A PROCESS FOR CONTROLLING THE SOLIDIFICATION AND/OR CRYSTALLISATION OF A FAT OR A FAT-CONTAINING FOOD

Abstract: The invention relates to a process for controlling the solidification and/or crystallisation of a fat or a fat-containing food, characterised in that solidification and/or crystallisation is carried out under the influence of a magnetic field. The process can be used particularly advantageously where the fat is polymorphic, for example cocoa butter, and the magnetic field allows the fat to be produced in a particular crystalline form. Thus, a cocoa butter containing product in solid form can be produced, the cocoa butter having been formed directly from a liquid phase in crystal form IV without having passed through another crystal form and without addition of seed crystals.

Description: A PROCESS FOR CONTROLLING THE SOLIDIFICATION AND/OR CRYSTALLISATION OF A FAT OR A FAT-CONTAINING FOOD The present invention relates to the processing, more particularly the solidification and/or crystallisation, of fats and fat-containing foods. Fats are widely used in solid or crystalline form in food products and the form in which the fat is solidified or crystallised may affect the properties of the foodstuff. Certain fats are polymorphic, i.e. they are capable of solidifying in more than one crystalline form, and the crystal forms may have important effects on the properties of the foodstuff. For example, cocoa butter is polymorphic and six crystal forms have been described (see Talbot in Industrial Chocolate Manufacture and Use (Ed. Beckett) , 1994, Chapter 11). Form V is desirable for processed chocolate since this form of cocoa butter gives chocolate snap, texture and gloss. However, form V converts with time to form IV which is responsible for the white sheen which may appear on chocolate known as bloom. WO 98/30108 discloses methods for making chocolate that minimize increases in viscosity associated with tempered chocolate. The method involves adding a seeding agent to molten chocolate and according to one embodiment this seeding agent can contain significant amounts of the form VI poly orph of cocoa butter although there is no direct evidence of the crystal form of the cocoa butter in the product finally obtained. Seeding using solid fat is not easy to perform on an industrial scale and most of the industry use continuous scraped surface heat exchangers (see Nelson in Industrial Chocolate Manufacture and Use (Ed. Beckett), 1994, Chapter 12) which machines are relatively complex and require critical temperature control. Research into the effects of magnetic fields on chemical processes has been sporadic. It was suggested in the 1930s that application of a magnetic field could remove scale from water pipes but in the absence of a convincing rationale for the effect the technique remained controversial for many years before being confirmed experimentally some 50 years later (Donaldson, Tube International, January 1988, 39 and Grimes, Tube International, March 1988, 111) . The effect of magnetic fields on precipitation and crystallisation in inorganic systems such as calcium carbonate and zinc phosphate is assumed to be on nucleation and the effect in reducing scale formation or even removing scale which has already formed appears to be a result of changes in solubility of the inorganic compound. In the case of organic molecules, it was found that when benzophenone was crystallised in a high magnetic field, the direction of the long axis of the needles formed tended to align perpendicular to the direction of the magnetic field (Katsuki et al , Chemistry Letters, 1996, 607-608). With a more complex organic molecule, a considerable degree of alignment was found when fibria was allowed to polymerise in a magnetic field and a possible effect on blood clotting in vivo was suggested (Yamagishi et al , J. Phys. Soc. Jpn. , 58 (7) , 2280-2283 (1989)). A more recent report has suggested that application of a magnetic field can influence the selectivity ratios in the nickel catalysed hydrogenation of fats such as sesame oil and soybean oil (Jart. JAOCS, 75(4) . 615-617 (1997)). Experiments have been reported in which passing sucrose solution through a magnetic field appeared to reduce the boiling point of the solution although a drop in boiling point was also noted for distilled water and tap water. The magnetic field also affected viscosity and surface tension of the sucrose solution but the various effects were not proportional to the intensity of the magnetic field (Bisheng et al , Int. Sugar Jnl., 98, 73-75 (1996)). It has also been suggested that the application of a magnetic field can reduce and control evaporator scale in the production of cane sugar (Cole & Clarke, Int, Sugar Jnl., 98., 71-72 (1996)). No effect on the sucrose crystals themselves was reported in either of the above papers. It has been reported that if aqueous silver nitrate solution is evaporated in a magnetic field, the solid silver nitrate produced contains extra tightly bound water as compared to product made in the absence of a magnetic field (Ohgaki et al , Che . Eng. Sci., 49 (6) , 911-913 (1994)) . The above effects of magnetic fields on solidification and/or crystallisation mostly relate to aqueous systems and the effects can be assumed to be related to the presence of water. There have been a small number of reports (including those on benzophenone and hydrogenation mentioned above) of workers investigating the effects of magnetic fields on organic systems but these have related generally to the effect on crystal size or on catalysis. It has now been found surprisingly that the application of magnetic fields can influence the rate of solidification and/or type of crystallisation of systems, which can be largely or completely non-aqueous, in which the liquid medium is fat. This finding has direct application to the processing of fats and fat-containing foods. According to one aspect, the present invention provides a process for controlling the solidification and/or crystallisation of a fat or a fat-containing food, characterised in that solidification and/or crystallisation is carried out under the influence of a magnetic field. According to the invention the processing of fats and fat- containing foods can be positively influenced by the application of a magnetic field either during solidification and/or crystallisation or to the liquid ingredients prior to solidification and/or crystallisation. The invention can be applied to fats and fat-containing foods generally but has particular application where the fat is polymorphic. For example, in certain cases the shelf-life of fats can be increased by influencing solidification and/or crystallisation in such a manner that particularly stable crystal forms of the fat are produced. According to one embodiment, the invention can be applied to the crystallisation of cocoa butter as an ingredient of such foods as chocolate. As already noted above, cocoa butter is polymorphic and form V converts with time to form VI. It had not previously been thought possible to produce form VI directly by crystallisation of liquid cocoa butter or a cocoa butter containing product such as chocolate (see Talbot, Physio-Chemical Aspects of Food Processing, 1995, page 150) but this has now been found to be possible by the application of certain types of magnetic fields to the cocoa butter before or during crystallisation. According to another aspect, the present invention provides a cocoa butter containing product in solid form, the cocoa butter having been formed directly from a liquid phase in crystal form VI without having passed through another crystal form. According to a further aspect, the present invention provides a cocoa butter containing product in solid form, the cocoa butter having been formed directly from a liquid phase in crystal form VI without having passed through another crystal form and without addition of seed crystals. For example the cocoa butter containing product may be chocolate. It is also possible according to the present invention to use the influence of a megnetic field to ensure that cocoa butter is produced directly in crystal form V. The cocoa butter may be part of a cocoa butter containing product such as chocolate. Use of magnetic fields to influence crystallisation enables greater control to be exercised over the crystallisation process. Much space is taken up in chocolate factories by cooling tunnels and/or multi-tier coolers in which the chocolate sets (see Nelson in Industrial Chocolate Manufacture and Use (Ed. Beckett), 1994, Chapter 13) and the expense of this space could be reduced if the chocolate could be made to set more rapidly. It has been found according to the present invention that the application of certain magnetic fields can (depending on the type and direction of the magnetic field) significantly increase the rate of setting of cocoa butter. For example, as illustrated in the examples presented hereinafter, cocoa butter can be induced to set up to 40% more quickly. The magnetic field which is used according to the invention can be applied in any desired manner including permanent magnets, any type of electromagnet (such as pulsed electromagnets and DC electromagnets) and radio frequency generated magnetic fields. The magnetic field can be applied to the fat or fat-containing food, for example, by the field surrounding the fat or fat-containing food, during solidification and/or crystallisation. Alternatively the magnetic field can be used to treat the liquid or partially set fat or fat-containing food prior to completion of crystallisation. The optimum field strength for any particular effect and the manner in which the magnetic field should be applied can be determined in any given case by routine experimentation. The effect of different types of magnetic field is discussed in more detail in the experimental work described below. As indicated above, it is surprising that magnetic fields exert an effect on crystallisation of fats. Without wishing to be bound by any theory as to how this effect is achieved, some literature exists on a phenomenon known as thermodielectric effect first documented in 1950 (Costa Ribeiro, Acad, Bras, Sci. An., 22., 325, (1950)). Costa Ribeiro discovered that electric charges are always produced at an interface between a solid and a liquid and may be observed when a phase change is occurring. In addition, charge transfer is produced in other changes of physical state when one phase is a solid. Charge separation and migration is known to occur in a solution of camphor in CC1 4 (Evans, J. Chem. Soc. Faraday Trans I, .80 / 2343-2348 (1984)). In the presence of a non- uniform electric field the charges are forced to the surface of the solution. External electric fields must influence a liquid at an interface where the permittivity e undergoes an abrupt change and therefore Δe is not zero, as in the bulk solution. As the field is increased, a force is exerted on the surface of the liquid. If the field is strong enough, surface disruption takes place and spikes appear and a nucleation centre is formed. As the field is further increased the spike grows into a platelike crystal. Similarly, ice nucleation is known to be influenced by non-uniform electric fields. This is the inverse of the thermodielectric effect. Similar effects occur using magnetic fields since the magnetic and electric properties of molecules are analogous. Molecules subjected to applied electric or magnetic fields will experience induced dipole moments or magnetic moments respectively. Phase changes produced by inhomogenous electric and magnetic fields are known as the Evans effects, and Group theoretical statistical mechanics were carried out (Evans, Mat. Res. Bull., 2_, 1557-1565 (1984)) providing the following indications: 1. The electric and magnetic Evans effects depend on the different symmetries on the liquid and crystalline sides of the interface. If there is no symmetry difference, there is no effect. 2. The interface between environments of different point group symmetry is in general forced into that of a lesser symmetry. Thus, a crystal grows into a liquid, a crystal into a gas etc. 3. The relevant consideration is the point group of the environment either side of the interface, not the point group of the molecules themselves. In consequence, electric and magnetic Evans effects are expected in molecular solutions, suspensions, colloids, aggregates etc. where the environmental point groups are different either side of the interface. 4. The mechanism proposed accounts for the fact that the field gradients produce linear force through interaction with the appropriate molecular multipole moment. 5. The point group analysis can be extended straightforwardly to interactions of electromagnetic fields with environments either side of the interface. The invention is illustrated by the following experimental work in which reference is made to the accompanying drawings as follows: Figure 1 is a schematic illustration of the equipment set- up used to study cocoa butter crystallisation; Figure 2 is an illustration of the permanent magnetic field set-up used in Experiment 2 ; Figure 3 is an illustration of the DC electromagnetic field set-up used in Experiment 3; Figure 4 is an illustration of the AC electromagnetic field set-up used in Experiment 4; Figure 5 is an illustration of the pulsed field set-up used in Experiment 5; Figure 6 is an illustration of the apparatus set-up used to apply a permanent magnetic field to molten cocoa butter; Figure 7 is an illustration of the apparatus set-up used to apply a DC electromagnetic field to cocoa butter; Figure 8 is an illustration of the apparatus set-up used to apply an AC electromagnetic field to cocoa butter; Figure 9 is an illustration of the pulsed magnetic field set-up applied to molten cocoa butter. EXPERIMENTAL Powder X-ray Diffraction was carried out using a Philips PW1710 Diffractometer with Cu Kα radiation. Incubators used in the studies were Sanyo MIR 152 and operate at a range of ±0.5°C to the set temperature. The torque stirrer used was a Heidolph RZR 2102 electronic torque stirrer and PC interface unit with speed set by a 2.83V signal from a power pack in all cases. The interface unit used was a Laplace Instruments SPCX-TC, and the signal datalogger was PCXA from Laplace Instruments with software. PART 1 - CRYSTALLISATION OF COCOA BUTTER IN APPLIED MAGNETIC FIELDS Experiment 1 - Control The apparatus illustrated in Fig. 1 was designed in order to study cocoa crystallisation. The power pack set to 2.83V is equivalent to a stirring speed of around 280rpm. The torque was measured through the signal datalogger and interface unit via the voltage output from the torque stirrer. Cocoa butter (100ml) placed in a 2cm diameter sealed test-tube was heated to 80°C for 1 hour using a water bath. The test-tube containing the molten cocoa butter was placed in incubator A at 50°C with the stirring paddle inserted in the molten cocoa butter, 1cm from the bottom of the test-tube, and was switched on. The datalogger equipment recorded torque measurements every 60 seconds while incubator A was set to run through the following cycle: 1. 50°C for 30 mins 2. 26°C for 4 hours 3. 28 °C for 4 hours 4. alternating between 26° and 28 °C every 4 hours during a 24 hour period. The cooling rate of incubator A (not the cocoa butter) from 50°C is around l°Cmin "1 in the cases of control and pulsed magnets experiments and around 0.75°Cmin "1 for all other experiments. The time taken to reach maximum torque during this period was recorded and noted. The test-tube containing the cocoa butter slurry was removed from incubator A and placed in incubator B (not shown) at 20°C for 24 hours in order to set the cocoa butter. Following removal of the set cocoa butter from the test tube, visual texture and surface features of the cocoa butter were noted. Powder XRD was carried out on the resulting cocoa butter sample. Experiment 2 - Crystallisation in a permanent magnetic field The same procedure as Experiment 1 was carried out with the addition of permanent magnets (arrangement and field strengths are illustrated in Fig. 2) around the test-tube containing the cocoa butter following placement in incubator A. Stirring and torque measurements were carried out as before.. Visual texture and surface features were noted, and Powder XRD was carried out on the resulting cocoa butter sample. Experiment 3 - Crystallisation in a DC electromagnetic field The same procedure as Experiment 1 was carried out with the addition of a DC electromagnet (set to operate at 12V and illustrated below in Fig. 3) around the test-tube during stirring of the molten cocoa butter in incubator A. Stirring and torque measurements were monitored and visual texture and surface features of the cocoa butter were recorded. Powder XRD was applied to the resulting cocoa butter sample. Experiment 4 - Crystallisation in an AC electromagnetic field The same procedure as Experiment 1 was carried out with the addition of an AC electromagnet (as illustrated below in Fig. 4) around the test-tube during stirring of the molten cocoa butter in incubator A. Stirring and torque measurements were monitored and visual texture and surface features were recorded. Powder XRD was applied to the resulting cocoa butter sample. Experiment 5 - Crystallisation in a pulsed field The same procedure as Experiment 1 was carried out with the addition of a pulsed magnetic field (see Fig. 5) around the test-tube containing cocoa butter during stirring of the molten cocoa butter in incubator A. Stirring and torque measurements were monitored and visual texture and surface features were recorded. Powder XRD was applied to the resulting cocoa butter sample. The magnets used in each experiment are summarised in Table 1 below. Table 1 Summary of applied fields employed in Experiments 1 to 5 N-S is North-South geometry and NH is Non-homogeneous, PART 2 - CRYSTALLISATION OF COCOA BUTTER FOLLOWING MAGNETIC TREATMENT Experiment 6 - Magnetic treatment using permanent magnets Cocoa butter in a sealed 2.0cm diameter test-tube was heated at 80°C for 1 hour. The molten cocoa butter was syphoned through lm length of 4mm diameter silicon tubing at 0.12 lmin " within incubator A at 50°C from test-tube A into test-tube B as illustrated in Fig. 6. The silicon tubing passes through the centre of the permanent magnets illustrated in Fig.2. Test-tube B was exchanged with test-tube A and vice-versa, and the syphoning process repeated. This process was repeated once more resulting in the cocoa butter having passed 3 times through the permanent field. The test-tube containing the cocoa butter then undergoes the same procedure described in Experiment 1. Visual texture and surface features of the resulting cocoa butter were noted and Powder XRD was carried out on the sample. Experiment 7 - Magnetic treatment using a DC electromagnet The same procedure as Experiment 6 was carried out with the DC electromagnet in place of the permanent magnets as illustrated in Fig. 7. Visual texture and surface features of the cocoa butter were recorded. Powder XRD was applied to the resulting cocoa butter sample. Experiment 8 - Magnetic treatment using an AC electromagnet The same procedure as Experiment 6 was carried out with the AC electromagnet in place of the permanent magnets as illustrated in Fig. 8. Visual texture and surface features of the cocoa butter were recorded. Powder XRD was applied to the resulting cocoa butter sample. Experiment 9 - Magnetic treatment using a pulsed magnet The same procedure as Experiment 6 was carried out with the silicon tube passing through the centre of the pulsed magnet as illustrated in Fig. 9. Visual texture and surface features of the cocoa butter were recorded. Powder XRD was applied to the resulting cocoa butter sample. The magnets used in each experiment are summarised in Table 2 below. Table 2 Summary of applied fields employed in Experiments 6 to 9 N-S is North-South geometry and NH is Non-homogeneous. RESULTS AND DISCUSSION 1. Methodology The aim of this study was to demonstrate that applied fields enhance the crystallisation of cocoa butter. In order to perform such a task, the system illustrated in Fig. 1 was set up and the temperature regime mimicked the tempering stage of chocolate processing that is a necessary prerequisite in chocolate manufacture and results in cocoa butter in Form V polymorph. A study under these conditions easily demonstrates any variations in form but is also of much use and relevance from a production perspective. The torque stirrer is set to stir at constant speed applied using a voltage of 2.83V and the PC monitors any changes in torque. The incubator runs through a 24 hour temperature cycle in order to induce cocoa butter crystallisation. Therefore, as crystallisation commences, the viscosity of the molten cocoa butter increases and the torque required by the stirrer to stir the cocoa butter at the same speed increases i.e. torque increases with the extent of crystallisation. Several variations in temperature were applied to the cocoa butter samples during crystallisation and the regime employed in this study was suitable to obtain Form V cocoa butter. Stage 1 - Melt the cocoa butter to destroy all crystal 'memory' . This was carried out in a sealed test-tube immersed in a water bath at 80°C, ensuring that water vapour did not come into contact with the cocoa butter. Stage 2 - The test-tube containing clear molten cocoa butter was placed in the incubator at 50°C with stirring in order to equilibrate the temperature. Stage 3 - The incubator temperature was reduced to 26°C for 4 hours in order to induce crystallisation. Stirring is a vital part of this process since application of a shear force breaks up the cocoa butter seed crystals and increases their number within the molten cocoa butter thus aiding crystallisation. Stage 4 - Increasing the incubator temperature to 28 °C for 4 hours is part of the tempering process that melts out all the lower melting forms of cocoa butter leaving Form V seed crystals. Stage 5 - Re-cooling the incubator temperature to 26°C induces cocoa butter crystal growth of Form V on the seed crystals that are present in the melt. Stages 4 and 5 are repeated for 24 hours forming a cocoa butter slurry which is opaque in appearance. Stirring is removed from the cocoa butter slurry and the test-tube moved to a second incubator set at 20°C for 24 hours in order to set and to stabilise the cocoa butter, essentially locking the form in which it has set. Part 1 - The magnetic field was applied during the entire stirring process and maintained unchanged during this time. The magnetic field was therefore removed before transportation of the cocoa butter slurry to the second incubator at 20°C. Part 2 - Magnetic treatment was- carried out by passing the molten cocoa butter through tubing that passed through the magnetic field. Previous research has shown that the magnetic field effects increase to a maximum at 6 passes, therefore 3 passes was chosen since measurable effects would be expected to be observed. The molten cocoa butter was then stirred, with no magnetic fields in place, and the same temperature regime as the control applied to the samples with recording of the torque measurements. The visual appearance of the resulting cocoa butter samples gives a very good indication of the form of cocoa butter that has resulted from the temperature cycle and applied magnetic fields. Smooth, glossy, yellow texture that shines, tends to correspond to well tempered Form V cocoa butter, while white powder or a dull appearance indicates the presence of less stable forms within the cocoa butter i.e. Forms III or IV generally. The time taken to reach maximum torque can be directly removed from the torque measurements obtained during stirring at constant speed. Decrease in time taken to reach maximum torque is taken to indicate enhanced crystallisation. The resulting form of cocoa butter can be determined from powder X-ray diffraction, since each form (and mixtures) can be identified from different characteristic patterns. 2. Results (a) Visual texture Table 3 Summary of the visual appearances of the cocoa butter samples. (b) Time taken to crystallise Table 4 Summary of time taken to reach maximum torque measurements (c) Powder X-ray Diffraction results Table 5 Summary of the Powder X-ray diffraction data 3. Discussion The visual observations of the cocoa butter samples are shown in Table 3 above. There were clearly visible differences in the cocoa butter samples obtained under different applied field conditions of crystallisation. As would be expected, the Control (Expt.l) resulted in smooth, shiny and glossy cocoa butter (Form V) . In most cases the cocoa butter sample obtained was of similar quality, however there were some examples (Expts. 3, 5, 6 and 8) where there were white, powdery circular areas throughout the shiny, glossy areas of the sample. It was assumed that some lower melting forms of cocoa butter had been obtained in addition to Form V cocoa butter. In addition, Expts. 7 and 9 resulted in cocoa butter samples that were particularly glossy and shiny compared to the other samples. The time taken to crystallise, measured as the time taken to reach maximum torque, for each experiment is shown in Table 4. The Control was repeated 5 times and in each case gave the time taken to crystallise as 21 hours. This was taken to be the standard under 'no field' conditions, to which all subsequent 'applied field' experiments would be compared. In all applied field cases, under both conditions of magnetic field application, the crystallisation time is enhanced. The least affected is the cocoa butter under the AC electromagnet field conditions, which measures time to crystallise as 19 hours. Other crystallisation times from Part 1 (Expts. 2, 3 and 5 under permanent magnetic, DC electromagnetic and pulsed magnetic field conditions respectively) are 15 or 16 hours to reach maximum torque which is an enhancement of crystallisation by around 20- 30%. In Part 2, the times taken to crystallise are enhanced to a greater degree; magnetic treatment of the cocoa butter using a pulsed magnetic field shows a crystallisation time enhancement of around 20%; all other magnets enhance crystallisation time by around 30-40%. These results are very significant since processing times for tempering could be reduced. Powder X-ray diffraction is a powerful technique which identifies the polymorph of the cocoa butter. As would be expected, the Control (Expt. 1) has a XRD trace that corresponds to 100% Form V cocoa butter. Cocoa butter samples obtained from exposure to permanent magnetic fields (Expts. 2 and 6) during crystallisation also show typical 100% Form V cocoa butter data. Similarly, AC electromagnetic field exposure (Expts. 4 and 8) does not appear to alter the Form of cocoa butter obtained from Form V. The XRD data from cocoa butter obtained from Experiments 3 and 5 (DC electromagnet and pulsed field exposure respectively) are typical of mixed cocoa butter forms in the ratios indicated, which explains the white powdery morphology observed in these samples. The most interesting and possibly significant results are however, from Experiments 7 and 9 (DC electromagnet and pulsed magnet field exposure respectively) since the XRD results indicate that 100% Form VI has been obtained in both cases. This is also in agreement with the observed morphology which is particularly shiny, glossy cocoa butter samples. Conclusions Applied magnetic fields reduce the length of time cocoa butter requires to crystallise whether applied to the stirring system during crystallisation or applied prior to stirring via a flowing system, by up to 40% in some cases depending on the particular field used. The obvious advantages are to be gained in decreased chocolate production times. The cocoa butter form may be modified from Form V to VI following magnetic treatment prior to stirring which is of particular use in the chocolate manufacturing industry since the ability to produce Form VI cocoa butter in chocolate would remove fat bloom problems and could possibly enhance shelf life.

Claims: CLAIMS : 1. A process for controlling the solidification and/or crystallisation of a fat or a fat-containing food, ; characterised in that solidification and/or crystallisation is carried out under the influence of a magnetic field. 2. A process according to claim 1 wherein the fat is polymorphic. 3. A process according to claim 1 or 2 wherein the magnetic field is used to produce the fat in a particular crystalline form. 4. A process according to claim 2 wherein the fat is cocoa butter. 5. A process according to claim 4 wherein the magnetic field is used to produce the cocoa butter in form VI directly from the liquid phase. 6. A process according to claim 4 wherein the magnetic field is used to produce the cocoa butter in form V directly from the liquid phase. 7. A process according to any of claims 1 to 6 wherein the magnetic field is produced by a permanent magnet, or an electromagnet or is a radio frequency generated magnetic field. 8. A process according to any of claims 1 to 7 wherein the magnetic field is applied to the fat or fat-containing food during solidification and/or crystallisation or is used to treat the liquid or partially set fat or fat- containing food prior to completion of crystallisation. 9. A cocoa butter containing product in solid form, the cocoa butter having been formed directly from a liquid phase in crystal form IV without having passed through another crystal form. 10. A cocoa butter containing product in solid form, the cocoa butter having been formed directly from a liquid phase in crystal form IV without having passed through another crystal form and without addition of seed crystals.

Inventors: BECKETT STEPHEN THOMAS, BECKETT, STEPHEN, THOMAS
Applicants: BECKETT STEPHEN THOMAS, NESTLE SA, BECKETT, STEPHEN, THOMAS, SOCIETE DES PRODUITS NESTLE S.A.
Application year: 1999
Main classification: A23G1
IPC codes: A23D7, A23D9, A23G1, A23G3, C11B15