Interfacial rheology

Last updated

Interfacial rheology is a branch of rheology that studies the flow of matter at the interface between a gas and a liquid or at the interface between two immiscible liquids. The measurement is done while having surfactants, nanoparticles or other surface active compounds present at the interface. Unlike in bulk rheology, the deformation of the bulk phase is not of interest in interfacial rheology and its effect is aimed to be minimized. Instead, the flow of the surface active compounds is of interest..

Contents

The deformation of the interface can be done either by changing the size or shape of the interface. Therefore interfacial rheological methods can be divided into two categories: dilational and shear rheology methods.

Interfacial dilational rheology

Pulsating drop method for dilatational interfacial rheology Pulsating drop method.png
Pulsating drop method for dilatational interfacial rheology

In dilatational interfacial rheology, the size of the interface is changing over time. The change in the surface stress or surface tension of the interface is being measured during this deformation. Based on the response, interfacial viscoelasticity is calculated according to well established theories: [1] [2]

where

Most commonly, the measurement of dilational interfacial rheology is conducted with an optical tensiometer combined to a pulsating drop module. A pendant droplet with surface active molecules in it is formed and pulsated sinusoidally. The changes in the interfacial area causes changes in the molecular interactions which then changes the surface tension. [3] Typical measurements include performing a frequency sweep for the solution to study the kinetics of the surfactant.

In another measurement method suitable especially for insoluble surfactants, a Langmuir trough is used in an oscillating barrier mode. In this case, two barriers that limit the interfacial area are being oscillated sinusoidally and the change in surface tension measured. [4]

Interfacial shear rheology

Interfacial shear rheology with the needle method Interfacial shear rheology.png
Interfacial shear rheology with the needle method

In interfacial shear rheology, the interfacial area remains the same throughout the measurement. Instead, the interfacial area is sheared in order to be able to measure the surface stress present. The equations are similar to dilatational interfacial rheology but shear modulus is often marked with G instead of E like in dilational methods. In a general case, G and E are not equal. [5]

Since interfacial rheological properties are relatively weak, it causes challenges for the measurement equipment. For high sensitivity, it is essential to maximize the contribution of the interface while minimizing the contribution of the bulk phase. The Boussinesq number, Bo, depicts how sensitive a measurement method is for detecting the interfacial viscoelasticity. [5]

The commercialized measurement techniques for interfacial shear rheology include magnetic needle method, rotating ring method and rotating bicone method. [6] The magnetic needle method, developed by Brooks et al [7] ., has the highest Boussinesq number of the commercialized methods. In this method, a thin magnetic needle is oscillated at the interface using a magnetic field. By following the movement of the needle with a camera, the viscoelastic properties of the interface can be detected. This method is often used in combination with a Langmuir trough in order to be able to conduct the experiment as a function of the packing density of the molecules or particles.

Applications

When surfactants are present in a liquid, they tend to adsorb in the liquid-air or liquid-liquid interface. Interfacial rheology deals with the response of the adsorbed interfacial layer on the deformation. The response depends on the layer composition, and thus interfacial rheology is relevant in many applications in which adsorbed layer play a crucial role, for example in development surfactants, foams and emulsions. Many biological systems like pulmonary surfactant and meibum are dependent on interfacial viscoelasticity for their functionality. [8] Interfacial rheology has been employed to understand the structure-function relationship of these physiological interfaces, how compositional deviations cause diseases such as infant respiratory distress syndrome or dry eye syndrome, and has helped to develop therapies like artificial pulmonary surfactant replacements and eye drops. [9]

Interfacial rheology enables the study of surfactant kinetics, and the viscoelastic properties of the adsorbed interfacial layer correlate well with emulsion and foam stability. Surfactants and surface active polymers used are for stabilising emulsions and foams in food and cosmetic industries. Proteins are surface active and adsorb at the interface, where they can change conformation and influence the interfacial properties. [10] Natural surfactants like asphaltenes and resins stabilize water-oil emulsions in crude oil applications, and by understanding their behavior the crude oil separation process can be enhanced. Also enhanced oil recovery efficiency can be optimized. [11]

Specialized setups that allow bulk exchange during interfacial rheology measurements are used to investigate the response of adsorbed proteins or surfactants upon changes in pH or salinity. [12] These setups can also be used to mimic more complex conditions like the gastric environment to investigate the in vitro displacement or enzymatic hydrolysis of polymers adsorbed at oil-water interfaces to understand how respective emulsion are digested the stomach. [13]

Interfacial rheology allows the probation of bacteria adsorption and biofilm formation at liquid-air or liquid-liquid interfaces. [14]

In food science, interfacial rheology was used to understand the stability of emulsions like mayonnaise, [15] the stability of espresso foam, [16] the film formed on black tea, [17] or the formation of kombucha biofilms. [18]

See also

Related Research Articles

<span class="mw-page-title-main">Colloid</span> Mixture of an insoluble substance microscopically dispersed throughout another substance

A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend the definition to include substances like aerosols and gels. The term colloidal suspension refers unambiguously to the overall mixture. A colloid has a dispersed phase and a continuous phase. The dispersed phase particles have a diameter of approximately 1 nanometre to 1 micrometre.

An emulsion is a mixture of two or more liquids that are normally immiscible owing to liquid-liquid phase separation. Emulsions are part of a more general class of two-phase systems of matter called colloids. Although the terms colloid and emulsion are sometimes used interchangeably, emulsion should be used when both phases, dispersed and continuous, are liquids. In an emulsion, one liquid is dispersed in the other. Examples of emulsions include vinaigrettes, homogenized milk, liquid biomolecular condensates, and some cutting fluids for metal working.

Rheology is the study of the flow of matter, primarily in a fluid state but also as "soft solids" or solids under conditions in which they respond with plastic flow rather than deforming elastically in response to an applied force. Rheology is the branch of physics that deals with the deformation and flow of materials, both solids and liquids.

<span class="mw-page-title-main">Surfactant</span> Substance that lowers the surface tension between a liquid and another material

Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word "surfactant" is a blend of surface-active agent, coined in 1950. As they consist of a water-repellent and a water-attracting part, they enable water and oil to mix; they can form foam and facilitate the detachment of dirt.

<span class="mw-page-title-main">Suspension (chemistry)</span> Heterogeneous mixture of solid particles dispersed in a medium

In chemistry, a suspension is a heterogeneous mixture of a fluid that contains solid particles sufficiently large for sedimentation. The particles may be visible to the naked eye, usually must be larger than one micrometer, and will eventually settle, although the mixture is only classified as a suspension when and while the particles have not settled out.

In colloidal and surface chemistry, the critical micelle concentration (CMC) is defined as the concentration of surfactants above which micelles form and all additional surfactants added to the system will form micelles.

<span class="mw-page-title-main">Ouzo effect</span> Phenomenon observed in drink mixing

The ouzo effect, also known as the louche effect and spontaneous emulsification, is the phenomenon of formation of a milky oil-in-water emulsion when water is added to ouzo and other anise-flavored liqueurs and spirits, such as pastis, rakı, arak, sambuca and absinthe. Such emulsions occur with only minimal mixing and are highly stable.

A Ramsden emulsion, sometimes named Pickering emulsion, is an emulsion that is stabilized by solid particles which adsorb onto the interface between the water and oil phases. Typically, the emulsions are either water-in-oil or oil-in-water emulsions, but other more complex systems such as water-in-water, oil-in-oil, water-in-oil-in-water, and oil-in-water-in-oil also do exist. Pickering emulsions were named after S.U. Pickering, who described the phenomenon in 1907, although the effect was first recognized by Walter Ramsden in 1903.

<span class="mw-page-title-main">Emulsion dispersion</span> Thermoplastics or elastomers suspended in a liquid state by means of emulsifiers

An emulsion dispersion is thermoplastics or elastomers suspended in a liquid state by means of emulsifiers.

Paint has four major components: pigments, binders, solvents, and additives. Pigments serve to give paint its color, texture, toughness, as well as determining if a paint is opaque or not. Common white pigments include titanium dioxide and zinc oxide. Binders are the film forming component of a paint as it dries and affects the durability, gloss, and flexibility of the coating. Polyurethanes, polyesters, and acrylics are all examples of common binders. The solvent is the medium in which all other components of the paint are dissolved and evaporates away as the paint dries and cures. The solvent also modifies the curing rate and viscosity of the paint in its liquid state. There are two types of paint: solvent-borne and water-borne paints. Solvent-borne paints use organic solvents as the primary vehicle carrying the solid components in a paint formulation, whereas water-borne paints use water as the continuous medium. The additives that are incorporated into paints are a wide range of things which impart important effects on the properties of the paint and the final coating. Common paint additives are catalysts, thickeners, stabilizers, emulsifiers, texturizers, biocides to fight bacterial growth, etc.

Adsorption is the accumulation and adhesion of molecules, atoms, ions, or larger particles to a surface, but without surface penetration occurring. The adsorption of larger biomolecules such as proteins is of high physiological relevance, and as such they adsorb with different mechanisms than their molecular or atomic analogs. Some of the major driving forces behind protein adsorption include: surface energy, intermolecular forces, hydrophobicity, and ionic or electrostatic interaction. By knowing how these factors affect protein adsorption, they can then be manipulated by machining, alloying, and other engineering techniques to select for the most optimal performance in biomedical or physiological applications.

Adsorption of polyelectrolytes on solid substrates is a surface phenomenon where long-chained polymer molecules with charged groups bind to a surface that is charged in the opposite polarity. On the molecular level, the polymers do not actually bond to the surface, but tend to "stick" to the surface via intermolecular forces and the charges created by the dissociation of various side groups of the polymer. Because the polymer molecules are so long, they have a large amount of surface area with which to contact the surface and thus do not desorb as small molecules are likely to do. This means that adsorbed layers of polyelectrolytes form a very durable coating. Due to this important characteristic of polyelectrolyte layers they are used extensively in industry as flocculants, for solubilization, as supersorbers, antistatic agents, as oil recovery aids, as gelling aids in nutrition, additives in concrete, or for blood compatibility enhancement to name a few.

The du Noüy–Padday method is a minimized version of the du Noüy ring method replacing the large platinum ring with a thin rod that is used to measure equilibrium surface tension or dynamic surface tension at an air–liquid interface. In this method, the rod is oriented perpendicular to the interface, and the force exerted on it is measured. Based on the work of Padday, this method finds wide use in the preparation and monitoring of Langmuir–Blodgett films, ink & coating development, pharmaceutical screening, and academic research.

Surface rheology is a description of the rheological properties of a free surface. When perfectly pure, the interface between fluids usually displays only surface tension. The stress within a fluid interface can be affected by the adsorption of surfactants in several ways:

Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.

Polyelectrolytes are charged polymers capable of stabilizing colloidal emulsions through electrostatic interactions. Their effectiveness can be dependent on molecular weight, pH, solvent polarity, ionic strength, and the hydrophilic-lipophilic balance (HLB). Stabilized emulsions are useful in many industrial processes, including deflocculation, drug delivery, petroleum waste treatment, and food technology.

Dispersion Technology Inc is a scientific instrument manufacturer located in Bedford Hills, New York. It was founded in 1996 by Philip Goetz and Dr. Andrei Dukhin. The company develops and sells analytical instruments intended for characterizing concentrated dispersions and emulsions, complying with the International Standards for acoustic particle sizing ISO 20998 and electroacoustic zeta potential measurement ISO 13099.

Dominique Langevin is a French researcher in physical chemistry. She is research director at the Centre national de la recherche scientifique and leads the liquid interface group in the Laboratory of Solid State Physics at the University of Paris-Sud. She was the Life and Physical Sciences Panel chair for the European Space Sciences Committee of the European Science Foundation from 2013-2021.

<span class="mw-page-title-main">Jean-Louis Salager</span>

Jean-Louis Salager was born in Montpellier, France, on May 22, 1944. He obtained the titles of BSc. in chemistry (1966) and chemical engineering (1967) at the University of Nancy (France), MSc. in chemical engineering (1970) and PhD in chemical engineering (1975) at the University of Texas and postdoctorate at the University of Texas (1977–1978). Admitted as assistant professor at the School of Chemical Engineering Universidad de Los Andes, Mérida, Venezuela (1970), where he recently obtained the professor emeritus category. He has supervised over 100 undergraduate and 60 MSc & Dr/PhD dissertations. He has written 20 book chapters and more than 600 articles and communications. He is the second most cited researcher in Venezuelan institutions, according to the Google Scholar Scitations ranking published in 2015.

<span class="mw-page-title-main">Emmie Lucassen-Reynders</span> Dutch chemist (1935–2023)

Emmie Helena Lucassen-Reynders, last name Reijnders in Dutch spelling, was a Dutch scientist specialising in colloid chemistry and theoretical physics. She worked in both academia and in industry.

References

  1. Miller, Reinhard. Liggieri, L. (Libero) (2009). Interfacial rheology. Brill. ISBN   978-90-04-17586-0. OCLC   907184149.{{cite book}}: CS1 maint: multiple names: authors list (link)
  2. Miller, Reinhard; Ferri, James K.; Javadi, Aliyar; Krägel, Jürgen; Mucic, Nenad; Wüstneck, Rainer (2010-05-01). "Rheology of interfacial layers". Colloid and Polymer Science. 288 (9): 937–950. doi:10.1007/s00396-010-2227-5. ISSN   0303-402X. S2CID   93640525.
  3. Rane, Jayant P.; Pauchard, Vincent; Couzis, Alexander; Banerjee, Sanjoy (2013-04-16). "Interfacial Rheology of Asphaltenes at Oil–Water Interfaces and Interpretation of the Equation of State". Langmuir. 29 (15): 4750–4759. doi:10.1021/la304873n. ISSN   0743-7463. PMID   23506138.
  4. Bykov, A.G.; Loglio, G.; Miller, R.; Noskov, B.A. (2015). "Dilational surface elasticity of monolayers of charged polystyrene nano- and microparticles at liquid/fluid interfaces". Colloids and Surfaces A: Physicochemical and Engineering Aspects. 485: 42–48. doi:10.1016/j.colsurfa.2015.09.004. ISSN   0927-7757.
  5. 1 2 Krägel, Jürgen; Derkatch, Svetlana R. (2010). "Interfacial shear rheology". Current Opinion in Colloid & Interface Science. 15 (4): 246–255. doi:10.1016/j.cocis.2010.02.001.
  6. Renggli, D.; Alicke, A.; Ewoldt, R. H.; Vermant, J. (2020). "Operating windows for oscillatory interfacial shear rheology". Journal of Rheology. 64 (1): 141–160. Bibcode:2020JRheo..64..141R. doi: 10.1122/1.5130620 . hdl: 20.500.11850/389068 . ISSN   0148-6055.
  7. Brooks, Carlton F.; Fuller, Gerald G.; Frank, Curtis W.; Robertson, Channing R. (1999). "An Interfacial Stress Rheometer To Study Rheological Transitions in Monolayers at the Air−Water Interface". Langmuir. 15 (7): 2450–2459. doi:10.1021/la980465r. ISSN   0743-7463.
  8. Leiske, Danielle L.; Leiske, Christopher I.; Leiske, Daniel R.; Toney, Michael F.; Senchyna, Michelle; Ketelson, Howard A.; Meadows, David L.; Fuller, Gerald G. (2012). "Temperature-Induced Transitions in the Structure and Interfacial Rheology of Human Meibum". Biophysical Journal. 102 (2): 369–376. Bibcode:2012BpJ...102..369L. doi:10.1016/j.bpj.2011.12.017. PMC   3260664 . PMID   22339874.
  9. Bertsch, Pascal; Bergfreund, Jotam; Windhab, Erich J.; Fischer, Peter (August 2021). "Physiological fluid interfaces: Functional microenvironments, drug delivery targets, and first line of defense". Acta Biomaterialia. 130: 32–53. doi: 10.1016/j.actbio.2021.05.051 . hdl: 20.500.11850/498803 . ISSN   1742-7061. PMID   34077806. S2CID   235323337.
  10. Bergfreund, Jotam; Diener, Michael; Geue, Thomas; Nussbaum, Natalie; Kummer, Nico; Bertsch, Pascal; Nyström, Gustav; Fischer, Peter (2021). "Globular protein assembly and network formation at fluid interfaces: effect of oil". Soft Matter. 17 (6): 1692–1700. Bibcode:2021SMat...17.1692B. doi: 10.1039/D0SM01870H . hdl: 20.500.11850/472320 . PMID   33393584.
  11. Ayirala, Subhash C.; Al-Saleh, Salah H.; Al-Yousef, Ali A. (2018). "Microscopic scale interactions of water ions at crude oil/water interface and their impact on oil mobilization in advanced water flooding". Journal of Petroleum Science and Engineering. 163: 640–649. doi:10.1016/j.petrol.2017.09.054. ISSN   0920-4105.
  12. Rühs, Patrick A.; Scheuble, Nathalie; Windhab, Erich J.; Mezzenga, Raffaele; Fischer, Peter (28 August 2012). "Simultaneous Control of pH and Ionic Strength during Interfacial Rheology of β-Lactoglobulin Fibrils Adsorbed at Liquid/Liquid Interfaces". Langmuir. 28 (34): 12536–12543. doi:10.1021/la3026705. PMID   22857147.
  13. Scheuble, N.; Geue, T.; Windhab, E. J.; Fischer, P. (11 August 2014). "Tailored Interfacial Rheology for Gastric Stable Adsorption Layers". Biomacromolecules. 15 (8): 3139–3145. doi:10.1021/bm500767c. PMID   25029559.
  14. Wu, Cynthia; Lim, Ji Youn; Fuller, Gerald G.; Cegelski, Lynette (August 2012). "Quantitative Analysis of Amyloid-Integrated Biofilms Formed by Uropathogenic Escherichia coli at the Air-Liquid Interface". Biophysical Journal. 103 (3): 464–471. Bibcode:2012BpJ...103..464W. doi: 10.1016/j.bpj.2012.06.049 . PMC   3414876 . PMID   22947862.
  15. Kiosseoglou, V. D.; Sherman, P. (June 1983). "The influence of egg yolk lipoproteins on the rheology and stability of O/W emulsions and mayonnaise: 3. The viscoelastic properties of egg yolk films at the groundnut oil-water interface". Colloid & Polymer Science. 261 (6): 520–526. doi:10.1007/BF01419836. S2CID   101091369.
  16. Piazza, L.; Gigli, J.; Bulbarello, A. (February 2008). "Interfacial rheology study of espresso coffee foam structure and properties". Journal of Food Engineering. 84 (3): 420–429. doi:10.1016/j.jfoodeng.2007.06.001.
  17. Giacomin, Caroline E.; Fischer, Peter (September 2021). "Black tea interfacial rheology and calcium carbonate". Physics of Fluids. 33 (9): 092105. Bibcode:2021PhFl...33i2105G. doi: 10.1063/5.0059760 . hdl: 20.500.11850/505412 . S2CID   239631952.
  18. Bertsch, Pascal; Etter, Danai; Fischer, Peter (2021). "Transient in situ measurement of kombucha biofilm growth and mechanical properties". Food & Function. 12 (9): 4015–4020. doi: 10.1039/D1FO00630D . hdl: 20.500.11850/485857 . PMID   33978026. S2CID   234169590.