Viscoelastic Surface Research Articles

Creating High Yield Stress Particle-Laden Oil/Water Interfaces Using Charge Bidispersity.

Interfacial engineering has been increasingly used to stabilize Pickering emulsions in commercial products and biomedical applications. Pickering emulsion stabilization is aided by interfacial viscoelasticity; however, typically the primary means of stabilization are steric hindrances between high surface concentration shells of particles around the drops. In this work, the concept of creating large interfacial viscoelastic yield stresses with low particle surface concentrations (<50%) using bidisperse charged particle systems is tested to evaluate their potential efficacy in emulsion stabilization. To explore this hypothesis, interfacial rheology and visualization experiments are conducted at o/w interfaces using positively charged amidine, negatively charged carboxylate, and negatively charged sulfate-coated latex spheres and compared to a model based on interparticle forces. Bidisperse particle systems have been observed to create more networked structures than monodisperse systems. For surface concentrations of <50%, bidisperse interfaces created measurable viscoelastic moduli ∼1 order of magnitude larger than monodisperse interfaces. Furthermore, these interfaces have measurable yield stresses on the order of 10-4 Pa·m when monodisperse systems have none. Bidispersity impacts surface viscoelasticity primarily by increasing the overall magnitude of attraction between particles at the interface and not due to changes in the microstructure. The developed model predicts the relative surface fraction that creates the largest moduli and shows good agreement with the experimental data. The results demonstrate the ability to create large viscoelastic moduli for small surface fractions of particles, which may enable stabilization using fewer particles in future applications.

Dynamics of impact of polymer droplets on viscoelastic surfaces

Dynamics of impact of polymer droplets on viscoelastic surfaces

Ionic Liquid-Based Immunization Patch for the Transdermal Delivery of Antigens.

Herein, we report a transdermal patch prepared using an ionic liquid-based solid in oil (IL-S/O) nanodispersion and a pressure-sensitive adhesive (PSA) to deliver the macromolecular antigenic protein, ovalbumin (OVA). The IL-S/O nanodispersion and a PSA were first mixed at an equal weight ratio, then coated onto a release liner, and covered with a support film. To evaluate the effect of the PSA, three types of PSAs, DURO-TAK 87-4098, DURO-TAK 87-4287, and DURO-TAK 87-235A, were used to obtain the corresponding IL-S/O patches SP-4098, SP-4287, and SP-235A, respectively. The prepared IL-S/O patches were characterized for surface morphology, viscoelasticity, and moisture content. In vitro skin penetration and in vivo immunization studies of the IL-S/O patches were performed using Yucatan micropig skin and the C57BL/6NJc1 mice model, respectively. The SP-4098 and SP-4287 delivered 5.49-fold and 5.47-fold higher amounts of drug compared with the aqueous formulation. Although both patches delivered a similar amount of drug, SP-4287 was not detached fully from the release liner after 30 days, indicating low stability. Mice immunized with the OVA-containing SP-4098 produced a 10-fold increase in anti-OVA IgG compared with those treated with an aqueous formulation. These findings suggested that the IL-S/O patch may be a good platform for the transdermal delivery of antigen molecules.

Flexural resonant frequencies of an AFM cantilever in viscoelastic surface contact mode using modified nonlocal elasticity theory

Flexural resonant frequencies of an AFM cantilever in viscoelastic surface contact mode using modified nonlocal elasticity theory

Investigations of skin friction drag mitigation over viscoelastic surfaces in supersonic flows

Investigations of skin friction drag mitigation over viscoelastic surfaces in supersonic flows

Effects of sodium oleate surface properties on the characteristics of two-phase foam in froth flotation

Aiming at the problem that the active agent foam is too stable during the flotation process, the experiments of the surface tension, surface viscoelasticity and gas-liquid two-phase foam performance of sodium oleate were carried out under the conditions of different concentrations, pH and temperature. The aim is to explain the changes in macroscopic blistering phenomena by changes in microscopic surface properties. The results show that concentration, pH and temperature all affected the foam properties of sodium oleate. When the sodium oleate solution is 10−3 mol/L (cmc), the foam stability is the best. The foam is most stable at pH of around 8.5. Temperature has a significant effect on the foaming property of sodium oleate, the foaming ability of sodium oleate is weak at a low temperature, while sodium oleate is unstable at high or low temperature. The lower the surface tension of the sodium oleate solution, the stronger the foaming performance; and the higher the expansion modulus, the more stable the foam. This study serves as a guide to control the parameters of sodium oleate flotation system and the optimal stabilisation of foam.

Combining in-situ observation and interfacial rheology as a tool to investigate the possible mechanism for improved emulsifying performance of gliadin-based colloid particles

Interfacial deformation and interfacial rheology behaviour of prolamin particles are relevant factors affecting their emulsification performance but have not yet been paid considerable attention to. Based on the finding that CMC modification significantly improved the emulsifying property of gliadin colloid particles (GCPs), the present study combined in situ observation and interfacial rheology as a tool to investigate the effect of CMC on the structure characteristics, interfacial deformation and interfacial rheology behaviour of GCPs and their correlation with emulsifying performance. The results demonstrated that gliadin/CMC complex particles (GCCPs) presented looser core-shell structures than GCPs. The interfacial deformation of particles and the formation of smooth interfaces were observed for both GCPs and GCCPs, and GCCPs exhibited faster deformation behaviour, which should correlate to the looser structure. Although GCCPs showed lower surface pressure and viscoelasticity modulus, the existence of CMC promoted the initial adsorption of particles and accelerated the formation of viscoelastic interfacial films, which contributed to the improvement of emulsifying performance. In addition, CMC endowed the interfacial layers with moderate viscosity and fluidity to resist the destabilisation induced by oil droplet deformation. The present study should provide insights for intuitive understanding and fine regulation of the interfacial behaviour of protein particles.

Rheological properties of fluorine-free foams stabilized by aluminum hydroxide nanoparticles and mixture of siloxane and hydrocarbon surfactants

Fluorine-free foam stabilized by nanoparticle (NP) is expected to become a new generation of environmental-friendly firefighting foam. Many problems on properties of NP-stabilized fluorine-free foams remain to be studied. The present paper focuses on the rheology and foam stability of fluorine-free foam stabilized by aluminum hydroxide NPs. The surface tension, conductivity, foamability, viscosity, and viscoelasticity of mixed dispersions were measured. The stability, viscosity, viscoelasticity, and thixotropy of foam was analyzed deeply by model fitting and mechanism explanation. The results show that the rheological properties and foam stability of mixed dispersions are both enhanced by the presence of NPs, and the enhancement amplitude increased with NP concentration. Both dispersions and NP-stabilized foams exhibit shear thinning behavior, and the viscosity variations in dispersions conform to the Cross model well. As NP concentration increases, the linear viscoelastic range of foam becomes wider, the flow point of NP foam is delayed, demonstrated enhanced viscoelasticity. The thixotropic recovery of foam decreases with the increasing NP concentration, and foam thixotropic recovery decreases with the increase of irreversible deformation degree. This study can provide design idea for the development of fluorine-free firefighting foam.

Effects of surface elasticity and surface viscoelasticity on liquid inclusions in solid materials

The effects of surface elasticity and surface viscoelasticity as well as surface tension on the deformation of solids with liquid inclusions are investigated using a finite element (FE) method. Both surface tension and surface elasticity stiffen the solids with liquid inclusions. The surface tension in elastic capillary number is replaced with surface Young’s modulus to define the second elastic capillary number. The aspect ratio of the included liquids is used to indicate the stiffening effect for both numbers. A smaller aspect ratio corresponds to a larger stiffening effect. In a typical FE analysis, when either number is 1 and the applied strain is 4%, the aspect ratio decreases by 7.4% due to surface tension and 2.6% due to surface elasticity. Compared to surface tension, surface elasticity has a similar but smaller influence on the deformation of solids with liquid inclusions. Extensive FE calculations are performed to establish the fitting formula for the aspect ratio as a function of elastic capillary number, the second elastic capillary number, and the applied strain. Surface viscoelasticity is modelled in the FE method by converting surface viscoelastic properties into the viscoelastic properties of the equivalent shell. The time-dependent aspect ratio due to surface viscoelasticity is presented and FE results show the same trend as those calculated from the approximated theory. The internal pressure of the included liquid is obtained from FE analysis and is compared with the theoretical estimation employing the Young–Laplace equation.

Pickering emulsions by combining nanocellulose/nanochitin and silk fibroin: Silk fibroin as a stabilizer or an emulsifier

Silk fibroin (SF) was considered as emulsifier due to its inherent amphiphilicity. Nevertheless, SF was also speculated to act as a stabilizer in emulsions because of its self-assembly in the interfaces and formation of viscoelastic surface or interfacial layers. Here, the emulsions were produced by mixing SF with 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized nanocellulose (TOCN) or partially-deacetylated nanochitin (DEChN) as a continuous phase. The performance of emulsions was examined in regard to the concentrations of TOCN, DEChN, and SF. And comparative emulsions stabilized by conventional surfactants alongside TOCN or DEChN were prepared. Emulsion stability and droplet size were influenced by TOCN or DEChN concentration, while SF concentration played a minor role. SF exhibited stability enhancement compared to conventional surfactants. Overall, emulsions remained highly stable over 30 days with substantial TOCN, DEChN, and SF (≥ 0.4%) concentrations. This work provides valuable insights into choosing stabilizers or emulsifiers for use in the emulsion.

Self-assembling and foaming properties of nonionic, cardanol-based surfactants in aqueous solutions

Surfactants from renewable sources have gained attention due to their potential as substituents for petroleum-based chemicals. In this sense, surfactants based on cardanol, a compound abundant in the cashew nutshell liquid, have been proposed as suitable candidates for this purpose. However, their application is hindered by the lack of quantitative and reliable information about their bulk and surface properties in aqueous solutions. In this work, for the first time, three nonionic, cardanol-derived surfactants (7EO, 9EO, and 12EO), with different number of ethylene oxide (EO) units in the polar headgroup, had their foaming performances analyzed and correlated with their respective surface (equilibrium and dynamic surface tension and surface viscoelasticity) and bulk (cloud points, critical micelle concentration, micelle diameter, and viscosity) properties. Depending on the EO number, different scenarios were seen. Solutions containing the 7EO surfactant were below the cloud point at room temperature and presented antifoaming properties. Aqueous solutions of 9EO and 12EO displayed foamability comparable to solutions prepared with a traditionally employed anionic surfactant (sodium dodecyl sulfate, SDS) at the same concentrations. The surfactant 12EO presented a rapid surface adsorption, thus favoring the formation of large amounts of foam during aeration. Furthermore, solutions of 9EO resulted in foams that were considerably more stable than the ones formed by SDS. Such an enhanced stability was attributed to the presence of elongated micelles, formed at the vicinity of the cloud point, that increased solution viscosity and delayed the liquid drainage in the foams. This surfactant also promoted the formation of highly viscoelastic surface films that contributed to foam stabilization. The obtained results suggest that these surfactants can be used in the formulation of new products with a more sustainable character and with improved properties. Moreover, they indicate the important interchange among bulk aggregates, surface properties and foam stability in aqueous surfactant systems.

Liquid DNA Coacervates form Porous Capsular Hydrogels via Viscoelastic Phase Separation on Microdroplet Interface

AbstractLiquid–liquid phase separation (LLPS) droplets of biopolymers are known as functional microdroplets in living cells and have recently been used to construct protocells and artificial cells. The formation of DNA coacervates (also referred to as DNA droplets) from branched DNA nanostructures and the control of their physical properties via DNA nanostructure design are demonstrated previously. For the construction of artificial cells or protocells, however, even though physical effects such as surface tension, wetting, and viscoelasticity are more important in a tiny (micrometer‐sized), confined environment than in a bulk solution environment, they have not been explored yet. This study shows that a tiny, confined environment using a water‐in‐oil (W/O) microdroplet interface modulates the phase separation dynamics of DNA coacervates, leading to micrometer‐sized porous capsular structures. The porous structures are produced via two types of viscoelastic phase separation (VPS) processes in DNA coacervates: i) simple VPS and ii) cluster‐cluster aggregation after VPS. Finally, it is shown that environmental chemical stimulation can manipulate porous capsular DNA hydrogels extracted from W/O microdroplets. These results provide an approach for designing and fabricating artificial cells or protocells with complex structures and physicochemical properties.

Effect of surface viscoelasticity on top jet drops produced by bursting bubbles.

Jet drops resulting from bubble bursting at a liquid surface play a key role in various mass transfer processes across the interface, including sea spray aerosol generation and pathogen transmission. However, the impact of structurally compound interfaces, characterized by complex surface rheology introduced by surface-active contaminants, on the jet drop ejection still remains unclear. Here, we experimentally investigate the influence of surface viscoelasticity on the size and velocity of the top jet drops from surface bubble bursting, examining both pure protein and mixed protein-surfactant solutions. We document that for bubble bursting at a pure-protein-laden surface where surface elasticity dominates, the increase in Ec, i.e. the interfacial elastocapillary number as the ratio between the effects of interfacial elasticity and capillarity, efficiently increases the radius and decreases the velocity of the top jet drop, ultimately inhibiting the jet drop ejection. On the other hand, considering the mixed protein-surfactant solution, we show that the top jet drop radius and velocity exhibit a different variation trend with Ec, which is attributed to the additional dissipation on the capillary waves as well as the retardation and resistance on the converging flow for jet formation from surface viscoelasticity. Our work may advance the understanding of bubble bursting dynamics at contaminated liquid surfaces and shed light on the potential influence of surface viscoelasticity on the generation of bubble bursting aerosols.

Phospholipase-catalyzed degradation drives domain morphology and rheology transitions in model lung surfactant monolayers.

Lung surfactant is inactivated in acute respiratory distress syndrome (ARDS) by a mechanism that remains unclear. Phospholipase (PLA2) plays an essential role in the normal lipid recycling processes, but is present in elevated levels in ARDS, suggesting it plays a role in ARDS pathophysiology. PLA2 hydrolyzes lipids such as DPPC-the primary component of lung surfactant-into palmitic acid (PA) and lyso-PC (LPC). Because PA co-crystallizes with DPPC to form rigid, elastic domains, we hypothesize that PLA2-catalyzed degradation establishes a stiff, heterogeneous rheology in the monolayer, and suggests a potential mechanical role in disrupting lung surfactant function during ARDS. Here we study the morphological and rheological changes of DPPC monolayers as they are degraded by PLA2 using interfacial microbutton microrheometry coupled with fluorescence microscopy. While degrading, domain morphology passes through qualitatively distinct transitions: compactification, coarsening, solidification, aggregation, network percolation, network erosion, and nucleation of PLA2-rich domains. Initially, condensed domains relax to more compact shapes, and coarsen via Ostwald ripening and coalescence up until the domains solidify, marked by a distinct roughening of domain boundaries that does not relax. Domains aggregate and eventually form a percolated network, whose elements then erode and whose connections are broken as degradation continues. The relative enzymatic activity of PLA2, set by the age of the sample, impacts the order and the duration of morphology transitions. The fresher the PLA2, the faster the overall degradation, and the earlier the onset of domain solidification: domains solidify before aggregating with fresh PLA2 samples, but aggregate and percolate before solidification with aged PLA2. Irrespective of the activity of the PLA2, all measured linear viscoelastic surface shear moduli obey the same dependence on condensed phase area fraction (log|G*| ∝ ϕ) throughout monolayer degradation. Moreover, the onset of domain solidification coincides with the time when the relative surface elasticity begins to increase.

Influence of Surfactant Structure on Polydisperse Formulations of Alkyl Ether Sulfates and Alkyl Amidopropyl Betaines.

Surfactants provide detergency, foaming, and texture in personal care formulations, yet the micellization of typical industrial primary and cosurfactants is not well understood, particularly in light of the polydisperse nature of commercial surfactants. Synergistic interactions are hypothesized to drive the formation of elongated wormlike self-assemblies in these mixed surfactant systems. Small-angle neutron scattering, rheology, and pendant drop tensiometry are used to examine surface adsorption, viscoelasticity, and self-assembly structure for wormlike micellar formulations comprising cocoamidopropyl betaine, and its two major components laurylamidopropyl betaine and oleylamidopropyl betaine, with sodium alkyl ethoxy sulfates. The tail length of sodium alkyl ethoxy sulfates was related to their ability to form wormlike micelles in electrolyte solutions, indicating that a tail length greater than 10 carbons is required to form wormlike micelles in NaCl solutions, with the decyl homologue unable to form elongated micelles and maintaining a low viscosity even at 20 wt % surfactant loading with 4 wt % NaCl present. For these systems, the incorporation of a disperse ethoxylate linker does not enable shorter chain surfactants to elongate into wormlike micelles for single-component systems; however, it could increase the interactions between surfactants in mixed surfactant systems. For synergy in surfactant mixing, the nonideal regular solution theory is used to study the sulfate/betaine mixtures. Tail mismatch appears to drive lower critical micelle concentrations, although tail matching improves synergy with larger relative reductions in critical micelle concentrations and greater micelle elongation, as seen by both tensiometric and scattering measurements.

A numerical model to simulate the transient frictional viscoelastic sliding contact

Sliding motion has always been one of the major concerns when it comes to the analysis of viscoelastic contact problems. A new model simulating the transient sliding contact of smooth viscoelastic surfaces is developed in this paper. By taking the dry contact friction and the coupling between shear tractions and normal pressure into account, the effect of the early partial slip period, which is often neglected in the study of viscoelastic sliding contact problems, is investigated numerically. Compared with solutions based on the frictionless assumption, the steady-state pressure profile is found to be slightly different under the effect of the partial slip regime, including a lower peak pressure and the shift of the contacting region in the direction opposite to the sliding motion. Furthermore, the time required for the viscoelastic contact to reach its steady state is delayed owing to the partial slip period preceding the global sliding motion.

Experimental study on application performance of foamed concrete prepared based on a colloidal NanoSiO2-stabilized foam

In this study, colloidal nanoSiO2 (CNS) was added into the foaming agent at 0, 0.5, 1, 1.6, and 2 wt% of the binder mass to enhance the stability of foaming agent and prefabricated foam, further the stability of foamed slurry and hardened foamed concrete. First, the stability of CNS on foaming agent and prefabricated foam was investigated by examining surface tension, surface viscoelastic modulus E, foam parameters, surface shear viscosity, and morphology. Prefabricated foam containing CNS was then used to prepare foamed concrete with a dry density of 700 kg/m3. The rheological characteristics, volume change, setting time, hydration properties, and gas content for fresh foamed slurry and the pore characteristics, compressive strength, and thermal conductivity of hardened foamed concrete were characterized. The microstructural crystalline structures of the foamed slurry and hardened foamed concrete were also investigated. Results of this study indicated that nanoSiO2 nanoparticles in colloidal state improved the stability of foam, especially when the CNS dosage was ≥ 1 wt%, because CNS caused increases in the surface viscoelasticity modulus E of the foaming agent and the surface shear viscosity of the prefabricated foam. Moreover, foamed slurry with a shorter hydration induction period, more stable volume, a shorter initial setting time, and higher viscosity was obtained when the CNS dosage was ≥ 1 wt%. Hardened foamed concrete with higher early compressive strength and superior thermal insulation properties was correspondingly obtained when fresh slurry with higher stability was used. However, the effect of CNS will decrease on the compressive strength of the hardened foamed concrete after 14 days of hydration. Finally, mechanisms were proposed regarding the stabilization effects of CNS on the prefabricated foams, foamed slurry, and hardened foamed concrete.

Surfactant Modified Bentonite Characterization: Effects and Comparative Analysis

Extensive soils can be found all over the world. The clay mineral montmorillonite is predominantly responsible for soil expansion. Because of their ability to shrink and swell with seasonal changes in moisture content, these expansive soils can cause significant damage to engineering construction. To stabilize the effects of swelling soil various ground improvement techniques, incorporate mineralogical modification of clays. The application of nanotechnology increased in past few years to deal with clay minerals as it possesses the same dimensional properties. To understand the behaviour of Nano modified clay, bentonite was selected as it represents the montmorillonite clay mineral. The characterization of surface-treated bentonite by nanomaterial was carried out. The study of physio-chemical properties and textural properties of surface-modified bentonite clay was carried out. Swelling pressure was evaluated by a consolidometer test. With the advanced nanotechnology instrumentation technique, particle size analysis, zeta potential, wettability, contact angle, infra-red spectroscopy, rheological properties, BET surface area, pH values, XRD, TGA, etc was carried out for treated and untreated soil, to understand the comparative behaviour of surface modification. It was found that by using Nano surfactant, liquid limit and shrinkage limit were reduced considerably. The increase in the quantity of surfactant increases the d-spacing. Thermal stability and particle size increase after surface treatment of bentonite clay. Soil reaches a visco-elastic state and BET surface area decreased after surface modification.

Exploring the dynamics of viscoelastic adhesion in rough line contacts

Modeling the adhesion of viscoelastic rough surfaces is a recent challenge in contact mechanics. Existing models have primarily focused on simple systems with smooth topography or single roughness scale due to the co-action of roughness and viscoelasticity leading to elastic instabilities and rate-dependent behavior, resulting in complex adhesion dynamics. In this study, we propose a numerical model based on a finite element methodology to investigate the adhesion between a randomly rough profile and a viscoelastic half-plane. Approach-retraction simulations are performed under controlled displacement conditions of the rough indenter. The results demonstrate that viscous effects dampen the roughness-induced instabilities in both the approach and retraction phases. Interestingly, even when viscous effects are negligible, the pull-off stress, i.e., the maximum tensile stress required to detach the surfaces, is found to depend on the stiffness modulus and maximum load reached during the approach. Furthermore, when unloading is performed from a relaxed state of the viscoelastic half-plane, both adhesion hysteresis and pull-off stress are monotonic increasing functions of the speed. Conversely, when retraction begins from an unrelaxed state of the material, the maximum pull-off stress and hysteretic loss are obtained at intermediate velocities.

Secondary Bubble Entrainment via Primary Bubble Bursting at a Viscoelastic Surface.

Bubble bursting at liquid surfaces is ubiquitous and plays a key role for the mass transfer across interfaces, impacting global climate and human health. Here, we document an unexpected phenomenon that when a bubble bursts at a viscoelastic surface of a bovine serum albumin solution, a secondary (daughter) bubble is entrapped with no subsequent jet drop ejection, contrary to the counterpart experimentally observed at a Newtonian surface. We show that the strong surface dilatational elastic stress from the viscoelastic surface retards the cavity collapse and efficiently damps out the precursor waves, thus facilitating the dominant wave focusing above the cavity nadir. The onset of daughter bubble entrainment is well predicted by an interfacial elastocapillary number comparing the effects of surface dilatational elasticity and surface tension. Our Letter highlights the important role of surface rheology on free surface flows and may find important implications in bubble dynamics with a contaminated interface exhibiting complex surface rheology.