CZ2000936A3 - Method of controlling crystallization of sugars - Google Patents

Abstract

A method for crystallizing sugars from their solutions, which is controlled due to the magnetic field applied before crystallization and / or during crystallization. It affects the magnetic field crystal growth rate, nucleation rate, morphology, the crystallinity, size and shape of the crystals formed.

Description

Process for controlling the crystallization of sugars

Technical field

The present invention relates to the crystallization of sugars, for example sucrose, and sugar crystals obtained by this process.

BACKGROUND OF THE INVENTION

Sugars such as sucrose are used on a large scale, especially in the food and confectionery industries, and the final stage in sugar production is often crystallization from an aqueous solution, whereby the sugar is then used in crystalline form. The crystallization of sugars is a complex process that is difficult to control and so it is often not possible to predict the size and shape of the obtained sugar crystals. When crystals of a certain size and shape are desired, for example, for certain applications in the confectionery industry, it is difficult to conveniently and reproducibly produce crystals in the desired form.

Sucrose generally crystallizes in anhydrous form, although the formation of hemipentahydrate (C ₁₂ H ₂₂ 0n 2.5H ₂ O) and hemiheptahydrate (C ₁₂ H ₂₂ 0n. 3.5H ₂ O) has also been reported at low temperature (-34 ° C) crystallization (Young & Jones, J. Phys. Colloid Chem., 53, 1334-20350 (1949)). This formation of crystalline hydrates was considered to be problematic in the storage of frozen fruits, and research has been conducted to find ways to prevent their formation (Young et al., Food Research, 16, 20-29 (1951)).

Engelsen and Pérez (Carbohydrate Res. 292, 21-38 (1996) suggested, based on molecular dynamics simulation (computer modeling method) and crystallographic investigations of the sucrose / protein complex, that sucrose may exist in aqueous solution in hydrated form, but these conclusions remain controversial .

• · · · · · · · · · · ·

Research on the effects of magnetic fields on chemical processes was only sporadic. In the 1930s, it was suggested that the use of a magnetic field could remove scale from water pipes, but without a scientific basis confirming the effects of this method, the method remained controversial for many years before being experimentally confirmed approximately 50 years later (Donaldson, Tube International, January 1988, 39 and Grimes, Tube International, March 1988, 111). The effect of magnetic fields on precipitation and crystallization in inorganic systems such as calcium carbonate and zinc phosphate is believed to be nucleation and coagulation, and the effect of reducing scale formation or even removing scale already formed appears to be due to changes in inorganic solubility compounds.

In the case of organic molecules, it has been found that when benzophenone was crystallized in a strong magnetic field, the longitudinal axis direction of the formed needles tended to be oriented perpendicular to the magnetic field direction (Katsuki et al., Chemistry Letters, 1996, 607 608). With a more complex organic molecule, a substantial degree of alignment was found when fibrin was allowed to polymerize in a magnetic field and possible effects on blood coagulation were proposed in vivo (Yamagishi et al., J. Phys. Soc., Jpn., 58 (7), 2280). 2283 (1989)). It has also recently been reported that the use of magnetic fields may affect selectivity ratios in the hydrogenation of fats such as sesame oil and soybean oil catalyzed by nickel. (Jart, JAOCS, 75 (4), 615-617 (1997)).

Experiments have also been reported in which the passage of a sucrose solution through a magnetic field appeared to lower the boiling point of the solution, although a decrease in the boiling point was also observed for distilled and tap water. The magnetic field also influenced the 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). · · · • .... .... .... .... ..... .... .... ....

... ·. . · · ·· ··

- 3 fields can reduce and control scale formation in vaporizers in cane sugar production (Cole & Clarke, Int. Sugar Jnl., 98, 71-72 (1996)). None of these documents disclose or suggest that any effect on the sucrose crystals themselves may occur, Chemical Abstracts, Volume 122, p. February 20, 1985, Columbus, Ohio, USA; abstract 84104-K, S. Guo et al., Describes studies of the effect of magnetic field on sucrose crystallization (p. 155; col. 1, XP002090986. FSTA / IFIS AN 76-4-03-14 AG Gasparyants et al., "Mass crystalization from Solutions ”, XP002090985 & IZVESTIA PUBLIC DEPOSIT JOURNAL, PISHCHEVAYA TEKHNOLOGIYA, 1975, describes the crystallization of sucrose in solution under alternating magnetic and electric field conditions.

SUMMARY OF THE INVENTION

The present invention relates to a method by which the crystallization of sugars can be influenced in such a way that a particular desired crystalline product can be conveniently and reproducibly formed.

According to one embodiment, the present invention provides a method for controlling the crystallization of sugars from a solution thereof, characterized in that crystallization is carried out under the influence of a magnetic field. The solution is preferably an aqueous solution, but the invention is also applicable to solutions of sugars in organic solvents such as alcohols.

The present invention may be applied to solutions, preferably aqueous solutions of any sugar, the term "sugar" generally being used to refer to any water-soluble crystalline mono- or oligosaccharide. The sugars to which the present invention may be used are in particular mono- and disaccharides such as sucrose, glucose, fructose, lactose and sugar alcohols such as sorbitol, mannitol and erythritol. The invention is particularly applicable to sucrose. According to the present invention, it has been found that the application of a magnetic field to a sugar solution prior to crystallization or preferably during crystallization affects factors such as crystal growth rate, nucleation rate, morphology and crystallinity, and in particular may be affected as desired. the size and / or shape of the crystals produced. Having determined the particular type and orientation of the magnetic field and the way it is used, resulting in crystals having the desired properties (size, shape, etc.), the use of this field allows further production of the desired crystals with a high degree of reproducibility.

In the case of the action of a magnetic field during crystallization, an immediate effect is observed on the formed crystals. When the magnetic field is applied to a sugar solution prior to crystallization, a persistent effect is still observed if crystallization occurs in unsaturated or supersaturated solutions at different rates. The effect of the magnetic field can still be observed even if the field was applied to the solution for several hours and possibly several days before crystallization. The magnetic field is preferably used during crystallization or for solution within one hour before crystallization.

The crystallization of sugars, especially sucrose, is a process of considerable economic importance which has been carried out on a large scale for many years. Therefore, it is surprising that this method can be influenced by the method described above, especially since in the above literature concerning the application of magnetic fields to sucrose solutions, no effect on crystallization as such or on the nature of the crystals formed has been suggested.

The magnetic field used in the present invention can be used in any desired manner including permanent magnets, any type of electromagnet (such as pulse electromagnets and direct electromagnets) and magnetic fields generated by radio frequencies. The optimum field strength for a particular effect and the way the magnetic field should be used can be determined by routine experimentation in the present case.

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Both homogeneous and inhomogeneous fields can be used for this purpose.

The effect of various types of magnetic fields is discussed in more detail in the experimental work described below. In general, however, DC electromagnetic fields promote euhedral growth (a more rectangular crystalline form) and also slow crystal growth, while the number of growth centers (nucleation centers) increases with increasing field strength. Permanent magnetic fields reduce the number of growth centers with increasing field strength.

The crystallization process of the present invention is generally carried out by dissolving a sugar, for example sucrose in a solvent, preferably water, and then allowing the solution to evaporate to induce crystallization of the sugar, and applied to the solution for a suitable time before crystallization and / or during the crystallization itself magnetic field. Crystallization is generally induced by evaporation of the solvent and can be carried out at any temperature at which the solvent evaporates up to the boiling point of the solvent. In the case of aqueous solutions, a temperature of about 50 ° C is preferred, although both lower and higher temperatures up to the boiling point of the sugar solution may be used.

In the laboratory scale operation described below, crystallization is performed in Petri dishes. On a commercial scale, crystallization can be carried out in a crystallizer commonly used in the sugar industry.

The use of methods such as differential scanning calorimetry (DSC), scanning electron microscopy (SEM), polarized light microscopy (PLM) and powder X-ray diffraction (XRD) showed that, in the case of sucrose, the properties of the formed crystals are consistent with those of parts of sucrose hydrates, probably mixtures of hemipentahydrate and hemiheptahydrate, along with some anhydrous sucrose. Because the literature states that these hydrates are formed only at low levels. . * · · · · · · · · · · · · · · · · · · · · ·

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6 temperatures, it is surprising that according to the invention they can be formed at normal or elevated temperatures.

According to another embodiment, the present invention provides a process for producing a crystalline sucrose product comprising sucrose hydrate, which comprises crystallizing an aqueous sucrose solution under the influence of a magnetic field.

The invention also relates to a crystalline sucrose product comprising sucrose hydrate obtainable by the process of the invention.

As used herein, the term hydrate means a crystal containing additionally water that can be firmly bound but which is detectable, for example, by the Karl Fischer method and which can also affect the DSC curve.

The fact that the present invention makes it possible to produce sugars of the desired crystal size and / or shape more conveniently and reproducibly will be advantageous in most uses of said sugar in which the sugar is to be used in solid form instead of being dissolved. However, there are some applications in the confectionery industry where it is preferable to produce sucrose with a certain crystal size, including the following uses:

• When making chocolate candy toppings (such as the product sold under the SMARTIES® brand name), it is important that the topping has an attractive bright and shiny appearance. This appearance, which at least in part depends on the particle size of the sugar, can be controlled by the use of microcrystalline sugar, which can be produced conveniently and reproducibly by the method of the present invention.

• In other confectionery applications such as the production of fruit pastilles, troches are coatings necessary large crystals of sucrose (100 microns to 2 or 3 mm) to their special properties • • · · · · · · · i ^'··· ·· ·

7 in terms of texture and light reflectance, and these crystals can again be conveniently manufactured by the method of the present invention. According to the process of the invention, sucrose crystals of certain shapes can be produced to achieve particular desired effects.

The ability to produce sucrose as a crystalline hydrate may be advantageous in other areas of the confectionery industry. For example, the production of milk chocolate involves the formation of so-called fractions, which are a mixture of milk powder, sucrose and cocoa butter. In the manufacture of some such fragments, amorphous sucrose is formed and entrains fat, resulting in an increase in the amount of fat needed in the final chocolate recipe. Milk fat is one of the most expensive ingredients of milk chocolate and the use of crystalline sucrose, which does not capture this fat, means the possibility to reduce the amount of this expensive ingredient. Reducing the amount of fat in the chocolate would also have an effect on reducing the caloric value. In addition, sucrose represents about half of the total weight of milk chocolate, and the use of sucrose in the form of a crystalline hydrate where water constitutes up to 10% by weight of added sucrose would also reduce the calorific value of the chocolate. The use of crystalline sucrose produced according to the present invention allows a substantial reduction in the calorific value of the chocolate without any adverse effects on the taste and other properties of the chocolate.

According to another embodiment of the present invention there is provided the use of the crystalline sucrose hydrate as defined above for the production of a confectionery product, preferably chocolate.

According to another embodiment, the present invention provides a confectionery product, preferably a chocolate, comprising crystalline sucrose as defined above.

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The lactose crystallized according to the invention can be used, for example, in sucrose-free chocolate. Erythritol crystallized according to the invention can be used in low calorie chocolate.

The invention is illustrated and further supported by the following experimental work, in which reference is made to the drawings, a brief description of which will now be given.

BRIEF DESCRIPTION OF THE DRAWINGS

Giant. 1 shows the magnetic field orientation referred to in Section 1.1 (c) below.

Giant. 2 shows in part (a) wedge growth and in part (b) dendritic growth of sucrose crystals.

Giant. 3 is a diagram of the above-described sucrose crystal growth under permanent magnetic field conditions located above and below the sample.

Giant. 4 is a diagram of a device composed of a pulse magnet and a sucrose solution.

Giant. 5 shows the general euhedral shapes of sucrose crystals obtained using a DC field in case (iii) below.

Giant. 6 shows the surface texture of crystallized sucrose in the absence of magnetic field observed using SEM at a magnification of 540x.

Giant. 7 shows microcrystalline material on the surface of a 700 G permanent magnetic field sucrose crystal observed using SEM at a magnification of 470x.

Giant. 8 shows the flat surfaces of a sucrose crystal that grew in a permanent magnetic field at 80 G observed using SEM at a magnification of 65x.

• · ····· ♦ · · · · · ·

FIG. 9 shows a layered crystal growth observed on the surface of a sucrose crystal that grew in a 700 G permanent magnet field observed using SEM at a magnification of 170X.

Giant. 10 shows the surface of a sucrose crystal that grew without the presence of a magnetic field when PLM and 10X magnification were observed.

Giant. 11 shows the microcrystalline material present on the surface of sucrose crystals formed in a DC 300 G field.

Giant. 12 shows the microcrystalline material present on the surface and on sucrose crystals formed in a permanent magnetic field with an intensity of 150 G.

Giant. 13 shows flat surfaces and sharp edges shown on sucrose crystals that grew in a 400 G DC electromagnetic field.

Giant. 14 shows the flat surface and sharp edges shown on sucrose crystals that grew in a 400 G DC electromagnetic field.

Giant. 15 shows a layered growth of sucrose crystal surfaces that grew in a permanent magnetic field with an intensity of 150 G.

Giant. 16 shows a layered growth of sucrose crystal surfaces that grew in a DC electromagnetic field of 350 G.

Giant. 17 shows a DSC melting profile for sucrose control crystals ("no field").

Giant. 18 shows a DSC melting profile for sucrose crystals that grew in a permanent magnetic field at an intensity of 300 G.

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Giant. 19 shows a DSC melting profile for sucrose crystals that grew in a permanent magnetic field with an intensity of 600 G.

Giant. 20 shows a schematic representation of a device for 5 crystallization of lactose in a permanent magnetic field in parallel from the sides.

Giant. 21 shows a schematic representation of a device for crystallizing lactose in a permanent magnetic field above and below a sample.

FIG. 22 shows a schematic representation of a device for crystallizing lactose in a pulsed magnetic field.

Giant. 23 shows a schematic representation of a device for crystallizing lactose in a DC magnetic field.

DETAILED DESCRIPTION OF THE INVENTION

1. Static crystallization of sucrose

1.1.0 Experimental part

Preliminary studies

Saturated 20 sucrose solutions on a hot plate at 50 ° C were prepared in 5 cm diameter Petri dishes by adding sucrose to an unspecified amount of deionized water until more sucrose was dissolved. In cases of greater sucrose addition, a small amount of water was added to bring the sucrose into solution. Sucrose solutions in Petri dishes placed in incubators at 50 ° C were allowed to evaporate and crystallize under the different magnetic field conditions (a) to (f) below.

(a) Crystallizing sucrose was not placed in the magnetic field.

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- 11 (b) Permanent magnets with field strengths (i) of 300 G at the edges, 265 G at the center of the Petri dish (ii) 400 G at the edges, 350 G at the center of the Petri dish (iii) 640 G at margins, 540 G in the center of the petri dish (iv) 760 G in the edges, 630 G in the center of the petri dish.

(c) The permanent magnets were placed in a square configuration around a Petri dish with the field strengths shown in Figure 1.

(d) Permanent magnets were placed above and below a Petri dish with a field strength of 60 G.

(e) A pulsed magnetic field acting alternately in two directions, with the Petri dish positioned above the center.

(f) DC electromagnets with poles placed on both sides of a Petri dish with field strengths (i) 100 G at the edges, 50 G at the center of the Petri dish (ii) 320 G at the edges, 140 G at the center of the Petri dish (iii) 500 G at margins, 195 G in the center of the Petri dish (iv) 600 G in the edges, 220 G in the center of the Petri dish.

After crystallization of the sucrose solutions, visual observations were recorded and the crystals were collected and dried.

Research under controlled conditions

The experiments were performed in the same configuration as above, using the following changes to prepare the samples before placing them in the incubators.

(a) 10 ml deionized water was placed in petri dishes,

- 12 (b) 4.66 g of sucrose (about 80% saturation) was added to the water and the dish was heated on a hot plate at 50 ° C for 2 hours until completely dissolved, (c) samples were prepared without the possibility of foreign material dust by covering Petri dishes during the dissolution of sucrose.

Each experiment was repeated three times and visual observations were recorded.

Results and discussion

Results of preliminary studies of static growth of sucrose crystals

The main objective of the experiment was to create a controlled environment that could allow water evaporation from aqueous sucrose solutions, ie slow crystallization of sucrose, and to determine the effects of different magnetic fields on the crystal growth process.

Petri dishes with a diameter of 5 cm were used as vessels for crystal growth because their size allowed evaporation and crystal growth over approximately 2 days. Preliminary experiments were prepared in Petri dishes in an unmeasured amount of deionized water. Incubators were used as temperature control means and provided with a fan to facilitate evaporation to circulate air inside the incubator.

Evaporation studies have shown that supersaturation led to catastrophic solidification in the form of small rectangular crystals that formed a film along the solution / air interface within two hours. Lower satiety generally led to crystal growth in a characteristic circular fan-like configuration. Growth starts from the nucleation site and continues circularly from the center, forming individual wedge crystals with larger crystal growth areas (see Figure 2 (a)). In some cases, finer needle-shaped crystals may form and become

These will be referred to as dendritic and in which the needles do not originate from the nucleation site but from the growth site at a certain distance from the center (see Fig. 2 (b)) Since different forms were obtained from different saturations, investigations continued under controlled conditions.

Visual observations of controlled studies

1.2.2 (a) Sucrose control or "field-free" crystals

Sucrose crystals grew in the absence of magnetic field and generally formed within 24 hours. The earliest nucleation centers led to the largest circular growth averages, which were predominantly on the surface of the sucrose solution. On average, there were five nucleation centers with three larger ones, which prevailed on the surface of the sucrose solution. Smaller crystal growths, which will be referred to as secondary nucleation, are formed in the remaining solution around larger areas of crystal growth until no more sucrose / air solution remains. The crystal surfaces were generally uneven, disordered, and robust, especially in cases where crystallization from different nucleation centers occurred and were in the form of wedge growth.

1.2.2 (b) Permanent magnetic fields

The general forms of sucrose crystals obtained in permanent magnetic field studies were similar to those in a "no field" situation, ie circular growth images were generated, with slight differences.

1.2.2 (b) (i) 300 G at the edges, 265 G at the center of the Petri dish

The weakest permanent field had a similar number of nucleation centers, ie an average of 6 or 7. The largest circular growth patterns • ·

- 14 came from three nucleation centers and there were also an average of three to four smaller growth patterns from secondary nucleations. The most noticeable visual difference was in the subtle structure that formed circular patterns of growth. The crystals had a very clear appearance and were formed by many fine wedges that grew in exact lines from the nucleation site. The boundaries of the circular growth patterns were almost straight lines and there were no disorganized areas. In general, crystal growth was more ordered and had a finer structure.

1.2.2 (b) (ii) 400 G at the edges, 350 G at the center of the Petri dish

The use of a slightly stronger permanent field resulted in an average number of nucleation centers, ie an average of five. In most cases, the growth of sucrose crystals came from the four nucleation centers that prevailed on the surface of the sucrose solution. In addition to the finer structure of sucrose crystal growth observed in the case of a weaker permanent field, some flat clear wedges were also observed. Again, the boundaries between the circular growth patterns were almost straight, and generally the sucrose crystals grew more organized under these magnetic field conditions than in a "no field" situation.

1.2.2 (b) (iii) 640 G at the edges, 540 G at the center of the Petri dish

Fewer nucleation centers (on average four) were observed when crystals were growing under stronger permanent magnetic field conditions. However, as there were no secondary nucleation centers, crystal growth was based on approximately four nucleation centers, resulting in larger growth rates. The growth of sucrose crystals was subtle in nucleation centers, but the crystals became wider, flat, clear wedges as they continued to grow away from the center. On the surface of the flat wedges there was an incomplete layered crystal growth, so that these wedges appeared to be

• ·

opaque. Again, the boundaries were very uniform and the patterns of growth were more orderly than under 'no field' conditions.

1.2.2 (b) (iv) 760 G at the edges, 630 G at the center of the Petri dish

Again, fewer nucleation centers (two on average) were observed under sucrose crystal growth conditions in a stronger permanent field. With crystal growth close to the nucleation center, the sucrose crystals were fine but dendritic. Some had the appearance of overlapping wedges. Growth further from the nucleation center led to large well formed wedges with visible layered growth. The boundaries of circular growth were in the form of interlocking zigzag lines that pointed to the formation of crystal twins and were regular and flat. Secondary nucleation was limited to a very small area and was, on average, formed by growth from only one or two centers. The resulting sucrose crystals from the secondary nucleation centers were aligned and fine. In summary, growth patterns led in most cases to very ordered and large wedges with some evidence of dendritic growth.

1.2.2 (c) Permanent magnetic fields in a square configuration around the sample

The square orientation of the permanent magnets led to crystals with a more acicular shape. The growth was dendritic and therefore no wedge shapes were observed. On average, there were two large spherulitic growths and three or four smaller ones. As the diameter of the spherulitic growth began to increase, more needles began to grow and most had a width of 2-3 mm and a variable length. The boundaries between spherulitic growths resemble interconnected zigzag lines (twin growth) and are well ordered and flat. The overall impression is that it is happening • · · · · «··· ·· ·· ·

- 16 more orderly crystal growth than in a field-free situation because the crystals are clear and well formed.

1.2.2 (d) Permanent magnetic field above and below the sample

The crystal growth was again fine and ordered, with the crystals mainly consisting of fine wedges or needles. In addition, larger wedges seemed to preferentially grow in one direction (see Figure 3).

In addition, an average of three nucleation centers has been created, which is a reduction compared to the "no field" case. Some secondary nucleation has been observed in some cases, but has been limited to very small areas of growth. Circular growth boundaries had the appearance of interconnecting zigzag lines (twin growth) and were ordered. Fine, almost needle-like wedges were very clear, but large wedges were opaque due to incomplete layers of crystal growth. In summary, sucrose crystals growing under these conditions led to more ordered crystals, but growth was shown to be preferentially in one direction. Giant. 3 shows the above growth of sucrose crystals under permanent magnetic field conditions located above and below the sample.

1.2.2 (e) Pulse magnetic field

The pulse magnet is inserted into the rectangular plastic device shown in Fig. 4.

A 5 cm diameter petri dish was placed on top of the magnetic unit because it was too large to fit into a normally used square hole. Primary nucleation occurred in several cases mainly on the right side of the Petri dish, but growth on this side was slow. Secondary nucleation on the left was followed by an increased growth rate. Most of the resulting crystallization

- 17 sucrose originated on the left from an average of three or four nucleation centers in large circular wedge-shaped fans. They were more organized than in a field-free situation and had sharper edges. On the right side there were on average four or five very small fine circular wedge-shaped growths.

This result was not always reproducible and the experiment was repeated several times. On one occasion there was no nucleation on the right side, only a large wedge-shaped growth from the nucleation center on the left. Two other experiments showed small circular growth patterns, an average of ten, with slight dendritic growth.

1.2.2 (f) DC electromagnetic fields

The general forms of sucrose crystals obtained from DC electromagnetic field studies have been altered in stronger fields compared to the "no field" situation in that euhedral growth generally prevailed.

1.2.2 (f) (i) 100 G at the edges, 50 G at the center of the Petri dish

Sucrose crystals under the influence of DC electromagnetic field conditions had on average three larger circular growths that prevailed on most of the surface of the sucrose solution. These fine wedge growths showed a small amount of dendricity and had a highly ordered appearance. In addition, approximately three or four smaller circular growths were present which were finer but worse aligned with some unorganized regions. Circular growth boundaries were interlocking zigzag lines and arranged. Overall, the sucrose crystals were fine and more orderly than in a field-free situation.

• »· · · · · · · · · · · ·

1.2.2 (f) (ii) 320 G at the edges, 140 G at the center of the Petri dish

More large nucleation centers (average of five) were observed, and approximately three or four smaller circular growths were also formed under these sucrose crystal growth conditions. Generally, a greater degree of dendricity and more irregular arrangements occur in the expected circular growth patterns. Layer growth is very well seen on most wedges and the crystals are predominantly more acicular in shape due to increased dendricity. In summary, there has been an increase in nucleation, but the growth is more irregular than in the case of a weaker field, although the crystals are more ordered than in the case of "no field presence".

1.2.2 (f) (iii) 500 G at the edges, 195 G at the center of the Petri dish

Stronger DC electromagnetic fields have led to more nucleation centers (six on average) with three or four smaller growths, but the shape of the obtained crystals is worth mentioning. The nucleation centers were not point-like as in all previous cases, but they were rectangular crystals. The growth of these rectangular shapes was also rectangular with flat edges, as shown in Figure 5, and which is normally called euhedral. The crystals had a more robust appearance and apparently improved crystallinity. The ends of the rectangular growth were square in shape and the boundaries between the circular growths were straight, indicating that no crystal twins were formed. In addition, crystal growth was slower and took about twice the time to crystallize at the surface area of the sucrose / air solution. In summary, the DC magnetic field has changed the sucrose morphology, growth rate and crystallinity.

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9 ·

999 ·· ··

- 19 1.2.2 (f) (iv) 600 G at the edges, 220 G at the center of the Petri dish

The effects of this last DC electromagnetic field were emphasized under these stronger conditions. In most cases, around ten or eleven nucleation centers were observed, with euhedral growth predominating. In addition, the growth rate appeared to be even slower than in (f) (iii), with crystallization over the entire surface of the sucrose solution taking about three days. In summary, the increased intensity of the DC electromagnetic field has decreased the rate of growth, increased the rate of nucleation, changed morphology and increased crystallinity.

The results are summarized in the following table:

Table 1.2

Geometry Field type and its intensity Number primary center nucleation Number secondary center nucleation Total number of centers nucleation ON Control 3 2 5 Parallel N-S permanent (265-300G) 3 3 to 4 6 or 7 Parallel N-S permanent (350-400G) 4 1 5 Parallel N-S permanent (540-640G) 4 0 4 Parallel N-S permanent (630-760G) 1 1 2 Square (fig. 1) permanent (60-260G) 2 3 or 4 5 or 6

• 9 · * * * ·

- 20 Table 1.2 - continued

Geometry Field type and its intensity Number primary center nucleation Number secondary center nucleation Total number of centers nucleation Above and below N-S permanent (60G) 3 0 3 ON pulse 3 or 4 4 or 5 7 to 9 N-S DC electromagnetic (50-100G) 3 3 or 4 6 or 7 N-S DC electromagnetic (140-320G) 5 3 or 4 8 or 9 N-S DC electromagnetic (195-500G) 6 3 or 4 9 or 10 N-S DC electromagnetic (220-600G) 10 or 11 0 10 or 11

1.3.0 Conclusion

These preliminary results show that the growth of the sucrose 5 crystals at rest can be influenced by external magnetic fields.

Magnetic fields appear to have changed crystal characteristics such as growth rate, nucleation rate, morphology and crystallinity.

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- 21 1.4.0 Further investigations of static crystallization of sucrose in magnetic fields

Differential scanning calorimetry (DSC) was performed on a Perkin Elmer DCS7. Powder X-ray diffraction (XRD) was performed on a Philips PW 1710 diffractometer using Cu K _alpha radiation. Scanning electron microscopy (SEM) was performed on a Cambridge 5250 stereoscan. Karl Fischer (KF) titrations were performed on an Orion Research Inc tritrator. Turbo 2 Titrator

Scanning electron microscopy (SEM) was used as described above at a magnification of approximately 50 x to 500 x to determine the more detailed structure of the formed sucrose crystals. There are also some considerable differences in the surface texture of the crystals.

The field-free control samples had a very irregular surface texture consisting of sucrose beads on the surface. Poorly crystallized clusters were present and the surface had an almost amorphous texture (see Figure 6).

In contrast, all sucrose samples crystallized in the magnetic field showed a large amount of microcrystalline material (see Fig. 7). These crystals are well formed and have edges and very flat surfaces. In addition, large crystals have very flat smooth surfaces with certain angles of growth areas, as shown in Fig. 8. These surfaces also exhibited layered crystal growth that appeared opaque (or cloudy) when viewed with the naked eye (see Fig. 9).

Microscopy in polarized light (PLM) at a magnification of ten times showed similar properties of sucrose crystals. The "field-free" control samples had a lumpy irregular surface structure as shown in Figure 10, while samples crystallized in magnetic fields contained a larger amount of microcrystalline material present, as shown in Figures 11 and 12. Flat regular surfaces are shown in Figure 13 and 14 and again the layered growth in FIGS. 15 and 16.

t · ···· 9 · · ·

5. «» · • »

9 «9 *

Differential Scanning Calorimetry (DSC) provides a melting profile of sucrose crystals. Normally, the sucrose crystals are anhydrous (i.e., water-free) and melt around 180-192 ° C. The DSC record for anhydrous sucrose is shown in Figure 17. There is literature data (above) regarding the formation of hydrated sucrose, but this product was formed exclusively at temperatures of -30 to 0 ° C.

In any case, the sucrose crystallization described in the present application in a magnetic field environment appears on the DSC curve with two or three additional phenomena with a second melting point of about 150 ° C and in some cases a third melting phase of about 170 ° C. to 192 ° C. These phenomena are shown in Figures 18 and 19.

Two possible explanations for the presence of other peaks on the DSC could be (1) the formation of sucrose hydrates, or (2) the new crystalline phase of sucrose.

The weight percent moisture content of sucrose crystals was measured by Karl Fischer titrations. The supplied crystalline sucrose had a moisture content of about 0.02% by weight, while the control samples (ie, without the presence of a magnetic field) had a moisture content of about 0.06% by weight. The most significant change in moisture content occurred for a sucrose crystal growing in a permanent magnetic field (field strength of approximately 380 Gauss), with a 15-fold increase in the water content of the sucrose crystal, so that the total water content was approximately 1% by weight.

There are three possible explanations for further increasing the amount of water: (1) surface water that is weakly bound to the surface of the sucrose crystal, (2) the "areas" of captured water (water inclusion) within the crystal that would again be weakly bound to the sucrose crystal or (3) water molecules included in the sucrose crystal lattice that are very tightly held in the molecular structure of sucrose.

···

• 4-- 4 · · * tě tě 4 • 4

To eliminate the possibilities of paragraphs (1) and (2), the crushed sucrose crystals produced according to the invention were dried over phosphorus pentoxide for 40 hours to remove any weakly bound water. The resulting DSC record of the dried sucrose crystal showed melting peaks at 150 ° C and 180 ° C, demonstrating that removal of weakly bound water did not alter the melting profile of the sucrose crystal.

A solid phase proton NMR was performed on the sample to identify the nature of this water. Immediate data after crushing the sample showed a broad peak indicating weakly bound water from inclusion water, such as sucrose syrup, around 5.5 ppm. The sample crushed several days in advance would not be expected to contain water inclusions, but showed a sharper peak at approximately

5.5 ppm. This indicates water bound within the sucrose crystal.

The results of the moisture content studies therefore confirm the assumption of obtaining a new sucrose hydrate at 50 ° C.

The X-ray powder diffraction (XRD) of the sucrose crystals produced according to the invention showed a complex diffraction pattern compared to the X-ray powder diffraction data from the literature for sucrose hemipentahydrate and sucrose hemiheptahydrate. Diffraction images showed much wider off-center peaks compared to standard sucrose, with inter-plane distances d much greater and less than those for standard sucrose, and greater intensity. The diffraction patterns of the samples were consistent with the presence of a mixture of two hydrates and anhydrous sucrose. Therefore, it is more likely that sucrose hydrates have been produced by applying magnetic fields to the crystallizing samples.

· · · · · • · · · · · · · · · · · · ·· · ·· ··

2. Dynamic investigations of sucrose crystallization using magnetic fields

Research has been conducted to allow up to eight times the flow of sucrose solution through the magnetic field. After each pass, an aliquot of the solution was removed and allowed to crystallize normally under controlled temperature conditions at 50 ° C. The general visual differences in the formed sucrose crystals were similar to those observed under static conditions.

In general, DC electromagnetic fields promote euhedral growth (i.e., a more rectangular form) and appear to slow crystal growth as the number of growth centers (i.e. nucleation) increases with increasing field strength. Permanent magnetic fields appear to reduce the number of growth centers with increasing field strength, and the crystals obtained are more crystalline than the "no field" control situation.

Differential scanning calorimetry measurements show the same melting profile as for static sucrose samples confirming the formation of sucrose hydrates.

3. Preliminary studies of static crystallization of lactose

Lactose crystallization was investigated under static conditions in the presence and absence of magnetic fields. The first observations show that the magnetic fields change crystal forms. Crystals formed under the influence of a magnetic field have a white appearance and surface texture as compared to the clear, shiny white surfaces observed in control crystals obtained in the absence of the field.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ···

- 25 4. Further studies on lactose crystallization

4.0 Experimental part

A 20% unsaturated solution of α-lactose monohydrate (340.00 g, 0.944 mol) was prepared and stored in an incubator at 50 ° C. Deionized water was used for the preparation and the solvent bottle was covered to prevent contamination with foreign materials. This stock solution was carefully kept away from any magnetic fields.

ml of unsaturated lactose solution was evaporated according to the general procedure in capless petri dishes at 50 ° C in an incubator. A tray of silica gel was placed at the bottom of the incubator to absorb any excess moisture to ensure that crystallization was not affected by the moisture present in the incubator environment.

Petri dishes containing lactose solution were exposed to different magnetic fields of different intensities, which are described in more detail below.

4.1 Studies in controlled environments

A stock solution of α-lactose monohydrate was accurately prepared and stored in an incubator at 50 ° C. A series of nine experiments were performed on the solution, each experiment being repeated three times.

4.1.1 Checks

Using a pipette, the lactose solution (10 ml) was transferred to a 5 cm diameter Petri 25 dish, with the lid closed before placing in the incubator. The solution was kept in the incubator at 50 ° C until the next day when crystallization was complete.

• · · · ·

4.1.2 The weakest permanent field parallel to the sides

Permanent magnetic fields were placed in parallel on a wooden pedestal. A 5 cm diameter petri dish containing 10 ml of lactose solution was placed centrally between the magnets on another empty Petri dish (used as a pedestal for elevation). Field intensities were measured at the edges of the dish where they reached approximately 300 G and in the center of the dish where approximately 265 G was measured. The solution was allowed to crystallize overnight.

4.1.3. Permanent medium intensity field parallel to the sides

Permanent magnetic fields were placed in parallel on a wooden pedestal. A 5 cm diameter petri dish containing 10 ml of lactose solution was placed centrally between the magnets on another empty Petri dish (used as a pedestal for elevation). The field intensities were measured at the edges of the dish to reach approximately 640 G and at the center of the dish where approximately 540 G was measured. The solution was allowed to crystallize overnight.

4.1.4 Non-stronger permanent field parallel to the sides

Around the magnets used in Experiment 3, two more magnets were placed, increasing the field strength to about 760 G at the edges of the dish and about 630 G at the center. A 5 cm diameter petri dish containing 10 ml of lactose solution was placed on an empty Petri dish in the center between the magnets. The solution was kept overnight for crystallization. The arrangement used in experiments 2-4 is schematically shown in Figure 20.

··· ··· ···· ····· ·· ·

- 27 4.1.5 Permanent field above and below the bowl in parallel

The wooden block with the strongest permanent field arrangement was turned to the side and a petri dish with a lactose solution (10 ml) was placed centrally between the parallel magnets on the raised paragraph.

The field strengths measured for the sample were approximately 630 G. The solution was then allowed to crystallize overnight. The arrangement used is shown schematically in FIG. 21.

4.1.6 Pulse field io The pulse magnet flowing through the water was placed to the side and a petri dish containing a lactose solution was placed on its top in a balanced manner. The solution was then allowed to crystallize overnight. The arrangement is shown schematically in FIG. 22.

4.1.7 The strongest DC electromagnetic field

A DC solenoid was inserted into the incubator, with connecting wires and tubing extending through the side opening in the incubator. The water circulation system has been set so that the DC magnet does not overheat. The field strength of the electromagnet was

600-220 Gauss and a petri dish containing a lactose solution (10 ml) was placed on an elevated pedestal between the two poles of the magnet. The solution was allowed to crystallize overnight.

4.1.8 Weakest DC electromagnetic field

The measured field strength of the electromagnet was 50-100 Gauss and a petri dish containing a lactose solution (10 ml) was placed on an elevated pedestal between the two poles of the magnet. The solution was allowed to crystallize overnight.

• · · · · · · · · · · ·

- 28 4.1.9 Medium intensity DC electromagnetic field

The measured field strength of the electromagnet was 160 to 420 Gauss, and a petri dish containing a lactose solution (10 ml) was placed on an elevated pedestal between the two poles of the magnet. The solution was allowed to crystallize overnight. The arrangement used in experiments 7 to 9 is schematically shown in Fig. 23.

4.2 Results and discussion

4.2.0 Introduction

The purpose of the studies was to investigate the effects of applied fields on the crystallization of lactose under static conditions in a controlled temperature and humidity environment. A 20% unsaturated solution was used to prevent crystallization from occurring too quickly and to allow an optimal effect of the applied fields on the lactose solution.

The following five methods were used to determine the morphology, size and properties of field-crystallized lactose solutions:

1. visual observation

2. differential scanning calorimetry

3. X-ray powder diffraction

4. scanning electron microscopy

5. Karl Fischer titration

The lactose crystals were removed from the petri dishes and visual observations were made with no changes in brittleness or strength observed, and the crystals were placed for drying in a Buchner funnel on a sintered glass. The crystals were then stored in sample tubes at room temperature before performing the other four methods.

· · · · · · · · · · · · · · · · · · · · · · · · · ·

- 29 4.2.1 Visual observation

Visual observations made to the naked eye are summarized in the following table.

Table 4.2.1

Sample Observation of crystal morphology 1 (2) 1 (2) Fragile, white-gray color indicates presence α-lactose monohydrate 2 (2) 2 (2) Similar results to Experiment 1 but crystals they were somewhat more fragile, again a white-gray color 3 (2) 3 (2) White-yellow color, two distinct layers are seen. The bottom layer was crystalline and glassy with thin "Gaps" in the macroscopic structure. Top layer it had a rough texture. The phase between these layers was highly crystalline. 4 (2) 4 (2) Similar observations to experiment 3. 5 (2) 5 (2) Similar to Experiments 3 and 4, the crystals were thin and covered with bark on the edges with uneven top surface. Again, small ones were observed gaps / joints, especially on the bottom layer. The crystals were more brittle than the crystals observed in experiment 4. 6 (2) 6 (2) Observations similar to experiment 5. (7) (7) (7) Similar observations as in Experiment 5, but the crystals were brittle, fine and powdered and very difficult to remove from the petri dish. 8 (2) 8 (2) Observations similar to experiment 7. 9 (2) 9 (2) Observations similar to experiment 8.

• ·

The first observable change was a change in color. Controls appeared glassy gray, while samples crystallized under the influence of the embedded field had a "whiter" appearance. Samples exposed to the permanent field in parallel on the sides (Experiments 2 (1) to 4 (3)) were visually similar to controls except for slight color change and increased brittleness. Experiments conducted using a permanent magnet placed above and below the sample (experiments 5 (1) to 5 (3)) and a pulse magnet with water flow (experiments 6 (1) to 6 (3)) yielded even more fragile crystals with a coarser texture. The DC electromagnetic field (experiments 7 (1) to 9 (3)) resulted in a very brittle and powdery crystal.

The results show that the crystallinity of α-lactose monohydrate is improved and well-formed discrete crystals and less amorphous glassy lactose are achieved. The increased brittleness could be attributed to a more structured structure, which in turn leads to better crystal splitting, in addition to less amorphous glassy lumps within the crystal.

Differential Scanning Calorimetry (DSC)

DSC provides thermal analysis of lactose crystals under controlled heating to obtain a melting profile. The results are shown in the following table, which gives the melting point in degrees Celsius for each of the three samples in each experiment.

• · · ·

Table 4.2.2

Exper. Sample 1 Sample 2 Sample 3 1 150.9 142.6, 252.0 139.7, 150.5 2 141.3, 150.8 143.2, 152.9 143.3, 150.7 3 142.0, 150.0 143.0, 151.7 145.0, 219.7 4 143.0, 150.5 142.7, 151.5 144.5, 150.2 5 148.2, 151.8 145.0, 150.6 141.2, 150.4 6 144.9, 218.2 143.0, 150.0 143.4, 219.2 7 143.0, 149.9 142.9, 216.5 143.4, 219.2 8 148.5, 221.2 143.8, 150.8, 198.0 142.2, 149.7 9 143.2, 148.6 141.2, 149.1 142.1, 217.7

The results from the literature show that α-lactose monohydrate has a melting point of -143 ° C to -147 ° C and -209 ° C, which decomposes in parallel with melting, and β-lactose has a melting point of -236 ° C. Most of the experimental results obtained correspond to the melting point of alactose, whereas in a smaller number of samples a melting peak was obtained at a higher temperature at -219 ° C, a feature of β-lactose. In particular, most experiments showed two melting peaks, one at 142 ° C and the other at -152 ° C, indicating α-lactose. Some samples exposed to medium intensity permanent field (experiment 3 (3)), pulse field (experiments 6 (1) and 6 (3)) and DC field (experiments 7 (2), 7 (3), 8 (1), 8 (2) and 9 (3)) showed a higher melting point at -219 ° C in addition to the melting point at -140 ° C, indicating the presence of β-lactose in the crystal. These observations may be explained by the mutarotation properties of lactose and, in particular, by the fact that α-lactose monohydrate is converted by mutarotation to the β-lactose form until equilibrium is reached, at ··

- 32 which is a higher concentration of β-lactose. The sample shows that β-lactose crystallizes together with α-lactose in some cases because higher melting points of -219 ° C are measured.

4.2.3. X-ray diffraction (XRD)

The characteristic inter-plane distances d of the different forms of lactose crystals are given in the following table:

Table 4.2.3

Structure of lactose Characteristic distances d (AND) Α-lactose monohydrate 4.43, 4.64, 5.39 Β-lactose anhydride 4.24, 4.63, 8.41 Unstable α-lactose anhydride 4.13 4.63, 4.93 Stable α-lactose anhydride 3.82, 4.21, 4.56 α-lactose + β-lactose (5: 3) 4.04, 4.42, 4.65

λ 1 A = 0.1 nm

Detailed XRD data are not shown, but the images produced were most likely α-lactose monohydrate, with characteristic peaks consistent with the observed peaks. Characteristic peaks from other lactose structures did not correlate well with the observed images, and this excludes the possibility that the structure of the crystals found could be the β-form of the α-anhydride or a mixture of both isomers.

Considering standard crystalline forms, it can be concluded that all samples are likely to be α-lactose monohydrate.

• · · ·

However, the results do not exactly match those reported in the literature where the inter-plane distances d are somewhat greater or less than expected. For example, in Experiment 1 (1), a distance d of 6.91 Å was obtained instead of 7.08 Å, and for Experiment 1 (2) a value of 7.23 Å was obtained (again instead of 7.0 Å). Further examples are Experiment 3 (1) where 5.37 Å was obtained instead of 5.41 Å and Experiment 4 (2) where 5.51 Å was obtained instead of 5.41 Å. It should be emphasized that these differences were only observed for values around 7.08 Å and 5.41 Å, while other results appear to correlate well with those reported in the literature.

Differences in the inter-plane distances d could indicate a change in the inter-plane distances due to the incorporation of water into the lactose crystal, although in this case it would be expected that the distances d would in all cases be greater instead of fluctuating around the actual value. The possibility of inaccuracy of the X-ray powder diffraction equipment cannot be excluded.

4.2.4 Scanning Electron Microscopy (SEM)

The lactose solution crystallized on two different interfaces, namely:

• solution / glass interface where the lactose solution was in contact with the petri dish • solution / air interface where the lactose solution was in contact with the air and is generally amorphous.

These areas were examined in the same way as the third area:

Solution crystals wherein the lactose solution crystallized between the two interfaces.

Individual SEM images are not shown.

• · ··· ··· ··· ····· ·· · ·· · ·

- 34 4.2.4.1 Solution / glass interface

In all cases where crystallization occurred in the magnetic field, there was less amorphous material at the solution / glass interface that was better defined and more acute compared to controls. Experiment 1 consisted of flocculent layers of block crystals where the surface appeared to be completely textured. Experiment 2 showed longer, flatter and more crystalline structures than the crystals observed in Experiment 1, growing in the direction of field lines. The crystals observed in Experiment 4 were well defined with sharp-edged shapes and contained a reduced amount of amorphous material in their vicinity than controls. Experiment 5 provided "block" crystals with large flat surfaces, and the growth appeared almost layered. More defined, more separate, flat, sharp-shaped crystals were observed in experiment 7, and more flake layers and less amorphous material were observed compared to controls. Experiments 8 and 9 showed similar results as in Experiment 7.

4.2.4.2. Solution / air interface

The solution / air interface shows a more crystalline, fibrous material that is almost amorphous with crystalline regions for all magnetic fields compared to control. Experiment 1 showed that the amorphous material has some form in the shape of a fan. In Experiment 2, less amorphous material was observed, as indicated by more crystalline areas on the surface. In Experiment 6, long, fibrous formations were formed on the surface, and compared to the control, the samples had some texture and well formed fibrous crystals. Aligned block crystals on the surface showing a similar direction on the elongated axis were observed in experiment 7 and the surface was not amorphous as in the controls. Experiment 8 showed crystals with long fan-like formations that appeared fibrous. Non-amorphous but acicular or fibrous crystals were observed in experiment 9.

«4« · · · · · ·

4 4 · 4 · · · · · · · · · · · · · · · · ·

- 35 4.2.4.3 Crystals formed from solution

Elongated, platelet-like crystals were observed in all samples in the magnetic field, especially those in the DC fields. In experiment 1, crystals with a regular, cubic shape with flat surfaces and sharp edges, covered with amorphous material, were shown. Experiment 2 gave crystals less defined than controls with rounded edges coated with amorphous material. Well defined and angular shapes with predominant layers were observed in experiment 4 and also appeared to contain less amorphous material than controls. Experiment 6 showed that crystals are better shaped with flatter and more acute surfaces than crystals in the case of controls. Experiment 7 produced crystals that were longer and more layered with less amorphous material than the controls. Experiments 8 and 9 again showed layer formation with elongated and well formed crystals.

In general, more crystallized crystals with less amorphous coating were obtained by crystallizing the solutions under the influence of magnetic field. In addition, the formation of elongated crystals was observed in samples crystallized under the influence of magnetic fields as compared to the more random form of crystals visible in the control experiments.

4.2.5. Karl Fischer titration (KF)

The expected moisture content of α-lactose monohydrate is 4.9997% by weight. Each sample was titrated three times and the mean percentages by weight and standard deviation were calculated. Data for individual samples not shown.

• · ···· · · · · · · · · · · · · · · · · · · · · · · ·

Experiment 1 (control) showed mean values from 5.34 wt% to 5.42 wt% with a standard deviation of ± 0.10 wt%. If the mean values of the water contents in percent by weight (taking into account the standard deviation) are within this range, the results of the moisture content measurement are not considered to be significantly different. In general, the rule is to extend the limits to two standard deviations.

The titration results show that samples crystallized in DC fields increase the moisture content around

7.5-11% by weight compared to controls, and permanent fields (above and below) show an increase in moisture content of ~ 7% by weight. Other samples did not have a significantly higher moisture content.

In addition to measuring additional water in the lactose molecule, X-ray powder diffraction results confirm that in all cases a crystalline form of α-monohydrate is obtained.

Conclusions

Obviously, the magnetic fields affect the crystallization of lactose, and a summary of all results is shown in Table 4.2.6 below. X-ray powder diffraction and KF titration show that the crystal form does not change using fields and remains as α-lactose monohydrate. The crystallinity of the lactose crystals increased, ie well-formed, brittle and powdered crystals were produced in the presence of magnetic fields in the lactose solution during crystallization. SEM results showed layer formation and different morphology, with crystals longer and regular instead of uneven blocks, as seen in the controls. The amorphous crystal content was reduced using a magnetic field. Karl Fischer titrations show the presence of additional water in the lactose crystal when the solution is exposed to magnetic fields. Water may be strongly bound in the crystal lattice or weakly bound as water inclusions. X-ray powder diffraction did not rule out any of these possibilities.

• · · · · · · · · · · · · · · · · · ·

- 37 Table 4.2.6

DSC (° C) XRD PULL KF 2 (1) 150.9 a-1 m Solution / glass - block 5,395 1 (1) 142.6, 152.0 ot-1 m flake crystals 1 (2) 139.7, 150.5 a-1 m layers. Solution / air - amorphous surface, some form shaped fans Crystals from solution - regular, flat surfaces with sharp edges with an amorphous coating. 2 (2) 141.3, 150.8 cc-Ι m Solution / glass - observed longer 5,411 2 (2) 143.2, 152.9 a-1 m crystals. 2 (2) 143.3, 150.7 a-1 m Solution / glass - less amorphous material on the surface in compared to controls. Crystals from solution - crystals have less form than controls. 3 (2) 142.0, 150.0 a-1 m Solution / glass - discreet, well 5,674 3 (2) 143.0, 151.7 a-1 m formed amorphous crystals 3 (2) 145.0, 219.7 a-1 m material in the gaps. Solution / air similar to 2 (2). Crystals from solution - well defined crystals with a certain amorphous material.

«· •« * * * «« «« «•« ««

4 (2) 143.0, 150.5 α-Ι m Solution / glass - well formed 5,532 4 (2) 142.7, 151.5 α-Ι m Sharp crystal with 4 (2) 144.5, 150.2 α-Ι m considerably less amorphous material. Solution / air - similar to 2 (2). Crystals from solution - well created, with sharp edges shapes, prevailing layers. 5 (2) 148.2, 151.8 α-Ι m Solution / glass - almost layered 5,758 5 (2) 145.0, 150.6 α-Ι m grow. 5 (2) 141.2, 150.4 α-Ι m Solution / air - certain amount of amorphous material on the surface. Crystals from solution - well formed crystals with a certain amorphous material. 6 (2) 144.9, 218.2 α-Ι m Solution / glass - regularly 5,634 6 (2) 143.0, 150.0 α-Ι m shaped, sharp-edged crystals 6 (3) 143.4, 219.2 α-Ι m with flat surfaces. Solution / air - very fibrous Surface. Crystals of solution - well shaped, flat, sharp-edged surfaces with a certain amount layers.

• * f · i * r · · · · <* * <<<

··· ··· · · «•» »»

7 (2) 143.0, 149.9 α-1 m Solution / glass - discreet, well 5,813 7 (2) 142,9, 216.5 α-1 m shaped crystals with 7 (3) 143,4, 219.2 α-1 m flocculated layers of material. Solution / air - arranged blocks with growth in one direction on the extended axis - they are not amorphous. Crystals from solution - very layered, with elongated shapes, a small amount of amorphous material. 8 mm (1) 148,5, 221.2 α-1 m Solution / glass - well formed, 5,868 8 mm (2) 143,8, 198.0 150.8 α-1 m flat, sharp-edged crystals - very little amorphous 8 (3) 142,2, 149.7 α-1 m material. Solution / air - fibrous, fronds - no longer amorphous. Crystals from solution - well shaped, discrete layered crystals. 9 (1) 143,2, 148.6 α-1 m Solution / glass - well formed, 6,092 9 mm (2) 141,2, 149.1 α-1 m acute crystals with small 9 (3) 142.1, 217.7 α-1 m amorphous material. Solution / air - crystalline, acicular layers - they are not amorphous. Solution crystals - elongated, defined crystals with formation layers.

9909 • 9 0900

0 «

9 0 0 »3 0

0 0 0 »0 * 0

-40 KF = Karl Fischer titration (% by weight) ct-1 m = α-lactose monohydrate

5. Production of milk chocolate

Following (under the name “old prescription”) Jackson's milk chocolate recipe in “Industrial Chocolate Manufacture and Use”, Blackies, 1988, p. 254, Table 13.5, along with a modified recipe (under the name “with sucrose hydrate”) uses sucrose hydrate containing 10% by weight of water.

Composition in percent old prescription with sucrose hydrate Cocoa mass 12 11.4 Milk powder 14 13.3 Sugar 52.25 49.8 Added cocoa butter 21.35 20.3 Lecithin 0.3 0.3 Water in hydrate 5.0 Calories / g (calculated) 5.5 (34 J / g) 5.2 (32.2 J / g)

Chocolate may be made by conventional methods, for example as disclosed in the above reference publication. Calorie / gram values are calculated on the following basis: fat 9 cal / g (55.7 J / g), carbohydrates and proteins = 4 cal / g (24.7 J / g) and assuming the presence of approximately 2.5% by weight of pulp.

Claims (11)

PATENT CLAIMS A method for controlling the crystallization of sugars from their solutions, 5, characterized in that the crystallization is carried out under the influence of a magnetic field. 2. A process according to claim 1, wherein the solution is an aqueous solution. Method according to claim 1 or 2, characterized in that sucrose, glucose, fructose, lactose, sorbitol, mannitol or erythritol and mixtures thereof are used as the sugar. 15 Dec Method according to claim 1 or 2, characterized in that sucrose is used as the sugar. A process for the production of a crystalline sucrose product comprising sucrose hydrate, characterized by: 20 comprising crystallizing an aqueous solution of sucrose under the influence of a magnetic field. Method according to one of claims 1 to 5, characterized in that the magnetic field is applied to the sugar solution 25 prior to crystallization and / or during crystallization to affect crystal growth rate, nucleation rate, morphology or crystallinity. • ·· ······ - 42 Method according to any one of claims 1 to 5, characterized in that the magnetic field is applied to the sugar solution before crystallization and / or during crystallization to influence the size and / or shape of the crystals formed. Method according to one of Claims 1 to 7, characterized in that the magnetic field is applied by means of a permanent magnet, an electromagnet or a radio-frequency generated magnetic field. A crystalline sucrose product comprising sucrose hydrate obtainable by the process of any one of claims 1 to 8. Use of the crystalline sucrose hydrate product according to 15 of claim 9 for making a confectionery product. A confectionery product comprising the crystalline sucrose product of claim 9. A confectionery product according to claim 11 which is chocolate.