Materials based on solid-stabilized emulsions

Solid-stabilized emulsions are obtained by shearing a mixture of oil, water, and solid colloidal particles. In this article, we present a large variety of materials, resulting from a limited coalescence process. Direct (o/w), inverse (w/o), and multiple (w/o/w) emulsions that are surfactant-free and monodisperse were produced in a very wide droplet size range, from micrometers to centimeters. These materials exhibit original properties compared with surfactant-stabilized emulsions: outstanding stability with respect to coalescence and unusual rheological behavior. For such systems, the elastic storage modulus G' is not controlled by interfacial tension but by the interfacial elasticity resulting from the strong adhesion between the solid particles adsorbed at the oil-water interface. Due to the wide accessible droplet size range, concentrated emulsions can be extremely fluid while emulsions with low droplet volume fraction can behave as solids.     

Selection of surfactants for stable paraffin-in-water dispersions, undergoing solid-liquid transition of the dispersed particles

A new experimental procedure is proposed for express evaluation of the coalescence stability of dispersions, in which the dispersed particles undergo solid-liquid phase transition. The procedure includes centrifugation of the dispersion concurrently with the phase transition of the particles and allows precise quantification of dispersion stability in terms of a critical pressure, at which the coalescence between the dispersed particles/drops takes place. The method is applied for studying the effects of surfactant type and concentration on the stability of paraffin-in-water dispersions, which have potential application in energy storage and transportation systems. Several types of water-soluble surfactants (anionic, nonionic, and polymeric) are compared, whereas hexadecane or tetradecane is used as a dispersed phase. Most of the studied individual surfactants are found to be inefficient stabilizers (except for the nonionic Tween 40 and Tween 60). However, the dispersion stability increases significantly after the addition of appropriate cosurfactants, such as hexadecanol, Brij 52, or cocoamidopropyl betaine. Surfactants and cosurfactants with longer hydrophobic tails are better stabilizers than those with shorter tails. The obtained results are discussed from the viewpoint of the mechanisms of particle/drop coalescence during the solid-liquid-phase transition. The consistency and the undercooling temperatures of the studied dispersions are also discussed, because these properties are important for their practical applications. The proposed procedure for evaluation of dispersion stability and some of the conclusions could be relevant to food emulsions, in which dispersed fat particles undergo solid-liquid-phase transition of similar type.     

Studies on droplet size distributions during coalescence in immiscible polymer blends filled with silica nanoparticles

The effect of silica nanoparticles on the morphology of （10/90 wt%） PDMS/PBD blends during the shear induced coalescence of droplets of the minor phase at low shear rate was investigated systematically in situ by using an optical shear technique. Two blending procedures were used： silica nanoparticles were introduced to the blends by pre-blending silica particles first in PDMS dispersed phase （procedure 1） or in PBD matrix phase （procedure 2）. Bimodal or unimodal droplet size distributions were observed for the filled blends during coalescence, which depend not so much on the surface characteristics of silica but mainly on blending procedure. For pure （10/90 wt%） PDMS/PBD blend, the droplet size distribution exhibits bimodality during the early coalescence. When silica nanoparticles （hydrophobic and hydrophilic） were added to the blends with procedure l, bimodal droplet size distributions disappear and unimodal droplet size distributions can be maintained during coalescence; the shape of the different peaks is invariably Gaussian. Simultaneously, coalescence of the PDMS droplets was suppressed efficiently by the silica nanoparticles. It was proposed that with this blending procedure the nanoparticles should be mainly kinetically trapped at the interface or in the PDMS dispersed phase, which provides an efficient steric barrier against coalescence of the PDMS dispersed phase. However, bimodal droplet size distributions in the early stage of coalescence still occur when incorporating silica nanoparticles into the blends with procedure 2, and then coalescence of the PDMS droplets cannot be suppressed efficiently by the silica nanoparticles. It was proposed that with this blending protocol the nanoparticles should be mainly located in the PBD matrix phase, which leads to an inefficient steric barrier against coalescence of the PDMS dispersed phase; thus the morphology evolution in these filled blends is similar to that in pure blend and bimodal droplet size distributions can be observed during the early coalescence. These results imply that exploiting non-equilibrium processes by varying preparation protocol may provide an elegant route to regulate the temporal morphology of the filled blends during coalescence.     

Miniemulsion polymerization of styrene using alkyl methacrylates as the reactive cosurfactant

 Stable styrene miniemulsions were prepared by using alkyl methacrylates as the reactive cosurfactant. Like conventional cosurfactants (e.g., cetyl alcohol (CA) and hexadecane (HD)), alkyl methacrylates (e.g., dodecyl methacrylate (DMA) and stearyl methacrylate (SMA)) may act as a cosurfactant in stabilizing the homogenized miniemulsions. Furthermore, the methacrylate group may be chemically incorporated into latex particles in subsequent miniemulsion polymerization. The data of the monomer droplet size, creaming rate and phase separation of monomer as a function of time were used to evaluate the shelf-life of miniemulsions stabilized by sodium dodecyl sulfate in combination with various cosurfactants. Polystyrene latex particles were produced via both monomer droplet nucleation and homogeneous nucleation in the miniemulsion polymerization using CA or DMA as the cosurfactant, with the result of a quite broad particle size distribution. On the other hand, the miniemulsion polymerization with HD or SMA showed a predominant monomer droplet nucleation. The resultant particle size distribution was relatively narrow. In miniemulsion polymerization, the less hydrophobic DMA is similar to CA, whereas the more hydrophobic SMA is similar to HD. Received: 19 November 1996 Accepted: 20 February 1997     

Polymerisable Miniemulsions Using Rotor‐Stator Homogenisers

The use of a rotor‐stator mixer as a homogenisation device to make miniemulsion droplets with industrially pertinent solid contents was investigated. Methyl methacrylate/butyl acrylate (50:50 w/w ratio) miniemulsions with droplet diameters from 2 µm to 300 nm and polydispersity indices from 1.2 to 3.6 were used. Miniemulsions with three different mean droplet diameters (300, 400, 600 nm) were polymerised and the evolution of particle size was observed. When 300 nm droplets were polymerised they yielded particles of similar diameter to the original droplets, whereas particle coalescence of the growing particles with a loss of control over the particle size distribution was observed for the 400 and 600 nm droplets. The influence of costabiliser, agitation speed, solid content, colloidal protectors and surface coverage on the evolution of the droplet size and size distribution as well as on the evolution of the average particle size and its distribution were examined. It was observed that changing the above parameters had no impact on the evolution of the particle size, suggesting we have a very robust miniemulsion system.

     

An NMR study of the freezing of emulsion-containing drops

Various nuclear magnetic resonance (NMR) techniques were used to monitor the freezing behaviour of suspended 2-mm-diameter drops. The drops were composed of hydrocarbon oils emulsified in either water or water/sucrose mixtures. As such they were good model systems for the study of spray freezing, sharing structural similarities with potential products such as ice cream. In particular, simple 1H NMR spectroscopy was used to monitor and individually quantify the freezing or solidification behaviour of the various constituent species of the drops. In addition, the effect of freezing on the emulsion droplet size distribution (and hence emulsion stability) was also measured based on NMR self-diffusion measurements. The effect of freeze/thaw cycling was also similarly studied. The nucleation temperature of the emulsion droplets was found to depend on the emulsion droplet size distribution: the smaller the droplets, the lower the nucleation temperature. Emulsion droplet sizing indicated that oil-in-sucrose-solution emulsions were more stable, showing minimal coalescence, whereas oil-in-water emulsions showed significant coalescence during freezing and freeze/thaw cycling.     

Water-in-carbon dioxide emulsions stabilized with hydrophobic silica particles

W/C emulsions were stabilized using hydrophobic silica particles adsorbed at the interface, resulting in average droplet diameters as low as 7.5 microm. A porous cross-linked shell was formed about a hydrophilic (colloidal and fumed) silica core with a trifunctional silylating agent, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethyoxysilane, to render the particles CO(2)-philic. The stability of emulsions comprising equal weights of CO(2) and water was assessed with visual observations of settling fronts and the degree of emulsion coalescence, and the average drop size was measured by optical microscopy. The effect of CO(2) density on both emulsion stability and droplet size was determined quantitatively. The major destabilizing mechanism of the emulsions was settling, whereas Ostwald ripening and coalescence were not visible at any density, even over 7 days. Flocculation of the settling droplets did not occur, although gelation of the emulsions through particle interactions resulted after longer periods of time. CO(2)-philic particles offer a new route to highly stable W/C emulsions, with particle energies of attachment on the order of 10(6)kT, even at CO(2) densities as low as 0.78 g ml(-1). At these low densities, surfactants rarely stabilize emulsions as the result of poor surfactant tail solvation.     

Study of cosurfactant effect on nanoemulsifying area and development of lercanidipine loaded (SNEDDS) self nanoemulsifying drug delivery system

The present study deals with the development and characterization of self-nanoemulsifying drug delivery system (SNEDDS) to improve the oral bioavailability of poorly soluble third generation calcium channel blocker lercanidipine (LER). Solubility of the LER was estimated in various oils, cosurfactants and surfactants which were grouped into two different combinations to construct pseudoternary phase diagrams. Various thermodynamic stability and dispersibility tests were performed on the formulations from phase diagram. After constructing phase diagram of two different combinations NL-I and NL-II, the effect of cosurfactants on the nanoemulsifying area was studied and the effect of number and length of hydrophobic alkyl chains of cosurfactant in its emulsification capacity was proved. Percentage transmittance, emulsification time, viscosity and droplet size analysis were used to characterize optimized formulations. The optimized formulation composed of Cremophor EL (45% wt/wt), (13.5% wt/wt) Caproyl 90 with (1.5% wt/wt) Transcutol® HP as per limits of inactive ingredients guidelines of FDA and Maisine oil (10% wt/wt). The mean droplet size in selected nanocarrier system was 20.01 nm. The in vitro dissolution profile of LER SNEDDS was found significant in comparison to the marketed LER (Zanidip) tablet and pure drug in pH 1.2, 4.5 and 6.8 buffers. Empty hard gelatin capsule shells were filled using Pfizer's Licap technology and charged on stability conditions of 30 °C/65% RH, 40 °C/65%RH and 50 °C/75% in glass bottles where no significant degradation (p > 0.05) was observed in 3 months. The results indicate that SNEDDS of LER, owing to nanosized, has potential to enhance the absorption of drug.     

A new modified low-energy emulsification method for preparation of water-in-diesel fuel nanoemulsion as alternative fuel

In this research, 24 of water-in-diesel fuel nanoemulsions were prepared using mixed nonionic surfactants of sorbitan monooleate and polyoxyethylene sorbitan trioleate (MTS). The emulsions were formed using a new modified low-energy method at hydrophilic-lipophilic balance (HLB) value of 10 and a working temperature of 20°C. Five HLB values of 9.6, 9.8, 10, 10.2, and 10.4 were prepared to identify the optimum value that gives low water droplet size at working conditions as: 5 wt% of water contents, 10 wt% of mixed surfactant concentration, and a temperature of 20°C. The effect of mixed surfactant concentration and water content on the droplet size for 0, 15, 30, 60, and 90 days has been studied. Droplet size of the prepared nanoemulsions was determined by dynamic light scattering and the nanoemulsion stability was assessed by measuring the variation of the droplet size as a function of time. Results show that the mean droplet sizes were formed between 26.23 and 277.1 nm depending on the surfactant concentrations, water contents, and storage time.     

Effect of Particle Size on Rate of Coalescence of Silica Nanoparticles

In high temperature processes, at high concentrations, aerosol particles grow by collisions and coalescence. The rate of coalescence is an important parameter for predicting the final primary particle size. For some materials, particularly silica, predictions of final primary particle size using coalescence rates based upon bulk material properties are not in agreement with experimental results. One explanation may be that the high internal pressure in very small particles (less than 10 nm in diameter) affects the mobility of material within the particles and hence the coalescence rate. In this Note, a new approach for estimating rates of coalescence of particles in the initial stages of growth is presented. Coalescence of liquid particles is assumed to be rate-limited by atomic mobility, and the effect of internal pressure on diffusivity is considered. Copyright 1999 Academic Press.     

Physical characteristics of freeze-dried griseofulvin-lipids nanoparticles

We have attempted to prepare micronized drug particles and to maintain the micronized state long-term in order to improve the solubility of a practically insoluble drug, griseofulvin (GF). GF nanoparticles (GFNPs) prepared by high-pressure homogenization were micronized to about 45 nm (mean particle size). GFNPs were subjected to transmission electron microscopy (TEM) observation. The mean particle size remained at about 50 nm for 3 months at 25 degrees C. However, increased to about 300 nm in 6 months. After 5% (w/v) sugar was added, GFNP was freeze-dried and rehydrated. The mean particle size of the rehydrated GFNPs was about 160 nm when the sugar was a monosaccharide. In contrast, it was about 55-65 nm when the sugar was a disaccharide. The powder X-ray diffraction pattern of the monosaccharide-containing freeze-dried GFNPs revealed a crystal state of sugar. On the other hand, that of the disaccharide-containing freeze-dried GFNPs indicated an amorphous state of sugar. From this result, it is considered that the high viscosity of an amorphous sugar prevents GFNPs from aggregating through retardation of molecular movement. Freeze-dried GFNPs stored for six months at 25 degrees C showed a good re-dispersibility. After the rehydration the mean particle size of GFNPs was 55-65 nm. It was found that freeze-dried GFNPs containing sucrose, maltose or trehalose were stable for longer periods than GFNP suspensions.     

Novel method for obtaining homogeneous giant vesicles from a monodisperse water-in-oil emulsion prepared with a microfluidic device

A novel technique called the "lipid-coated ice droplet hydration method" is presented for the preparation of giant vesicles with a controlled size between 4 and 20 microm and entrapment yields for water-soluble molecules of up to about 30%. The method consists of three main steps. In the first step, a monodisperse water-in-oil emulsion with a predetermined average droplet diameter between 4 and 20 microm is prepared by microchannel emulsification, using sorbitan monooleate (Span 80) and stearylamine as emulsifiers and hexane as oil. In the second step, the water droplets of the emulsion are frozen and separated from the supernatant hexane solution by precipitation, followed by a removal of the supernatant and followed by the replacement of Span 80 by using a hexane solution containing egg yolk phosphatidylcholine, cholesterol, and stearylamine (5:5:1, molar ratio). This procedure is performed at -10 degrees C to keep the water droplets of the emulsion in a frozen state and thereby to avoid extensive water droplet coalescence. In the third step, hexane is evaporated at -4 to -7 degrees C and an external water phase is added to the remaining mixture of lipids and water droplets to form giant vesicles that have an average size in the range of that of the initial emulsion droplets (4-20 microm). The entrapment yield and the lamellarity of the vesicles obtained depend on the lipid/water droplet ratio and on the composition of the external water phase. At high lipid/water droplet ratio, the giant vesicles have a thicker membrane (indicating multilamellarity) and a higher entrapment yield than in the case of a low lipid/water droplet ratio. The highest entrapment yield ( approximately 35%) is obtained if the added external water phase contains preformed unilamellar egg phosphatidylcholine vesicles with an average diameter of 50 nm. The addition of these small vesicles minimizes the water droplet coalescence during the third step of the vesicle preparation, thereby decreasing the extent of release of water-soluble molecules originally present in the water droplets. The GVs prepared can be extruded through polycarbonate membranes to yield large unilamellar vesicles with about 100 nm diameter. This size reduction, however, leads to a decrease in the entrapment yield to about 12% due to solute leakage from the vesicles during the extrusion process.     

A Visible Spectroscopic Study of Microstructure of O/W Microemulsions of Anionic Surfactants: Effect of Cosurfactant

The microstructure of o/w microemulsions, stabilized by sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS) with different cosurfactants, has been studied by partitioning of a dye, phenol red, between the oil‐water interface and bulk water. The cosurfactants used are propan‐1‐ol, propan‐2‐ol, butan‐1‐ol, butan‐2‐ol, pentane‐1‐ol, pentane‐2‐ol, and pentan‐3‐ol. The effects of changing the oil volume fraction and surfactant‐cosurfactant w/w ratio on the oil‐water interface and droplet size have also been discussed. Larger droplet size was predicted for SDS than SDBS. The predicted droplet radius increased with increase in the oil fraction, decrease in the surfactant concentration, increase in the C‐number of the linear cosurfactant, and decrease in branching of the cosurfactant. Surfactant‐cosurfactant ratio and pH did not affect the droplet size significantly. The minimum concentrations of surfactants with which microemulsions were formed were found to be higher for larger oil fraction, smaller C‐number of the alcohol, more branching of the alcohol, and higher pH.     

Synthesis and characterization of the n-butyl palmitate as an organic phase change material

In this research, the n-butyl palmitate was synthesized using the esterification reaction of the PA with n-butanol. The ¹H nuclear magnetic resonance and Fourier transform infrared illustrated that the hydroxyl group and carboxyl group disappeared, and the ester bond appeared after the reaction, explaining that n-butyl palmitate was successfully fabricated. The differential scanning calorimetry indicated that the phase-transition temperature and latent heat are 12.6 °C and 127.1 J g^?1, which was suited to use in low-temperature fields such as food, pharmaceutical, and biomedical. The thermogravimetric analysis suggested that it had great thermal stability during the phase change process. In addition, the thermal conductivity of the n-butyl palmitate was slightly higher than other fatty acid ester, and the 500 thermal cycles test results indicated that it had excellent thermal reliability. Therefore, the n-butyl palmitate is deduced to share great thermal energy storage ability in terms of latent heat thermal energy system applications.

     

Synthesis and heavy-metal-ion sorption of pure sulfophenylenediamine copolymer nanoparticles with intrinsic conductivity and stability

Novel copolymer nanoparticles were easily synthesized with a polymerization yield of 59.3 % by an oxidative precipitation polymerization of aniline (AN) and m-sulfophenylenediamine (SP) in HCl without any external stabilizer. The polymerization yield, size, morphology, electroconductivity, solubility, solvatochromism, lead and mercury ion adsorbability of the HCl-doped copolymer salt particles were studied by changing the AN/SP ratio. The AN/SP (80:20) copolymer particles are found to have the minimal number-average diameter(84.4 nm), minimal size polydispersity index (1.149), high stability, good long-term stability, powerful redispersibility in water, high purity, and clean surface because of a complete elimination of the contamination from external stabilizer. The copolymer salts possess a remarkably enhanced solubility, interesting solvatochromism, and widely adjustable electroconductivity moving across nine orders of magnitudes from 10(-9) to 10(0) S cm(-1). The AN/SP (70:30) copolymer particles have the highest Hg2+ adsorbance and adsorptivity of 497.7 mg g(-1) and 98.8 %, respectively, which are much higher values than those of other materials. The sorption mechanism of lead and mercury ions on the particles is proposed. The copolymer bases with 5-10 mol % SP unit show excellent film formability, flexibility, and smooth appearance. The copolymer should be very useful in the fabrication of cost-effective conductive nanocomposite with low percolation threshold and in removal of toxic metallic ions from waste water.     

Nanoparticles of varying hydrophobicity at the emulsion droplet-water interface: adsorption and coalescence stability

The coalescence stability of poly(dimethylsiloxane) emulsion droplets in the presence of silica nanoparticles ( approximately 50 nm) of varying contact angles has been investigated. Nanoparticle adsorption isotherms were determined by depletion from solution. The coalescence kinetics (determined under coagulation conditions at high salt concentration) and the physical structure of coalesced droplets were determined from optical microscopy. Fully hydrated silica nanoparticles adsorb with low affinity, reaching a maximum surface coverage that corresponds to a close packed monolayer, based on the effective particle radius and controlled by the salt concentration. Adsorbed layers of hydrophilic nanoparticles introduce a barrier to coalescence of approximately 1 kT, only slightly reduce the coalescence kinetics, and form kinetically unstable networks at high salt concentrations. Chemically hydrophobized silica nanoparticles, over a wide range of contact angles (25 to >90 degrees ), adsorb at the droplet interface with high affinity and to coverages equivalent to close-packed multilayers. Adsorption isotherms are independent of the contact angle, suggesting that hydrophobic attraction overcomes electrostatic repulsion in all cases. The highly structured and rigid adsorbed layers significantly reduce coalescence kinetics: at or above monolayer surface coverage, stable flocculated networks of droplets form and, regardless of their wettability, particles are not detached from the interface during coalescence. At sub-monolayer nanoparticle coverages, limited coalescence is observed and interfacial saturation restricts the droplet size increase. When the nanoparticle interfacial coverage is >0.7 and <1.0, mesophase-like microstructures have been noted, the physical form and stability of which depends on the contact angle. Adsorbed nanoparticle layers at monolayer coverage and composed of a mixture of nanoparticles with different hydrophobisation levels form stable networks of droplets, whereas mixtures of hydrophobized and hydrophilic nanoparticles do not effectively stabilize emulsion droplets.     

A microfluidic method to study demulsification kinetics

We present the results of experiments studying droplet coalescence in a dense layer of emulsion droplets using microfluidic circuits. The microfluidic structure allows direct observation of collisions and coalescence events between oil droplets dispersed in water. The coalescence rate of a flowing hexadecane-in-water emulsion was measured as a function of the droplet velocity and droplet concentration from image sequences measured with a high-speed camera. A trajectory analysis of colliding droplet pairs allows evaluation of the film drainage profile and coalescence time t(c.) The coalescence times obtained for thousands of droplet pairs enable us to calculate coalescence time distributions for each set of experimental parameters, which are the mean droplet approach velocity (v(0)), the mean dispersed phase fraction (φ) and the mean hydraulic diameter of a droplet pair (d(p)). The expected value E(t(c)) of the coalescence time distributions scales as E(t(c)) is proportional to (v(0))(-0.105±0.043)(d(p))(0.562±0.287), but is independent of φ. We discuss the potential of the procedure for the prediction of emulsion stability in industrial applications.     

Formation and Release of Cobalt(II) Sorption and Precipitation Products in Aging Kaolinite-Water Slurries

A comprehensive simulation of the coarsening mechanism coalescence-induced coalescence (CIC) is developed to predictthe growth rate of inviscid droplets in a viscous matrix fluid. In CIC, the shape relaxations of coalescing droplets establish flow fields that drive other droplets into contact, thus creating a cascade of coalescence events. It is believed that CIC is responsible for droplet growth in some demixed polymer solutions, such as isotactic polypropylene (iPP) and diphenyl ether (DPE). A cascade of coalescence events is simulated using a three-dimensional molecular dynamics-like simulation of a dispersed two-phase isopycnic fluid system. The coalescence-induced flow is driven mostly by the strong gradients in curvature at the neck of a coalescing pair of droplets, and the flow is modeled analytically by approximating it as due to a ring of point forces. The resultant velocity of each droplet in the suspension is calculated by superimposing all of the coalescence-induced flow fields and applying Faxen's Law. The mean droplet size grows like t(xi), where t is the coarsening time and xi a growth exponent that increases with increasing minority phase volume fraction varphi. Good agreement with experimental values of xi (0.22/=0.23. It is also shown that the droplet size distribution broadens for semidilute suspensions (varphi/=0.54). A phenomenological kinetic theory of coalescence is proposed. It is believed that in nondilute emulsions, CIC can account for coarsening that has been attributed previously to more traditional coalescence mechanisms. Copyright 2000 Academic Press.     

Properties of water-in-oil (W/O) nano-emulsions prepared by a low-energy emulsification method

Properties of water-in-oil (W/O) nano-emulsion formed by a low-energy emulsification method are described in this work. Nano-emulsions have been formed in water/mixed non-ionic surfactant/decane. Several mixtures of Span 20, Span 80, Tween 20 and Tween 80 were studied. Phase behavior studies and stability studies allowed to determine zones where nano-emulsions can be formed. Bluish and transparent W/O nano-emulsion with droplet sizes as low as 30 nm was formed. Nano-emulsion droplet size was measured by Dynamic Light Scattering. Nano-emulsions stability was studied by multiple light scattering and by dynamic light scattering. The results showed the evolution with time of the average radius droplet. The nano-emulsions prepared showed high kinetic stability for weeks, without phase separation, sedimentation or creaming. Nevertheless, their droplet size increased slightly over time. Stability studies show that nano-emulsion breakdown could be attributed to Ostwald ripening and coalescence mechanism, depending on the water concentration.     

Sol–gel matrices for controlled release: from macro to nano using emulsion polymerisation

By combining sol–gel technology with emulsion chemistry, it is possible to produce spherical particles with a designed microstructure based on a judicious choice of solvent/surfactant and sol–gel reaction parameters. When an active molecule is located in the aqueous droplet of a water-in-oil (W/O) emulsion, encapsulation occurs as the silicon precursors polymerise to build an oxide cage around the active species. By changing the solvent–surfactant combination, the particle size can be varied from 10 nm to 100 μm. The size of the particles is controlled by the size of the emulsion droplet, which acts as a nano-reactor for the sol–gel reaction. The release profiles can be tailored, independently of the particle size, by controlling the internal structure of the particles: pore volume, pore size, tortuosity, and surface chemistry (e.g. by introduction of trialkoxysilane). This can be easily achieved by controlling sol–gel processing parameters such as the water-to-alkoxide ratio, pH, alkoxide concentration, ageing, drying time and temperature. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.