The crystallization of sugar seems to be a widely investigated topic but nevertheless in practice there are still some difficulties (unresolved issues). The application of sugar in the food industry is often as one component in a complex mixture. New ingredients are often used during the development of new products. This replacement or addition of new ingredients can change the product properties and the manufacturing process in a desired or undesired way. These can lead to problems during the production of e.g. confectionaries.
The influence of hydrocolloids on the crystallization of sugar has been investigated because they are potential additives which certainly change the rheological properties of products.
The coating of food is often realized by the use of an additional production step. The aim of the work was to reduce this additional production step and to realize the coating and shaping of e.g. gel materials at the same time. The combination of the processes of crystallization and the formation of gels was successfully implemented on the basis of commercially available products with an outer crystallized sugar layer and a liquid core inside. Changes in the process and also in the product, which occur through the use of different hydrocolloids, have been identified. The used hydrocolloids are thermo-reversible like e.g. gelatin, agar or carrageenan. The use of different types of hydrocolloids and different amounts shows significant influences on the crystallization of sugar.
The results of this work show different aspects, which help to avoid difficulties while crystallizing sugar in the presence of hydrocolloids. The properties of the initial hydrocolloid-sugar solutions containing different types and amounts of hydrocolloids were investigated.
Beside the pH-value, the knowledge on the supersaturation (sugar concentration in Brix%), nucleation, solubility as well as on the viscosities (at temperatures > 70 °C) play an important role while crystallizing highly viscous supersaturated solutions. Effects of hydrocolloids on crystalline sweets (end products) were evaluated by determining the sugar decrease within the gel core over time, layer thickness measurements, stability measurements of the end products, storage stability evaluation as well as the proof of the purity of the crystallized layers. Beside the composition of the end product also the use of different seed materials has got an influence on the shaped and crystallized end products. The properties of the used seed materials (size, surface and moisture content) are important to enforce the crystalliza-tion of sugar.
Neutral conditions (with respect to pH) are beneficial because inversion of sugar and degradation of macromolecules of hydrocolloids is prevented. The viscosity is increased by the use of hydrocolloids. A strong increase in the viscosity (at 70 - 110 °C) of a sugar solution was shown by the application of ι-carrageen. Gelatin shows the smallest viscosity increase
96 (70 - 100 °C) compared to the other tested hydrocolloids. These texture changes due to the application of hydrocolloids can lead to problems (tailing) during the filling of the solutions into the powder molds. It is therefore important, to avoid these problems by a suitable controlling of the temperature.
The measured sugar concentration of the initial sugar solutions with hydrocolloids is slightly increased due to water evaporations during the production process. But generally, this water evaporation can be avoided by a closed system. Furthermore, the decrease of the sugar concentration within the gel core is slower than without the application of hydrocolloids. The mass transport within a three-dimensional network of a gel is hindered and therefore slowed down. The solubility (metastable zone) of a sugar solution with gelatin and ι-carrageen is shifted to lower temperatures whereas the use of agar and κ-carrageen shows only little effects on the metastable zone. The changed solubility of sugar in a gelatin containing solution affects the formation of crystallized layers. A shift to lower temperatures means a higher solubility of sugar in the three-dimensional network of gelatin and therefore a lower amount of sugar can crystallize. The resulting layer thickness is thinner than for products without gelatin. A contrary effect was shown for the layer thicknesses of agar. The layer thicknesses are thicker due to detectable incorporations of agar cluster within the crystallized layer. The proof of gelatin and carrageenan was successful. Mostly, the addition of all hydrocolloids leads to unpure crystallized sugar layers. The detectable occurrence of hydrocolloids in the crystalline sugar layer can explain the reduced storage stability. End products produced with hydrocolloids show an increased loss of water during storage time.
Therefore, the products lose their initial nature and properties. The layer crystallizes further during the storage time due to a loss of solvent and the gel core decreases in volume till no loss of water is possible anymore. Therefore, it is essential to protect the end product against the loss of water by e.g. additional coating with chocolate or wax as well as the enabling of constant storage conditions (temperatures and humidity).
The conventional used corn starch as a powder for shaping of gel articles as well as for the production of crystallized sweets (crust pralines) can be altered by other materials.
Therefore, different starches, powdered sugar and flours were tested as seed materials to enforce the crystallization. Beside the used materials (hydrocolloid types and sugar) the used external seed material has got an effect on the end products. Particle size (< 10 µm), moisture content (< 6 %) and surface appearance of the seed particles have to be controlled to achieve an enforced, desired crystallization of the supersaturated sugar solution as well as good shaped end products. The crystallization can thus be triggered in a uniformly, controlled and reproducible way. Round and big particles lead to worse crystallizing and shaping results than small and edged seed material particles. Too high moistures within the seed materials (> 10 – 15 %), however, are not beneficial.
Summary
97 The knowledge on the influence of additives (hydrocolloids) on the crystallization of sugar, especially, in confectionary industries is demonstrably essential.
In summary can be said, that the scientific problems:
1. The combination of crystallization of sugar and the gelation of hydrocolloids in one production step,
2. Description of changes during the crystallization process of highly viscous supersaturated sugar solutions (especially, for a coating purpose) in the presents of hydrocolloids (agar, gelatin and carrageenans), with the clarification of the effects of hydrocolloids on:
2.a: The liquid phase by changes in the diffusion process (slower molecule transportation) and
2.b: The solid phase that means the formation of crystals (installation kinetics with effects on the purity of the layers),
3. The enforcement of the nucleation process in the crystallization of high viscous supersaturated sugar solutions by external seed materials,
could be described and solved successfully, based on crystalline coated gels (end products).
The results lead to a summary of important product properties, which are achievable and desired as well as process parameters, which can be adapted. These important parameters, which should be controlled during the production of crystalline coated gels, are e.g.
temperature, time, supersaturation, viscosity and texture properties, layer thicknesses of the crystallized material, as well as storage stability after the production of the end products by e.g. detecting the weight losses (syneresis quantification). Only a testing of different process parameters and adjusting them according to the used materials leads to a consistent product quality.
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