The effect of silica nanoparticles on the stability of aqueous foams

An experimental study was performed on aqueous foams stabilized by a mixture of hexadecyltrimethylammonium bromide (HTAB) and negatively-charged silica nanoparticles. The effects of the nanoparticles on the stability of foams at different HTAB concentrations were investigated. The foams were characterized by measuring their foamability and stability. Rheological behavior of the foams was also studied. Furthermore, rheology of the air–water interfaces was studied in the linear and nonlinear deformation ranges. The thickness of the monolayer at the interface was measured. The actual size of the silica nanoparticles at the air–water interface was measured by transmission electron microscopy. Based on these measurements, the interaction between the monolayers across the foam film containing HTAB and nanoparticles was investigated. Smaller silica nanoparticles (i.e. diameter less than 10?nm) adsorbed at the air–water interface whereas the larger particles remained in the sub-phase or in the bulk liquid phase. It was found that these nanoparticles strongly influenced the foaming behavior at the low HTAB concentrations (i.e. below the CMC). A Langmuir-type monolayer was formed. The presence of the nanoparticles at the air–water interface provided mechanical strength to the foam films and prevented their rupture. This hindered coalescence of the bubbles, which resulted in a stable foam.     

Effect of Lipid Phase State and Foam Film Type on the Properties of DMPG Stabilized Foams

The drainage and stability of DMPG (l-α-phosphatidyl-dl-glycerol dimyristoyl) foams were studied by a microconductivity method under conditions where three different foam film types could be formed—thin foam films (TFF), common black foam films (CBF), and Newton black foam films (NBF). Foaming properties were investigated at 20 and 28°C where DMPG is in the gel and liquid-crystalline states. Higher conductivity signals were observed at the higher temperature where DMPG was in the liquid-crystalline state, which is indicative of wetter or more stable foams under these conditions. This effect was observed independent of foam film type. However, for a given phase state, the type of foam films formed significantly influenced the stability and rate of drainage of the foam. Indeed, the water content of the foams, obtained under conditions for formation of different foam films, is ranked in the order TFF > CBF > NBF. When the temperature was increased to 28°C (i.e., in the liquid-crystalline state), CBF and NBF showed a slight decrease in film thickness and an increase in film lifetime and surface molecular diffusion coefficient in the adsorbed layer. It is likely that the fluidity of the interfacial layer is an important factor contributing to DMPG foam stabilization.     

气相二氧化硅/季铵Gemini表面活性剂稳定的泡沫体系

以zeta电位法研究了季铵Gemini表面活性剂亚甲基-α, ω-双(十二烷基二甲基溴化铵) (12-s-12, s=2, 6)在水溶液中修饰气相二氧化硅(F-SiO₂)粒子。这些粒子随表面活性剂浓度C增加经历了表面从原先的亲水到疏水再重新亲水的改变,其中疏水粒子可以自发吸附在气泡液膜中,从而很好地稳定泡沫。重新亲水的粒子脱附出液膜,仅留下表面活性剂稳定气泡。强的液膜弹性对应于稳定的泡沫。联接链长度影响了Gemini在F-SiO₂粒子表面的吸附,因而也影响了液膜的弹性和对泡沫的稳定。超短s=2联接链的12-2-12由于反离子解离不完全而带有较少的正电荷,在粒子表面的初始吸附弱于12-6-12,但因此减少了吸附分子头基间的静电排斥,可以形成更致密的吸附层。由于12-2-12本身比12-6-12具有更强的界面吸附能力,F-SiO₂粒子和12-2-12的协同作用可以更好地稳定泡沫体系。     

Unusually stable liquid foams

Obtaining stable liquid foams is an important issue in view of their numerous applications. In some of these, the liquid foam in itself is of interest, in others, the liquid foam acts as a precursor for the generation of solid foam. In this short review, we will make a survey of the existing results in the area. This will include foams stabilised by surfactants, proteins and particles. The origin of the stability is related to the slowing down of coarsening, drainage or coalescence, and eventually to their arrest. The three effects are frequently coupled and in many cases, they act simultaneously and enhance one another. Drainage can be arrested if the liquid of the foam either gels or solidifies. Coalescence is slowed down by gelified foam films, and it can be arrested if the films become very thick and/or rigid. These mechanisms are thus qualitatively easy to identify, but they are less easy to model in order to obtain quantitative predictions. The slowing down of coarsening requests either very thick or small films, and its arrest was observed in cases where the surface compression modulus was large. The detail of the mechanisms at play remains unclear.     

Protein adsorption at the electrified air-water interface: implications on foam stability

The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams.     

Long-term stabilization of foams and emulsions with in-situ formed microparticles from hydrophobic cellulose

We report a simple method to produce foams and emulsions of extraordinary stability by using hydrophobic cellulose microparticles, which are formed in situ by a liquid-liquid dispersion technique. The hydrophobic cellulose derivative, hypromellose phthalate (HP), was initially dissolved in water-miscible solvents such as acetone and ethanol/water mixtures. As these HP stock solutions were sheared in aqueous media, micron sized cellulose particles formed by the solvent attrition. We also designed and investigated an effective and simple process for making HP particles without any organic solvents, where both the solvent and antisolvent were aqueous buffer solutions at different pH. Consequently, the HP particles adsorbed onto the water/air or water/oil interfaces created during shear blending, resulting in highly stable foams or foam/emulsions. The formation of HP particles and their ability for short-term and long-term stabilization of interfaces strongly depended on the HP concentration in stock solutions, as well as the solvent chemistry of both stock solutions and continuous phase media. Some foams and emulsion samples formed in the presence of ca. 1 wt% HP were stable for months. This new class of nontoxic inexpensive cellulose-based particle stabilizers has the potential to substitute conventional synthetic surfactants, especially in edible, pharmaceutical and biodegradable products.     

Thermodynamic and Mechanical Timescales Involved in Foam Film Rupture and Liquid Foam Coalescence

Recent advances in the coalescence in liquid foams are reviewed, with a special focus on the multiscale structure of foams. Studies concerning the stability of isolated foam films, on the one hand, and the coalescence process in macroscopic foams, on the other hand, are not always in good agreement. This discrepancy reveals that two routes can induce coalescence in a foam. The first route is thermodynamic and shows that coalescence is governed by a stochastic rupture of foam films. The second route relies on a mechanically induced rupture of the films, due to the spontaneous evolution of foams. From a literature review, the evaluation of the different timescales involved in these mechanisms allows defining the limiting parameters of foam coalescence.     

Effect of liquid paraffin on the stability of aqueous foam in the presence and absence of electrolytes

The foam stability of dodecyl diphenyl ether disulfonate solution with liquid paraffin droplets in the presence and absence of electrolytes was evaluated, and the stabilization mechanisms were deduced. The foam film is stabilized when the monovalent and divalent counterion concentration is lower than a critical value. However, the foam stability declined with the addition of trivalent counterions. There are two mechanisms we have speculated. Firstly, the counterions reduce the repulsive interaction between the polar groups of surfactants adsorbed at the air/water and oil/water interfaces in the pseudo-emulsion film. Secondly, comparing with the monovalent counterions, the multivalent counterions are not only able to interconnect head groups of adjacent ionic surfactant molecules which are adsorbed at the air/water or oil/water interface, but also to attract the couples of neighboring surfactant head groups adsorbed at the air/water and oil/water interfaces. The attractive interaction between both the interfaces promotes the emulsified droplets piercing the air/water interface.     

Foams stabilized by mixed cationic gemini/anionic conventional surfactants

The mixed adsorption of a cationic gemini surfactant, ethanediyl-1,2-bis(dodecyldimethylammonium bromide) (abbreviated as 12-2-12), and an anionic conventional surfactant, sodium dodecyl sulfate (SDS), was examined using surface tension measurements. The viscoelastic properties of the mixed films were investigated by dilational interfacial rheology technique. The results showed that the addition of SDS promoted the close packing of adsorbed molecules at the interface, which increased the dilational elasticity of the mixed films. The stability of the foams was determined by the half-life of foam height collapse. The foams generated by 12-2-12/SDS mixtures were more stable than that formed by pure 12-2-12. In the presence of sodium bromide, the foam stability was further enhanced and the surfactant concentration required to attain the maximum effect in stabilizing foams was greatly reduced. The high foam stability could well relate to the high elasticity of the film.     

Interfacial and foaming properties of prolylenglycol alginates. Effect of degree of esterification and molecular weight

In the present work we have studied the characteristics of propylene glycol alginates (PGA) adsorption at the air–water interface and the viscoelastic properties of the films in relation to its foaming properties. To evaluate the effect of the degree of PGA esterification and viscosity, different commercial samples were studied—Kelcoloid O (KO), Kelcoloid LVF (KLVF) and Manucol ester (MAN). The temperature (20 °C) and pH (7.0) were maintained constant. For time-dependent surface pressure measurements and surface dilatational properties of adsorbed PGA at the air–water interface an automatic drop tensiometer was used. The foam was generated by whipping and then the foam capacity and stability was determined. The results reveal a significant interfacial activity for PGA due to the hydrophobic character of the propylene glycol groups. The kinetics of adsorption at the air–water interface can be monitored by the diffusion and penetration of PGA at the interface. The adsorbed PGA film showed a high viscoelasticity. The surface dilatational modulus depends on the PGA and its concentration in the aqueous phase. Foam capacity of PGA solutions increased in the order KO > MAN > KLVF, which followed the increase in surface pressure and the decrease in the viscosities of PGA solutions. The stability of PGA foams monitored by the drainage rate and collapse time follows the order MAN > KLVF > KO. The foam stability depends on the combined effect of molecular weight/degree of esterification of PGA, solution viscosity and viscoelasticity of the adsorbed PGA film.     

Foaming,foam films,antifoaming and defoaming

A general introduction to foams, the initial stages in the production of foams in aqueous solution, foam structures and the classification of bulk foams according to their lifetimes and stability are presented. Fundamental studies on horizontal and vertical isolated foam lamellae with emphasis on drainage and stability are reviewed. For freshly prepared foams containing fairly thick lamellae, the mechanical-dynamical properties of the surface adsorbed layers (surface tension gradients) are decisive for retaining stability. Important parameters to be taken into consideration are the surface elasticity, viscosity (bulk and surface), gravity drainage and capillary suction. Also the film should exhibit low permeability to gases. Providing the stability of a foam film (containing dilute surfactant) is retained during the initial dynamic drainage process, then eventually a static (equilibrium) situation will be reached at film thicknesses < 100 nm. In this region, interfacial interactions dominate and the stability of the film must be discussed in terms of the intermolecular forces (electrostatic double layer repulsion, dispersion force attraction and steric forces). This may lead to the formation of common black and Newton black films and these structures have been shown to be resilient to rupture and have low gas transfer characteristics. At high surfactant concentrations (>c.m.c.) stabilization of films and foams can occur by a micellar laying mechanism (stratification). Antifoaming and defoaming theories are presented, together with the mechanisms of heterogeneous antifoaming agents (non-polar oil, hydrophobic solid particles or mixtures of both) including recent theories describing the role of the emulsion and pseudo-emulsion film in the stability of foams containing oil droplets. Finally, defoaming by ultrasonic waves is briefly reviewed.     

Effect of protein aggregates on foaming properties of β-lactoglobulin

Our paper aims at determining the respective part of protein aggregates and non-aggregated proteins in the foam formation and stability of β-lactoglobulin. We report results on fractal aggregates formed at neutral pH and strong ionic strength (aggregates size from 30 to 190 nm). Pure aggregates and mixtures of non-aggregated/aggregated proteins at varying ratios were used. The capacity of aggregates to form and stabilize foams has been studied in relation with their ability to absorb at air/water interfaces. Our results show that protein aggregates are not able by themselves to improve the foaming properties but participate to a better foam stabilization in the presence of non-aggregated proteins. Non-aggregated proteins appear to be necessary to produce stable foams. We have shown that the amount and the size of aggregates had an influence on the drainage rate.     

The Acoustics of Liquid Foams

Beside other transport properties of liquid foams, like the optical or electrical ones, the acoustics of liquid foams reveals a great complexity and non-trivial features. Here we present a review of recent experimental and theoretical results on how a sound wave interacts with either a macroscopic foam sample or with its isolated building blocks (films and Plateau borders). The analysis of the literature allows us to determine what is now well understood, what could be measured in foams by acoustics, and what are the remaining issues and perspectives in this research field.     

Interfacial shear rheology of protein-surfactant layers

The shear rheology of adsorbed or spread layers at air/liquid and liquid/liquid phase boundaries is relevant in a wide range of technical applications such as mass transfer, monolayers, foaming, emulsification, oil recovery, or high speed coating. Interfacial shear rheological properties can provide important information about interactions and molecular structure in the interfacial layer. A variety of measuring techniques have been proposed in the literature to measure interfacial shear rheological properties and have been applied to pure protein or mixed protein adsorption layers at air/water or oil/water interfaces. Such systems play for example an important role as stabilizers in foams and emulsions. The aim of this contribution is to give a literature overview of interfacial shear rheological studies of pure protein and protein/surfactant mixtures at liquid interfaces measured with different techniques. Techniques which utilize the damping of waves, spectroscopic or AFM techniques and all micro-rheological techniques will not discuss here.     

FOAMABILITY OF PEO-PPO-PEO TRIBLOCK COPOLYMERS (P85 AND F108) AND ROLE OF THE FOAM FILMS

The foamability of two commercial PEO-PPO-PEO triblock copolymers (Synperonic P85 and F108, ICI) was studied and compared to the properties of single foam films. The volume of a steady-state foam column created with a combined pneumatic-mechanical device is used as a measure of the copolymers foamability. Experiments were carried out at bulk copolymer concentrations corresponding to full surface coverage, i.e. constant area per molecule, under equilibrium conditions. The foamability of F108 solutions was higher than that of P85 although the surface activity of both copolymers was similar. The foam volume increases with increasing the bulk copolymer concentration. Higher electrolyte concentration or lower pH caused the foam volume to diminish. A pronounced parallelism between the properties of dynamic foams and single microscopic foam films was observed: when thicker single foam films were formed (from F108 solutions) the steady     

Surfactant in the gaseous phase I. Formation of foams and thin liquid films

A new possibility of obtaining foams and single thin liquid films by supplying a surfactant through the gaseous phase is presented. Argon saturated with vapors ofn-amyl orn-decyl alcohol was passed through the water phase and formation of the foam was measured as a function of time, gas flow rate, and volume of the water phase. Formation and properties of microscopic thin liquid films were measured as a function of the time of their contact with the surfactant vapors. Two possible mechanisms of foam formation by supplying surfactant via the gaseous phase are discussed. A theoretical model of surfactant dissolution is presented and its predictions are compared with the experimental results. It is shown that foam formation resulted mainly from dissolution of the surfactant vapors in the water phase.     

Surfactant in the gaseous phase II. Influence on stability of foams and thin liquid films

The influence of the vapors ofn-amyl orn-decyl alcohol on the stability of single thin liquid films, single bubbles, and foam columns was determined. It was found that the presence of surfactant vapors lowered the stability of foams and single foam films. The mechanism of the destabilizing action of the surfactant vapors on wet, dynamic foams under dynamic conditions is discussed. It is shown that the destabilizing action of the surfactant vapors is a further indication that surface elasticity forces are the main factor determining stability of wet, dynamic foams.     

Flexible supercapacitors based on carbon nanotubes

This review provides an overview of recent progress towards the development of flexible supercapacitors based on macroscopic carbon nanotubes-based electrodes, including one-dimensional (1D) fibers, 2D films, and 3D foams, with a focus on electrode preparation and configuration design as well as their integration with other multifunctional devices.     

Gemini表面活性剂乙烷基-α,ω-双十四烷基二甲基溴化铵产生的高稳定泡沫

报道了由gemini表面活性剂乙烷基-α,ω-双十四烷基二甲基溴化铵(14-2-14)产生的高稳定泡沫体系.泡沫塌陷到初始高度一半所对应的时间(t1/2)用来表征泡沫的稳定性.测得14-2-14体系的t1/2高达961min,远大于乙烷基-α,ω-双十二烷基二甲基溴化铵(12-2-12)产生泡沫的t1/2(754min),表明带有一根短联接链和两条长尾链的gemini表面活性剂是高效的泡沫稳定剂.为了揭示界面弹性与泡沫稳定性之间的关联,测量了表面活性剂吸附膜的扩张流变行为.在指定的表面过剩量下,吸附膜的高频极限弹性再一次被发现与泡沫稳定性相关,较大的极限弹性很好地对应更加稳定的泡沫.     

Foam formation and stabilisation by pre-denatured ovalbumin

Various mild heat-treatments of ovalbumin solutions were applied to produce molecular species with different conformational states, and having different kinetics of adsorption to the air/water interface and different foaming properties. Molecular species with a higher degree of shear-induced deformation and a low degree of thermal conformational stability showed a slight enhancement of the rate of decrease of surface tension, 5 min after the creation of the fresh interface, and decreasing long-term values of surface tension. Solutions of ovalbumin molecular species exhibiting such initial structural patterns were shown to have enhanced foam capacity and stability against liquid drainage. Ovalbumin molecules with some degree of secondary and tertiary structural changes and increased viscosity, before adsorption at the air/water interface, were shown to be relevant to produce more or less hydrated foams with more or less stability against liquid drainage.