Classifications

• • 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
  • A23G1/00—Cocoa; Cocoa products, e.g. chocolate; Substitutes therefor
  • A23G1/30—Cocoa products, e.g. chocolate; Substitutes therefor
  • A23G1/50—Cocoa products, e.g. chocolate; Substitutes therefor characterised by shape, structure or physical form, e.g. products with an inedible support
  • A23G1/52—Aerated, foamed, cellular or porous products, e.g. gas expanded

Definitions

• the present invention relates to the field of chocolate confectionery compositions that comprise gas bubbles therein (commonly known as aerated chocolate).
• aerated chocolate commonly known as aerated chocolate
• One preferred embodiment of the invention relates to an optimum bubble properties for micro-aerated chocolate.
• Micro-aerated chocolate mass is very sensitive to any form of mechanical stress, which causes coalescence. A pressurized deposit, directly into the mould is therefore required to ensure optimal aeration quality. Until recently the focus has been to micro-aerate to low levels, primarily for cost reduction reasons.
• micro-aerated chocolate compositions exhibit unexpected properties which are advantageous to the end consumer and also during manufacture. These properties may make the product easier to manufacture and/or produce more desired and/or consistent organoleptic properties in the final confectionery product.
• the invention provides for methods to prepare such micro-aerated chocolate compositions and different uses of such chocolate compositions.
• micro-aerating chocolate to achieve high porosities would be difficult and expensive, with no added benefit leading to unstable and adversely tasting products. This is the reason that the few prior art micro-aerated products made in practise contain small amounts of gas micro-bubbles to achieve a porosity of at most 8%, often much lower.
• the applicant has surprisingly found a method for preparing a novel micro-aerated chocolate where the chocolate contains much higher proportion of gas than incorporated heretofor and the micro-bubbles are characterised by optimum parameters (as described herein).
• Such micro-aerated chocolate exhibits several beneficial properties which have never been appreciated before.
• EP2298080 (Kraft) (also referred to herein as Kraft080) discloses a method and apparatus for making aerated food product which details the use of a microporous gas diffuser for the aeration of food products in a low shear mixing method. These products include, allegedly, chocolate, though the single example provided is a chocolate flavoured wafer filling and is not chocolate
• microporous diffuser is typically in the range of from 1 to 200 Pa.s, and preferably within the range of 1 to 60 Pa.s. '
• Paragraph [0027] states: 'The gas volume fraction incorporated into the food product depends on the specific application and is typically in the range of 5 to 75% vol., preferably 5 to 40% vol., and most preferably 10 to 30% vol. '
• Microcellular generally implies gas cells of an average size of 100 [im or less.
• the average cell size is less than 50 [im and most preferably, the average cell size falls within the range of 5 to 30 [im. In the most preferred embodiments, 90% of the cells have a size between 10 and 50 [im. '
• the product of the process according to the present invention typically contains 30% or less by volume of gas.
• the gas volume fraction is less than 25% and most preferable it is in the range of 10 to 25%. The best results are obtained when the aforementioned preferred gas volumes and preferred cell sizes are realised in combination.
• Kraft080 discloses a very broad range of viscosities (from 1 to 200 Pa.s) for food media stated to be successfully aerated by this method. It is not credible that all food with such a broad range of viscosities can be aerated by the same method described in Kraft 080 and such statements must be considered highly speculative. For example chocolate masses used to prepare moulded chocolate products have typical plastic viscosities of from 1 to 20 Pa.s and high shear mixing would be required to provide homogenous aeration. The aeration method described in Kraft080 injects gas under low shear with a micro-diffuser. It is doubtful this method could aerate viscous chocolate masses, with viscosities in the high end of the claimed range.
• Kraft080 also describes products aerated with very wide gas volume ranges (from 5 to 70%). There is no appreciation of the unique properties of chocolate. The applicant has found aerating chocolate with micro-bubbles at gas volumes above 20% increases the chocolate viscosity leading to difficulty in removing such chocolate from moulds. Therefore the micro-aerated chocolate described in Kraft080, even if was ever made, is far from satisfactory.
• Haedelt2005 describes vacuum-induced bubble formation in liquid-tempered chocolate.
• Haedelt2005 acknowledges (page E159, col. 2, lines 7 to 1 1 ) that:
• the bubble sizes of the aerated chocolate prepared by Haedelt2005 are clearly macro- sized. This can be seen from Table 2 on page E161 which describes samples having a bubble size with mean diameter (mm) prepared at various gas pressures, namely 0.85 mm ⁇ 0.4 standard deviation (SD) (at 1000 Pa); 0.4 mm ⁇ 0.16 mm SD) (at 5000 Pa); and 0.37 mm ⁇ 0.19 mm SD (at 10,000 Pa).
• SD standard deviation
• Table 3 on page E161 describes samples having a bubble size with the following mean diameters (mm) prepared from chocolate with viscosity tempered at the given temperatures, namely: 0.4 mm ⁇ 0.19 mm SD (at 27°C); 0.41 mm ⁇ 0.16 mm SD) (at 30°C); and 0.49 mm ⁇ 0.19 mm SD ) (at 33°C).
• Haedelt2007 investigated the sensory properties produced by using different gases to micro-aerate chocolate, namely carbon dioxide, nitrogen, nitrous oxide, and argon. Haedelt2007, does not consider or disclose the effect of varying any other parameters on the sensory properties of aerated chocolate.
• WO2002-13618 (Danone) describes an apparatus for aerating a foodstuff including chocolate.
• EP2543260 (also referred to herein as Kraft060) discloses use of a frozen cone process for micro-aerating a chocolate shell. Such thin shells are very different from thicker moulded chocolate products such as tablets. The use of a cold stamping process avoids challenges associated with flow characteristics of micro-aerated chocolate.
• the aerated shell layer has a total gas content of at least 5%, the gas content being calculated using the following formula (1):
• M1 is the mass of the aerated shell layer having volume V1
• M2 is the mass of a non-aerated shell layer having volume V1 and being formed from the same edible liquid as the aerated shell layer and in the same manner as the aerated shell layer.
• the aerated edible liquid to be deposited into the mould cavity in step (ii) suitably has a total gas content of at least 5%, the gas content being calculated using the following formula (2):
• Gas content of aerated edible liquid (M2 - M1) /M1 wherein M3 is the mass of the aerated edible liquid having volume V2, and M4 is the mass of the same volume of the edible liquid without aeration. This means that the mass of the edible liquid per unit volume (V2) is reduced by at least 5% upon aerating the liquid.
• a gas content of at least 5% is advantageous in terms of providing a good texture and reducing the calorie content of the shell.
• the gas content of the aerated edible liquid can be at least 10%, at least 15%, at least 20%, at least 25%, at least 30% or at least 40%, and in some embodiments the gas content is within the range 5-40%, 5-25% or 10-20 mass% so that there is not an excessive loss of gas from the liquid during cold-stamping.
• a higher initial gas content leads to a greater degree of de-aeration relative to the initial gas content. This is because the gas bubbles have a greater chance of coalescing to form larger bubbles. Large bubbles quickly escape from the liquid due to the large difference between their densities and the density of the liquid.
• the liquid contains no more than 14 vol%, no more than 18 vol% or no more than 22 vol% of gas.
• a suitable minimum gas content is 10 vol%.
• a gas content of 10-22 vol% is advantageous in terms of taste and mouthfeel.
• the aerated liquid can have a density or no more than 1.10 g/cm 3 , no more than 1.05 g/cm 3 , no more than 1.00 g/cm3, or no more than 0.95 g/cm 3 .
• a density within the range of 0.98-1.10 g/cm 3 is optimal in terms of taste and mouthfeel.
• Kraft060 is more concerned in improving methods for making thin chocolate shells than aerating a large chocolate mass such as those used to produce chocolate tablets.
• the method described in Kraft060 uses cold stamping form a thin shell.
• Kraft060 does not suggest how to produce a controlled size distribution of small bubbles in a micro-aerated chocolate. This is due in part due to the rapid cooling associated with the cold stamping method, meaning less time for expansion and coalescence of the bubbles. Cooling times for a chocolate tablet are significantly longer due to the use of long cooling tunnels and a much larger mass of chocolate in the mould cavity.
• the stamping process leads to bubble destruction through the physical force of the stamp impacting the aerated chocolate.
• Kraft060 The problem of how to ensure uniform distribution of bubbles homogeneously within a solid chocolate product is not addressed by Kraft060 as for a thin shell this not an issue.
• the method of Kraft060 is not designed for and would be unsuitable to use to aerate thicker moulded product such as tablets.
• the process of Kraft060 is designed for the production of chocolate shells for the addition of a further component.
• US2006-0057265A1 discloses a method for producing confectionary products having an outer shell made of a substance that is placed inside a mould into which a temperature controlled male die is subsequently introduced. The substance is placed under pressure after the male die is introduced.
• EP201881 1 discloses an apparatus for moulding foodstuffs.
• EP0589820 (Aasted-Mikroverk) discloses a method of moulding chocolate articles.
• DE 102005018415 discloses a method for making candy products (and candy moulding station) that uses a cold stamp protected from an air by filling the chamber in which stamping occurs with a gas has such as helium that is less dense than air. A mixing zone is formed between the area with the protective gas and air.
• WO2009-040530 (Cadbury) discloses an aerated centre filled confectionery composition.
• EP0914774 (Aasted-Mikroverk) discloses a method, system and apparatus for producing shells of fat-containing chocolate like masses.
• CH68041 1 (Lindt) describes a method of forming a semi-solid , fatty, aerated masses, especially chocolate and / or chocolate like masses and a device for its implementation.
• US5238698 (Jacob Suchard) describes a product and process for producing a lower density milk chocolate composition, substantially free of sucrose and having the taste and mouthfeel of a traditional milk chocolate.
• the milk chocolate composition is aerated with an inert gas under a pressure of about 1.2 about 8 bar at temperature of 27° C. to about 45° C.
• EP0230763 (Morinaga) describes aerated chocolate composition with a gaseous continuous phase and the dispersed phase of fine grains of conglomerated solid chocolate.
• the aerated chocolate has an apparent density of 0.23 to 0.48 g / cm 3 .
• the composition is made by agitating a melted chocolate whilst cooling from 8 to 14 °C lower than the fat contained within the chocolate, to incorporate gas therein.
• the apparent density of the composition is allowed to reach from 0.7 to 1 .1 g / cm 3 and then the composition is exposed to a reduced pressure of 150 Torr or less to expand the composition and convert the gas and solid phases.
• EP1346641 (Aasted-Mikroverk) discloses a method of making chocolate shells.
• WO2001 -080660 (Effem Foods) describes a confectionery product comprising low density chocolate surrounded by a sugar based coating and a process for producing this product. The product is stated to be shelf stable even at elevated ambient temperatures.
• GB1305520 (Abalo) describes a continuous process for making foamed candies having a continuous outer shell of non aerated chocolate shell and a foamed chocolate filling in the centre.
• WO2000-078156 (APV) describes use of micro-aerated chocolate for enrobing
• the lentils are analogous to products available commercially from Mars under the registered trademark M&M®.
• the chocolate core is dispersed with gas bubbles having an average diameter of less than 25 microns. Typically the average diameter of the gas bubbles is less than about 17 microns.
• the dispersion is preferably homogeneous throughout the core.
• WO2013-143938 discloses how colorants can be added to ice cream coatings to counteract the impact of micro-aeration.
• 80% of the cumulative area weighted size air bubble distribution is below 60 [im.
• 95% of the cumulative area weighted size air bubble distribution is below 125 [im, preferably below 100 [im.
• 99% of the cumulative area weighted size air bubble distribution is below 150 [im.
• the preferred volume fraction of the gas micro-bubbles is greater than or equal to
• the preferred volume fraction of the gas micro-bubbles is less than or equal to 5.0%, and more particularly less than or equal to 4.5% or still to 4%.
• volume fraction of the gas micro-bubbles is less than or equal to 3.5%, or to 3.0% more particularly less than or equal to 2.8% or to 2.0%.
• the preferred volume fraction of the gas micro-bubbles is selected in the range from 0.2% to 4.5%, advantageously in the range from 0.3% to 2.5%.
• the volume fraction of the gas micro-bubbles is selected in the range between 0.5% to 2%.
• the gas micro-bubbles present have a diameter less than or equal to 100 [im.
• the diameter of the micro-bubbles may have a diameter from 1 ⁇ im to 100 [im, preferably a diameter from 1 ⁇ im to 30 [im and in a more preferred embodiment a diameter from 1 ⁇ im to 10 ⁇ m.'
• composition [is] a volume fraction from 0.1 to 5.0% of gas micro-bubbles of diameter ranging from 1 ⁇ im to 100 [im.
• EP2016836 (Mondelez) describes a method of producing a confectionery product includes the steps of: a) depositing into a mould an aerated confectionery mass (such as chocolate) such that the equipment keeps the mass under super atmospheric pressure and allows it to flow into the mold, b) depositing at least one particulate material in and/or on the confectionery mass; and c) repeating at least step a) at least once.
• This method avoids applying shearing forces to the mass typical of extrusions method and thus allows the gas bubbles to be maintained in the final product.
• the method is a one pass process that matches the aeration rate to the production of the chocolate so no aerated chocolate is wasted and reused.
• the filling comprises a fat system and has a solid fat content (SFC) of 35 to 65% at 0°C and 1 to 8% at 30°C.
• SFC solid fat content
• the fat system is prepared from palm oil mid fraction.
• the filling is soft at low temperature so that it is palatable. However, it does not melt at ambient temperatures and therefore does not require refrigeration / freezing for storage or transport.
• WO2015-101965 (Mondelez) describes a process for the preparation of a confectionery composition and compositions producible by the process.
• the process comprises providing a first sheet (10) of edible film having a plurality of first recesses (12) therein and a second sheet (22) of edible film, optionally having a plurality of second recesses (24) therein.
• a liquid filling (18) is supplied to the first recesses (12) and then sealed between the first and second sheets (10, 22) to form capsules (26).
• Molten chocolate (14) may be applied to the first recesses and/or the second recesses before the liquid filling.
• the capsules may be placed in a chocolate shell.
• WO2015-072942 (Eti Gidan Sanayi) describes an industrial food product with high water activity and filler and free of preservative, colouring agent and emulsifier.
• the invention is a production method for an industrial convenience food product with ready-to-eat, high water activity and filler, and free of preservative, colouring agent and emulsifier, comprising the process steps of a) preparation and cooking of the bakery products, b) in order to prepare the filler (2), obtaining by product by executing agitation-condensation-pasteurization- homogenization processes within a single unit, reducing the temperature of the by-product and fixing the same at a certain range (50-55°C), processing the by-product with fixed temperature in individual passages (K1 ,K2,K3,K4), and cooling down the same to a temperature (down to +8°C) far below the freezing point (15°C) without allowing
• JP03-883479 (Meji) describes a method for making pneumatic combined oily confectionery comprising a shell of pneumatic oily confectionery and using a moulding method.
• the method comprises pouring pneumatic combined oily confectionery dough into a mould where a thin layer of oily confectionery is formed, pressing the mould using a pressing pattern to make a doubled shell, and charging edible material as a centre stuffing inside the shell.
• the method comprises the following process: directly pouring pneumatic combined oily confectionery dough into a heated mould to make its interfacial part melt, forming a thin layer on the interfacial part with the inner surface of the mould followed by pressing the dough using a cooled pressing pattern to make a shell, and charging edible material as a centre stuffing inside the shell.
• Jacob's Club® The chocolate coated biscuit available commercially in the UK under the registered trade mark Jacob's Club® contained both aerated cream and chocolate and was believed to have been aerated intentionally. Interestingly a significant difference between the level of aeration on the top and sides parts of the product was observed, where the porosity of the chocolate forming the top coating was 8.5 % (average bubble size 281 microns ⁇ 31 1 ) whereas at the sides the chocolate porosity was 3.7% (average bubble size 202 microns ⁇ 184). It is worth noting that the average bubble size obtained for the Jacob's Club product is significantly larger than that which would typically be considered micro-aerated (100 microns or less) and the bubbles would be visible to the consumer by naked eye.
• the Dove® milk chocolate had a porosity of 1 .8% and it is believed that this low porosity is much more likely to result from natural micro-aeration as a by-product of a conventional process rather than gas being incorporated intentionally.
• the Mars® and M&M® eggs were more likely to be aerated deliberately possibly, as these eggs are quite large, as a means to reducing the amount of chocolate for cost saving whilst maintaining product size. They also appear to have been produced using a frozen cone/cold stamping method (perhaps similar to that described in Kraft060 above), where aeration stability is less of a concern due to the rapid cooling associated with this process.
• choco-materials can readily moulded into micro-aerated choco products such as chocolate tablets, bars and other moulded chocolate confectionery such as moulded chocolate coated wafers (e.g. prepared using a wet filled mould).
• the object of the present invention is to solve some or all of the problems or disadvantages (such as identified herein) with the prior art, including optionally overcoming the technical prejudice described above preventing the wide adoption of micro-aeration in choco- confectionery.
• an aerated choco-material having a plastic viscosity before aeration as measured according to ICA method 46 (2000) of from 0.1 to 20 Pa.s, where:
• composition has dispersed therein bubbles of an inert gas, the dispersed bubbles being characterised by the following parameters
• a total bubble surface area also referred to herein as TSA of from 0.5 to 1 .2 m 2 per 100g of the aerated choc-material
• parameters (a) and (b) are determined from X-ray tomography and/or confocal laser scanning microscopy (CLSM) and parameter (c); and where
• the gas bubbles are homogenously distributed within the choco-material, having a homogeneity index of at least 0.8.
• TSA may be determined by any suitable empirical method, well known to those skilled in the art and/or may be determined by calculation. In one preferred embodiment of the invention the TSA is determined from equation (1 ):
• TSA total bubble surface area
• P porosity of the aerated choco-material
• m ac mass of aerated composition (g)
• c/ ac density of aerated composition (g/cm 3 )
• r is the radius of a bubble of mean size (cm).
• the aerated choco-material of the invention is a chocolate mass.
• the plastic viscosity of the pre-aerated choco-material of the invention is measured herein according to ICA method 46 (2000) under standard conditions unless otherwise stated and more preferably is from 0.1 to 10 Pa.s.
• the micro-aerated choco-material of the invention described herein has a total bubble surface area (TSA) of from 0.5 to 1.2; preferably from 0.55 to 1 .10, more preferably from 0.6 to 1.0; most preferably from 0.65 to 0.90, for example from 0.7 to 0.8 m 2 per 100 g of the aerated choco- material.
• TSA total bubble surface area
• the term surface area or total surface area (TSA) referred to herein can be calculated from equation (1 ) herein and/or measured by any suitable apparatus or method known to those skilled in art.
• the TSA is a specific surface area (SSA) and may be measured as described in the article 'Determination of Surface Area.
• the choco-material is chocolate or compound, more usefully chocolate, most usefully dark and/or milk chocolate, for example milk chocolate such as a moulded milk chocolate tablet (optionally with inclusions and/or fillings therein).
• the homogeneity index that measures how uniformly the bubbles are distributed within the composition may be determined by taking an image (from X-ray tomography and/or CLSM) and measuring the number of bubbles that intersect along at least 3 parallel horizontal lines of equal length (preferably at least 1 cm) located on the image to be equally spaced from each other and the image edges.
• the ratio of the minimum number of bubbles on one of these lines to the maximum number of bubbles on one of these lines can be defined as a number bubble homogenous distribution index (NBHDI) which may be at least 0.8, preferably greater than or equal to 0.85, more preferably greater than or equal to 0.9, most preferably ⁇ 0.95, for example about 1.
• NBHDI number bubble homogenous distribution index
• the homogeneity index that measures how uniformly the bubbles are distributed may be determined by taking an image (from X-ray tomography and/or CLSM) and measuring along each of at least 3 parallel horizontal lines of equal length (preferably at least 1 cm) located on the image to be equally spaced from each other and the image edges, the length of each line that lies inside the void of a gas bubble.
• the ratio of the minimum void length on one of these lines to the maximum void length on one of these lines can be defined as a void length bubble homogenous distribution index (VLBHDI) which may be at least 0.8, preferably greater than or equal to 0.85, more preferably greater than or equal to 0.9, most preferably ⁇ 0.95, for example about 1 .
• VLBHDI void length bubble homogenous distribution index
• Bubble size may be measured from images obtained using suitable instruments and methods known to those skilled in the art.
• Preferred methods comprise X-ray tomography and/or confocal laser scanning microscopy (CLSM), more preferably X-ray tomography. Both these methods are described more fully later herein.
• micro-aeration increases the viscosity of the aerated chocolate mass post deposit. It is believed that the small bubbles act analogously to small particles an increase the internal surface area for interactions to occur within the fluid chocolate mass.
• the applicant has selected the parameters used to define the present invention as those such that the degree of aeration is enough to increase the viscosity of the aerated chocolate mass sufficiently to stabilise the gas bubbles and reduce or eliminate coalescence.
• the micro-sized bubbles that are formed have a more uniform size (narrow size distribution) and are dispersed more homogeneously throughout the chocolate that in previous micro-aerated chocolates. This produces micro-aerated chocolate of high quality (e.g. as determined by the resultant advantageous properties described herein).
• choco-material and related terms are defined later in this application, preferred choco-materials of the invention being chocolate and related compositions such as compound also defined later herein.
• inert gas denotes a gas that is substantially unreactive with the components of a choco-material and are also food grade approved i.e. suitable to form part of a foodstuff which will be consumed by human beings.
• inert gases will not contain components which might substantially oxidise the choco-material (or components thereof), for example gases which contain significant amounts of oxygen (such as air) are not inert gases as used herein.
• the inert gas is selected from nitrogen, nitrous oxide and/or carbon dioxide; more preferably from nitrogen and/or carbon dioxide; most preferably is nitrogen.
• the bubble size as defined by the parameters of the present invention is also referred to herein as micro-aerated.
• the amount of gas in the choco-material may optionally also be determined by the porosity of the choco-material when solid.
• the amount of inert gas dispersed in the micro-aerated choco-material may be sufficient to produce a porosity (as defined herein) in the ranges and/or of the values described herein.
• the amount of gas used to achieve the defined porosities can be for example using the flow rates and/or temperatures as described herein.
• the micro-aerated choco-material of the invention may have a porosity (as defined herein) of greater than or equal to 10% usefully greater than or equal to 1 1 %, more usefully ⁇ 12%, even more usefully ⁇ 13%, most usefully ⁇ 14%.
• the micro-aerated choco-material of the invention may have a porosity (as defined herein) less than or equal to 19%, conveniently ⁇ 18%, more conveniently ⁇ 17%, even more conveniently ⁇ 16%, most conveniently ⁇ 15%.
• the micro-aerated choco-material of the invention may have a porosity (as defined herein) of from 1 1 % to 19%, advantageously from 12% to 18%, more advantageously from 13% to 17%, even more advantageously from 14% to 16%, most advantageously from 14.5% to 15.5%.
• a further aspect of the invention provides a micro-aerated choco-material, fat based composition and/or confectionery product obtained and/or obtainable from a process of the present invention.
• a yet other aspect of the invention broadly provides a foodstuff and/or confectionery product comprising a micro-aerated choco-material, composition of the present invention and/or component(s) thereof as described herein.
• fat based and/or “fat based edible product' denotes a composition, preferably a choco-confectionery that comprises a matrix of edible hydrophobic material (e.g. fat) as the continuous phase and a dispersed phase comprising solid particles dispersed within the edible hydrophobic continuous phase.
• edible hydrophobic material e.g. fat
• fat denotes hydrophobic material which is also edible.
• fats are edible material (preferably of food grade) that are substantially immiscible with water and which may comprise one or more solid fat(s), liquid oil(s) and/or any suitable mixture(s) thereof.
• solid fat denotes edible fats that are solid under standard conditions and the term “oil” or “liquid oil” (unless the context indicates otherwise) both denote edible oils that are liquid under standard conditions.
• Preferred fats are selected from one or more of the following: coconut oil, palm kernel oil, palm oil, cocoa butter (CB), cocoa butter equivalents (CBE), cocoa butter substitutes (CBS), cocoa butter replacers (CBR), butter oil, lard, tallow, oil / fat fractions such as lauric or stearic fractions, hydrogenated oils, and blends thereof as well as fats which are typically liquid at room temperature such as any vegetable or animal oil.
• fats that are most preferred for use herein for use in preparing the micro-aerated choco-materials of the present invention are CB, CBE, CBS, CBR and/or any mixtures and/or combinations thereof.
• the liquid oil may comprise mineral oils and/or organic oils (oils produced by plants or animals), in particular food grade oils.
• oils include: sunflower oil, rapeseed oil, olive oil, soybean oil, fish oil, linseed oil, safflower oil, corn oil, algae oil, cottonseed oil, grape seed oil, nut oils such as hazelnut oil, walnut oil, rice bran oil, sesame oil, peanut oil, palm oil, palm kernel oil, coconut oil, and emerging seed oil crops such as 25 high oleic sunflower oil, high oleic rapeseed, high oleic palm, high oleic soybean oils & high stearin sunflower or combinations thereof.
• the fat content in the product of the present invention may be provided by fats of any origin.
• the fat content is intended to indicate the total fat content in the composition, comprising either the content coming from solid fats and/or the content of liquid oils and thus the oil content will also contribute to the total amount of fat content as described herein for a fat based confectionery composition.
• 'fat based composition and/or mass' respectively identifies a fat-based composition and/or mass (including its recipe and ingredients) which is used for the preparation of the products of the invention.
• the term 'fat based confectionery composition and/or mass' identifies a confectionery composition and/or mass (including its recipe and ingredients) which is used for the preparation of fat based confectionery products such as micro-aerated choco-material of the invention.
• the present invention relates specifically to a confectionery product, composition and/or mass that that comprise choco-material (preferably chocolate and/or compound, more preferably chocolate) as defined herein as well as optionally other confectionery products and/or components thereof.
• choco-material preferably chocolate and/or compound, more preferably chocolate
• 'chocolate' denotes any product (and/or component thereof if it would be a product) that meets a legal definition of chocolate in any jurisdiction and also include product (and/or component thereof) in which all or part of the cocoa butter (CB) is replaced by cocoa butter equivalents (CBE) and/or cocoa butter replacers (CBR).
• CBD cocoa butter equivalents
• CBR cocoa butter replacers
• 'chocolate compound' or 'compound' as used herein denote chocolate-like analogues characterized by presence of cocoa solids (which include cocoa liquor/mass, cocoa butter and cocoa powder) in any amount, notwithstanding that in some jurisdictions compound may be legally defined by the presence of a minimum amount of cocoa solids.
• choco-material includes products that are based on chocolate and/or chocolate analogues, and thus for example may be based on dark, milk or white chocolate and/or compound.
• choco-material comprises chocolate and/or compound
• more preferred choco-material comprises chocolate
• most preferred choco-material comprises chocolate as legally defined in a major jurisdiction (such as Brazil, EU and/or US).
• 'choco-coating' denotes coatings made from any choco-material.
• the terms 'chocolate coating' and 'compound coating' may be defined similarly by analogy.
• the terms 'choco-composition, (or mass)', 'chocolate composition (or mass)' and 'compound composition (or mass)' denote compositions (or masses) that respectively comprise choco-material, chocolate and compound as component(s) thereof in whole or part. Depending on their component parts the definitions of such compositions and/or masses may of course overlap.
• 'choco-confectionery' denotes any foodstuff which comprises choco- material and optionally also other ingredients and thus may refer to foodstuffs such confections, wafers, cakes and/or biscuits whether the choco-material comprises a choco- coating and/or the bulk of the product.
• Choco-confectionery may comprise choco-material in any suitable form for example as inclusions, layers, nuggets, pieces and/or drops.
• the confectionery product may further contain any other suitable inclusions such as crispy inclusions for example cereals (e.g. expanded and/or toasted rice) and/or dried fruit pieces.
• the choco-material of the invention may be used to mould a tablet and/or bar, to coat confectionery items and/or to prepare more complex confectionery products.
• the choco-confectionery product comprises a substantially solid moulded choco-tablet, choco-bar and/or baked product surrounded by substantial amounts of choco-material.
• choc-material forms a substantial or whole part of the product and/or a thick outside layer surrounding the interior baked product (such as a wafer and/or biscuit laminate).
• a mould is substantially filled with chocolate are to be contrasted with products that comprise moulded thin chocolate shells which present different challenges.
• a mould is coated with a thin layer of chocolate, the mould being inverted to remove excess chocolate and/or stamped with a cold plunger to define the shell shape and largely empty the mould.
• the mould is thus coated with a thin layer of chocolate to which further ingredients and fillings may be added to form the interior body of the product.
• the challenges to maintain a uniform and consistent level of micro-aeration throughout the body of a thick or solid chocolate product such as a tablet or bar are different from micro-aerating a thin chocolate shell.
• Thin shells are also made by enrobing or frozen cone methods (some of which have been described in the prior art acknowledged previously) which would be unsuitable for micro- aeration.
• choco-confectionery as used herein can readily be replaced by and is equivalent to the term chocolate confectionery as used throughout this application and in practice these two terms when used informally herein are interchangeable. However where there is a difference in the meaning of these terms in the context given herein, then chocolate confectionery and/or compound confectionery are preferred embodiments of the choco- confectionery of the present invention, a preferred embodiment being chocolate confectionery.
• Preferred choco-confectionery may comprise one or more choco-product(s) and/or choco- ingredients therefor, for example selected from the group consisting of: chocolate product(s). compound product(s), chocolate coating(s) and/or compound coating(s).
• the products may comprise uncoated products such as choco-bar(s) and/or choco-tablet(s) with or without inclusions and/or products coated with choco-material such as coated biscuits, cakes, wafers and/or other confectionery items.
• any of the aforementioned may comprise one or more cocoa butter replacer(s) (CBR), cocoa-butter equivalent(s) (CBE), cocoa-butter substitute(s) (CBS) and/or any suitable mixture(s) thereof.
• CBR cocoa butter replacer
• CBE cocoa-butter equivalent
• CBS cocoa-butter substitute
• Such products may generally comprise one or more fat(s) selected from the group consisting of: lauric fat(s) (e.g. cocoa butter substitute (CBS) obtained from the kernel of the fruit of palm trees); non-lauric vegetable fat(s) (e.g.
• CBR cocoa butter replacer
• CBE cocoa butter equivalent(s)
• Some CBE, CBR and especially CBS may contain primarily saturated fats and very low levels of unsaturated omega three and omega six fatty acids (with health benefits). Thus in one embodiment in choco-confectionery of the invention such types of fat are less preferred than CB.
• one aspect of the present invention may provide for a choco- confectionery composition, preferably which has a lower total fat content (at least 5 parts or 5% by weight) than previously obtainable from prior art choco-material.
• One embodiment of the invention provides a multi-layer product optionally comprising a plurality of layers of baked foodstuff (preferably selected from one or more wafer and/or biscuit layers, and/or one or more fillings layers there between with at least one coating layer located around these layers foodstuff, the coating comprising a choco-material of or prepared according to the invention.
• a further embodiment of the invention provides a choco-confectionery product, further coated with chocolate (or equivalents thereof, such as compound) for example a praline, chocolate shell product and/or chocolate coated wafer or biscuit any of which may or may not be layered.
• chocolate or equivalents thereof, such as compound
• the chocolate coating can be applied or created by any suitable means, such as enrobing or moulding.
• the coating may comprise a choco-material of or prepared according to the invention.
• Another embodiment of the invention provides a choco-confectionery product of and/or used in the present invention, that comprises a filling surrounded by an outer layer for example a praline, chocolate shell product.
• the foodstuff comprises a multi-layer coated choco- product comprising a plurality of layers of wafer, choco-material, biscuit and/or baked foodstuff, with filling sandwiched between them, with at least one layer or coating being a choco-material (e.g. chocolate) of the invention.
• the multi-layer product comprises a choco-confectionery product (e.g. as described herein) selected from sandwich biscuit(s), cookie(s), wafer(s), muffin(s), extruded snack(s) and/or praline(s).
• An example of such a product is a multilayer laminate of baked wafer and/or biscuit layers sandwiched with filling(s) and coated with chocolate.
• Baked foodstuffs used in the invention may be sweet or savoury.
• Preferred baked foodstuffs may comprise baked grain foodstuffs which term includes foodstuffs that comprise cereals and/or pulses.
• Baked cereal foodstuffs are more preferred, most preferably baked wheat foodstuffs such as wafer(s) and/or biscuit(s).
• Wafers may be flat or shaped (for example into a cone or basket for ice-cream) and biscuits may have many different shapes, though preferred wafer(s) and/or biscuit(s) are flat so they can be usefully be laminated together with a confectionery filling of the invention (and optionally a fruit based filling).
• More preferred wafers are non-savoury wafers, for example having a sweet or plain flavour.
• a non-limiting list of those possible baked foodstuffs that may comprise choco-compositions that comprise choco-material of and/or used in the present invention are selected from: high fat biscuits, cakes, breads, pastries and/or pies; such as from the group consisting of: ANZAC biscuit, biscotti, flapjack, kurabiye, lebkuchen, leckerli, macroon, bourbon biscuit, butter cookie, digestive biscuit, custard cream, extruded snacks, florentine, garibaldi gingerbread, koulourakia, kourabiedes, Linzer torte, muffin, oreo, Nice biscuit, peanut butter cookie, polvoron, pizzelle, pretzel, croissant, shortbread, cookie, fruit pie (e.g. apple pie, cherry pie), lemon drizzle cake, banana bread, carrot cake, pecan pie, apple strudel, baklava, berliner, bichon au citron and/or similar products.
• ANZAC biscuit biscotti, flapjack, kurabiy
• micro-aerated choco-material of or prepared according to the invention may be suitable for use as (in whole or in part as a component) of one or more coatings and/or fillings.
• the coating and/or filling may comprise a plurality of phases for example one or more solid and/or fluid phases such as fat and/or water liquid phases and/or gaseous phases such as emulsions, dispersions, creams and/or foams. Therefore broadly a further aspect of the invention comprises a foodstuff comprising choco- material and/or choco-composition as described herein.
• a yet further aspect of the invention broadly comprises use of a choco-material of or prepared according to the invention as a choco-confectionery product and/or as a filling and/or coating for a foodstuff of the invention as described herein.
• Such utility may be direct for example where a moiety has the required properties for the aforementioned uses and/or indirect for example where a moiety has use as a synthetic intermediate and/or diagnostic and/or other tool in preparing other moeity of direct utility.
• these terms also denote that sub-entity of a whole (such as a component and/or ingredient) is compatible with producing effective, acceptable, active and/or suitable end products and/or compositions.
• Preferred utility of the present invention comprises use as a food stuff, preferably as a confectionery product and/or intermediate in the manufacture thereof.
• boundary value is included in the value for each parameter. It will also be understood that all combinations of preferred and/or intermediate minimum and maximum boundary values of the parameters described herein in various embodiments of the invention may also be used to define alternative ranges for each parameter for various other embodiments and/or preferences of the invention whether or not the combination of such values has been specifically disclosed herein.
• substantially may refer to a quantity or entity to imply a large amount or proportion thereof. Where it is relevant in the context in which it is used “substantially” can be understood to mean quantitatively (in relation to whatever quantity or entity to which it refers in the context of the description) there comprises an proportion of at least 80%, preferably at least 85%, more preferably at least 90%, most preferably at least 95%, especially at least 98%, for example about 100% of the relevant whole.
• substantially-free may similarly denote that quantity or entity to which it refers comprises no more than 20%, preferably no more than 15%, more preferably no more than 10%, most preferably no more than 5%, especially no more than 2%, for example about 0% of the relevant whole. Preferably where appropriate (for example in amounts of ingredient) such percentages are by weight.
• Improved properties as used herein means the value of the component and/or the composition of and/or used in the present invention is > +8% of the value of the known reference component and/or composition described herein, more preferably > +10%, even more preferably > +12%, most preferably > +15%.
• Comparable properties as used herein means the value of the component and/or composition of and/or used in the present invention is within +/-6% of the value of the known reference component and/or composition described herein, more preferably +/- 5%, most preferably +/- 4%.
• the percentage differences for improved and comparable properties herein refer to fractional differences between the component and/or composition of and/or used in the invention and the known reference component and/or composition described herein where the property is measured in the same units in the same way (i.e. if the value to be compared is also measured as a percentage it does not denote an absolute difference).
• the aerated samples are filled to the brim in containers of the same size and the surface levelled off to be initially flush with the rim of the container. After the same amount of time at room temperature or higher but not above 30 degrees (a few minutes unless otherwise indicated) the containers are re-assessed visually.
• the aeration is unstable the bubbles coalesce to from a large bubbles with a greater overall volume and this will create a dome on the test sample. The larger the dome that is formed on the sample the more unstable the aeration is.
• Samples where the aerated matrix is stable do not change volume and do not form a dome, exhibiting an unchanged a flat surface at the container rim.
• bubble size values given herein are measured by X-ray tomography and/or confocal laser scanning microscopy (CLSM) as described below.
• Bubble size may be determined by measuring the volume distribution of the sample by plotting volume (%) versus size (microns) for example from images generated using the techniques described herein. Bubble size is then quoted as the linear dimension which corresponds to the diameter of an approximate spherical bubble having the same volume as the mean volume calculated from the measured volume distribution and is referred to herein as mean bubble size in microns.
• a normal bubble size distribution (BSD) with single maximum peak (mono modal) is assumed in most cases for the bubbles generated in the present invention.
• BSDs e.g. multimodal such as bimodal
• the BSD is measured by the standard derivation from the mean bubble size also measured in microns.
• d90 may also be used (also expressed in linear dimensions) which denotes the size of bubble below which 90% (by number) of the bubbles in a given aerated sample lie.
• the parameter denoted by a symbol in the format XP, O is measured in units of length (e.g. microns) and denotes that bubble diameter for which P % of the total number of bubbles counted in the sample have a diameter smaller or equal to the length given for this parameter.
• Xso.o 1 micron
• Parameter X 5 o,o is commonly used to indicate number weighted diameter but analogously, parameters Xgo.o and Xio,o (the diameters below wich respectively 90 % and 10 % of all bubbles lie) may also be used.
• SPAN (Q0) may be calculated for the number based bubble size distribution by determining the ratio of (X9o,o- Xio,o) / X5o,o. This is a measure to evaluate the width of the number weighted bubble size distribution.
• a lower SPAN (Q0) value indicates a narrower bubble size distribution and with this a more homogenous and more stable foam structure.
• the parameter denoted by the symbol in the format XP, 3 is measured in units of length (e.g. microns) and denotes that bubble diameter for which P % of the total volume taken by the bubbles in the sample have a diameter smaller or equal to the length given for this parameter.
• Xso,3 1 micron
• Parameter X 5 o,3 is commonly used to indicate volume weighted diameter but analogously, parameters Xgo,3 and Xio,3 (the diameters at which respectively 90 % and 10 % of the volume occupied by all bubbles lie) may also be used.
• SPAN (Q3) was calculated for the volume weighted bubble size distribution by determining the ratio of (Xgo,3 - Xio,3) / Xso,3. This is a measure to evaluate the width of the volume weighted bubble size distribution.
• a lower SPAN (Q3) value indicates a narrower bubble size distribution and with this a more homogenous and more stable foam structure.
• a rotating sample is bombarded with polychromatic X-rays, and X-ray intensity resulting from interaction with the sample is spatially recorded by a pixelated planar detector which forms a two dimensional image of the projected absorption of the sample.
• a three dimensional reconstruction of the sample is then performed from the collection of 2D projections using back projection algorithms. This is described in 'Principle of X-ray tomography', K.S Lim, M. Barigou, X-ray micro-computed tomography of cellular food products, Food Research International 37 (2004) 1001-1012.
• X-ray tomography is non-invasive and is a powerful technique for mapping air voids embedded in a solid matrix (such as the bubbles in micro- aerated chocolate).
• X-ray tomography has a high resolution of up to 1 ⁇ and no sample preparation is required, it provides an easy, quantitative means of evaluating bubble sizes from the images generated.
• samples evaluated herein by X-ray tomography used the instrument MicroCT 35 available commercially from Scanco medical AG.
• the samples (e.g. chocolate pieces) to be X-rayed were gently cut in the z-axis using razor blades and small cylinder like samples were trimmed and placed in sample holders.
• CLSM complementary metal-oxide-semiconductor
• samples evaluated herein by CLSM used the confocal microscope available commercially from Leica instrument under the trade designation LAS, Type DM6000.
• the samples (e.g. chocolate pieces) to undergo CLSM were gently cut in the z-axis using razor blades and small cylinder like samples were trimmed and placed in sample holders. Then samples were then dyed for the confocal microscope using first Nile red then adding Fast green (as shown in the table below).
• the Nile red signal is displayed in a red look-up-table and the Fast green one in a green look-up-table. The remaining dark areas having a circular shape are therefore assumed to be gas bubbles.
• the sugar is represented by smaller black areas with irregular borders.
• bubble diameter can be measured using the scale which is integrated into the image software.
• Porosity values (P) stated as a percentage were derived from computed tomography evaluation. Porosity describes the ratio of void fraction to the total volume of a sample. Hence porosity represents the ratio of the volume of gas VG within a sample to the total sample volume V S , hence VGA S. Porosity may also be estimated as otherwise described herein or calculated from Over-Run (OR) measurements (also stated as a percentage) in standardized plastic cups using the following equations.
• Foamed confectionary samples were stored below 5 °C until analysis.
• the samples may be analyzed using a CT 35 (Scanco Medical, Brijttisellen, Switzerland) operated in a climate chamber set to 15 °C.
• the bubble detection resolution of the device is 6 micron.
• Cumulative bubble size distributions Q(x) (characterized by: Xso,3 X9o,3 Xio,3 and ⁇ , ⁇ ⁇ , ⁇ ⁇ , ⁇ ), VG and Vs, may be measured by computer X-ray tomography and extracted by image analysis. From the bubble sizes X5o,3 X9o,3 Xio,3 and ⁇ , ⁇ ⁇ , ⁇ the size distribution widths
• SPAN(Q3), SPAN(QO) can also be derived.
• standard conditions e.g. for defining a solid fat or liquid oil
• standard conditions means, atmospheric pressure, a relative humidity of 50% ⁇ 5%, ambient temperature (22°C ⁇ 2°) and an air flow of less than or equal to 0.1 m/s. Unless otherwise indicated all the tests herein are carried out under standard conditions as defined herein.
• Texture of foodstuffs is perceived as a composite of many different characteristics comprising various combinations of physical properties (such as mechanical and/or geometrical properties) and/or chemical properties (such as fat and/or moisture content).
• physical properties such as mechanical and/or geometrical properties
• chemical properties such as fat and/or moisture content
• the composition texture can be related to the viscosity of the composition as a fluid when subjected to shear stress.
• apparent viscosity can be used herein as a guide to indicate texture.
• viscosity refers to the apparent viscosity of a fluid as measured by conventional methods known to those skilled in the art but in particular the method described herein is preferred.
• the viscosity of the compositions according to the invention and/or prepared by a method of the invention, as well as comparative examples, can be characterized by two measurements, one at about 5s "1 for low flow situations to approximate to the yield value and a second one at 20s "1 for higher flow rates. (See Beckett 4th edition, chapter 10.3).
• the yield value of viscosity is used to determine texture measured at a low flow rate of 5s "1 .
• the preferred method for measuring the yield value for viscosity uses an instrument denoted by the trade designation RVA 4500 (available commercially from Rapid Viscosity Analyzer, Newport Scientific, Australia) measured under standard conditions (unless otherwise indicated) and at a rate of 5s "1 .
• RVA 4500 available commercially from Rapid Viscosity Analyzer, Newport Scientific, Australia
• 10 grams of the sample composition are added to the canister supplied with the RVA instrument and then measurement is performed using the following profile: a constant temperature of 35°C, mixing vigorously at 950 rpm for 10 seconds then at 160 rpm for the duration of the test which is 30 minutes.
• the test is done in duplicates or triplicates to ensure repeatability.
• the final viscosity is used for comparison as well as the quality of the RVA viscosity curve.
• Figure 1 is a photograph of a cross section of comparative chocolate of the invention (Comp A) which was aerated with nitrogen to achieve a porosity of 5%. As can been many larger bubbles are formed with overall a wider size distribution of bubbles due to coalescence of the initially smaller bubbles when a low amount of gas is initially dispersed into the chocolate mass.
• Figure 2 is a photograph showing the difference in stability between chocolate aerated to from left to right Comp B (porosity of 10%), Example 1 (porosity of 12.5%) and Example 2 (porosity 15%).
• Figure 3 is a photograph showing the instability of chocolate aerated at a higher level (from left to right Comp C (porosity 20%) and Comp D (porosity 25%)
• Figure 4 to 8 herein show tablets produced using the same chocolate mass, all temper and process parameters being kept constant, apart from the gas flow which was adjusted to give the desired porosity level.
• Figure 4 shows a micro-aerated dark chocolate with 5% porosity (Nestle, Brazil). Please note the visible bubbles and also marks resulting from poor de-moulding.
• Figure 5 shows a micro-aerated dark chocolate with 10% porosity: good de-moulding and invisible bubbles. The mass did rise during the cup test, showing some signs of instability.
• Figure 6 shows a micro-aerated dark chocolate with 15% porosity: good homogeneous aeration and de-moulding properties. The 'cup' test showed the aeration to be very stable.
• Figure 7 shows a micro-aerated dark chocolate with 20% porosity: bubbles have started to coalesce and are clearly visible inside the bar.
• Figure 8 shows a micro-aerated dark chocolate with 23% porosity: bubbles have started to coalesce and are clearly visible inside and at the surface of the bar. It was not possible to increase the porosity any further than 23% by just adjusting the gas flow alone.
• Figures 9, 10 and 1 1 are images of a micro-aerated sample of the chocolate mass used (when unaerated) to prepare the confectionery product sold by the applicant in Brazil as chocolate tablets under the trade mark Garoto® (see Example 5 and Table 2 herein), where Figure 9 was generated with X-ray tomography, Figure 10 with confocal microscopy (CLSM) and Figure 1 1 is a 3D visualization of the micro-aerated Garoto® chocolate.
• Comparative example A is a chocolate aerated with nitrogen to achieve a porosity of 5%.
• Comp A contains many large bubbles (some of which are very visible to the naked eye) and overall exhibits a wide distribution of bubble sizes. Without wishing to be bound by any theory the applicant believes that this may be due to coalescence of the small bubbles initially formed when a low amount of the nitrogen gas was dispersed into the chocolate mass.
• FIG. 2 is a photograph showing these examples (respectively from left to right Comp B, Example 1 and Example 2) after undergoing the aeration stability test as described herein.
• Comp B forms a dome whereas Examples 1 and 2 do not, which indicates the improved stability of Ex 1 and 2, which compared to Comp B.
• aerated compositions of the invention that have a porosity and bubble sizes and distribution as defined herein have desirable properties. Such parameters have been found to define an optimum region that is selected from the general scope of parameters within aerated compositions can be prepared.
• Figure 3 is a photograph showing the instability of these samples (left to right Comp C and D) after they have undergone the aeration stability test as described herein. Visible aeration can be seen on the surface of the chocolate especially for Comp D.
• Comp C and D were also found to exhibit too large a viscosity to be easily handled especially in an industrial process under the normal temperatures at which moulding and demoulding occurs. For example these samples were found to be too viscous to readily flow into moulds to provide good surface definition.
• the resultant moulded products nmade from Comp C or Comp D were also very difficult to be removed from a mould (demould) without damage to the product. So surprisingly the applicant has found that there is an upper limit to micro- aerating chocolate. Adding gas to chocolate as small bubbles (micro-aeration) to achieve porosity levels of 20% or above has been shown to be impractical.
• the optimal porosity range is believed to be from 12.5% - 15% for the micro-aerated chocolate masses tested. Surprisingly these porosities were found to gives a workable viscosity and a stable and homogeneous micro-aeration (invisible bubbles to the naked eye) as seen in the profile of bubble size distribution. For micro-aerated chocolate with porosities above 15%, viscosity starts to become a challenge, before significant coalescence occurs at porosity above 20%. Micro-aerated chocolate prepared with much lower porosity (e.g. see Comp A oft 5% porosity) also forms inhomogeneous bubbles which is both visually unappealing and effects the organoleptic properties of the chocolate.
• the following product recipe for a chocolate mass (sold by the applicant in Mexico as a chocolate tablet under the registered trademark Carlos V) was aerated with Nitrogen
• the bubble size and BSD present in various samples of conventional chocolate masses, which were then micro-aerated at different levels) were evaluated using two methods of bubble measurement, X-ray tomography and CLSM.
• KitKat® Micro-aerated samples of the chocolate mass used (when unaerated) to coat the confectionery product sold under the trade mark KitKat®, referred to in Table 2 as KitKat®. It can be seen that a low levels of aeration (Comp E), the bubbles coalesce and are thus have a larger mean size (> 200 microns) and broader BSD. The larger bubbles are noticeable to the naked eye. At higher levels of aeration surprisingly both the mean bubble size and standard deivation decreases (narrower BSD, i.e more uniform, smaller bubble size).
• Pictures of micro-aerated Garoto obtained with X-ray tomography are shown in Figure 9 and confocal microscopy (CLSM) in Figure 10.
• a 3D visualization of micro-aerated Garoto chocolate is shown in Figure 1 1 where the different colours represent the different depths and highlight the presence of bubbles as described herein.

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