transfer rate in pool boiling. Introducing two-phase flow in narrow channels further improves heat transfer. Use of expanding taper microgap geometry further enhances heat transfer, and proper balancing of taper angles and flow lengths leads to self-sustained flow boiling in tapered microgap geometries. This paper focuses on understanding the underlying enhancement mechanism by studying the bubble behavior as they expand and accelerate in the direction of increased taper. The present study conducts a 2D simulation analysis of bubble growth in tapered microgaps with numerical simulations to identify the effect of the fluid properties and tapered angle in the bubble and fluid dynamics behavior. Ansys-Fluent is customized with user-defined-functions (UDFs) accounting for the interfacial heat and mass transport, including a sharp interface and direct calculation of mass transfer with temperature gradients. The study was conducted using air injection and boiling simulation from the conception to the departure of a bubble. The tapered angles were 5°, 10°, and 15°, with flowrates between 3 ml/min to 30 ml/min, 1 mm air inlet, and at 1 mm distance from the convergent end. The departure time of 10 subsequent bubbles was recorded to check the configuration with the quickest bubble removal. A critical flowrate and surface tension region was established for the escape direction of the bubble. In addition, the numerical simulation considered the tapered microgap with a nucleating bubble at atmospheric conditions with a wall superheats of 5 K. The results show that the bubble growing over the heated surface creates fluid circulations and interfacial conditions that suppress the thermal boundary layer leading to an increased local heat transfer coefficient within a range of 1 mm from the interface.

One-step Ziegler-Natta polymerization of 4-methylpent-1-ene with pentafluorostyrene – A solution processable copolymer with super hydrophobic properties

Hydrophobic polymers are of high interest in modern membrane applications ranging from blood oxygenation devices to gas diffusion layers in fuel cells. Poly(4-methyl-1-pentene) (PMP) is an interesting membrane material because of its chemical resistance, paired with low density, hydrophobicity, optical transparency, and excellent gas diffusion characteristics. However, the current method of producing PMP membranes through melt processing is not ideal. A more suitable method would be phase inversion via immersion precipitation, but the low solubility of PMP prevents this process. To overcome this processing problem, we propose creating a copolymer of PMP and a fluorinated polymer, which would offer improved solubility and increased hydrophobicity without loss of gas permeability. We successfully synthesize such a copolymer using Ziegler-Natta polymerization of 4-methyl-1-pentene (4 MP) and pentafluorostyrene (PFS). The resulting copolymer exhibits good solubility in a variety of solvents and a critical surface tension γc of 25 mN/m, enabling electrospinning into non-wovens with superhydrophobic properties.

Synthesis and surface activity of novel amino acid surfactants

AbstractAmino acid surfactants (AASs) based on environmentally friendly biomasses have the characteristics of renewable, easy biodegradation, antibacterial and low toxicity, and have been widely used in daily chemicals, pharmaceuticals, and other fields. This study concerned the use of octanal and amino acids as raw materials. In addition, seven types of amino acid‐based surfactants, through Collins reagents, Wittig‐Hornor reaction, and aza‐Micheal addition reaction, and amino acid head groups were connected with the alkyl chain by the CN bond. The structures were confirmed by infrared spectroscopy (FT‐IR) and nuclear magnetic resonance spectroscopy (1HNMR). Its surface activity and adsorption properties are evaluated. The physical properties of amino acid‐based surfactants were tested by surface tension and dynamic contact angle. The results demonstrated that histidine‐based amino acid surfactant (C8His) has the lowest critical micelle concentration (CMC) and surface tension at CMC (γCMC), 0.39 mmol L−1 and 28.79 mN L−1, respectively. Amino acid residues contribute to reducing the critical micelle concentration of surfactant. The interfacial adsorption of glycine‐based amino acid surfactant (C8Gly) significantly improved with the increase in temperature, so the surface tension decreased significantly. In addition, sodium chloride could effectively enhance the interfacial adsorption, and the gas–liquid interfacial tension and contact angle of AASs decrease.

Performance matching of common pesticides in banana plantations on the surface of banana leaves at different growth stages.

The effective deposition of pesticide droplets on a target leaf surface is critical for decreasing pesticide application rates. The wettability between the target leaf surface and the pesticide spray liquid should be investigated in depth, with the aim of enhancing the adhesion of pesticide solutions. The wetting and deposition behavior of pesticides on target leaves depends on the properties of the liquid and the physical and chemical properties of the leaves. The physical and chemical properties of leaves vary with growth stage. This study aims to investigate the wetting behavior of banana leaf surfaces at different stages. The microstructures and chemical compositions of banana leaf surfaces at different stages were studied using modern methods. The surface structure of banana leaves exhibited a wide variety of characteristics at different growth stages, and the chemical composition changed marginally. The surface free energy (SFE) and polar and non-polar components of banana leaves at different growth stages were measured by examining the contact angles (CA) of different test solutions on the surface of banana leaves. Previous research has suggested that changes in the CA and SFE correlate with changes in leaf surface wettability. In general, the new upper leaves of banana trees are composed of polar components and exhibit hydrophobicity. Non-polar components become dominant as the leaf grows. The back surface of banana leaves was non-polar at all growth stages, with a trend that was opposite to that of the front surface. The critical surface tension of the banana leaf surface at different growth stages ranged from 7.83 to 24.22 mN m-1 , thus falling into the category of a low-energy surface. The surface roughness and chemical characteristics of banana leaves affected the wettability of the leaf surface. Differences in the free energy and the polar and non-polar components of the leaf surface at were seen at different growth stages. This study provides a favorable reference for the rational control of pesticide spraying parameters and the enhancement of wetting and adhesion of the solution on banana leaf surfaces. © 2023 Society of Chemical Industry.

Effect of Sophorolipid Adsorption on the Coal Microstructure: Experimental and Wettability Mathematical Model Discussion.

Green biosurfactants are emerging as a promising area of research. However, there is a limited focus on the adsorption and wetting characteristics of biosurfactants on coal dust. This study explores the effects of sophorolipid (SL) biosurfactants on the microstructure and wettability of different coalification degree coal. The microstructure parameters of SL adsorbed on coal dust were measured using a surface tensiometer, contact angle analyzer, and particle size analyzer. The results indicate that SL has the lowest critical surface tension, leading to a 9.25° decrease in the contact angle for low-rank bituminous coal (YZ-LRBC). Furthermore, SL significantly altered the particle size distribution of lignite (NM-LC) and YZ-LRBC. The pore size structure of SL-infiltrated coal dust was quantified using a specific surface area analyzer, revealing a decrease in the specific surface area and an increase in the average pore size. The infrared analysis demonstrated that SL permeation significantly increased the percentage of hydrophilic functional groups (hydroxyl structures) while reducing the hydrophobic functional groups (aliphatic hydrocarbon and aromatic structure). Based on the measured microstructure parameters, a regression equation for contact angle was established: [contact angle (°)] = 73.800 - 0.860 × [D10 (nm)] + 4.280 × [specific surface area (m2/g)]. Notably, the characteristic particle size D10 had a significant negative effect on the contact angle, while the specific surface area had a significant positive effect. These findings provide a theoretical foundation for the application of biosurfactants in water injection to reduce dust and improve the wetting efficiency.

A two-step organic modification strategy for improving surface hydrophobicity of zeolites

The organic modification using a silane coupling agent can significantly improve the surface hydrophobicity of zeolite powders. However, insufficient hydroxyl group content on surface of the zeolites greatly limits the immobilization dosage of the agent, making the samples less hydrophobic. In this study, a two-step organic modification strategy using 1,2-bis(triethoxysilyl)ethane (BTESE) and dodecyltrimethoxysilane (DTMS) was adopted and developed to synthesize highly hydrophobic organic modified zeolite powders. The results showed that the BTESE modification could significantly increase the hydroxyl group content on the surface of zeolite powders, and relatively higher amount of DTMS could be then modified on the BTESE-modified samples. The mean critical surface tension, water vapor adsorption capacity, and water drop contact angle/penetration time of the 0.5% DTMS modified 10% BTESE-zeolite powders were 46.20 mN /m, 27 mg/g, and 142°/˃25 s, while those of the 0.5% DTMS modified zeolite powders were > 71.60 mN/m, 45 mg/g, and 124°/19.48 s, respectively, indicating that the sample synthesized by this two-step method was much more hydrophobic than the sample synthesized by traditional method. This two-step organic modification method appears to be a simple and effective way to prepare highly hydrophobic zeolite powders.

Carbamate‐functional, biobased surfactants derived from cardanol, carbon dioxide, and amino acids: Their synthesis and properties

AbstractThree biobased, CO2‐consuming, and carbamate‐groups‐containing surfactants (CC‐G, CC‐T, CC‐L) were synthesized separately by combination of Cardanol, CO2, Glycine sodium salt (G), Taurine sodium salt (T), and Lysine sodium salt (L). The chemical structures of CC‐G, CC‐T, CC‐L were confirmed by 1H NMR and IR spectra. Thermal properties of these surfactants were studied with TGA and DSC. Their critical micelle concentration (CMC) and surface tension at CMC (CMC) in aqueous solution were obtained by surface tension and conductivity methods, respectively. The amount of excess concentration () and the average occupied surface area () of three surfactants were calculated. of CC‐G, CC‐T and CC‐L was 2.35 × 10−7 mmol/m2, 2.23 × 10−7 mmol/m2, and 6.16 × 10−7 mmol/m2, separately. of CC‐G was 0.71 nm2/mmol, CC‐T 0.74 nm2/mmol, CC‐L 2.70 nm2/mmol. The Krafft point, emulsification, and foaming power of these surfactants were investigated as well. The Krafft points were 0°C (CC‐G), 5°C (CC‐T) and 20°C (CC‐T). For CC‐G, the separation time of 10 mL double distilled water (DDW) was 43 min, CC‐T 40 min, and CC‐L 37 min. It was inferred from the calculated packing parameters that shape of the micelle of CC‐G, CC‐T were cylindrical in aqueous media, while CC‐L was spheroidal in aqueous media.

Effect of hydrophilic chain length on the impact and wetting behavior of nonionic surfactants regulating droplets on hydrophobic surfaces

Regulation of the droplet impact and wetting behavior of hydrophobic surfaces is a difficult problem to solve. The addition of surfactants is commonly used to improve droplet retention by modifying interfacial properties. The effect of the surfactant structure on the regulation of droplet rebound and wetting behavior needs further research. In this study, the physicochemical properties and regulation of droplet behavior for nonionic surfactants with different hydrophilic chain lengths were investigated. The results indicate that with an increasing hydrophilic chain (Epoxyethane (EO) numbers) length, Isodecyl polyoxyethylene ether (XL) surfactant solutions could better regulate the droplet impact behavior on hydrophobic surfaces and better suppress droplet rebound. This mainly attributed to a faster diffusion of surfactant molecules to newly formed interfaces, thus leading to better wetting reversal and deposition of substrates. Additionally, it was found that with the reduction of the hydrophilic chain length, XL surfactant solutions could better regulate droplet wetting, mainly attributed to its critical micelle concentration and surface tension, creating greater Marangoni forces during spreading and leading to faster spreading rates and larger spreading areas. The results from this study promote understanding of the mechanism for regulation of impact behavior and surfactant solution wetting on hydrophobic surfaces by regulating the EO chain length. This provides an effective strategy in regulating droplet deposition on hydrophobic surfaces and provides the basic data or guidance for the use of nonionic surfactants as tank-mixing adjuvants in unmanned aerial vehicle plant protection.

Analytical theory for a droplet squeezing through a circular pore in creeping flows under constant pressures

We derived equations and closed-form solutions of transit time for a viscous droplet squeezing through a small circular pore with a finite length at microscale under constant pressures. Our analyses were motivated by the vital processes of biological cells squeezing through small pores in blood vessels and sinusoids and droplets squeezing through pores in microfluidics. First, we derived ordinary differential equations (ODEs) of a droplet squeezing through a circular pore by combining Sampson flow, Poiseuille flow, and Young–Laplace equations and took into account the lubrication layer between the droplet and the pore wall. Second, for droplets wetting the wall with small surface tension, we derived the closed-form solutions of transit time. For droplets with finite surface tension, we solved the original ODEs numerically to predict the transit time. After validations against experiments and finite element simulations, we studied the effects of pressure, viscosity, pore/droplet dimensions, and surface tension on the transit time. We found that the transit time is inversely linearly proportional to pressure when the surface tension is low compared to the critical surface tension for preventing the droplet to pass and becomes nonlinear when it approaches the critical tension. Remarkably, we showed that when a fixed percentage of surface tension to critical tension is applied, the transit time is always inversely linearly proportional to pressure, and the dependence of transit time on surface tension is nonmonotonic. Our results provided a quick way of quantitative calculations of transit time for designing droplet microfluidics and understanding cells passing through constrictions.

Revealing foam stability for cationic and zwitterionic triethylsilyl-containing surfactants

A fundamental understanding of surfactant structure–property–performance relationships will inform the design of next-generation alternatives to perfluoroalkyl substances (PFAS) in aqueous film-forming foams. This manuscript describes the synthesis, solution properties, and foam stability of novel triethylsilyl-containing surfactants, which elucidated the influence of the hydrophilic head group on critical micelle concentration (CMC), surface tension, and foam stability. Photocatalyzed hydrosilylation of triethylsilane and N,N-dimethyl allylamine yielded N,N-dimethyl-3-(triethylsilyl)propane-1-amine. Subsequent functionalization with either propane sultone or bromoethane afforded zwitterionic sulfobetaine surfactant, 3-(dimethyl(3-(triethylsilyl)propyl)ammonio)propane-1-sulfonate (TESDMAPS) and cationic quaternary ammonium surfactant, and N-ethyl-N,N-dimethyl-3-(triethylsilyl)propane-1-ammonium bromide (TESDMABr), respectively. Dynamic light scattering and cryo-transmission electron microscopy (TEM) characterized micelle size and shape in solutions above the CMC. Surface tensiometer analysis determined minimum TESDMAPS and TESDMABr solution surface tensions of 37.7 and 35.9 mN/m, respectively. Molecular dynamics simulations related this decrease in surface tension to a larger average interfacial area of 88 Å2 per TESDMABr molecule compared to 66 Å2 per TESDMAPS molecule. Steady-shear rheological measurements showed consistent exponential viscosity-scaling relationships between TESDMAPS and TESDMABr solutions ≤ 30 wt. %. Above this concentration, TESDMAPS displayed solution viscosities greater than TESDMABr, and a mixture of surfactants provided an intermediate concentration dependent viscosity scaling. Dynamic foam analysis revealed TESDMABr foams displayed longer 25% foam drainage times than TESDMAPS. The oscillatory rheology of TESDMABr solutions demonstrated solid-like solution behavior at low shear rates. Finally, polarized light-imaging rheology highlighted the formation of birefringent structures in TESDMABr solutions under shear. For the first time, this work relates solution viscoelasticity from shear-induced surfactant assembly to foam stability with implications on fluorine-free, next-generation, fire-fighting foams.

Ceramic membranes activation via piranha reagent– A facile way for significant enhancement in membrane performance

A simple, green, and highly effective method for the performance improvement of titania membranes applied for vacuum membrane distillation (VMD) was developed. The activation step turned the hydrophilic material into superhydrophilic (CA ca. 5°) and superaerophobic (underwater CA 160°) owing to the abundance of hydroxyl moieties. Such pretreatment boosted the functionalization efficiency with silane-based modifiers by 20% generating highly hydrophobic membranes (104.1°–148.2°) suitable for membrane distillation. The in-depth studies showing the meaning of modifier type (number of carbon atoms in the alkyl chain, presence of fluorine, number of reactive groups) on membrane performance and physiochemical membrane features (surface charge, wettability, critical surface tension, spreading pressure) were accomplished. All materials were successfully applied in vacuum membrane distillation for the removal of hazardous VOCs (methyl-tert-butyl ether - MTBE and ethyl acetate -EtAc). A significant improvement in separation (separation factor β increased up to 2.5 times) and transport (process separation index PSI was improved up to 8 times ) was noticed owing to membrane activation, particularly for samples modified with nonfluorinated molecules and FC6Cl3. The best performance was found for FC6Cl3 and C6Cl3. Owing to the formation of semi-dense membranes (pore size of ca. 2 nm) after the functionalization process, it was revealed that the mechanism of separation is a solution-diffusion one. The observed significant differences in the McCabe-Thiele diagram (separation efficiency) additionally confirmed the type of mechanism controlling separation and ensured that grafted nanolayer is taking an active part in the separation process. Combined with good stability (long-lasting test of up to 4 years), the results have proven the technical feasibility of applying piranha pretreated membranes for highly effective VOCs removal by vacuum membrane distillation.

Thermodynamic Consideration of the Solid Saponin Extract Drop-Air System.

The aim of this research was to elucidate the surface active properties of Saponaria officinalis (soapwort) extract containing the plant surfactants saponins. To this end, the advancing contact angle (θ) of water, formamide and diiodomethane on the glass, as well as θ of the aqueous solution of S. officinalis extract fractions on PTFE, PMMA and glass, were studied. Based on the obtained results, the wetting behaviour of saponins was considered with regard to the surface tension components and parameters of the solutions and solids. The investigations also involved the description of the θ isotherms, the dependences between the cosine of contact angle and/or the adhesion of the solution to the solid surfaces and solution surface tension, as well as the critical surface tension of PTFE, PMMA and glass wetting. These dependences were studied based on the saponin adsorption at the different interfaces, which was deduced from the dependence between the adhesion and surface tension of the solution, as well as using the Gibbs and Frumkin isotherm equations. This proved that the saponins are poor wetting agents and that the contact angle isotherm can be described by the exponential function of the second order as well as the Szyszkowski equation, but only for PTFE.