Prediction of Cloud Point Curves of Alkyl Ethoxylates with the Hydrophilic–Lipophilic‐Difference and Net‐Average‐Curvature (HLD‐NAC) Framework

Choi, Francis; Zarate-Muñoz, Silvia; Acosta, Edgar

doi:10.1002/jsde.12304

Cited by 9 publications

(25 citation statements)

References 20 publications

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“…After sealing the tubes, these tubes were mixed via gentle wrist turning 20 times until the solution was well mixed. The test tubes were then settled Note: (a) Value of EACN reported by Baran et al (1994); (b) Value of EACN reported by Choi (2020).…”

Section: Phase Behavior Studiesmentioning

confidence: 99%

“…The test tubes in Figure 6 suggest a salinity window of 9.2%-10.8% NaCl. The phase scan picture in Figure 6 was taken after 1 week of settling (Choi, 2020). The high interfacial rigidity of extended surfactants (Acosta et al, 2012) can produce metastable Type I and II μEs, and therefore, the experimental salinity window could be larger than that displayed in the picture of Figure 6 if one waited for several weeks.…”

Section: Hld-nac and Hld Bi -Nac Fits Of Phase Behavior (Salinity) Scansmentioning

confidence: 99%

“…To assess the appropriateness of these equations, the optimal salinities (S*) of mixtures of SDHS-F I G U R E 6 Salinity scan (wt/vol% NaCl) for C10PO4S-ethyl caprate-NaCl brine system reported by Choi (2020). The dashed lines are the μE boundaries predicted via (a) the HLD bi -NAC and (b) the HLD-NAC.…”

Section: Comparison Between Hld Hldn and Hld Bimentioning

confidence: 99%

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The characteristic curvature (Cc) definition and its use in assessing Cc for single ionic surfactants

Leng

Acosta

2022

J Surfact & Detergents

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The hydrophilic–lipophilic‐difference (HLD) is a set of empirical equations that correlate the formulation conditions at phase inversion (HLD = 0). Based on partition studies for nonionic surfactants, the HLD can be interpreted as a normalized chemical potential difference between the surfactant dissolved in water and oil. The net‐average curvature (NAC) model extrapolates this interpretation into a curvature form that has been used to fit and predict the phase behavior of surfactant‐oil–water (SOW) systems. The curvature interpretation led to renaming the HLD surfactant parameter, sigma (σ), as the characteristic curvature (Cc). This work tests the validity of the curvature interpretation of the HLD, and the Cc concept, for single ionic surfactants and the use of this concept as a method to assess the Cc without the use of reference surfactants or alcohols. To this end, the net curvature of six anionic and two cationic surfactants was evaluated from solubilization data at the characteristic condition of 25°C, no added cosolvent, in the presence of an oil mixture with equivalent alkane carbon number (EACN) of zero, and as a function of salinity. These studies showed that the original HLD equation for ionic surfactant could not be interpreted as chemical potential or curvature because a salinity prefactor (coefficient) “bi” was missing. The revised equation, HLDbi = bi∙ln(S)‐kbi∙EACN+Ccbi ‐aTbi∙(T‐25°C), could now be interpreted as a curvature expression, and it was demonstrated that Cc could be obtained from curvature using the expression Cc = Ccbi/bi. This single surfactant method produces uncertainties that, for most surfactants, ranged from 0.2 to 1 Cc units, similar to the uncertainty obtained with the conventional method of Cc determination using mixtures of test and reference surfactants.

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Section: Phase Behavior Studiesmentioning

confidence: 99%

Section: Hld-nac and Hld Bi -Nac Fits Of Phase Behavior (Salinity) Scansmentioning

confidence: 99%

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The characteristic curvature (Cc) definition and its use in assessing Cc for single ionic surfactants

Leng

Acosta

2022

J Surfact & Detergents

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“…The advancement of surfactant formulation science through the development of the HLD framework has received a high degree of attention over the past 40 years and continues to be an area of vigorous research (Acosta, 2008; Choi et al, 2019; Salager et al, 1979, 2020). This semiempirical framework focuses on surfactant‐oil–water (SOW) systems and seeks to describe the competing affinities of surfactant towards oil and towards water via a scaling that defines HLD = 0 as the condition in which surfactant affinity is exactly balanced.…”

Section: Introductionmentioning

confidence: 99%

Non‐linearchanges in phase inversion temperature for oil and water emulsions of nonionic surfactant mixtures

Dado

Knox

Lang

et al. 2021

J Surfact & Detergents

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Hydrophilic–lipophilic deviation (HLD) is a semiempirical framework for surfactant‐oil–water (SOW) formulation that has effectively assimilated SOW properties such as phase inversion temperature (PIT) and Winsor Type I ↔ II ↔ III ↔ IV microemulsion behavior. The HLD system's reliance on surfactant and oil parameters necessitates their experimental determination when relevant and accurate values are not available. In this study, experiments have been of the type commonly used to generate test surfactant HLD parameters based on perturbation of a well‐defined SOW reference system and assumption of linear mixing behavior for PIT versus component mole fractions. The reference SOW compositions comprised n‐octane, 0.01 M aqueous NaCl, and pure n‐decyl tetraethylene glycol ether (C10E4) reference surfactant. Test surfactants were primary alcohol ethoxylates and nonylphenol ethoxylates comprising disperse PEG (polyethylene glycol) chain lengths that are inherent to commercial production of nonionic ethoxylate surfactants. We observe non‐linear behavior of PIT versus test surfactant mole fraction, even when accounting for surfactant concentration effects, so the desired linear correlation that could otherwise be used to assign an HLD parameter has not been obtained. Since an objective of this study has been to improve the predictive utility of the HLD framework for commercial nonionic surfactants, relevant terms in the HLD equation have been assessed in terms of their potential contributions to non‐linear behavior. One current working‐explanation relates substantial non‐linear PIT contribution to oil‐like surfactant components in disperse commercial ethoxylates.

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“…More recently, the concept of HLB has been extended and refined via the introduction of the so-called HLD (hydrophilic–lipophilic difference) − (Figure ). The HLD analysis takes into account not only the nature of the surfactant but also the nature of the oil itself.…”

Section: Data-driven and Semiphenomenological Modelingmentioning

confidence: 99%

Mesoscale Modeling of Micellization and Adsorption of Surfactants and Surfactant-Like Polymers in Solution: Challenges and Opportunities

Ginzburg

2022

Ind. Eng. Chem. Res.

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Surfactants and surfactant-like amphiphilic polymers play important roles in many industrial processes (e.g., home and personal care, laundry, paints and coatings, and biopharmaceuticals). In the past two decades, significant progress has been achieved in understanding and modeling crucial surfactant properties (e.g., critical micellization concentration [CMC], cloud points, adsorption, and stabilization of colloidal particles against flocculation), but many challenges still remain. In this review, several popular data-driven, atomistic, and coarse-grained modeling approaches are described that are used to study surfactant properties. Then, specific examples of how these approaches are used for specific applications are provided. Finally, opportunities and challenges for surfactant theory and modeling are discussed.

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Prediction of Cloud Point Curves of Alkyl Ethoxylates with the Hydrophilic–Lipophilic‐Difference and Net‐Average‐Curvature (HLD‐NAC) Framework

Cited by 9 publications

References 20 publications

The characteristic curvature (Cc) definition and its use in assessing Cc for single ionic surfactants

The characteristic curvature (Cc) definition and its use in assessing Cc for single ionic surfactants

Non‐linearchanges in phase inversion temperature for oil and water emulsions of nonionic surfactant mixtures

Mesoscale Modeling of Micellization and Adsorption of Surfactants and Surfactant-Like Polymers in Solution: Challenges and Opportunities

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