A low‐energy emulsification batch mixer for concentrated oil‐in‐water emulsions

This work shows the formation of a high internal phase ratio oil‐in‐water (O/W) emulsion using a new type of a two‐rod batch mixer. The mixture components have sharply different viscosities [1/3400 for water‐in‐oil (W/O)], similar densities (1/0.974 for W/O), and an O/W ratio of 91% (wt/wt). The simple design of this mixer leads to a low‐energy process (10⁶ < energy density [J m^?3] < 10⁷), characterized by low rotational speed and laminar flow. The droplet size distribution during the emulsification was investigated according to different physical and formulation parameters such as stirring time (few minutes < t < 1 h), rotational speed (60 < Ω < 120 rpm), surfactant type (Triton X‐405 and X‐100), concentration (from 1 to 15.9 wt % in water), and salt addition (30 g/L). We show that all studied parameters allow a precise control of the droplet size distribution and the rheology. The resulting emulsions are unimodal and the mean droplet diameter is between 30 μm and 8 μm. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Effect of emulsifiers on the preparation of food‐grade oil‐in‐water emulsions using a straight‐through extrusion filter

This paper describes the preparation characteristics of food‐grade soybean oil‐in‐water (O/W) emulsions using a novel straight‐through extrusion filter, named a silicon straight‐through microchannel (MC). Polyglycerol fatty acid ester (PGFE), polyoxyethelene sorbitan monolaurate (Tween 20), and sucrose fatty acid ester were tested as emulsifiers. Optical observations of the emulsification process exhibited that monodisperse oil droplets were stably formed from an oblong straight‐through MC for PGFE and Tween 20. The effect of the emulsifier on the straight‐through MC emulsification behavior is discussed. The selected PGFE‐ and Tween 20‐containing systems enabled us to prepare monodisperse O/W emulsions with droplet diameters of 38—39 μm and coefficients of variation below 3% using an oblong straight‐through MC with a 16 μm‐equivalent channel diameter.     

In situ encapsulation of tetradecane droplets in oil‐in‐water emulsions using amino resins

Microcapsules of tetradecane enclosed by a polymeric wall of amino resin were synthesized by the in situ polymerization using melamine‐formaldehyde precondensates. It was found that resin concentrations of 60–240 g L^‐1 for a phase volume fraction of 0.14 and 0.29 and concentrations of 50–240 g L^‐1 for a phase volume fraction of 0.43 lead to stable microcapsules. Furthermore, the dependence of the shell thickness from the resin concentration for a phase volume fraction of 0.29 was investigated whereas the shell thickness was calculated from the density and the mean diameter of the capsules. It was found that below a concentration of 100 g L^?1 the density and thus the shell thickness increases linear with the resin concentration whereas at higher concentrations it almost remains constant and only the amount of the resin precipitated in solution increases. Additionally, it was shown that the mean droplet size (which is almost equal to the capsule size) in dependence of the stirring speed can be derived from the theory of droplet disruption. Thereby the coherence beginning with the stirring speed and the mean diameter to the total surface and the shell thickness is described. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of highly stable monodisperse argan oil‐in‐water emulsions using microchannel emulsification

Argan oil is well known for its nutraceutical properties. Its specific fatty acid composition and antioxidant content contribute to the stability of the oil and to its dietetic and culinary values. There is an increasing interest to use argan oil in cosmetics, pharmaceutics, and food products. However, the formulation of highly stable emulsions with prolonged shelf life is needed. In this study, argan oil‐in‐water (O/W) emulsions were prepared using microchannel (MC) emulsification process, stabilized by different non‐ionic emulsifiers. The effects of processing temperature on droplet size and size distribution were studied. Physical stability of argan O/W emulsions was also investigated by accelerated stability testing and during storage at room temperature (25 ± 2°C). Highly monodisperse argan O/W emulsions were produced at temperatures up to 70°C. The obtained emulsions were physically stable for several months at room temperature. Furthermore, emulsifier type, concentration, and temperature were the major determinants influencing the droplet size and size distribution. The results indicated that a suitable emulsifier should be selected by experimentation, since the interfacial tension and hydrophilic–lipophilic balance values were not suitable to predict the emulsifying efficiency. Practical applications: MC emulsification produces efficiently monodisperse droplets at wide range of temperatures. The findings of this work may be of great interest for both scientific and industrial purposes since highly stable and monodisperse argan oil‐in‐water emulsions were produced which can be incorporated into food, cosmetic, or pharmaceutical formulations.     

New insights in dispersion mechanisms of carbon black in a polymer matrix under shear by rheo‐optics

The dispersion behavior of different carbon black grades was investigated in a common elastomer matrix under shear using a transparent plate‐and‐plate counter‐rotating shear cell coupled with an optical microscope. The objective was to investigate the effect of carbon black intrinsic characteristics (specific area and structure) on dispersion mechanisms. Shear conditions were selected to study independently erosion and rupture mechanisms. The independent study of rupture and erosion mechanisms brings new findings on the respective effect of the filler intrinsic characteristics on each mechanism: (a) Rupture is a sudden mechanism occurring above a critical shear stress, which depends on the pellet size. The rupture criterion appears not to depend on the carbon black specific area or the structure. (b) Erosion proceeds via the detachment of a fixed eroded volume per strain unit and is driven by the applied shear stress and strain. Erosion is a local mechanism. The erosion rate depends on the carbon black characteristics. Faster erosion was measured for a carbon black with a higher structure at equivalent specific area or with a lower specific area at equivalent structure. This in situ characterization of dispersion mechanisms highlights that the effect of the carbon black characteristics on the two main dispersion mechanisms (rupture and erosion) is completely different. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of phospholipid oil‐in‐water microspheres by microchannel emulsification technique

A novel microchannel (MC) emulsification technique for producing super‐monodisperse microspheres (MS) was recently proposed. In this study, we investigated the formation of monodisperse oil‐in‐water (O/W)‐MS using lecithin and lysophosphatidylcholine (LPC) as surfactant by applying the MC emulsification technique. When we used lecithin to produce O/W‐MS, we observed coalescence of the formed MS and the continuous outflow of the oil phase through the MC. This was probably due to the insufficient interfacial activity of lecithin and the subsequent wetting of the MC surface by the oil phase during the emulsification process. The monodisperse O/W‐MS could not be produced when lecithin was used as the only surfactant. However, we successfully produced monodisperse O/W‐MS by using hydrophilic LPC dissolved in the water phase. Also, a more stable emulsification process producing monodisperse O/W‐MS was found using lecithin in the oil phase and LPC in the water phase. The monodisperse O/W‐MS production was improved by a special surface oxidation treatment of the MC plate.     

Aryl acrylate porous functional polymer supports from water‐in‐oil‐in‐water multiple emulsions

Porous functional polymer supports are a class of material of wide interest due to the possibility of immobilising reactive species. A simplified procedure was applied for the preparation of porous polymer supports using a water‐in‐oil‐in‐water multiple emulsion. The primary emulsion was a high internal phase emulsion, having a volume fraction of water phase up to 95%. Two reactive acrylates, namely 4‐nitrophenyl acrylate and 2,4,6‐trichlorophenyl acrylate, were (separately) incorporated in the oil phase in order to obtain porous reactive polymer supports. Both acrylates were crosslinked with either divinylbenzene or ethylene glycol dimethacrylate, and beads of size ca 60 µm were obtained after the polymerisation of droplets suspended into the secondary aqueous phase. In the case of 4‐nitrophenyl acrylate and divinylbenzene as a crosslinker, particles with a star shape, the core being ca 60 µm in diameter and the arms ca 180 µm in length, were obtained. The polymers were functionalised with morpholine, tris(2‐aminoethyl)amine, piperidine or piperazine yielding supports with loadings of reactive groups of between 2.6 and 6.6 mmol g^?1. The results show that multiple emulsions can be precursors for porous polymer preparation. Copyright © 2007 Society of Chemical Industry     

Antioxidant activity of phenolic compounds in sunflower oil‐in‐water emulsions containing sodium caseinate and lactose

The aim of this work was to study the evolution of oxidation and the efficiency of phenolic antioxidants in sunflower oil‐in‐water emulsions containing sodium caseinate and lactose (Cas‐Lac) or stabilized by Tween‐20 (T‐20). Two groups of phenolic antioxidants which are structurally similar were tested, i.e. (1) α‐tocopherol and its water‐soluble analogue, Trolox; and (2) gallic acid and its ester derivatives propyl gallate and dodecyl gallate. Emulsion samples were oxidized at 40 °C and the progress of oxidation was followed through quantitation of oxidized triacylglycerol monomers, dimers and oligomers. Results showed that Cas‐Lac emulsions were more stable to oxidation than T‐20 emulsions. In both types of emulsions, the most protective antioxidants were the compounds of lower polarity, namely, α‐tocopherol and dodecyl gallate. It was also found that substantial amounts of α‐tocopherol coexisted with significant polymerization, which was indicative of the heterogeneity of oxidation, i.e. differences of oxidation rate in oil droplets.     

Antioxidant activity of pine bark procyanidins in bulk corn oil and corn oil‐in‐water emulsions

In this work, the ability of pine bark procyanidins to hinder oxidation in bulk corn oil and corn oil‐in‐water‐emulsion has been investigated. A preliminary characterisation of the obtained aqueous (AF) and organic (OW) fractions and subfractions suggested a very polar character and showed that both fractions possess remarkable antioxidant activity when minimum concentrations of 2 mg/mL are used. OW fractions and subfractions derived from both pine varieties were able to inhibit oxidation in oils. More specifically, two organic subfractions were the most efficient for retarding the degradation process, with levels of 62% and 50% after 8 days of treatment, respectively. Organic subfractions obtained from both varieties of pine also rendered possible inhibition levels in oil‐in‐water‐emulsions up to 80% after 4 days of oxidation, more than 3 times higher than the levels provided by tocopherol, a well‐known model commercial antioxidant, which confirms the excellent antioxidant potential of procyanidins from pine bark. Practical application: Lipid deterioration leads to losses in quality and nutritional value and to the development of off‐flavours in many foodstuffs. One way to overcome this drawback is by using antioxidants of natural origin, which is a subject of a great scientific and industrial interest, reflected by the growing number of papers and patents published during the last years. Since aqueous and organic fractions obtained from Pinus pinaster and Pinus radiata bark turned out to be an adequate source of procyanidins in previous investigations of our group, their possible antioxidant role in model lipid systems was investigated. This approach entails also another benefit in terms of waste valorisation, since pine bark is a typical residue of agroforestal industries.     

Effect of different antioxidants on lycopene degradation in oil‐in‐water emulsions

There is interest in incorporating lycopene into foods because it is a natural pigment and can also play a role in preventing disease. Therefore, the effect of the addition of various antioxidants in lycopene containing oil‐in‐water emulsions stabilized with Tween 20 at acidic pH was studied in order to determine protection systems against lycopene oxidation. In this model, EDTA showed pro‐oxidant activity while other chelators like citric acid and tripolyphosphate showed no effect. The free radical scavengers, propyl gallate (PG), gallic acid (GA), and α‐tocopherol all had the ability to decrease lycopene oxidation with α‐tocopherol being the most effective. The combination of 1 µM α‐tocopherol and 10 µM GA was more effective than the individual antioxidants. Addition of ascorbic acid to the combination of α‐tocopherol and GA system accelerated lycopene loss. These results suggest that by the proper selection of free radical scavenging antioxidants, lycopene stability in oil‐in‐water emulsions could be significantly improved. Practical applications: Evidence that dietary lycopene decreases the risk for a number of health conditions has generated new opportunities for addition of lycopene to functional foods. A successful strategy to deliver lycopene into foods is by means of oil‐in‐water emulsions. However, lycopene may decompose thus causing nutritional loss and color fading. In order to prevent this, the effectiveness of various antioxidants and their combinations in Tween 20 stabilized oil‐in‐water emulsions was studied. Overall, lycopene oxidation in oil‐in‐water emulsions could be significantly reduced by the proper selection of free radical scavengers. This fact is of interest to food industry for increasing the shelf‐life of lycopene containing functional foods where the lycopene is dispersed in the food in the form of an oil‐in‐water emulsion.     

Polymerizable oil‐in‐oil emulsions: poly(vinyl pyrrolidone) dispersions in reactive PDMS medium

The system N‐vinyl‐2‐pyrrolidone (VP)/polydimethylsiloxane diglycidylether (PDMS‐DGE) is a typical example of an oil‐in‐oil emulsion formed by two non‐miscible liquids, where both phases are polymerizable in a ‘one‐pot’ procedure by two distinct reaction mechanisms. These oil‐in‐oil emulsions were characterized by their stability and by the particle size of the dispersed VP phase. Non‐aqueous dispersions (NADs) are obtained in a first step by free radical polymerization of the dispersed VP phase. The reaction kinetics, studied as a function of the initiator type and concentration, show that the polymerization rate is mainly influenced by the partition coefficient of the initiator between both phases. The NAD particle size could be tailored from a micrometer to a nanometer range by in situ formation of PVP‐PDMS graft copolymer. Hydrophilic–hydrophobic two‐phase materials can be obtained by polycondensation, in the presence of polyamines, of the epoxy‐functionalized PDMS continuous NAD phase. Copyright © 2007 Society of Chemical Industry     

Rheo‐Raman spectroscopic study of microscopic deformation behavior for ultra‐low‐density polyethylene

In situ Raman spectroscopy was applied to ultra‐low‐density polyethylene (ULDPE) to investigate the microscopic deformation behavior under uniaxial stretching. It was found that the crystalline chains of ULDPE show a bimodal molecular orientation parallel and perpendicular to the stretching direction beyond the elastic region. The peak shifts of C ? C stretching modes of the crystalline chains obviously depend on the polarization direction, suggesting that the microscopic load sharing is anisotropic. Whereas the stretching stress is applied on the crystalline chains oriented in the stretching direction, the compression stress is applied on those oriented perpendicular to the stretching direction. This anisotropic load sharing is caused by the Poisson shrinkage of the specimen owing to the rubber‐like properties of ULDPE. © 2018 Society of Chemical Industry     

Healthier lipid combination oil‐in‐water emulsions prepared with various protein systems: an approach for development of functional meat products

Five protein‐stabilized oil‐in‐water emulsions were prepared using sodium caseinate (O/SC), soy protein isolate (O/SPI), sodium caseinate and microbial transglutaminase (O/SC + MTG), sodium caseinate, microbial transglutaminase and meat slurry (O/SC + MTG + MS) and SPI, sodium caseinate and microbial transglutaminase (O/IPS + SC + MTG); their composition (proximate analysis and fatty acid profile) and physicochemical characteristics were examined. The lipid phase was a combination of healthy fatty acids from olive, linseed and fish oils, containing low proportions (15%) of saturated fatty acids (SFA) and high proportions of monounsaturated fatty acids (MUFA, 47%) and polyunsaturated fatty acids (PUFA, 36%), with a PUFA/SFA ratio >2, and a n‐6/n‐3 PUFA ratio of 0.4. All the oil‐in‐water emulsions showed high thermal and creamy stability. Results of penetration test and dynamic rheological properties showed la existencia de different types of oil‐in‐water emulsion structures according to stabilizing system of emulsion. Those structures ranged from concentrate solution‐like (stabilized only with SC) (gel strength 0.06 mJ) to gel‐like (samples containing MTG) behaviours (gel strength ranged between 3.4 and 6.2 mJ). Morphological differences in the organization of the network structure were observed (by scanning electron microscopy) as functions of the protein system used to stabilize the oil‐in‐water emulsions.     

Preparation of acrylic/acrylate copolymeric surfactants by emulsion polymerization used in pesticide oil‐in‐water emulsions

In this work, acrylic/acrylate copolymeric surfactants, which can be used in the preparation of pesticide oil‐in‐water emulsions (EW), were synthesized by emulsion polymerization, using potassium persulfate (K₂S₂O₈) as an initiator, dodecyl mercaptan (DDM) as a chain transfer agent at the temperature range of 82–85°C. When the weight ratio of monomers was m(butyl acrylate) : m(methyl methacrylate) : m(acrylic acid) = 4 : 4 : 1.6 and the dosage of DDM was 2% (percentage of monomer mass), the prepared acrylic/acrylate copolymeric surfactants had a number‐average molecular weight of 2.5 × 10⁴ and exhibited good stability for pesticide EW. The carboxylic group distribution studies show that only the surface carboxylic groups make dispersed pesticide oil droplets more stable. The acrylic/acrylate copolymeric surfactants prepared by shot‐monomer had the most surface carboxylic group distribution (46.6%). To obtain greater surface carboxylic group distribution, maleic anhydride (MA) was used to modify the polymer system. Adding 2% MA (percentage of monomer mass) to the polymerization system, the surface carboxylic groups were increased 12% over unmodified acrylic/acrylate copolymeric surfactants. Compared with traditional pesticide EW, the avermectin EW prepared with acrylic/acrylate polymeric surfactant had much better stability. Meanwhile, its pesticide effect was similar to that of a control (1.8% abamectin emulsifiable solution). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of oil phase concentration on droplet size distribution and stability of oil‐in‐water emulsions

The objective of this study was to investigate the effect of oil phase concentration, at different emulsification conditions concerning homogenization time and emulsifier content, on droplet size distribution and stability of corn oil‐in‐water emulsions. Emulsions were prepared with 3, 5, 10, and 20% w/w triethanolamine oleate (calculated on oil amount), 0.53% w/w carboxymethylcellulose (calculated on water amount), and 5, 10, 20, 30, or 40% w/w oil, and homogenized 5, 10, 20, and 60 min. It was found that increase in oil phase concentration led to decrease in specific surface area and increase in polydispersity of emulsion at lower emulsifier concentration and less intense homogenization. At emulsifier concentrations ≤10% and homogenization time ranges of 20–60 min the non‐monotonous variation in droplet size parameters with oil concentration was observed, as a result of the interaction between triethanolamine oleate and carboxymethylcellulose, which were confirmed by viscosity measurements. However, at emulsifier concentration of 20% an increase in specific surface area and decrease in polydispersity with the increase in oil concentration occurred due to an increase in equilibrium concentration of emulsifier in the continuous phase. Further, influence of oil concentration on emulsion creaming stability was found to be independent on emulsifier concentration and homogenization time. Therefore, a decrease in creaming with increase in oil concentration was observed in all the examined triethanolamine oleate (TEAO) concentration and homogenization time ranges. Practical applications: Emulsions are colloidal systems which can be encountered in different industrial sectors, such as food, pharmaceutical, cosmetics, oil industry, etc. Determination of the droplet size of emulsion is probably the most important way of their characterization, since it influences the properties of emulsion such as rheology, texture, shelf life stability, appearance, taste, etc. The size of the droplets depends on a wide range of parameters. One of them is certainly the concentration of the oil phase. However, since the impact of one parameter is often influenced with the intensity of the other variable involved in the emulsion generation, the aim of the present work was to examine the effect of corn oil concentration on droplet size parameters and stability of oil‐in‐water emulsions at different emulsification conditions. Therefore a step toward creation of emulsions with desired final properties was made.     

Effects of addition of diacylglycerols on fat crystallization in oil‐in‐water emulsion

The effects of addition of diacylglycerols (DAGs) on the crystallization behavior of n‐hexadecane dispersed in oil‐in‐water emulsion (oil 20% and water 80%, v/v) were studied by differential scanning calorimetry (DSC) and ultrasonic velocity measurement. In an attempt to modify the crystallization rate of n‐hexadecane, five DAGs having the fatty acid moieties of behenic (DAB), stearic (DAS), palmitic (DAP), lauric (DAL) and oleic acid (DAO) were added to n‐hexadecane, which was mixed with water and Tween 20 for emulsification. The DSC study showed that the addition of DAB, DAS or DAP (1.0 wt‐% with respect to n‐hexadecane) increased the crystallization temperature (Tc) of a n‐hexadecane/water emulsion from 3 °C (without DAG) to 8 °C, whereas the addition of DAL and DAO showed no effect. The ultrasonic velocity measurement also revealed that the addition of DAGs resulted in increasing the Tc of n‐hexadecane in O/W emulsion. These effects were discussed by taking into account the formation of molecular aggregates at the interface due to the addition of DAGs, which act as a template for crystallization of n‐hexadecane. The template‐assisted crystallization depends on the structure of the fatty acid chains present in the DAG: the longer the fatty acid moiety of DAG , the more is the crystallization of n‐hexadecane in O/W emulsion accelerated.