4 Starch solutions

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4 Starch solutions
Starch and starch derivatives are almost without exception used in swollen or dissolved form7. It is therefore not surprising that a good description of the characteristics of solutions is very important for the starch industry.

4.1 Viscosity, texture and transparency of starch solutions In order to dissolve potato starch well, drastic circumstances are needed as regards the temperature (>100C and under high pressure or a short heating period up to 160C). Moreover a certain amount of water is needed to hydrate the starch completely. Very well dissolved potato starch in contents of up to 30% (30 g per 100 ml) is crystal clear. The solutions are fairly stable in time i.e. the viscosity of the solution only changes slowly in time. In 4.3 more extensive details are provided of the stability of the starch solutions. When the boiling step has been less effective, there can be molecular clusters present in the solution. Due to these clusters, spacial networks, formed by different starch molecules and internally filled with large quantities of water, the transparency decreases; a characteristic of non-homogeneous (anisotropic) systems. The viscosity of such a solution is higher than that of the perfect starch solution. In comparison with the perfect starch solution less well dissolved starch is less stable. The clusters are also responsible for this: With a moderate cooking process there even remain (strongly swollen) grain fragments in the solution. The solution is more transparent than clear. The grain fragments can be noticed as a structure in the solution. The surface is not smooth but has an apple sauce like appearance8. At the point when the highest viscosity is developed, the solution mainly consists of very strongly swollen grains. The solution formed, flows badly. Some of this product sticks to a spatula which is pulled from such a solution without having contact with the solution. This characteristic is called short. At this point the external features of the moderately boiled mixture (texture) drastically differ compared to the well dissolved starch. Very well boiled (dissolved) starch flows easily and forms long threads between the solution and the spatula which is pulled out of the solution. We call this a long character. This flowing behaviour can be explained by realising that the molecules are completely hydrated in perfectly dissolved starch and that they are situated in a continuous phase, generally water. Although there is certainly mutual interaction, the molecules easily flow past each other. In the case of not very well dissolved starch not all interactions which were present in the grain between the molecules, have been broken off. These clusters of polymers absorb as much water as they can and thus form highly concentrated solutions within a solution. The clusters hardly have any interaction. The result is an incoherent starch solution. When boiled badly (heating), the grains do not even fully swell. The solutions can be white and turbid and have a pasty external appearance at a sufficiently high concentration. Lower concentrations can even sag without stirring.

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4 Starch solutions

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The grain starches are even more difficult to dissolve than potato starch. In chapter 3 a number of causes for this were mentioned such as phosphate and the fat content. Moreover the fats will easily form complexes with the well dissolved amylose molecules. This is the reason why grain starches form turbid solutions, in which not only amylose-fat complexes but also grain structures can be found. Picture 1 Picture 2

4.2 Influence of stirring When stirring takes place in a potato starch/water mixture while the temperature is kept at a constant 90C, the viscosity reduces. This can be ascribed to the fact that the fragile, strongly swollen grains, which form the mixture with a maximum of viscosity , are destroyed by the stirring. The effect of the viscosity change as a result of stirring, caused by the break down of large macro-molecular structures, is called structure viscosity. After treatment the solutions have a smoother, less apple sauce like appearance. In not fully disperged solutions the viscosity will increase due to stirring, because the clusters which have not yet swollen are destroyed by rubbing and end up in the water together with the larger macro-molecular structure. In perfect solutions, in which macro-molecular structures no longer occur, stirring therefore causes no change in the viscosity. Still, at extremely strong stirring, we do see the viscosity decreasing. This can be ascribed to chain breach. A glucosidic compound breaks, causing smaller molecule fragments to remain.

4.3 Stability of starch solutions From 4.2 we know that potato starch which has been molecularly dissolved, is crystal clear. The grain starches such as maize and wheat starch are turbid as a result of the presence of insoluble amylose-fat complexes, which diffuse the light. A starch solution prepared by heating is not stable. During the change which occurs two processes can be distinguished: - When we prepare a diluted solution of potato starch and we slowly let this solution cool, a turbidity slowly appears in the initially crystal clear solution, which in the long run forms a white sediment. - A more concentrated solution which moreover cools down more quickly, forms a gel. In the beginning this gel is turbid and flexible, but eventually it becomes white and hard. In figure 4.1 both proceses, known as the retrogradation of starch, are schematically represented.

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Figure 4.1 In retrogradation processes amylose plays the most important role. The regular structure enables this polymer to form H-bridges over large parts of the molecule together with other amylose molecules. For a firm network it is necessary to form many H-bridges. During the first proces (slowly cooling) the amylose has all the time it needs to enter into the energetically most favourable interactions. We call such a process thermodynamically determined. The amylose molecules can mutually form H-bridges in the full length of the molecule. Building in water hardly plays a role in this. The amylose agglomerate is insoluble. The process is virtually irreversible; only at a very high temperature (160C) does it dissolve again. The retrogradation speed appears to depend on the chain length as figure 4.2 reveals.

Figure 4.2 At an increasing chain length (DP, degree of polymerisation), the number of H-bridges increases, enabling the forming of enough firm agglomerates. From a certain chain length however, the polymer encounters difficulty to find the optimal conformation (for amylose a parallel orientation of the chains) which reduces the tendency to aggregate again. In the second process (quick cooling, forming gel) time lacks for an optimal conformation. H-bridges are made as soon as the possibility is there. As there is an abundancy of water, the majority of this is incorporated into the network via H-bridges. Other molecules can be captured as well. The gel forming is reversible, i.e. at heating it dissolves again. Table 4.1: characteristics of starch solutions

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viscosity potato maize wheat waxy maize very high medium low-medium medium-high

texture long short short long

transparency clear opaque turbid clear

stirring proof low-medium medium medium low

v retrogradation medium high high very low

Picture 1 Picture 2

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