Hollow silica nanoparticles possess unique properties derived from their nanoscale hollow interior enclosed by a solid silica shell. To fully exploit these features, independent control and evaluation of the inner and outer shell surfaces are essential. In this study, we apply time-domain nuclear magnetic resonance (TD-NMR) to separately characterize these two surfaces for the first time. A quantitative framework was established to distinguish outer and inner surface contributions based on particle concentration and cavity size. The T2 relaxation curves of hollow particle-ethanol suspensions were resolved into long and short components. The long T2 decreased with increasing particle concentration, similar to dense particles, indicating ethanol molecules bound to the outer surface in exchange with bulk liquid. In contrast, the short T2 remained nearly constant regardless of concentration, suggesting liquid confined within the hollow interior where the surface-to-liquid ratio is fixed. A critical minimum cavity size required to detect inner-surface relaxation was identified. These results demonstrate that TD-NMR enables rapid characterization of occluded liquids and shell microstructure, offering a practical tool for porous material evaluation and routine quality control. (c) 2026 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan.
Multi-component liquid mixtures can be both complex and fascinating, with some systems being amenable to simple experimentation at home, giving valuable insight into fundamental aspects of bulk and interfacial phase behaviour. One particularly interesting mixture is the popular drink ouzo, which has charmed both the general public and scientists by virtue of its ability to display spontaneous emulsification when water is added. When these two clear (and potable) liquids are poured into each other, a single milky-coloured liquid is formed. In previous work [Archer et al., Soft Matter 20, 5889 (2024)], the equilibrium phase-diagram for the stable liquid phases of ouzo was captured via experiment and modelling. Here we consider the case when the two liquid phases also coexist with the vapour phase (i.e. along a line of triple points) and within our model uncover the complex bulk phase behaviour for this simple beverage. As a consequence, this leads to some interesting observations, that also apply more widely, about visualising phase diagrams in ternary systems of this type. We also examine the interfacial behaviour, connecting microscopic density functional theory results with macroscopic (Neumann) predictions for the shape of droplets at interfaces.
Ouzo is a well-known drink in Mediterranean countries, with ingredients water, alcohol and trans-anethole oil. The oil is insoluble in water, but completely soluble in alcohol, so when water is added to the spirit, the available alcohol is depleted and the mixture exhibits spontaneous emulsification. This process is commonly known as the louche or ouzo effect. Although the phase boundaries of this archetypal ternary mixture are well known, the properties of coexisting phases have not previously been studied. Here, we present a detailed experimental investigation into the phase behaviour, including tie-lines connecting coexisting phases, determination of the critical point (also called the plait point in ternary systems) and measurements of the surface tension and density for varying alcohol concentrations. Additionally, we present a theory for the thermodynamics and phase diagram of the system. With suitable selection of the interaction parameters, the theory captures nearly all features of the experimental work. This simple model can be used to determine both bulk and non-uniform (e.g. interfacial) properties, paving the way for a wide range of future applications of the model to ternary mixtures in general. We show how our accurate equilibrium phase diagram can be used to provide improved understanding of non-equilibrium phenomena.
We analyze the diffusion-controlled evaporation of multiple droplets placed near each other on a planar substrate. Specifically, we calculate the change in the volume of sessile droplets with various initial contact angles that are arranged in different configurations. The calculations are supplemented by experimental measurements using a technique that interprets the variable magnification of a pattern placed beneath the droplet array, which is applied to the case of initially hemispherical droplets deposited in four distinct arrangements. We find excellent agreement between the predictions based on the theory of Masoud et al. [Evaporation of multiple droplets, J. Fluid Mech. 927, R4 (2021)] and the data gathered experimentally. Perhaps unexpectedly, we also find that when comparing different arrays, the droplets with the same order of disappearance within their respective array, i.e., study provides not only experimental validation of the theoretical framework introduced by Masoud et al., but also offers additional insights into the evolution of the volume of individual droplets when evaporating within closely-spaced arrays.
The specificity of ions in inducing conformational changes in macromolecules is introduced as the Hofmeister series; however, the detailed underlying mechanism is not comprehensible yet. We utilized surface-specific sum frequency generation (SFG) vibrational spectroscopy to explore the Hofmeister effect at the air/polyvinylpyrrolidone (PVP)/water interface. The spectral signature observed from the ssp polarization scheme reveals ion-specific ordering of water molecules following the Hofmeister series attributed to the ion-macromolecule interactions. Along with this, the presence of ions does not reflect any significant influence on the structure of the PVP macromolecule. However, the ppp-SFG spectra in the CH-stretch region reveal the impact of ions on the orientation angle of vinyl chain CH2-groups, which follows the Hofmeister series: SO42- > Cl- > NO3- > Br- > ClO4- > SCN-. The minimal orientation angle of CH2-groups indicates significant reordering in PVP vinyl chains in the presence of chaotropic anions ClO4-, and SCN-. The observation is attributed to the ion-specific water-macromolecule interactions at the air/aqueous interface. It is compelling to observe the signature of spectral blue shifts in the OH-stretch region in the ppp configuration in the presence of chaotropic anions. The origin of spectral blue shifts has been ascribed to the existence of weaker interactions between the interfacial water molecules and the backbone CH- and CH2-moieties of the PVP macromolecules. The ion-specific modulation in water-macromolecule interactions is endorsed by the relative propensity of anion's adsorption toward the air/aqueous interface. The experimental findings highlight the existence and cooperative participation of ion-specific water-macromolecule interactions in the mechanism of the Hofmeister effect, along with the illustrious ion-water and ion-macromolecule interactions.
The incorporation of bubbles in foods has created a positive market response from consumers since their first introduction over 70 years ago and has resulted in an expanding market over this period. However, although the physics and chemistry of most ingredients in commercial food products are reasonably well understood, the behaviour of bubbles in foods are much less established and their behaviour not fully appreciated. In fact, bubbles are perhaps the least studied of all food ingredients even though aeration is still one of the fastest growing unit operations in processing. Although many of these manufactured aerated food products are perceived as lighter with lower calorific values, problems in manufacturing remain even today and it is generally difficult to optimize the size, the size distribution, the deviation the from spherical shapes and the stability of the bubbles during the different stages of the processing. In this review, we discuss the dispersion of the various food ingredients and the different processes involved in introducing bubbles into the melt, producing well dispersed multiphase systems. The second part of this review focusses on aerated chocolate and the above aspects are particularly important and are discussed in some detail since it has been well established that the bubble size and size distribution can influence the texture, the mouthfeel, the crispness, the melting temperature, and the brit-tleness of the product. Understanding the science involved in the transformation from the liquid state containing dispersed bubbles to a solid chocolate foam, stabilization of the bubbles and the control of the bubble size are highlighted. Although CO2 is usually used to generate bubbles in chocolate, several different gases including N2O, Ar and N2 have also been evaluated. One of the research aims of food companies is to improve control over the stability of the systems. This has been investigated with respect to drainage, by carrying out experiments under zero gravity conditions.
We present an experimental "pattern-distortion" (PD) technique which connects the shape of a liquid lens to its magnification. We demonstrate how to optimize the technique for arbitrary droplet sizes and optical configurations, and demonstrate its widespread utility in three distinct situations. Firstly, we consider multiple sessile droplets. Although ubiquitous in nature, understanding of their complex interactions is limited, partly due to experimental limitations in determining individual droplet volumes for arbitrary configurations. We use the PD technique to overcome these limitations, and we find excellent agreement between our experimental data and three recent theoretical models. Secondly, we show how our technique can be used to inform the design of liquid lenses. Thirdly, we extend the method to composite droplets systems, using it to extract the size of an air bubble trapped inside a liquid droplet.
The evaporation of multiple sessile droplets is both scientifically interesting and practically important, occurring in many natural and industrial applications. Although there are simple analytic expressions to predict evaporation rates of single droplets, there are no such frameworks for general configurations of droplets of arbitrary size, contact angle or spacing. However, a recent theoretical contribution by Masoud, Howell & Stone (J. Fluid Mech., vol. 927, 2021, R4) shows how considerable insight can be gained into the evaporation of arbitrary configurations of droplets without having either to obtain the solution for the concentration of vapour in the atmosphere or to perform direct numerical simulations of the full problem. The theoretical predictions show excellent agreement with simulations for all configurations, only deviating by 25% for the most confined droplets.
Formulation of particulate dispersions is a difficult industrial problem, with a multitude of system details influencing the final outcome. Solvent relaxation NMR is shown to help optimise the formulation of particulate dispersions of a range of widely used commercial silicas. Solvent at the particle interface is sensitive to details of the formulation, and it is shown that the average solvent spin-relaxation time in a dispersion can be used to monitor wetted surface area, sample sedimentation, and additive amounts; chemical syntheses and mechanical degradation of silicas are also monitored to optimise the dispersions. The experiments, which can be carried out on bench-top or on-line spectrometers, are not limited to silicas and can be generalised to other particles in a range of aqueous and non-aqueous dispersions, providing useful feedback to the formulator anywhere surfactants, polymers, pH, ionic strength, Hamaker constants, and surface charge play a role in stabilisation.
Evaporation is an interfacial phenomenon in which a water molecule breaks the intermolecular hydrogen (H-) bonds and enters the vapor phase. However, a detailed demonstration of the role of interfacial water structure in the evaporation process is still lacking. Here, we purposefully perturb the H-bonding environment at the air/water interface by introducing kosmotropic (HPO4-2, SO4-2, and CO3-2) and chaotropic ions (NO3- and I-) to determine their influence on the evaporation process. Using time-resolved interferometry on aqueous salt droplets, we found that kosmotropes reduce evaporation, whereas chaotropes accelerate the evaporation process, following the Hofmeister series: HPO4-2 < SO4-2 < CO3-2 < Cl- < NO3- < I-. To extract deeper molecular-level insights into the observed Hofmeister trend in the evaporation rates, we investigated the air/water interface in the presence of ions using surface-specific sum frequency generation (SFG) vibrational spectroscopy. The SFG vibrational spectra reveal the significant impact of ions on the strength of the H-bonding environment and the orientation of free OH oscillators from ∼36.2 to 48.4° at the air/water interface, where both the effects follow the Hofmeister series. It is established that the slow evaporating water molecules experience a strong H-bonding environment with free OH oscillators tilted away from the surface normal in the presence of kosmotropes. In contrast, the fast evaporating water molecules experience a weak H-bonding environment with free OH oscillators tilted toward the surface normal in the presence of chaotropes at the air/water interface. Our experimental outcomes showcase the complex bonding environment of interfacial water molecules and their decisive role in the evaporation process.
The selection of appropriate solvents into which inorganic and organic sub-micron particles can be dispersed is important for product manufacturability and performance. Molecular-level interactions determine solvent suitability but are difficult to measure; existing experimental approaches require slow/expensive tests of dispersion stability. Solvent relaxation NMR measurements are shown to be a fast indicator of solvent suitability, with sensitivity to the solvent-particle intermolecular forces making it a reliable proxy for stability measurements. A structured approach to relaxation measurements with a selection of both good and poor solvents yields the Hansen Solubility Parameters (HSP) for the particle surface. Suitable solvents can be selected from a database of HSP values, and solvents can be blended to match the particle interface. The application of the approach is illustrated using a range of surface modified zinc oxide and aluminum oxide particles, with similarities and differences between the particle surfaces becoming evident through the analysis.
The evaporation dynamics of multiple droplet arrays is important in inkjet printing and spray coating, where co-operative "shielding " effects increase the overall evaporation time. However, current measurement methods provide limited information on how individual droplets contribute to the overall dynamics. In this work, we present a simple interferometric technique for precise measurements of droplet evaporation rates, which is not possible via traditional approaches. We validate the technique on a single droplet. We then extend our analysis to ordered and random 2D arrays of droplets. We demonstrate that the evaporation rate is highly dependent on the position of the droplet within the array and its confinement. The more confined droplets exhibit lower evaporation rates. Our results of ten different configurations and well over 100 droplets are in good quantitative agreement with a recent analytical model of co-operative evaporation rates. Our approach opens up possibilities for studies of collective evaporation effects, including in areas of current importance such as sneezes and exhaled breath.
Although street artists have the know-how to blow bubbles over one meter in length, the bubble width is typically determined by the size of the hoop, or wand they use. In this article we explore a regime in which, by blowing gently downwards, we generate bubbles with radii up to ten times larger than the wand. We observe the big bubbles at lowest air speeds, analogous to the dripping mode observed in droplet formation. We also explore the impact of the surfactant chosen to stabilize the bubbles. We are able to create bubbles of comparable size using either Fairy liquid, a commercially available detergent often used by street artists, or sodium dodecyl sulfate (SDS) solutions. The bubbles obtained from Fairy liquid detach from the wand and are stable for several seconds, however those from SDS tend to burst just before detachment.
One of the most interesting and everyday natural phenomenon is the formation of different patterns after the evaporation of liquid droplets on a solid surface. The analysis of dried patterns from blood droplets has recently gained a lot of attention, experimentally and theoretically, due to its potential application in diagnostic medicine and forensic science. This paper presents evidence that images of dried blood droplets have a signature revealing the exhaustion level of the person, and discloses an entirely novel approach to studying human dried blood droplet patterns. We took blood samples from 30 healthy young male volunteers before and after exhaustive exercise, which is well known to cause large changes to blood chemistry. We objectively and quantitatively analysed 1800 images of dried blood droplets, developing sophisticated image processing analysis routines and optimising a multivariate statistical machine learning algorithm. We looked for statistically relevant correlations between the patterns in the dried blood droplets and exercise-induced changes in blood chemistry. An analysis of the various measured physiological parameters was also investigated. We found that when our machine learning algorithm, which optimises a statistical model combining Principal Component Analysis (PCA) as an unsupervised learning method and Linear Discriminant Analysis (LDA) as a supervised learning method, is applied on the logarithmic power spectrum of the images, it can provide up to 95% prediction accuracy, in discriminating the physiological conditions, i.e., before or after physical exercise. This correlation is strongest when all ten images taken per volunteer per condition are averaged, rather than treated individually. Having demonstrated proof-of-principle, this method can be applied to identify diseases.
Hansen Solubility Parameter (HSP) Semi-empirical approach Uses measures of interactions: dispersion, D, polar/dipolar, P and hydrogen bonding, H provides coordinates of solute in a 3-D interaction space Solubility of polymer evaluated in a range of liquids selected across "Hansen space" Probe solvents ranked as good or poor depending on efficiency to dissolve the polymer Sphere defining boundary between good and poor solvent coordinates constructed Relative Energy Difference * C. Hansen, Hansen Solubility Parameters: A User's Handbook, 2 nd Ed., CRC Pres (2007)An RED <1 is "good" and an RED >1 is "poor" HSP originally developed to describe the interaction (solubility) of polymers in different liquids → uses paradigm that "like dissolves like"* * htpps://www.hansen-solubility.com
PURPOSE:This work demonstrates specifically tailored microbubble-based preparations and their suitability as MRI contrast agents for ingestion and measuring temporal and spatial pressure variation in the human stomach. METHODS:Enhanced alginate spheres were prepared by incorporating gas-filled microbubbles into sodium alginate solution followed by the polymerization of the mixture in an aqueous calcium lactate solution. The microbubbles were prepared with a phospholipid shell and perfluorocarbon gas filling, using a mechanical cavitational agitation regime. The NMR signal changes to externally applied pressure and coming from the enhanced alginate spheres were acquired and compared with that of alginate spheres without microbubbles. In vivo investigations were also carried out on healthy volunteers to measure the pressure variation in the stomach. RESULTS:The MR signal changes in the contrast agent exhibits a linear sensitivity of approximately 40% per bar, as opposed to no measurable signal change seen in the control gas-free spheres. This novel contrast agent also demonstrates an excellent stability in simulated gastric conditions, including at body temperature. In vivo studies showed that the signal change exhibited in the meal within the antrum region is between 5% and 10%, but appears to come from both pressure changes and partial volume artifacts. CONCLUSION:This study demonstrates that alginate spheres with microbubbles can be used as an MRI contrast agent to measure pressure changes. The peristaltic movement within the stomach is seen to substantially alter the overall signal intensity of the contrast agent meal. Future work must focus on improving the contrast agent's sensitivity to pressure changes.
Kefirian milk is a fermented beverage consumed worldwide. Originally produced in animal skins, it is now prepared both industrially and at home by adding symbiotic cultures of bacteria and yeast known as kefir grains to fresh milk. There is significant literature on the biological aspects of this process but little focus on the fermentation effects on the bulk milk as a function of the grain morphology. Changes in the Magnetic Resonance (MR) signal as measured using a whole body clinical magnetic resonance imaging scanner are found to be proportional to traditional gas measurements with correlation coefficients in excess of 0.95. Magnetic Resonance Imaging is then also used to determine the effect of grain size on the rate of fermentation of milk. It is found that larger grains result in signal intensity changes on the order of 0.03 a.u per hour, but by breaking the grains into pieces around 3mm, the reaction rate can be more than doubled to 0.07 a.u. per hour. It is thought that this shows promise as a method to improve the speed of production of kefirian milk and by arresting the process partway through fermentation, gives control over the properties of the end product.