A Normalized HLD (HLDN) Tool for Optimal Salt-Concentration Prediction of Microemulsions

Kittithammavong, Virin; Charoensaeng, Ampira; Khaodhiar, Sutha

doi:10.3390/app11199151

Cited by 8 publications

(17 citation statements)

References 65 publications

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“…In the very first significant report [195], mixtures of two surfactants (1 and 2) with the same KA value in the original HLD correlation showed a surprisingly accurate straight line variation LnSmix = X1 LnS1 + X2 LnS2 = X1 (LnS1-LnS2) + LnS2 (17) This relation, dividing by KA and replacing SCP by the surfactant parameter symbol "" was exactly the same as equation ( 16). This kind of straight line was found with many other cases of surfactant types, i.e., many other KA values in the original correlation, as well as many other scans (T, P, EON, SAT, co-surfactant type or concentrations) with essentially two conditions [175,178,180]. The first and most important condition was mixing two surfactants with no specific interactions between them, i.e., with a zero mixing energy term.…”

Section: The Normalized Hydrophilic-lipophilic Deviation (Hldn) As a ...supporting

confidence: 53%

“…Despite the conceptual advances of Winsor and Beerbower and the development of the hydrophilic-lipophilic deviation equation in its normalized form (HLDN), there are still advances to make, including resolving a confusion of the surfactant parameter with a "characteristic curvature" of the surfactant [67]. Also, using the HLD-NAC equation with different units (mixing anionic and cationic, or nonionic HLD equations) leads to significant deviations when complex systems are formulated, as was experimentally shown recently [180]. Basically, the HLD correlation is a sum of effects equal to zero at the so-called optimum formulation, that is, an exact balance between the phases.…”

Section: Discussionmentioning

confidence: 99%

“…This method using two compensating effects produced by a bi-dimensional variation has been carried out in the past 40 years with all variables susceptible to alter the surfactant interactions with oil and water, i.e., salinity, ACN, temperature, pressure, surfactant head, surfactant tail, surfactant intermediate for extended type, co-surfactant type and concentration, pH, and probably others. The corresponding data schematically illustrated in Figure 7 can be found in old [103,104,[167][168][169][159][160][161][162][163][164][165][166] and new articles [170,171,180,[172][173][174][175][176][177][178][179], including a comprehensive review book [78] and recent general articles [2,136,157], which report the numerical value of the coefficients, i.e., the numerical value of the slope of the optimum line indicated in Figure 7 plots. It is worth noting some particularities in these schematic plots.…”

Section: The Normalized Hydrophilic-lipophilic Deviation (Hldn) As a ...mentioning

confidence: 99%

“…The first and most important condition was mixing two surfactants with no specific interactions between them, i.e., with a zero mixing energy term. When non-ideal mixtures are present, the Margules' equation has been used to compensate for the deviation, although this is often a rough approximation [180,209] with a quite non-linear expression as a function of the composition of the binary mixture X up to the third power. This has to be eliminated to keep the HLD expression as linear in X, as it is for all other formulation variables.…”

Section: The Normalized Hydrophilic-lipophilic Deviation (Hldn) As a ...mentioning

confidence: 99%

“…Therefore, it may be said that even with the currently recognized complexity, mixtures are used, and probably will be more used in the future, when an improved understanding of complex systems is attained. In any case, it should be stressed that recently the HLDNmix expression has been corroborated as more accurate than HLDmix in complex mixture systems [180], and thus should be the used one. However, it cannot be forgotten that the mixture linearity could be completely erroneous if there is a partitioning of the different species, as in many commercial surfactants, particularly the ethoxylated nonionics that have an interfacial distribution very different from the one in the bulk of the system [181,188,191].…”

Section: The Normalized Hydrophilic-lipophilic Deviation (Hldn) As a ...mentioning

confidence: 99%

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Formulation in Surfactant Systems: From-Winsor-to-HLDN

Salager¹,

Márquez²,

Bullón³

et al. 2022

Preprint

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Formulation is an ancient concept, although the word has been used only recently. The first formulations made our civilization advance by inventing bronze, steel, and gunpowder; then, it was used in medieval alchemy. When chemistry became a science and with the golden age of organic synthesis, the second formulation period began. This made it possible to create new chemical species and new combinations “à la carte.” However, the research and developments were still carried out by trial and error. Finally, the third period of formulation history began after World War II, when the properties of a system were associated with its ingredients and the way they were assembled or combined. Therefore, the formulation and the systems’ phenomenology were related to the generation of some synergy to obtain a commercial product. Winsor’s formulation studies in the 1950s were enlightening for academy and industries that were studying empirically surfactant-oil-water (SOW) systems. One of its key characteristics was how the interfacial interaction of the adsorbed surfactant with oil and water phases could be equal by varying the physicochemical formulation of the system. Then, Hansen’s solubility parameter in the 1960s helped to reach a further understanding of the affinity of some substances to make them suitable to oil and water phases. In the 1970s, researchers such as Shinoda and Kunieda, and different groups working in Enhanced Oil Recovery (EOR), among them Schechter and Wade’s group at the University of Texas, made formulation become a science by using semiquantitative correlations to attain specific characteristics in a system (e.g., low oil-water interfacial tension, formulation of a stable O/W or W/O emulsion, or high-performance solubilization in a bicontinuous microemulsion system at the so-called optimum formulation). Nowadays, over 40 years of studies with the hydrophilic-lipophilic deviation equation (HLD) have made it feasible for formulators to improve products in many different applications using surfactants to attain a target system using HLD in its original or its normalized form, i.e., HLDN. Thus, it can be said that there is still current progress being made towards an interdisciplinary applied science with numerical guidelines. In the present work, the state-of-the-art of formulation in multiphase systems containing two immiscible phases like oil and water, and therefore systems with heterogeneous or micro-heterogeneous interfaces, is discussed. Surfactants, from simple to complex or polymeric, are generally present in such systems to solve a wide variety of problems in many areas. Some significant cases are presented here as examples dealing with petroleum, foods, pharmaceutics, cosmetics, detergency, and other products occurring as dispersions, emulsions, or foams, that we find in our everyday lives.

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