WO2010121490A1 - Procédé de préparation de mousses et mousses comprenant des particules d'éthylcellulose - Google Patents

Procédé de préparation de mousses et mousses comprenant des particules d'éthylcellulose Download PDF

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Publication number
WO2010121490A1
WO2010121490A1 PCT/CN2010/000550 CN2010000550W WO2010121490A1 WO 2010121490 A1 WO2010121490 A1 WO 2010121490A1 CN 2010000550 W CN2010000550 W CN 2010000550W WO 2010121490 A1 WO2010121490 A1 WO 2010121490A1
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WIPO (PCT)
Prior art keywords
ethylcellulose
water
particles
nanometer
foam
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PCT/CN2010/000550
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English (en)
Inventor
Theodorus Berend Jan Blijdenstein
Jian Cao
Petrus Wilhelmus Nicolaas De Groot
Weichang Liu
Simeon Dobrev Stoyanov
Weizheng Zhou
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Unilever N.V.
Unilever Plc
Hindustan Unilever Limited
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Application filed by Unilever N.V., Unilever Plc, Hindustan Unilever Limited filed Critical Unilever N.V.
Publication of WO2010121490A1 publication Critical patent/WO2010121490A1/fr

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/44—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor characterised by shape, structure or physical form
    • A23G9/46—Aerated, foamed, cellular or porous products
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L23/00—Soups; Sauces; Preparation or treatment thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P30/00—Shaping or working of foodstuffs characterised by the process or apparatus
    • A23P30/40—Foaming or whipping
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the present invention relates to a method for preparation of an aqueous foam, as well as to a method for preparation of an aerated food product. Moreover the present invention relates to foams comprising ethylcellulose particles, food products comprising such a foam, ethylcellulose particles, and use of ethylcellulose particles to stabilise foams and in aerated food products.
  • Aerated food products or foams are generally known, and such foods include frozen and chilled food products, such as ice cream, mousses, and whipped cream.
  • Gases commonly used for 'aeration' include air, nitrogen and carbon dioxide.
  • Known additives include proteins such as sodium caseinate and whey, which are highly foamable, and biopolymers, such as carrageenans, guar gum, locust bean gum, pectins, alginates, xanthan, gellan, gelatin and mixtures thereof, which are good stabilisers.
  • proteins such as sodium caseinate and whey, which are highly foamable
  • biopolymers such as carrageenans, guar gum, locust bean gum, pectins, alginates, xanthan, gellan, gelatin and mixtures thereof, which are good stabilisers.
  • WO 2008/019865 A1 discloses aqueous foams and food products containing these.
  • the gas bubbles in the foam are stabilised by interfacially-active particles (e.g. proteins), which are considered to be colloidal particles having a diameter between 0.5 nanometer up to several tens of a micrometer.
  • Aerated food products are produced by mixing a preformed aqueous foam into a food product.
  • WO 2007/060462 A1 discloses foams which are stabilised by polystyrene latex particles which may have an average particle size between 0.05 and 10 micrometer.
  • the latex particles are produced by a polymerisation reaction.
  • the latex particles may be stabilised by water-soluble/hydrophilic polymers forming a shell on the latex particles, like water-soluble poly(meth)acrylates, and various cellulosic derivatives (e.g. e.g. methylcellulose, ethylcellulose, hydroxypropylcellulose or carboxymethylcellulose).
  • Polymer latexes stabilized with a polyacid form stable foams below the pKa value, (e.g.
  • the polymer latex dispersion stabilized with poly(acrylic acid) may have a pH of less than 4, e.g. a pH ranging from 1 to 3.5.
  • Plasari et al. disclose a process to precipitate ethylcellulose nanoparticles from a solution of ethanol, using water as non- solvent, under various process conditions.
  • the average particle size of the nanoparticles was reported to be from about 35 to about 100 nanometer, which partly aggregated into agglomerates having a size between 300 and 600 nanometer.
  • the size of the nanoparticles was strongly dependent on the initial concentration of ethylcellulose in the solvent.
  • the zeta-potential of the ethylcellulose nanoparticles was not determined, and will be about -40 mV, as the dispersion containing the ethylcellulose nanoparticles is not acidified, nor contains salt ions.
  • EP 1 992 323 A1 discloses a foamed oil-in-water emulsion, wherein the emulsion is a Pickering-emulsion.
  • the emulsion may be stabilised by ethylcellulose particles.
  • WO 2008/046699 A1 discloses aerated food products in the form of a stable foam, comprising 5-80 vol% gas bubbles, 15-90 wt% water and 0.001 to 10 wt% fibres, and further containing surface-active particles at the air-water interface. These aerated food products are very stable due to attractive interaction between the surface-active particles and the fibres.
  • the fibers preferably have a length from 1 to 50 micrometer. These fibres may be made from materials like microcrystalline cellulose or citrus fibers, or waxy materials, like camauba wax, shellac wax, or bees wax.
  • the surface-active particles are preferably made from modified celluloses, modified starches, and insoluble proteins.
  • They are preferably present in an amount between 0.001 and 10 wt%, and preferably have a volume weighted mean diameter between 0.01 and 10 micrometer, more preferably between 0.1 and 1 micrometer.
  • a combination of microcrystalline cellulose fibers and ethylcellulose particles is disclosed.
  • WO 2009/033592 A1 discloses foams used for foods, wherein the foam may comprise ethylcellulose and a hydrocolloid.
  • WO 2006/067064 A1 discloses a shelf stable mousse, containing a hydrocolloid as foam stabiliser.
  • the hydrocolloids are water-soluble and may be carboxymethyl cellulose or other cellulose derivatives like methyl cellulose, hydroxypropyl cellulose.
  • EP 1 668 992 A1 discloses foamable food compositions and food foams, in which the foam is stabilised by solid inert particles, preferably silicates.
  • US 4,346,120 discloses a frozen dessert product which is aerated. It comprises a water-soluble stabiliser and a so-called blocking agent which are for example microcrystalline cellulose and cellulose fibers.
  • WO 2007/038745 A1 discloses cream compositions containing hydroxypropyl methylcellulose (HPMC) 1 hydroxypropyl cellulose (HPC) 1 methyl hydroxyethyl cellulose (MHEC), methyl cellulose (MC) or ethyl cellulose (EC), at a concentration up to about 0.15%, and water-soluble or water-swellable hydrocolloids like microcrystalline cellulose, hydroxyethyl cellulose, pectin, gum arabic, and others at a concentration of preferably 0.02 and 0.05%. These compositions can be used in producing whipped food compositions.
  • HPMC hydroxypropyl methylcellulose
  • HPC hydroxypropyl cellulose
  • MHEC methyl hydroxyethyl cellulose
  • MC methyl cellulose
  • EC ethyl cellulose
  • Marsh et al. (Particuology, vol. 7, 2009, p. 121-128) measure the zeta-potential of microfibrous cellulose as function of pH.
  • the potential is about -10 mV at pH 4-12, and increases from about -10 mV to about 0 mV when the pH is decreased from 4 to 2.
  • WO 2008/046698 A1 discloses stable aerated food products containing between 0.5 and 20 wt% protein, as well as fibres and surface-active particles that assemble at the air-water interface. In the examples a combination of microcrystalline cellulose fibers and ethylcellulose particles is disclosed.
  • WO 2008/046742 A1 also discloses aerated food products containing at least 10 wt% of water and optionally fat, wherein the amount of fat and water taken together is at least 60 wt%, as well as surface active particles and surface active fibers. Moreover the volume weighted mean diameter of the particles is smaller than the length of the fibers. In the examples a combination of microcrystalline cellulose fibers and ethylcellulose particles is disclosed, as well as a combination of citrus fibers and ethylcellulose particles.
  • WO 2007/068344 A1 discloses surface-active fibres, wherein the fibres have an aspect ratio of more than 10 to 1 ,000, and a length of preferably 1 to 50 micrometer.
  • the fibers may be organic, like cellulose fibers such as citrus fibers, or inorganic, like calcium carbonate. These fibers may be used to stabilise foams. Also disclosed are aerated food products containing these fibers.
  • One of the examples discloses a mixture of the fibers and ethylcellulose particles for creating a foam.
  • WO 2008/006691 A1 discloses surface-active fibres that are made of a waxy material, such as camauba or shellac wax or bee wax. It may be used in aerated food products to stabilise foams.
  • WO 2008/046732 A1 discloses a frozen aerated food product (e.g. icecream) comprising 0.001 to 10 wt%, of surface-active fibres, which have an aspect ratio of 10 to 1 ,000.
  • the fibers Preferably have a length from 1 to 50 micrometer.
  • These fibres may be made from food-grade waxy materials, like carnauba wax, shellac wax, or bees wax, or from non-waxy materials like microcrystalline cellulose or calcium carbonate.
  • the food product may contain surface active particles that modify the surface active fibers, for example ethylcellulose or hydroxypropylcellulose.
  • a method for production of a frozen aerated product is disclosed wherein particles and fibers are mixed to form a self-assembled structure, followed by a freezing step.
  • WO 2008/046729 A1 discloses aerated liquid food products having an overrun of at least 100%, which are gastric stable and increase satiety. These products contain microcrystalline cellulose.
  • US 2007/0178209 A1 discloses aerated food products which are stabilised by hydrophobic denatured protein particles, preferably egg white and egg yolk proteins.
  • the diameter of the protein particles are that at least 50% of the particles has a diameter of more than 3 micrometer, and less than 35 micrometer.
  • the protein particles are prepared by acidifying an aqueous protein solution to a pH of preferably below 3.6, while being sheared, at a temperature below 70 0 C.
  • the aerated food products may comprise water-soluble stabilisers like gelatin, gum arabic, cellulose derivatives such as sodium carboxymethyl cellulose, microcrystalline cellulose, methyl and methylethyl celluloses, or hydroxylpropyl and hydroxypropylmethyl celluloses.
  • Dickinson E. Cold-stabilized emulsions into which air bubbles are introduced via simultaneous whipping and slow acidification. Aerated emulsion gels of good foam stability can be formulated.
  • Shrestha L.K. et al. disclose aqueous foams stabilized by dispersed surfactant solid particles and lamellar liquid crystalline phase. Stable foam in the C18G5/water system was mainly due to the finely dispersed small surfactant solid particles. The average particle diameter of ⁇ -solid phase and La dispersion, respectively, was found to be less than 1 ⁇ m, to be around 0.15 ⁇ m. Shreshta et al. indicate that with decreasing particle size, improved stability of foam can be obtained.
  • foams may be stabilised by nanoparticles.
  • particles having a primary particle size of 20 nm are mentioned, but these may also be aggregated into larger particles.
  • EP 1 048 690 A1 discloses a cellulose-containing composite that comprises a fine cellulose and a low-viscosity water-soluble dietary fiber, which may act as a foam stabilizer, and wherein the average particle size of the fine cellulose is 30 micrometer or less when the composite is dispersed in water.
  • US 6,372,280 discloses acidic (pH less than 4) whipped topping, which are stable foams in an acidic environment.
  • the foam may contain a non-ionic stabilizer, which could be water-soluble stabiliser like guar gum or locust bean gum. Also non water- soluble compounds have been disclosed, like unmodified cellulose and ethylcellulose.
  • US 2005/0163904 A1 discloses the preparation of a cappuccino having a frothy surface.
  • the foam should remain stable for at least 3 minutes, more preferably 5 minutes.
  • the composition for making the foam may comprise a biopolymer, which may be water- soluble or not water-soluble, for example xanthan gum, gum Arabic, ethyl cellulose, starches.
  • the stabiliser preferably is a cheap and commonly available raw material.
  • the foams have high overruns and relatively small, uniformly sized gas bubbles.
  • the use of only a low concentration of stabiliser in the food product would be advantageous.
  • the stabilising system does not require a multitude of stabilising compounds without nutritional value.
  • Such foams can be used in food products to create a favourable mouthfeel, like a creamy mouthfeel, without having high caloric value of food products which normally have a smooth and creamy mouthfeel.
  • stable foams can be produced containing ethylcellulose particles as a stabiliser, by a method comprising a step wherein acid or salt or a combination of these is added to suspended ethylcellulose particles, prior to creating a foam.
  • highly stable foams can be made having high overrun.
  • fibres are substantially absent from the foams produced by the method according to the invention.
  • the present invention provides a method for preparation of an aqueous foam, comprising the steps: a) dissolving ethylcellulose in an organic solvent which is miscible in water; b) addition of water to the mixture of step a), wherein the amount of water is at a weight ratio between 10:1 and 1:2 based on the organic solvent; c) evaporating organic solvent and water to a concentration of ethylcellulose of at least 1% by weight; d) addition of an acid to a pH of 4 or lower, or addition of a water-soluble salt to an ionic strength of at least 20 millimolar; or addition of a combination of acid and water-soluble salt; e) introduction of gas bubbles to the composition of step d) to create a foam.
  • the present invention provides a method for preparation of an aerated food product, comprising the steps: a) dissolving ethylcellulose in an organic solvent which is miscible in water; b) addition of water to the mixture of step a), wherein the amount of water is at a weight ratio between 10:1 and 1 :2 based on the organic solvent; c) evaporating organic solvent and water to a concentration of ethylcellulose of at least 1 % by weight; d) addition of an acid to a pH of 4 or lower, or addition of a water-soluble salt to an ionic strength of at least 20 millimolar; or addition of an acid and a water-soluble salt; e) introduction of gas bubbles to the composition of step d) to create a foam; f) mixing the foam from step e) with one or more food ingredients; g) optionally mixing the composition from step f) with one or more other food ingredients.
  • the present invention provides an aqueous foam composition comprising aqueous foam composition
  • the present invention provides a food composition comprising an aqueous foam according to the third aspect of the invention, wherein the food composition has an overrun of at least 1%.
  • the present invention provides the use of ethylcellulose in the form of particles having a volume weighted mean diameter between 30 and 500 nanometer to stabilise foams.
  • the present invention provides the use of ethylcellulose in the form of particles having a volume weighted mean diameter between 30 and 500 nanometer in aerated food products.
  • the average particle diameter is expressed as the d 4>3 value, which is the volume weighted mean diameter, unless stated otherwise.
  • the volume based particle size equals the diameter of a sphere that has the same volume as a given particle.
  • the term 'aerated' means that gas has been intentionally incorporated into a composition, for example by mechanical means.
  • the gas can be any gas, but is preferably, in the context of food products, a food-grade gas such as air, nitrogen, nitrous oxide, or carbon dioxide.
  • a food-grade gas such as air, nitrogen, nitrous oxide, or carbon dioxide.
  • the extent of aeration is measured in terms of 'overrun', which is defined as:
  • weights refer to a fixed volume of aerated product and unaerated mix (from which the product is made). Overrun is measured at atmospheric pressure.
  • a stable foam or aerated food product in the context of the present invention is defined as being stable for at least 30 minutes, more preferred at least an hour, more preferred at least a day, even more preferred at least a week, and most preferred at least a month.
  • a stable foam can be defined to be stable with regard to total foam volume, and/or gas bubble size, and looses maximally 20% of its volume during 1 month storage, more preferably maximally 10% of its volume during 1 month storage.
  • systems may exist which loose more than 20% of its volume during 1 month storage, which nevertheless are considered to have a good stability, as the stability of such foams is much better than comparative foams.
  • Stability can be described as that the foam and gas bubbles are stable against Ostwald ripening, which leads on the one hand to relatively small bubbles decreasing in size and relatively large bubbles increasing in size. This is caused by diffusion of gas from small to large bubbles, due to a higher effective Laplace pressure in the small bubbles as compared to the larger bubbles.
  • Ostwald ripening can be considered to be most important mechanism responsible for instability of the gas bubbles.
  • An alternative mechanism for instability is coalescence, wherein two or more gas bubbles merge due to the breakage of the liquid interface between the bubbles and form one larger bubble with a larger volume.
  • Ethylcellulose In the present invention ethylcellulose is used as stabiliser for foams.
  • the general structural formula of ethylcellulose is:
  • the degree of substitution of the ethylcellulose used in the present invention is preferably between 2 and 3, more preferably about 2.5.
  • the average number of hydroxyl groups substituted per anhydroglucose unit (the 'monomer') is known as the 'degree of substitution' (DS). If all three hydroxyls are replaced, the maximum theoretical DS of 3 results.
  • Suitable ethylcellulose preferably has a viscosity between 5 and 300 cP at a concentration of 5 % in toluene/ethanol 80:20, more preferably between 100 and 300 cP at these conditions.
  • the present invention provides a method for preparation of an aqueous foam, comprising the steps: a) dissolving ethylcellulose in an organic solvent which is miscible in water; b) addition of water to the mixture of step a), wherein the amount of water is at a weight ratio between 10:1 and 1 :2 based on the organic solvent; c) evaporating organic solvent and water to a concentration of ethylcellulose of at least 1 % by weight; d) addition of an acid to a pH of 4 or lower, or addition of a water-soluble salt to an ionic strength of at least 20 millimolar; or addition of a combination of acid and water-soluble salt; e) introduction of gas bubbles to the composition of step d) to create a foam.
  • the concentration of ethylcellulose in the solvent is preferably between 0.1 and 6% by weight, more preferably between 0.1 and 4% by weight, more preferably between 0.1 and 3% by weight, even more preferably between 0.1 and 2% by weight, and most preferably between 0.5 and 1 % by weight.
  • concentration of ethylcellulose in step a) is that a lower ethylcellulose concentration in solvent yields a smaller volume weighted average particle diameter. A smaller average particle size suitably leads to increased stability of the foams that can be created.
  • the solvent in step a) can be any polar solvent suitable for ethylcellulose.
  • the organic solvent comprises acetone or ethanol or a combination of these solvents, preferably at a purity of at least 98%.
  • the ratio of water to organic solvent in step b) of the method according to the first aspect of the invention, is based on the purity of the organic solvent.
  • the temperature in step a) is preferably between 10 and 60 0 C, more preferably between 25 and 40 0 C. The temperature that will be applied is preferably dependent on the solvent that is used. If the solvent evaporates at a relatively low temperature, then the temperature in step a) will be lower than when a solvent is used with a higher boiling point.
  • step b) water is added to the solution of ethylcellulose, which leads to a partial precipitation of ethylcellulose into particles.
  • the water is preferably distilled or de- ionised water, more preferably it is double distilled water.
  • these ethylcellulose particles that precipitate have a volume weighted mean diameter between 30 and 500 nanometer. More preferred the ethylcellulose particles have a volume weighted mean diameter between 30 and 300 nanometer, even more preferred between 50 and 300 nanometer, most preferred between 60 and 300 nanometer, and even more preferred between 70 and 300 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 30 and 100 nanometer, preferably between 30 and less than 100 nanometer, preferably between 30 and 95 nanometer, preferably between 30 and 90 nanometer, preferably between 30 and 80 nanometer, preferably between 30 and 70 nanometer, preferably between 30 and 60 nanometer, preferably between 30 and 50 nanometer, or alternatively preferably between 50 and 70 nanometer, preferably between 50 and 60 nanometer or between 60 and 70 nanometer.
  • the volume weighted mean diameter of the precipitated ethylcellulose particles is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 150 and 500 nanometer, preferably between 150 and 400 nanometer, alternatively preferably between 150 and 300 nanometer, preferably between 150 and 200 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 200 and 500 nanometer, preferably between 200 and 400 nanometer, preferably between 200 and 300 nanometer or between 300 and 400 nanometer.
  • step b) preferably the weight ratio between the amount of water and the organic solvent is between 5:1 and 1 :2, more preferably between 2:1 and 1 :2. Most preferably the weight ratio between water and organic solvent in step b) is 1 :1 , or about 1 :1.
  • the water is added to the mixture while being stirred, preferably under high shear conditions.
  • the temperature in step b) is preferably between 10 and 60 0 C, more preferably between 25 and 40 0 C.
  • the evaporation step c) is performed in such a way that the concentration of ethylcellulose becomes at least 1 % by weight. More preferably the concentration of ethylcellulose after step c) is at least 2% by weight.
  • the acid preferably is chosen from hydrochloric acid, tartaric acid, acetic acid, and citric acid, or any combination of these acids, which are acids compatible for use in foods.
  • the salt preferably comprises NaCI, KCI, MgCI 2 or CaCI 2 , or any combination of these salts, which are salts compatible for use in foods.
  • step d) preferably the ionic strength that is obtained is maximally 200, more preferably maximally 150 millimolar.
  • the strength of the combination is similar to use of only an acid to a pH of 4 or lower, or to the use of only a water-soluble salt to an ionic strength of at least 20 millimolar.
  • the zeta-potential of the ethylcellulose particles is changed.
  • the zeta-potential is a measure for the surface charge of a colloidal particle, and determines whether particle attract or repulse each other.
  • the ethylcellulose particles are well dispersed, due to repulsion of the particles. This behaviour is observed at a zeta-potential of the particles having an absolute value above 25 millivolt.
  • the zeta-potential of the particles is decreased to an absolute value below 25 millivolt, the ethylcellulose particles aggregate, leading to the ethylcellulose particles being able to stabilise a foam.
  • step d) Upon addition of acid in step d) to reach a pH of 4 or lower, the surface charge of the ethylcellulose particles is modified, and the zeta-potential of the ethylcellulose particles is decreased to an absolute value below 25 millivolt. Similarly, upon addition of a water- soluble salt to reach an ionic strength of at least 20 millimolar, the zeta-potential of the ethylcellulose particles is decreased to an absolute value below 25 millivolt. Also a combination of an acid and a water-soluble salt may be added in step d), in order to reach a zeta-potential of the ethylcellulose particles lower than 25 millivolt. A lower zeta-potential means that the ethylcellulose particles become more hydrophobic.
  • step d) leads to an absolute zeta-potential of the ethylcellulose particles below 25 millivolt.
  • step e) gas bubbles are introduced to the composition of step d) to create a foam, that preferably has an overrun of at least 50%.
  • the overrun may vary from at least 50% to at least 100% or even to 400% or to 600% to about 700% or even more.
  • Gasses which may be introduced in step e) are preferably gases which are suitable for use in foods, such as air, nitrogen, nitrous oxide (laughing gas, N 2 O), and carbon dioxide.
  • step e) The temperature at which step e) is performed usually is between 0 and 100 0 C, more preferably between 15 and 80 0 C, most preferred from 20 to 40°C.
  • the aeration step can be performed by any suitable method which produces small enough gas bubbles. Methods of aeration include (but are not limited to):
  • a rotor-stator device such as an Oakes mixer (E. T. Oakes Corp), a Megatron mixer (Kinematica AG) or a Mondomix mixer (Haas-Mondomix BV);
  • ethylcellulose dispersions as prepared can be also be whipped vigorously by shaking the dispersion. When the mixing shear that is applied is high, then in general the bubbles in the foam are small, while at lower shear the bubbles are bigger.
  • the bubbles are also relatively small (average 10 to 50 micrometer), while at the higher overruns, the bubbles may reach an average diameter of 200 micrometer or even higher.
  • the bubbles may reach an average diameter of 200 micrometer or even higher.
  • more particles are required, as the total bubble surface area increases with smaller bubble diameter (at a given total fixed foam volume).
  • the ratio between ethylcellulose particle diameter and bubble diameter is preferably larger than 1 :5, more preferably larger than 1 :10, based on the volume weighted mean diameter of the particles as defined before.
  • the gas bubbles are sufficiently small that they are not visible to the naked eye. This has the advantage that a food product is not obviously aerated and has a similar appearance to unaerated food products, which may be preferred by consumers. The aerated products may nonetheless be somewhat lighter in colour or more opaque due to light scattering by the small bubbles.
  • an aerated food product has a significantly reduced calorie content per unit volume, whilst being similar in appearance to the unaerated food product, (determined from the normalised culmulative frequency as described in examples 1 and 2 below).
  • the average diameter of the air bubbles in the foams ranges from about 1 to about 500 micrometer.
  • at least 50% of the number of gas bubbles in the foam has a diameter smaller than 200 micrometer, more preferably at least 50% of the number of gas bubbles in the foam has a diameter smaller than 100 micrometer.
  • Even more preferred at least 75% of the number of gas bubbles has a diameter smaller than 75 micrometer, more preferred at least 50% of the number of gas bubbles in the foam has a diameter smaller than 50 micrometer, and most preferred at least 50% of the number of gas bubbles in the foam has a diameter smaller than 30 micrometer.
  • Gas bubble size can be measured using a spectrophotometer that can be loaded with a glass tube containing a foam sample. Light transmitted at the tube and reflected is measured and this is translated into an average bubble diameter. Alternatively a foam can be frozen to lock the structure and subsequently cut in thin slices. The average bubble diameter in these slices can be determined by microscopy. Another method is to determine the bubble size in a sample using confocal microscopy.
  • the foam generated in step e) of the method according to the first aspect of the invention suitably has a concentration of ethylcellulose of at least 0.01% by weight, and at most 30% by weight of the foam composition, more preferably between 0.1 and 20% by weight of the foam composition, most preferably between 0.1 and 10% by weight of the foam composition.
  • the water-level of the foam composition created in step e) is at least 10% by weight of the foam composition.
  • the composition further comprises particles of a wax, wherein the particles have a volume weighted mean diameter between 30 nanometer and 2 micrometer. More preferably the particles have a volume weighted mean diameter between 30 nanometer and 1 micrometer, even more preferred between 30 nanometer and 500 nanometer.
  • Preferred waxes according to the present invention are one or more waxes chosen from carnauba wax, shellac wax or beeswax.
  • the wax is a food-grade waxy material.
  • the particles may have any shape, like spherical or elongated or rod-like.
  • the concentration of the waxy material in step a), if present, preferably ranges from 0.01% to 10% by weight.
  • the weight ratio of EC to wax in the aqueous dispersion ranges from 1000:1 to 1 :1 , preferably from 100:1 to 10:1.
  • a wax is a non-glyceride lipid substance having the following characteristic properties: plastic (malleable) at normal ambient temperatures; a melting point above approximately 45°C (which differentiates waxes from fats and oils); a relatively low viscosity when melted (unlike many plastics); insoluble in water but soluble in some organic solvents; hydrophobic.
  • Preferred waxes are one or more waxes chosen from carnauba wax, shellac wax or beeswax.
  • the particles may have any shape, like spherical or elongated or rod-like or platelet-like.
  • Waxes may be natural or artificial, but natural waxes, are preferred. Beeswax, carnauba (a vegetable wax) and paraffin (a mineral wax) are commonly encountered waxes which occur naturally. Some artificial materials that exhibit similar properties are also described as wax or waxy. Chemically speaking, a wax may be an ester of ethylene glycol (ethane-1 ,2-diol) and two fatty acids, as opposed to fats which are esters of glycerine (propane-1 ,2,3-triol) and three fatty acids. It may also be a combination of fatty alcohols with fatty acids.
  • the foam is mixed with a water-soluble thickening agent or an aqueous solution or dispersion of a water-soluble thickening agent.
  • Preferred thickening agents are water-soluble polysaccharides such as xanthan gum, guar gum, agar, gellan gum, and gum arabic, or a combination of these.
  • Other suitable compounds are a protein such as gelatine, or other polymers such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyethyleneglycol (PEG) or a combination of these.
  • PVP polyvinylpyrrolidone
  • PVA polyvinylalcohol
  • PEG polyethyleneglycol
  • the concentration of the water-soluble thickening agent if present, ranges from 0.001 wt% to 5.0 wt%, preferably from 0.05 wt% to 1.0 wt%.
  • fibres are substantially absent from the aerated composition prepared by the method according to the first aspect of the invention. This means that if present, then preferably at a maximum concentration of 0.001 % by weight of the aerated composition.
  • 'fibre' is meant a compound having an insoluble, particulate structure, and wherein the ratio between the length and diameter ranges from 5 to infinite.
  • Such fibres are microcrystalline cellulose, citrus fibres, onion fibres, fibre particles made of wheat bran, of lignin, and stearic acid fibres.
  • the aqueous aerated composition prepared by the method according to the first aspect of the invention comprises maximally 0.001% by weight of microcrystalline cellulose, more preferably less than 0.001% by weight of microcrystalline cellulose.
  • the composition further comprises a water-insoluble thickening agent.
  • a water-insoluble thickening agent are chosen from microcrystalline cellulose, bacterial cellulose, silica, clay, etc., or a combination of these.
  • thickening agents are fibre-like materials. Very often such fibres are also food-grade.
  • Other preferred water-insoluble thickening agents are citrus fibres, onion fibres, tomato fibres, cotton fibres, silk, their derivatives and copolymers.
  • the fibres preferably used in the present invention have a length of preferably 0.1 to 100 micrometer, more preferably from 1 to 50 micrometer.
  • the diameter of the fibres is preferably in the range of 0.01 to 10 micrometer.
  • the aspect ratio (length / diameter) is preferably more than 10, more preferably more than 20 up to 1 ,000.
  • the fibres keep the bubbles separated by forming a kind of layer or barrier in between the interfaces of several bubbles, and increase the viscosity of the continuous phase. Therewith the bubbles become more stable.
  • the concentration of the water-insoluble thickening agent in step a), if present, preferably ranges from 0.01 to 10 % by weight, more preferably 0.05 to 1.0 % by weight.
  • the foam prepared using the method according to the first aspect of the invention can be used to create an aerated food product, by mixing the foam into a food product or into one or more food ingredients which subsequently can be mixed with one or more other food ingredients to provide an aerated food composition.
  • the invention provides a method for preparation of an aerated food product, comprising the steps: a) dissolving ethylcellulose in an organic solvent which is miscible in water; b) addition of water to the mixture of step a), wherein the amount of water is at a weight ratio between 10:1 and 1 :2 based on the organic solvent; c) evaporating organic solvent and water to a concentration of ethylcellulose of at least 1 % by weight; d) addition of an acid to a pH of 4 or lower, or addition of a water-soluble salt to an ionic strength of at least 20 millimolar; or addition of an acid and a water-soluble salt.
  • All preferred embodiments of the method according to the first aspect of the invention may also be preferred embodiments of the method according to the second aspect of the invention, as applicable mutatis mutandis.
  • the preferred embodiments of the first aspect of the invention can also be combined with each other to give preferred embodiments of the second aspect of the invention, as applicable mutatis mutandis.
  • the foam that is created in step e) has an overrun of at least 50%.
  • the overrun may vary from at least 50% to at least 100% or even to 400% or even to 600% to about 700% or even more.
  • the foam may be left to drain after step e), before being mixed with the food product or food ingredient.
  • the aerated composition obtained in step f) preferably has an overrun of at least 5%.
  • the one or more food ingredients disclosed in step f) can be in a Yaw' form, thus not yet formulated as a ready food product. They could also be in ready form, as a food product into which the foam from step e) is mixed.
  • the product from step f) could be a ready food product as such, or otherwise can be further processed to be mixed with one or more other food products.
  • step d) may be mixed with the composition from step d) prior to the foaming step e).
  • steps e) and f) could be performed simultaneously.
  • the aerated food product produced according to the second aspect of the invention suitably has a concentration of ethylcellulose of at least 0.01% by weight, and at most 20% by weight of the food composition, more preferred between 0.01 and 10% by weight of the aerated food composition.
  • the aerated food product produced according to the second aspect of the invention comprises maximally 0.001% by weight of microcrystalline cellulose, more preferably less than 0.001 % by weight of microcrystalline cellulose.
  • the invention provides an aqueous foam composition
  • aqueous foam composition comprising ethylcellulose particles having a volume weighted mean diameter between 30 and 500 nanometer, wherein the foam has an overrun of at least 50%.
  • the aqueous foam according to the third aspect of the invention suitably has a concentration of ethylcellulose of at least 0.01% by weight, and at most 30% by weight of the foam composition, more preferably between 0.1 and 20% by weight of the foam composition, and most preferred between 0.1 and 10% by weight of the foam composition.
  • the water-level of the foam composition created is at least 10% by weight of the foam composition.
  • the aqueous foam composition according to the third aspect of the invention comprises ethylcellulose particles having a volume weighted mean diameter between 30 and 300 nanometer, even more preferred between 50 and 300 nanometer, most preferred betweeen 60 and 300 nanometer, and even more preferred between 70 and 300 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 50 and 200 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 30 and 100 nanometer, preferably between 30 and less than 100 nanometer, preferably between 30 and 95 nanometer, preferably between 30 and 90 nanometer, preferably between 30 and 80 nanometer, preferably between 30 and 70 nanometer, preferably between 30 and 60 nanometer, preferably between 30 and 50 nanometer, or alternatively preferably between 50 and 70 nanometer, preferably between 50 and 60 nanometer or between 60 and 70 nanometer.
  • the volume weighted mean diameter of the precipitated ethylcellulose particles in the aqueous foam composition is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the volume weighted mean diameter of the ethylcellulose particles is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 150 and 500 nanometer, preferably between 150 and 400 nanometer, alternatively preferably between 150 and 300 nanometer, preferably between 150 and 200 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 200 and 500 nanometer, preferably between 200 and 400 nanometer, preferably between 200 and 300 nanometer or between 300 and 400 nanometer.
  • One of the advantages of an average ethylcellulose particle size at the lower end of the indicated preferred ranges is that the overrun reached can be higher than with particles at the higher end of the preferred ranges.
  • the zeta-potential of the ethylcellulose particles has an absolute value below 25 millivolt, leading to stable foams. Consequently the third aspect of the invention also provides an ethylcellulose particle, having a diameter between 30 and 500 nanometer, wherein the absolute value of the zeta-potential of the particle is below 25 millivolt.
  • such particle having an absolute value of the zeta-potential of the particle of below 25 millivolt has a diameter between 30 and 300 nanometer, even more preferred between 50 and 300 nanometer, most preferred betweeen 60 and 300 nanometer, and even more preferred between 70 and 300 nanometer.
  • such ethylcellulose particles have a volume weighted mean diameter between 50 and 200 nanometer.
  • such ethylcellulose particles have a volume weighted mean diameter between 30 and 100 nanometer, preferably between 30 and less than 100 nanometer, preferably between 30 and 95 nanometer, preferably between 30 and 90 nanometer, preferably between 30 and 80 nanometer, preferably between 30 and 70 nanometer, preferably between 30 and 60 nanometer, preferably between 30 and 50 nanometer, or alternatively preferably between 50 and 70 nanometer, preferably between 50 and 60 nanometer or between 60 and 70 nanometer.
  • the volume weighted mean diameter of the ethylcellulose particles in the aqueous foam composition is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the volume weighted mean diameter of the precipitated ethylcellulose particles is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 150 and 500 nanometer, preferably between 150 and 400 nanometer, alternatively preferably between 150 and 300 nanometer, preferably between 150 and 200 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 200 and 500 nanometer, preferably between 200 and 400 nanometer, preferably between 200 and 300 nanometer or between 300 and 400 nanometer.
  • the absolute value of the zeta-potential of the ethylcellulose particles is below 20 millivolt, more preferred below 15 millivolt.
  • the aqueous foam composition comprises gas bubbles, wherein at least 50% of the number of gas bubbles has a diameter smaller than 200 micrometer. More preferred, at least 50% of the number of gas bubbles has a diameter smaller than 100 micrometer. Even more preferred at least 75% of the number of gas bubbles has a diameter smaller than 75 micrometer, more preferred at least 50% of the number of gas bubbles in the foam has a diameter smaller than 50 micrometer, and most preferred at least 50% of the number of gas bubbles in the foam has a diameter smaller than 30 micrometer.
  • the aqueous foam composition according to the third aspect of the invention comprises maximally 0.001 % by weight of microcrystalline cellulose, more preferably less than 0.001% by weight of microcrystalline cellulose.
  • All preferred embodiments of the methods according to the first and second aspects of the invention may also be preferred embodiments of the composition of the third aspect of the invention, as applicable mutatis mutandis. These preferred embodiments may also be combined to give preferred embodiments of the third aspect of the invention, as applicable mutatis mutandis.
  • the aqueous foam according to the third aspect of the invention is used to make a food composition comprising such an aqueous foam, wherein the food composition has an overrun of at least 1%. More preferred, such food composition has an overrun of at least 5%, even more preferred at least 10%, most preferred at least 20%. Preferably the food product has an overrun of at most 150%, more preferably at most 120%, most preferably at most 100%.
  • the food product according to the fourth aspect of the invention contains an ethylcellulose particle according to the third aspect of the invention.
  • the food product according to the invention preferably comprises an ethylcellulose particle, having a diameter between 30 and 500 nanometer, wherein the absolute value of the zeta-potential of the particle is below 25 millivolt.
  • Preferred aspects of the ethylcellulose particles with regard to mean particle size and zeta-potential have been given in the context of the third aspect of the present invention. These preferred aspects are also applicable to the fourth aspect of the present invention, mutatis mutandis.
  • the food product comprises maximally 0.001% by weight of microcrystalline cellulose, more preferably less than 0.001 % by weight of microcrystalline cellulose.
  • the food products comprising the foams according to the invention remain stable for at least a month, preferably several months.
  • stable is meant that the foam is stable, which means that gas bubbles in the foam do not coalescence to become larger gas bubbles.
  • ethylcellulose particles prevent shrinking of small bubbles and consequently formation of larger bubbles, hence the particles lead to reduced Ostwald ripening.
  • Suitable aerated food products are for example dressings like mayonnaise.
  • Such dressings may have a total oil content ranging from 5% to 70% or 80% by weight. All such products are within the scope of the present invention.
  • the foams can also be used in food products to provide solid or semi-solid (e.g. spreadable) food products having a lower calorie content, while not being visible in the food product.
  • preferred food products are cereal bars, chocolate bars, cookies and biscuits, confectionery products, condiments, confectionary, beverages, desserts, snacks, spreads like margarine or low fat margarines or dairy spreads, ice cream, dressings, mayonnaise, sauces, bakery products like bread, shortenings, cheese (soft cheese, hard cheese), soups, dairy drinks, fruit drinks or juices, vegetable drinks or juices, combinations of dairy, and/or fruit, and/or vegetable drinks, cocoa drinks, and especially dairy mini-drinks.
  • frozen foods such as frozen confections like icecream, or other frozen desserts.
  • soups both in dry form (which have to be reconstituted with water), as well as liquid soups are within the scope of the present invention.
  • foam By incorporation of the foam into such food products, a creamy soup can be obtained, which does not have the calories associated normally with creamy soups (to which generally cream is added).
  • the food product is a beverage, more specifically a fruit drink, or combination of fruit and dairy drink, it preferably comprises at least 10% by weight of the composition of a fruit component, wherein the fruit component is selected from fruit juice, fruit concentrate, fruit juice concentrate, fruit puree, fruit pulp, comminuted fruit, fruit puree concentrate, and combinations thereof.
  • fruit components are orange juice, apple juice, grape juice, peach pulp, banana pulp, apricot pulp, concentrated orange juice, mango pulp, concentrated peach juice, raspberry puree, strawberry puree, apple pulp, raspberry pulp, concentrated grape juice, concentrated aronia juice, and concentrated elderberry juice.
  • a beverage comprises at least 30% by weight of the beverage of said fruit component, more preferred at least 40% by weight of the beverage of said fruit component.
  • any commonly available fruit component might be used in the beverages according to the invention, and may be selected from one or more of the following fruit sources: citrus fruit (e.g. orange, tangerine, lemon or grapefruit); tropical fruit (e.g. banana, peach, mango, apricot or passion fruit); red fruit (e.g. strawberry, cherry, raspberry or blackberry), or any combination thereof.
  • citrus fruit e.g. orange, tangerine, lemon or grapefruit
  • tropical fruit e.g. banana, peach, mango, apricot or passion fruit
  • red fruit e.g. strawberry, cherry, raspberry or blackberry
  • the food product is a spread such as water-in-oil emulsions, for example a margarine or low fat margarine type food product.
  • a spread may also be an oil-in-water emulsion, like dairy spreads or fresh soft cheeses.
  • the total triglyceride level of such a spread may range from about 1% by weight to 90% by weight of the composition, preferably from 10% by weight to 85% by weight of the composition, more preferred from 20% to 70% by weight, most preferred from 30% to 60% by weight of the composition.
  • dairy drinks which may for instance be used as a meal replacer.
  • the food product may be dried and contain less than 40% water by weight of the composition, preferably less than 25%, more preferably from 1 to 15%.
  • the food may be substantially aqueous and contain at least 40% water by weight of the composition, preferably at least 50%, more preferably from 65 to 99.9%.
  • the food preferably comprises nutrients including carbohydrate (including sugars and/or starches), protein, fat, vitamins, minerals, phytonutrients (including terpenes, phenolic compounds, organosulfides or a mixture thereof) or mixtures thereof.
  • the food may be low calorie (e.g. have an energy content of less than 100 kCal per 100 g of the composition) or may have a high calorie content (e.g. have an energy content of more than 100 kCal per 100 g of the composition, preferably between 150 and 1000 kCal).
  • the food may also contain salt, flavours, colours, preservatives, antioxidants, non- nutritive sweetener or a mixture thereof.
  • AII preferred embodiments of the methods according to the first and second aspects of the invention, and the composition of the third aspect of the invention may also be preferred embodiments of the composition of the fourth aspect of the invention, as applicable mutatis mutandis. These preferred embodiments may also be combined to give preferred embodiments of the fourth aspect of the invention, as applicable mutatis mutandis.
  • the present invention provides the use of ethylcellulose in the form of particles having a volume weighted mean diameter between 30 and 500 nanometer to stabilise foams.
  • the present invention provides the use of ethylcellulose in the form of particles having a volume weighted mean diameter between 30 and 500 nanometer in aerated food products.
  • the ethylcellulose particles have a volume weighted mean diameter between 30 and 300 nanometer, even more preferred between 50 and 300 nanometer, most preferred betweeen 60 and 300 nanometer, and even more preferred between 70 and 300 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 50 and 200 nanometer.
  • such ethylcellulose particles have a volume weighted mean diameter between 30 and 100 nanometer, preferably between 30 and less than 100 nanometer, preferably between 30 and 95 nanometer, preferably between 30 and 90 nanometer, preferably between 30 and 80 nanometer, preferably between 30 and 70 nanometer, preferably between 30 and 60 nanometer, preferably between 30 and 50 nanometer, or alternatively preferably between 50 and 70 nanometer, preferably between 50 and 60 nanometer or between 60 and 70 nanometer.
  • the volume weighted mean diameter of the ethylcellulose particles is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the volume weighted mean diameter of the precipitated ethylcellulose particles is between 100 and 200 nanometer, or even between 100 and 150 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 150 and 500 nanometer, preferably between 150 and 400 nanometer, alternatively preferably between 150 and 300 nanometer, preferably between 150 and 200 nanometer.
  • the ethylcellulose particles have a volume weighted mean diameter between 200 and 500 nanometer, preferably between 200 and 400 nanometer, preferably between 200 and 300 nanometer or between 300 and 400 nanometer.
  • the zeta-potential of the ethylcellulose particles in the fifth aspect and sixth aspect of the invention have an absolute value below 25 millivolt, preferably below 20 millivolt, more preferred below 15 millivolt, leading to stable foams and/or stable aerated food products.
  • the fifth aspect of the present invention provides a method for the use of ethylcellulose in the form of particles having a volume weighted mean diameter between 30 and 500 nanometer to stabilise foams, comprising adding the particles to a fluid, and injecting a gas into the fluid to aerate it.
  • the sixth aspect of the present invention provides a method for the use of ethylcellulose in the form of particles having a volume weighted mean diameter between 30 and 500 nanometer in aerated food products, comprising adding the particles to a fluid, injecting a gas into the fluid to aerate it, and adding the aerated fluid to a food ingredient or a food product.
  • Figure 1 Typical curve of zeta-potential of ethylcellulose particles as function of pH, showing increasing zeta-potential upon decreasing pH, from example 2.
  • Figure 2 Cryo-SEM-images of foams prepared from 2wt% ethylcellulose dispersions, from example 2:
  • Figure 3 Transport mean free path evolution ⁇ (t)/ ⁇ (0) of gas bubbles in mayonnaise aerated by whipping (open diamonds 0) and by aeration using ethylcellulose foam
  • A 1 wt% ethylcellulose; left fresh, right temperature abused;
  • Figure 5 SEM-image of a temperature abused frozen aerated composition, product B from example 7.
  • the arrows show a close up of small gas bubbles, covered by a corrugated layer of ethylcellulose particles.
  • Figure 6 SEM-images of frozen aerated composition product D from example 7; WPC 80; left fresh, right temperature abused
  • Figure 7 SEM-image of frozen aerated compositions containing 4wt% ethylcellulose, product E from example 8.
  • Aqualon ® Ethylcellulose (type N 100) was purchased from Hercules (Widnes, UK). Ethoxyl content was 48.0-49.5%, and degree of substitution was 2.46-2.57. Viscosity was 80-105 mPa.s (at 5% and 25 0 C in 80/20 toluene/ethanol).
  • Acetone analytical grade, was obtained from Sigma Chemicals (Schnelldorf, Germany) and used without further purification.
  • Zein from corn was obtained from Sigma-Aldrich.
  • Dynamic light scattering measurements were carried out using a Zetasizer Nano ZS instrument (Malvern Instruments, Malvern, UK) to determine the average particle diameter. Samples were measured without any dilution at 25°C. The viscosity of water was assumed in all cases and a refractive index of 1.59 was used in the analysis. The results from the measurements are the z-average particle size and the standard deviation of the z-average particle size (which relates to the peak width of a distribution curve of the particle size). For monodisperse systems with a narrow distribution, which is the case for ethylcellulose particles of the present invention, the difference between the z-average particle diameter and volume weighted mean diameter (d 4 , 3 ) is smaller than 10%. In the present case the z-average diameter is about 10% larger than d 4 3 -
  • the zeta-potential is determined by electrophoresis, also using the Metasizer Nano ZS instrument (Malvern Instruments, Malvern, UK). For this purpose, an electric field is applied to a dispersion containing colloidal particles. From the velocity of the particles in this electric field, i.e. their electrophoretic mobility, the zeta potential can be calculated by using the Henry equation with the Smoluchowski approach (P. C. Hiemenz, Principles of Colloid and Surface Chemistry, Second edition, Marcel Dekker Inc., New York, 1986, Chapter 13).
  • Bubble diameter The bubble diameter in the foams is estimated using a turbiscan turbidity measurement. In principle this is a spectrophotometer that can be loaded with a glass tube containing a foam sample. Light transmitted at the tube and reflected is measured. This is translated into average bubble diameter.
  • BS backscattering
  • the transport mean free path of light is related to the mean diameter (d) and the volume fraction ( ⁇ ) of the gas bubbles through:
  • g and Q are optical constants given by Mie theory (G. F. Bohren and D.R.Huffman, Absorption and Scattering of Light by Small Particles. Wiley, New York, 1983). For foam dispersed in a transparent liquid, this method provides an estimate of the number average bubble size.
  • Example 1 Food product stabilised by ethylcellulose particles
  • Foams stabilised by ethylcellulose particles were prepared, starting from several initial concentrations of ethylcellulose in organic solvent (see table 1), by the following method:
  • Ethylcellulose powder was dissolved in 100 ml acetone (purity >98%) at 35°C in a 500 mL beaker until completely dissolved; at the concentration of ethylcellulose in acetone as indicated in table 1. 2.
  • An equal volume of distilled water (at room temperature, about 22°C) was quickly added into the ethylcellulose solution under strong stirring to precipitate the ethylcellulose into particles.
  • the measured z-average diameter of the ethylcellulose was as indicated in table 1 ; the corresponding volume weighted mean diameter d 4 3 of the precipitated ethylcellulose particles was consequently between about 0.09 and about
  • the dispersion was whipped with air, using a Kenwood Chef mixer for 10 minutes) at maximum speed.
  • the stability of the foam was determined by measuring the average air bubble diameter as function of time, which is a measure for the stability of the foam. It was observed that all foams were stable, with best results for the smallest average particle diameter. With the smallest average ethylcellulose particle diameter, least bubble coalescence and coarsening occurred.
  • the foam according to sample 2 was manually mixed with a commercially available mayonnaise (Calve) having an oil content of 70%, to create an aerated mayonnaise. The concentration of ethylcellulose based on the total product was 0.35% by weight. The amount of air in the aerated mayonnaise was 10% by volume, which amounts to an overrun of about 11 %. The aerated mayonnaise was stable for 9 months, which was visually checked by observation of bubble diameter in the product. Coalescence of air bubbles was not observed during storage of the aerated mayonnaise.
  • Example 2 Foams stabilised by ethylcellulose particles, comparison between non-activated and activated ethylcellulose
  • Foams stabilised by ethylcellulose particles were prepared, starting from 1% weight per volume of ethylcellulose in acetone (see table 2), by the following method:
  • Ethylcellulose powder was dissolved in 100 ml acetone (purity >98%) at 35°C in a 500 ml_ beaker until completely dissolved.
  • the ethylcellulose disperson was divided in four parts, and four portions of 20 ml_ were added into four beakers of 60 ml_. Subsequently pH or salt concentration were changed by adding required amounts of tartaric acid, NaCI or MgCI 2 , all in solid powder form, as indicated in table 2.
  • the evolution of the zeta-potential of the ethylcellulose particles upon decrease of the pH is shown in Figure 1, for the particles which are acidified by adding tartaric acid. This shows that at a pH lower than 4, the absolute value of the ethylcellulose particles is lower than 25 mV. 5.
  • Figure 2 illustrates this difference further.
  • Picture A shows a part of a gas bubble 11 at the left, a part of a gas bubble 12 at the right, and the interface 13 between the bubbles 11 and 12.
  • the structures that can be seen in the volume of the interface 13 between the bubbles 11 and 12 are concentrations of ethylcellulose particles and these particles do not have a particular tendency to accumulate at the interfaces 14 and 15.
  • gas bubble 21 The structure that is shown in gas bubble 21 within the dashed triangle, is the internal surface of the gas bubble 21 , which (if it would be in 3D) bends out of the picture downward left. It is shown that this surface is more covered by ethylcellulose particles, than in sample 1.
  • Picture C shows a part of a gas bubble 31 at the left, a part of a gas bubble 32 at the right, and the interface 33 between the bubbles 31 and 32. It can be seen that the ethylcellulose particles have a strong tendency to accumulate at interfaces 24 and 25, which is different than in comparative sample 1 and similar to sample 2.
  • gas bubble 32 The structure that is shown in gas bubble 32 within the dashed triangle, is the internal surface of the gas bubble 32, which (if it would be in 3D) bends out of the picture downward right. It is shown that this surface is more covered by ethylcellulose particles, than in sample 1.
  • this difference between the comparative sample 1 and the samples according to the invention indicates that decreasing pH or having sufficient ionic strength allows ethylcellulose particles to accumulate at the air-water surface and be functional as foam stabiliser.
  • Example 3 Production of foams stabilised by ethylcellulose particles
  • Foams stabilised by ethylcellulose particles were prepared, starting from several initial concentrations of ethylcellulose in organic solvent (see table 3), by the following method:
  • Ethylcellulose powder was dissolved into acetone (purity >98%) at 35°C in a 500 mL beaker until completely dissolved; at various concentrations of ethylcellulose in acetone as indicated in table 3.
  • the measured z-average diameter of the ethylcellulose was as indicated in table 3; the corresponding volume weighted mean diameter d 4 ⁇ 3 of the precipitated ethylcellulose particles was consequently between about 45 nanometer and about 200 nanometer.
  • Tartaric acid was added to the dispersion of ethylcellulose particles, to reach a pH of 3.
  • Hollandaise sauce stabilised by ethylcellulose particles was prepared by the following method:
  • Ethylcellulose powder was dissolved into acetone (purity >98%) at 35 C C in a 500 ml. beaker until completely dissolved; at a concentration of 1% by weight of ethylcellulose in acetone
  • the concentration of ethylcellulose in water was set to 2% by weight.
  • the sauce with ethylcellulose particles was transferred into a standard stainless steel cream dispenser.
  • the dispenser was fitted with a N 2 O cream charger and the content was shaken for 10 seconds.
  • the sauce was then sprayed onto a metal dish.
  • Foamability was compared to a system where 18 gram water (pH 4) was added to the sauce Hollandaise, in order to create the same dilution of the sauce Hollandaise.
  • the overrun of the sauce Hollandaise with ethylcellulose particles was 233% compared to 144% for the sauce Hollandaise with added water.
  • Example 5 Aerated full fat mayonnaise comprising ethylcellulose foam
  • the bubble size evolution of a mayonnaise aerated with ethylcellulose foam will be compared to that of a mayonnaise which is aerated in the absence of ethylcellulose.
  • An approximation of the bubble size evolution is probed by turbidimetry, using the method as described herein before.
  • For an aerated mayonnaise the relative increase of the transport mean free path ⁇ (t) at time t is plotted, as compared to the initial transport mean free path ⁇ (0).
  • the ratio ⁇ (t)/ ⁇ (0) is used as an approximation of the bubble size evolution, since mayonnaise contains a high concentration of oil droplets in addition to the air bubbles. Since the emulsion droplet size is known to constant over time, the increase in mean free path ⁇ is considered to be caused by the bubble coarsening.
  • Figure 3 shows the relative increase in transport mean free path ⁇ (t)/ ⁇ (O) of the invention product and the reference, measured over 9 days. Taking into account that much of the bubble size evolution is masked by the concentrated emulsion in the mayonnaise, still a significant difference in evolution can be observed between the two samples.
  • the reference mayonnaise shows an increase in optical path length after about 0.1 day, whereas for the reference sample it takes at least 10 days to reach this bubble size increase.
  • the bubble diameter d is proportional to the transport mean free path ⁇ (t)
  • the scattering of the values of mayonaise aerated with ethylcellulose foam is caused by disturbance by the oil droplets, nevertheless the trend can be clearly observed.
  • Example 6 Food product stabilised by ethylcellulose particles Whipped cream with half of its volume replaced by ethylcellulose dispersion was prepared by the following method:
  • Ethylcellulose powder was dissolved into acetone (purity >98%) at 35°C in a 500 mL beaker until completely dissolved; at a concentration of ethylcellulose in acetone of 1% by weight.
  • An equal volume of distilled water (water at room temperature, about 22°C) was quickly added into the ethylcellulose solution under strong stirring to precipitate the ethylcellulose into particles, having a z-average particle size of about 130 nm.
  • the solution was left to stir for another 10 minutes after which the acetone and some of the water was evaporated under low pressure in a rotary evaporator. 4.
  • the concentration of ethylcellulose in water was set to 2%.
  • Overrun and stability were compared to systems consisting of 100 gram of whipped cream (same cream as in step 5) and of 50 gram liquid cream (same cream as in step 5) with 50 gram added water. Aeration conditions for these two systems were the same as in step 6. Results for overrun, yield stress and modulus of these systems are shown in table 4.
  • the yield stress of a material is defined as the stress at which a material begins to flow. Prior to the yield point the material will deform elastically and will return to its original shape when the applied stress is removed. Once the yield point is passed some fraction of the deformation will be permanent and non-reversible.
  • An elastic modulus (or storage modulus) is a measure of an object or substance's tendency to be deformed elastically when a force is applied to it.
  • oscillation measurements were performed on a rheometer (TA Instruments AR1000, New Castle, DE, USA) fitted with a cone and 60 mm parallel plate geometry with a gap of 1000 micrometer. Measurements were done at 20 0 C with a frequency of 1 Hz between 0.1 to 100% strain.
  • the foam containing ethylcellulose particles has improved yield stress and modulus as compared to the standard whipped cream: in spite of dilution of the cream by a factor 2, the yield stress is the same as for the undiluted whipped cream.
  • the modulus of the whipped cream with ethylcellulose is lower than the modulus of the standard whipped cream, nevertheless only about 38% lower, and not 50% as you would expect based on the two-fold dilution. Hence the conclusion can be made that the ethylcellulose particles lead to stabilisation of the foam.
  • Example 7 Frozen aerated products containing ethylcellulose particles at pH- neutral conditions
  • Three frozen aerated products (A, B, C) were produced where the surface active component principally used to stabilise the foam phase was ethylcellulose particles, produced in the same way as described in steps 1-3 of sample 2 in example 1 (1 wt% ethylcellulose in acetone).
  • Two stock dispersions of ethylcellulose were used, one which was concentrated by evaporation to 2 wt% ethylcellulose and one where the water was evaporated to make a dispersion of 6 wt% ethylcellulose.
  • the ethylcellulose was activated by adding MgCI 2 to a concentration of 50 mM in the premix.
  • the air phase stability of the products was compared to that of a reference product produced with whey protein concentrate WPC80 as stabiliser (Product D).
  • the formulations are given in table 5.
  • the general procedure for preparation of a frozen aerated product in a stirred pot apparatus is the following: a. add 80 mL premix, having a formulation as indicated in table 5; b. set the cooling bath to a temperature of -18 0 C; c. chill the stirred pot by circulating the cooling liquid for 10 seconds; d. stir 1 minute at 100 rpm; e. stir 1 minute at 1000 rpm; f. start cooling the vessel by circulating the cooling liquid; g. stir 3 minutes at 1000 rpm; h. stir at 300 rpm until the mix has obtained a temperature of -5°C; i. the aerated frozen product is then dosed into ca.
  • the stirred pot apparatus consisted of a cylindrical, vertically mounted, jacketed stainless steal vessel with internal proportions of height 105mm and diameter 72mm, which contained an agitator.
  • the agitator consisted of a rectangular impeller (72mm x 41.5mm) which scrapes the edge of the vessel as it rotates and two semi-circular blades (60mm diameter) positioned at a 45° angle to the impeller.
  • Fresh samples of the frozen aerated products were stored at -80 0 C, at which temperature the texture of the frozen aerated products is stable, air bubbles do not change their average diameter.
  • the bubble stability of the samples was determined by storing the frozen aerated products at -10 0 C for 1 week, which is a test of product stability at an elevated storage temperature. This is called 'temperature abuse'. Subsequently the frozen aerated products were brought to -80 0 C again, in order to capture the structure.
  • the average air bubble size can be determined by freeze fracturing samples of the frozen aerated products at -80 0 C, and observing the ice cream fractured surface by scanning electron microscopy, both before and after storage at -10 0 C for 1 week.
  • Product A, B and C ( Figure 4): Aerated frozen products A, B, and C were prepared as explained above and this resulted into overruns indicated in table 5.
  • the microstructure of products A, B, and C both fresh and after 1 week temperature abuse at -10°C are shown in Figure 4.
  • the stabiliser in these products is ethylcellulose.
  • the fresh sample (stored at -80 0 C) shows an homogeneous dispersion of air bubbles of approximately 50 to 100 micrometer diameter (black and grey structures).
  • Example 8 Frozen aerated products containing ethylcellulose particles at acidic condition
  • Product E This product was prepared as explained above and this resulted into an overrun stated in table 6.
  • the stabiliser in this product is ethylcellulose. At -8O 0 C (fresh),
  • Product F This product was prepared as explained above and this resulted into an overrun stated in table 6. This product serves as comparative example using a standard ingredient known in the art for stabilising air bubbles in aerated frozen products.
  • the microstructure of Product F both fresh and after 1 week temperature abuse at -10 0 C, was observed by electron microscopy. At -80 0 C (fresh), a homogeneous dispersion of air bubbles could be observed, having an average diameter of about 50 to 100 micrometer. After keeping at -1O 0 C during 1 week, the product showed strong coarsening of the microstructure. Air bubbles have grown much larger than 100 micrometer and the growth is accompanied by coalescence and channel formation. The larger bubbles appear bigger than those in Product B.
  • the experiment illustrates that ethylcellulose offers improved air-phase stability upon temperature abuse, compared to the reference system.
  • the small bubbles can survive a temperature abuse regime and show only limited Ostwald ripening, as being stabilised by ethylcellulose.
  • Comparative example 9 Food product stabilised by zein particles
  • Foams stabilised by zein particles were created:
  • Zein powder was dissolved in 100 ml ethanol (with a purity of >99%), at 35°C in a 500 ml_ beaker until completely dissolved; at a concentration of zein in ethanol of 1 wt%. 2. An equal volume of distilled water was quickly added into the zein solution under strong stirring to precipitate the zein into particles.
  • the z-average particle size of the zein particles was 426 nanometer.
  • the dispersion was diluted to a zein concentration of 1%.
  • the foam obtained using zein particles as stabiliser was not stable, as bubbles collapsed already during the draining step. This bubble collapse was observed by listening to the created foam: small ticks could be heard, caused by expanding and breaking air bubbles.
  • the foam was not stable enough to be mixed with a food product like mayonnaise.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • General Preparation And Processing Of Foods (AREA)

Abstract

L'invention concerne un procédé de préparation d'une mousse aqueuse, un procédé de préparation d'un produit alimentaire aéré, une mousse aqueuse comprenant des particules d'éthylcellulose, des produits alimentaires comprenant la mousse aqueuse, des particules d'éthylcellulose et l'utilisation de celles-ci. Le procédé de préparation d'une mousse aqueuse comprend les étapes consistant à: a) dissoudre l'éthylcellulose dans un solvant organique miscible dans l'eau; b) ajouter de l'eau au mélange obtenu à l'étape a), la quantité d'eau présentant un rapport en poids compris entre 10:1 et 1:2 sur la base du solvant organique; c) évaporer le solvant organique et l'eau afin d'obtenir une concentration d'éthylcellulose d'au moins 1% en poids; d) ajouter un acide présentant une valeur de pH égale ou inférieure à 4, ou ajouter un sel soluble dans l'eau présentant une force ionique d'au moins 20 millimolaires; ou ajouter une combinaison d'acide et de sel soluble dans l'eau; e) introduire des bulles de gaz sans la composition obtenue à l'étape d) pour produire une mousse.
PCT/CN2010/000550 2009-04-24 2010-04-22 Procédé de préparation de mousses et mousses comprenant des particules d'éthylcellulose WO2010121490A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2628395A1 (fr) 2012-02-14 2013-08-21 Unilever N.V. Composition aérée comprenant des particules d'éthylcellulose et polymère cationique
WO2014001033A1 (fr) 2012-06-27 2014-01-03 Unilever N.V. Matières particulaires de type feuilles comprenant un éther de cellulose alkylé et leur procédé de fabrication
EP2708134A1 (fr) 2012-09-17 2014-03-19 Unilever N.V. Compositions de pâte comprenant une phase de gras structuré
EP3473239A4 (fr) * 2016-06-16 2020-01-15 Nippon Paper Industries Co., Ltd. Composition d'aérosol moussable

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4770892A (en) * 1987-10-28 1988-09-13 General Foods Inc. Stable whippable emulsion and process for producing same
US6372280B1 (en) * 1999-11-02 2002-04-16 Kraft Foods, Inc. Stable foams in a high acid environment
WO2008046732A1 (fr) * 2006-10-17 2008-04-24 Unilever N.V. Produits alimentaires aérés congelés comprenant des fibres tensioactives
WO2008046742A1 (fr) * 2006-10-17 2008-04-24 Unilever N.V. Composition alimentaire comprenant des bulles de gaz et son procédé de préparation
WO2008046699A1 (fr) * 2006-10-17 2008-04-24 Unilever N.V. Produit alimentaire aéré et son procédé de préparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4770892A (en) * 1987-10-28 1988-09-13 General Foods Inc. Stable whippable emulsion and process for producing same
US6372280B1 (en) * 1999-11-02 2002-04-16 Kraft Foods, Inc. Stable foams in a high acid environment
WO2008046732A1 (fr) * 2006-10-17 2008-04-24 Unilever N.V. Produits alimentaires aérés congelés comprenant des fibres tensioactives
WO2008046742A1 (fr) * 2006-10-17 2008-04-24 Unilever N.V. Composition alimentaire comprenant des bulles de gaz et son procédé de préparation
WO2008046699A1 (fr) * 2006-10-17 2008-04-24 Unilever N.V. Produit alimentaire aéré et son procédé de préparation

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ANDREW L. CAMPBELL ET AL.: "Scalable fabrication of anisotropic micro-rods from food-grade materials using an in shear flow dispersion-solvent attrition technique", J. MATER. CHEM., vol. 18, 17 July 2008 (2008-07-17), pages 4074 - 4078 *
BERNARD P. BINKS ET AL.: "Effect of pH and Salt Concentration on the Phase Inversion of Particle-Stabilized Foams", LANGMUIR, vol. 23, 7 August 2007 (2007-08-07), pages 9143 - 9146 *
DAVID F. WILLIAMS ET AL.: "The Aggregation of Colloidal Particles at the Air-Water Interface", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 152, no. 1, August 1992 (1992-08-01) *
E. PLASARI ET AL.: "influence of process parameters on the precipitation of organic nanoparticles by drowning-out", TRANS ICHEME, vol. 75, no. PART A, February 1997 (1997-02-01) *
ERIC DICKINSON ET AL.: "Factors Controlling the Formation and Stability ofAir Bubbles Stabilized by Partially Hydrophobic Silica Nanoparticles", LANGMUIR, vol. 20, 25 August 2004 (2004-08-25), pages 8517 - 8525 *
HARTMUTA. WEGE ET AL.: "Long-Term Stabilization of Foams and Emulsions with In-Situ Formed Microparticles from Hydrophobic Cellulose", LANGMUIR, vol. 24, 23 July 2008 (2008-07-23), pages 9245 - 9253 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2628395A1 (fr) 2012-02-14 2013-08-21 Unilever N.V. Composition aérée comprenant des particules d'éthylcellulose et polymère cationique
WO2014001033A1 (fr) 2012-06-27 2014-01-03 Unilever N.V. Matières particulaires de type feuilles comprenant un éther de cellulose alkylé et leur procédé de fabrication
EP2708134A1 (fr) 2012-09-17 2014-03-19 Unilever N.V. Compositions de pâte comprenant une phase de gras structuré
EP3473239A4 (fr) * 2016-06-16 2020-01-15 Nippon Paper Industries Co., Ltd. Composition d'aérosol moussable
US11648189B2 (en) 2016-06-16 2023-05-16 Nippon Paper Industries Co., Ltd. Foamable aerosol composition

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