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Food Products using the Alginate/Calcium Reaction

CONTENTS
THE ALGINATE/ CALCIUM REACTION . . . . . . . . . 35 STRUCTURED FRUITS . . . . . . . . . . . . . . . . . . . . . . . . . 6-8 STRUCTURED VEGETABLES . . . . . . . . . . . . . . . . . 8-10 STRUCTURED MEAT & FISH . . . . . . . . . . . . . . . 10-12 WATER-BASED DESSERT GELS . . . . . . . . . . . . . . 12-17 MILK-BASED PRODUCTS . . . . . . . . . . . . . . . . . . . 17-18 STRUCTURED POTATO PRODUCTS . . . . . . . . . 18-22 APPENDIX . . . . . . . . . . . . . . . . . . . 22-23 TECHNICAL SERVICE . . . . . . . . . . .23

2 ISP Food Ingredients Alginate/Calcium Reaction

The Alginate/Calcium Reaction

e term algin is used to describe alginic acid and its various inorganic salt forms, which are derived from brown seaweeds (Phaeophyceae). e monovalent salts, often referred to as alginates, are hydrophilic colloids and these, especially sodium alginate, are widely used in the food industry. In a great number of food applications, the now well-known reactivity of alginates with calcium ions is utilized. Although this reaction has been known for over a century, its true potential as a structuring agent for food systems has not yet been fully realized. e purpose of this brochure is to highlight the state of the art in the application of the alginate/calcium reaction in structured foods and, in so doing, provide a strong technical base from which new product opportunities can evolve. Since sodium alginate is the normal starting material for this reaction, the terms alginate and algin can be taken for the purposes of the discussion to be synonymous with sodium alginate. Alginate is a linear co-polymer composed of two monomeric units, D-mannuronic acid and L-guluronic acid. ese monomers occur in the alginate molecule as regions made up exclusively of one unit or the other, referred to as M-blocks or G-blocks, or as regions in which the monomers approximate an alternating sequence. e calcium reactivity of alginates is a consequence of the particular molecular geometries of each of these regions. e shapes of the individual monomers are shown in Figure 1. e D-mannuronic acid exists in the 1C conformation and in the alginate polymer is connected in the `-con guration through the 1- and 4-positions; the L-guluronic acid has the 1C conformation and is _-1, 4- linked in the polymer. Because of the particular shapes of the monomers and their modes of linkage in the polymer, the geometries of the G-block regions, M-block regions, and alternating regions are substantially di erent. Speci cally, the G-blocks are buckled while the M-blocks have a shape referred to as anextended ribbon, as shown in Figure 2. If two G-block regions are aligned side by side, a diamond shaped hole results. is hole has dimensions that are ideal for the cooperative binding of calcium ions. When calcium ions are added to a sodium alginate solution, such an alignment of the G-blocks occurs; and the calcium ions are bound between the two chains like eggs in an egg box, as shown in Figure 3. us the calcium reactivity of alginates is the result of calcium-induced association of the G-block regions. Depending on the amount of calcium present in the system, these inter-chain associations can be either temporary or permanent. With low levels of calcium, temporary associations are obtained, giving rise to highly viscous, thixotropic solutions. At higher calcium levels, precipitation or gelation results from permanent associations of the chains. Many of the structured foods discussed in this brochure utilize alginate gelation.

Figure 1. D-mannuronic Acid and L-guluronic Acidthe align monomers.

Figure 3. Egg box for alginate gelation.

Figure 2. Block shapes in alginates.

ISP Food Ingredients Alginate/Calcium Reaction 3

Commercial alginates are derived from a variety of seaweed sources. Since di erent seaweeds yield alginates that di er in monomeric composition and block structure, a given alginate has its own characteristic calcium reactivity and gelation properties. Although the ratio of mannuronic acid to guluronic acid (M:G ratio) can be obtained relatively easily, the detailed molecular compositions of alginates in terms of block lengths and block distributions are much more di cult to determine. As a result, alginates are usually referred to as high M or high G, depending on the proportions of mannuronic acid and guluronic acid they contain. Lessonia avicans provides a high G alginate and both seaweeds are utilized by our alginate manufacturing plant in Scotland. In general terms, high G alginates produce strong, brittle gels that are heat stable, while high M alginates provide weaker, more elastic gels that have less heat stability but more freeze/thaw stability. Final gel strength, however, can be adjusted by manipulation of the gel chemistry and in some product situations, high G and high M alginates are interchangeable. In practice, alginate gels are obtained using three major methods; namely, di usion setting, internal setting, or setting by cooling.

Diffusion Setting
Di usion setting is the simplest technique and, as the term implies, the gel is set by allowing calcium ions to di use into an alginate solution. Since the di usion process is slow, this approach can only be e ectively utilized to set thin strips of material (e.g., pimiento strips, lms, coatings, etc.), or to provide a thin gelled coating on the surface of a food product such as an onion ring. e di usion rate can be increased by increasing the calcium concentration in the setting bath. is has limitations, however, since calcium chloride, the most common source of calcium ions for di usion, imparts an unpleasant taste to foods when used at high levels. Also, calcium lactate, another setting agent, has a relatively low solubility (ca. 5 percent by wt.) in water.

Internal Setting
In internal or bulk setting, which is normally carried out at room temperature, the calcium is released under controlled conditions from within the system. Although the detailed reaction kinetics are extremely complex, involving both high molecular weight polymers and small organic and inorganic molecules, a qualitative understanding of the reaction, su cient for practical purposes, has been acquired. is has led to the development of structured fruits, structured pet foods, and a host of cold prepared desserts. Calcium sulfate (usually as the dihydrate), gypsum, and dicalcium phosphate (calcium hydrogen orthophosphate) are the sources of calcium most commonly used. e rate at which the calcium is made available to the alginate molecules depends primarily on pH and the amount, particle size and intrinsic solubility characteristics of the calcium salt. Small particle size and low pH favor rapid release of calcium. In most situations, calcium release during the mixing of the ingredients is so rapid that a calcium sequestrant is required to control the reaction by competing with the alginate for calcium ions. Typical food-approved sequestrants are sodium hexametaphosphate, tetrasodium pyrophosphate, and sodium citrate.

4 ISP Food Ingredients Alginate/Calcium Reaction

Although disodium phosphate (disodium hydrogen orthophosphate) has little a nity for calcium at pH less than 5, it is sometimes usefully employed in the preparation of alginate gels to remove (as insoluble dicalcium phosphate) calcium ions from tap water. Removal of these ions permits more e cient hydration and subsequent gelation of the alginate. For a given level of alginate and calcium salt, an increase in the level of sequestrant causes a decrease in the setting rate of the gel. is results in a progressively weaker nal gel, since the ultimate distribution of the calcium ions between the alginate and the sequestrant increasingly favors the latter. In other words, the so-called conversion of the sodium alginate into the gelled calcium form is progressively reduced. Control of the gelling reaction with sequestrants is only necessary during mixing to prevent premature gelation and irreversible breakdown of the gel structure. Obviously, with highly e cient and rapid-mixing equipment only a relatively small amount of sequestrant is required because only a small proportion of the calcium salt has the opportunity to dissolve during the mixing process. In these situations, extremely fast setting, strong gels are obtained.

Setting by Cooling
e third method of preparing alginate gels involves dissolving the gelling ingredients, alginate, calcium salt, acid, and sequestrant in hot water and allowing the solution to set by cooling. Unlike gelatin gels, these alginate gels are not thermo-reversible and can be used as desserts in countries where the ambient temperature is su ciently high to melt gelatin gels. e calcium salts and sequestrants used in this system are the same as those already mentioned for internal setting. Although the calcium ions required for the setting reaction are already in solution with the alginate, setting does not occur at elevated temperatures because the alginate chains have too much thermal energy to permit alignment. It is only when the solution is cooled that calcium-induced inter chain associations can occur. An interesting feature of this type of gel is its stability syneresis or water loss from the network is minimal. is stability is due to the fact that the calcium required for gel formation is available in solution to all of the alginate molecules at the same time, allowing the formation of a thermodynamically stable network. In contrast, in di usion setting, the alginate molecules closest to the calcium ions in the setting bath react rst, and in internal setting the molecules closest to the macroscopic particles of dissolving calcium salt react rst. In other words, in these two systems, the molecules do not have the opportunity to align all at the same time, and the resulting gel networks have a certain amount of builtin instability. is instability gives rise to some gel shrinkage and syneresis. In certain product situations, steps must be taken to ensure that shrinkage and syneresis are maintained at an acceptable level. e above discussion covers the basic principles of the alginate/calcium reaction. e following sections illustrate the practical applications of this reaction.

ISP Food Ingredients Alginate/Calcium Reaction 5

Structured Fruits
Internal Setting
Alginate Mix Fruit Mix

e.g.

Oakes

fruit slab

Figure 4. The internal set structured fruit system.

Alginate Mix Ingredient

Manugel DMB Sodium Alginate Dicalcium Phosphate, Anhydrous Sodium Phosphate, Dibasic 12 H2O Glucose (Dextrose) Sucrose Water Total

Internal setting is used to prepare fruit analogs (such as apple, peach, pear and apricot) that have a close-to-uniform texture. A two-mix process involving rapid mixing is employed. One mix contains the alginate and the calcium ion source, anhydrous dicalcium phosphate (DCP); the other mix contains fruit puree, sequestrant and acid, as shown in Figure 4. Since the alginate is predissolved, no alginate hydration problems are encountered. Also, although the calcium source is in the alginate solution, no reaction occurs since DCP is essentially insoluble at neutral pH. (Use of dicalcium phosphate dihydrate is not recommended because the solubility of this material is su ciently high to cause premature reaction with the alginate.) e structured fruit is prepared by pumping the two mixes through a suitable mixer, e.g., an Oakes mixer, and allowing the nal mixture to set under shear-free conditions. e gelling reaction is brought about by the calcium ions released from the DCP, which dissolves as the pH is lowered on contact with the puree phase. If the reaction is too rapid and gelation begins in the mixer or while the nal mix is still under shear, the gel structure is broken irreversibly. us, the gel must be allowed to set under shear-free conditions. Furthermore, since the gel reaction begins immediately after the puree mix contacts the alginate mix, these two mixes should be kept separate until they reach the mixing chamber. A convenient method of preparing structured fruit on a continuous basis is to extrude the mix as a slab on to a moving conveyor (see Figure 4). e formulation can be adjusted to allow the gel to set by the time it reaches the end of the conveyor belt so it can be diced or cut into fruit-like shapes prior to further processing. A typical internal set formulation using fresh peach puree is shown in Table 1. To assist in gum dissolution, part of the sugar is dry blended with the alginate. is internal set approach can also be used to make fruits such as peach or apricot halves. In these cases, the nal mix is extruded through separate nozzles into individual molds. An on-o valve system is used to ensure that each mold receives approximately the same amount of mix. At the same time, a continuous ow of exudate from the mixer into the valves is maintained.

Percent
0.85 0.30 0.07 5.00 5.00 38.78 50.00

Fruit Mix Ingredient

Fresh Peach Puree Sucrose Glucose (Dextrose) Citric Acid, Anhydrous Sodium Citrate Dihydrate Total

Percent
33.55 10.00 5.00 0.80 0.65 50.00

Table 1. Internal set peach formulation. Note: For bench preparation, mixing should be carried out quickly, 10-15 seconds, using a hand held electric mixer. *Manugel is a trademark of ISP Corp.

6 ISP Food Ingredients Alginate/Calcium Reaction

As already indicated, extremely fast setting gels can be obtained by using very rapid and e cient mixing. is signi cantly reduces the amount of calcium salt that dissolves during mixing and also reduces the levels of sequestrant required for slowing down the reaction. A typical example would be the inline preparation of structured fruit for ice cream products, where the gel must be set before the nal product enters the freezing tunnel.

Alginate Mix Ingredient

Manugel DMB Sodium Alginate Sugar Sodium Phosphate, Dibasic 12 H2O Water Total

Percent
0.80 12.00 0.07 37.13 50.00

Diffusion Setting
Di usion setting is employed to prepare structured fruits such as cherries using calcium chloride or calcium lactate in the setting bath. (See Table 2) For taste reasons, calcium lactate is usually preferred and is added to the bath with sugar and a fruit acid. e pH of the bath is kept above 4 to prevent formation of alginic acid gels; and the sugar level is adjusted to ensure that the cherries do not sink to the bottom of the bath, making their removal easier. In commercial production, structured cherries are best obtained using the two-mix system employed for internal setting. However, DCP is omitted from the alginate solution since calcium ions are not required in the internal phase. Rapid and continuous mixing is again used but, in this case, the exudate from the mixer is fed through a series of tubes attached to a plate located below the surface of the bath. As the mix exits into the bath, it is sliced by a rotating cutter into small pieces that form cherry-shaped spheres. Since di usion is slow, there is usually not enough time during processing to permit complete setting of the cherries. If the cherries are then stored at ambient temperature, for example, as a shelf-stable pie lling, the setting reaction continues because of the excess calcium in the berries; and setting throughout is obtained. If the cherries are subjected to frozen storage immediately after production, setting will not continue. Under these circumstances, if complete setting is required, a combination of internal setting and di usion setting can be used. In structured fruit production, usually it is desirable to facilitate processing by matching the viscosities of the fruit and alginate mixes. ickeners such as modi ed starches, galactomannans or xanthan gum can be used for this purpose. Inclusion of these thickeners also improves freeze/thaw stability of the structured fruit. Di usion setting is ideally suited to the preparation of fruits with an outer skin and a liquid center, such as blackcurrants or blueberries. Again, an alginate mix and a puree mix are used, but in this case these are kept separate and fed through nozzles consisting of two co-axial tubes as shown in Figure 5. is process is sometimes referred to as co-extrusion. A key element of the process is maintenance of a continuous ow of alginate solution, coupled with intermittent pulsing of the central puree stream, using, for example, a rotating valve. As each pulse of puree breaks away from the nozzle, it is coated or encapsulated with a thin, uniform coat of alginate solution. If the rheology of the mixes is correct, the extruded berry capsules form spheres which, on contact with the setting bath, rapidly acquire a resilient calcium alginate skin. If the puree center is higher in sugar concentration than the nal surrounding medium, di usion of water into the berries occurs, imparting turbidity and a realistic bite. Although the berries

Fruit Mix Ingredient

Cherry Puree Sugar Water Total

Percent
35.00 13.00 2.00 50.00

Setting Bath Ingredient

Calcium Lactate Pentahydrate Malic Acid Sugar Water Total

Percent
5.00 0.40 20.00 74.60 100.00

Table 2. Structured cherry formulation. *Manugel is a trademark of ISP Corp.

Figure 5. Co-extrusion system for preparing blackcurrants.

ISP Food Ingredients Alginate/Calcium Reaction 7

Alginate Mix Ingredient

Manugel DMB Sodium Alginate Water Total

Percent
2.00 98.00 100.00

are relatively strong after the setting reaction, they are somewhat weak as they initially fall into the setting bath. Breakage at this point can be minimized by causing turbulence in the bath (below the nozzles) with air. e co-extrusion technique is a simple concept that is readily amenable to high throughput production. A typical di usion set formulation for blackcurrants is shown in Table 3.

Fruit Mix Ingredient

Blackcurrant Puree heavy or light syrup Citric Acid, Anhydrous Calcium Lactate Sugar Instant Cleargel* Xanthan Gum Water Total

Setting by Cooling
e third method of preparing structured fruit involves gel formation by cooling hot solutions containing fruit, alginate and other gelling reagents. is approach o ers a number of interesting product opportunities. Essentially, this system provides a structured fruit ingredient for multi-component products, which can be handled as a liquid at elevated temperatures. For example, it can be used as a central lling in ice cream popsicles. e ice cream shell of the popsicle is made by a standard ll and suckout technique. Using normal dosing equipment, the structured fruit center is pumped and lled as a liquid. It then sets very quickly (becoming a chewy, jelly center) as it cools from contact with ice cream. A typical formulation for this type of fruit is shown in Table 4. Fruit avors rather than fruit puree can be used if required. What advantages do structured fruit o er? Since structuring is a means of raw materials extension, cost savings can be obtained, especially if expensive fruits are used. In fruit processing factories, wastage of high quality fruit is unavoidable. is waste can be utilized by structuring with alginates. A major advantage of structuring is that formulations can be built up to meet speci c end product requirements. For instance, warm eating fruit that remains soft and edible in frozen products can be formulated by the inclusion of added sugar, which depresses the freezing point. Since alginate gels are quite heat stable, strong gels can be produced for pie llings that withstand breakdown during pasteurization and subsequent cooking in the nal product. is results in fruit pieces with good texture and a recognizable shape, rather than a mush. Preparation of fruit pieces of uniform size, often highly advantageous for in-line dosing, is another advantage.

Percent
41.00 0.20 1.00 12.70 1.70 0.50 42.90 100.00

Setting Bath Ingredient

Calcium Lactate Water Total

Percent
3.00 97.00 100.00

Table 3. Structured blackcurrants formulation. *Available from National Starch & Chemical Corporation

Ingredient Part A
Manucol DM Sodium Alginate Sodium Hexametaphosphate Calcium Sulfate Dihydrate Sugar Deionized Water

Percent
1.00 0.42 0.10 7.00 33.48

Part B
Sugar Glucose Monohydrate

Percent
20.00 7.00

Structured Vegetables
Internal Setting
As indicated earlier, the internal setting system in structured fruit relies on the low pH of the puree mix to release the calcium ions required for gelation from the calcium salt, dicalcium phosphate. Many foods, however, are non-acidic; and the preparation of items such as structured vegetables by internal setting requires some modi cations. Calcium sulfate dihydrate is used in place of calcium phosphate and the gelling ingredients are distributed between the two mixes as shown in Figure 6. e sequestrant is included in the alginate mix rather than with the puree. e calcium sulfate cannot be added to the alginate because it is soluble enough to induce premature gelation. Consequently, the calcium sulfate is mixed with the vegetable puree.

Part C
Raspberry Puree Citric Acid, Anhydrous Total

Percent
30.00 1.00 100.00

Table 4. Formulation for preparation of fruit gel by cooling. Note: Dry blend ingredients in Part A and add to water, followed by sugars in Part B. Heat mix to 71 C (160F), add Part C and allow to cool. *Manugel and Manucol are trademarks of ISP Corp.

8 ISP Food Ingredients Alginate/Calcium Reaction

Control of the gelling reaction not only depends on factors such as the level of sequestrant, the mixing time, and the level of calcium sulfate, but also on the amount of dissolved calcium in the puree phase prior to mixing. is, in turn, depends on the amount of water in the puree phase. If too much water is present, the calcium ion concentration in solution becomes too high to prevent pregelation. A key element in formulating these systems is, therefore, to ensure that the water in the puree phase is kept low. In practice this is not too di cult since most of the water in a vegetable puree is still bound within the individual particles, and only a small amount is available to dissolve the calcium sulfate. Despite this requirement of limited calcium sulfate dissolution prior to mixing, the alginate and the puree mixes can still be formulated in proportions that are su ciently balanced to permit ease of processing. One of the important attributes of vegetable gels is that they can be dehydrated by air-drying to produce dry vegetable pieces that hydrate in hot water. Such pieces can be used as ingredients in dry mix products as an improved alternative to air-dried or freeze-dried vegetables. For example, air-dried peppers have skin that can adhere to the teeth, while freeze-dried vegetables are expensive and sometimes have poor color and texture after reconstitution. A formulation for pepper pieces suitable for air-drying is shown in Table 5. Air-drying is not restricted to non-acidic alginate gels. Structured tomato pieces, prepared by structured fruit technology, give good rehydratable particulates. Fruit gels can also be air-dried to provide confectionery-type jellies. Drying costs depend on the amount of water to be removed. By structuring, the solids level can be increased, reducing drying costs.

Figure 6. Basic system for the production of internal set structured vegetables.

Alginate Mix Ingredient

Manugel DMB Sodium Alginate Sodium Phosphate, Dibasic 12 H2O Deionized Water Total

Percent
1.40 0.30 65.90 67.60

Puree Mix Ingredient

Sweet Red Pepper puree Calcium Sulfate Dihydrate Col-Flo 67 (modi ed starch) Total

Percent
30.00 0.40 2.00 32.40

Table 5. Formulation for sweet red pepper pieces. Available from National Starch and Chemical Corp.

Diffusion Setting
Di usion setting can also be used to prepare structured vegetables. A wellknown example is the structured pimiento strip, which is used for stu ng olives. e typical starting formulation outlined in Table 6 is simple and consists of four basic ingredients; namely, sodium alginate, pimiento puree, water and another hydrocolloid (normally guar gum). Potassium sorbate is sometimes included as a preservative. e alginate and guar gum are dry blended and dissolved with vigorous agitation in the water. Hot water is sometimes used to obtain faster hydration. e puree is then added, followed by the sorbate; and the mixture is pumped onto a conveyor, which carries it as a sheet into a calcium chloride setting bath. Prior to entry into the bath, the sheet is usually washed or sprayed with calcium chloride to initiate setting on the surface. Since the sheet is 4-6mm. thick, complete setting throughout by di usion of the calcium ions is slow and can take around 30 minutes. After the setting time, the sheet is strong, resilient and exible and can be cut into thin strips, which are subsequently allowed to equilibrate for several days in a solution of salt and calcium chloride. During this period, rearrangement of the alginate gel network takes place, resulting in syneresis and shrinkage of the strip. e guar gum is included to reduce syneresis and shrinkage to an acceptable level. After aging, the strip is ready for use in the olive stu ng machine, where it is cut at right angles to its major axis into thin lengths that

Ingredient
Manugel DMB Sodium Alginate Guar Gum Potassium Sorbate Pimento Concentrate Deionized Water Total

Percent
1.60 0.80 0.10 14.00 83.50 100.00

Setting Bath Ingredient

Calcium Chloride Anhydrous Potassium Sorbate Water Total

Percent
8.00 0.10 91.90 100.00

Aging Bath Ingredient

Sodium Chloride Calcium Chloride Anhydrous Lactic Acid Potassium Sorbate Water Total

Percent
8.00 2.00 1.20 0.10 88.70 100.00

Table 6. Structured pimento strip formulation. *Manugel is a trademark of ISP Corp.

ISP Food Ingredients Alginate/Calcium Reaction 9

Ingredient
Minced, Dehydrated Onion Flour Salt Manucol DMF Sodium Alginate Water Total

Percent
20.00 14.00 0.10 1.10 64.80 100.00

are bent double like a hairpin and fed into the hole in the olive with the rounded end protruding. If the strip is not su ciently strong and exible at this stage, undesirable breakage can occur. Also, if shrinkage has not terminated prior to stu ng, it continues within the olive and may result in the pimiento gel slipping out of the core of the olive, giving an unsightly product in the jar. If the end use of the olives involves cooking, alginate-structured pimiento does not melt, since these gels are heat stable. Structured onion rings are one of the best known examples of food products obtained by using the alginate/calcium reaction. Since the alginate gel is set by di usion, the reaction chemistry is simple. Formation of the characteristic onion ring shape, however, has involved the development of specialized equipment. A suitable base formulation for onion rings is given in Table 7. Minced, dehydrated onions are allowed to soak and swell in water and the alginate is then added together with other optional dry ingredients such as salt, our, and avors. e resulting paste is formed into onion rings using the forming device; and these are gelled or set by immersion in a setting bath, typically 3-5 percent calcium chloride, or by spraying with a calcium chloride solution. Usually, time in the setting bath is insu cient to give complete gel formation throughout the ring, and only a gelled skin is formed. is skin is strong enough to permit handling of the onion ring during breading and frying.

Table 7. Structured onion ring formulation.

Meat Pieces
Meat pieces 3 Textureze MT 200 Alginate Textureze MT 230 Calcium Lactate

Parts by Weight
100 1.0 0.6

Table 8. Structured meat formulation.

Alginate Mix Ingredient

Thawed, minced sh Manucol DMF Sodium Alginate Water Total

Percent
50.00 1.70 48.30 100.00

Structured Meat & Fish

Meat Binding System
ISPs Textureze MT 200 and MT 230 meat binding system provides processors a means of preparing meat products from trimmings that taste and look like whole muscle meat, with consistent size and shape. One of the key bene ts of this system is its unique ability to bind meats in both the raw and cooked state. e USDA approved system provides end products that are phosphate-free and low in sodium. e end product is phosphate-free and low in sodium. Fat and cholesterol levels can be reduced using lean beef. e formulation (Table 8) uses pieces of lean meat, preferably < 20% fat, to which the dry alginate and calcium lactate are added in sequence using gentle mixing. e alginate is mixed until dissolved in the meat, mixing time usually being only a few minutes. e calcium lactate is then added and mixed only long enough to disperse it throughout the meat mix, again requiring only a few minutes. e nal mix is extruded into a casing or formed into a shape and placed in a refrigerator or freezer overnight in order to set. is meat binding system is approved for beef, lamb, veal, pork and poultry, and may be applicable in sh and other seafood. ese end products can be presented in a variety of forms, e.g., slices for sandwiches or cubes for stews or kebabs. Binding is retained under retort conditions. Natural meat avors are not masked. Good color is maintained.

Table 9. Diffusion set sh formulation. *Manucol and Textureze are trademarks of ISP Corp.

Diffusion Setting
Table 9 provides a simple formulation for structured sh prepared by di usion setting. Preferably, the alginate is rst dissolved in the water by mixing, and then the minced sh is added to the alginate solution. e nal paste is formed

10 ISP Food Ingredients Alginate/Calcium Reaction

into the desired shape by depositing in molds, and the initial setting is brought about by spraying the surface of the mold and the exposed surface of the paste with a calcium chloride solution. When a su ciently strong skin is formed on the shaped sh piece, setting can be conveniently completed in a setting bath. A typical bath composition would be calcium lactate (1 percent), lactic acid (1 percent), and sodium chloride (8 percent). To simulate the aky structure of lleted sh and avoid the sh cake texture of minced sh, the gelled sh may be formed in thin strips that are stacked in speci c orientations in the end product. Clearly, the number of possible product concepts with these and the other structured materials discussed is only limited by the imagination of the food technologist.

Pet Food
At the commercial level, the structuring of meat and sh using alginate gel technology has been most successfully utilized in the pet food industry. In pet foods, the alginate gelling reaction is used to provide either structured meat chunks or a gelled matrix that holds the meat pieces together. In both of these cases, a superior, more appealing product is obtained. Meat chunks can be prepared by internal setting, as already described, or by di usion setting, depending on the speci c shape required. In the preparation of meat chunks for canned pet foods, the alginate gel network is sometimes required only temporarily to maintain the shape of the pieces during processing and in the early stages of sterilization. Long-term shape retention is achieved by setting of the meat proteins during the heating state. A pet food in which the meat pieces are bound together in a jelly or aspic can be obtained by combining the pieces with an alginate solution and causing the solution to gel by internal setting. Setting is brought about by using a calcium salt that is sparingly soluble at neutral pH but soluble at acid pH, and triggering the reaction with glucono- b -lactone (GDL). Since the GDL hydrolyzes to its acid form slowly in water, release of the calcium ions does not occur too rapidly, allowing su cient time for mixing prior to the onset of gelation. A formulation for

ISP Food Ingredients Alginate/Calcium Reaction 11

Ingredient Part A
Cooked, drained, minced meat

Percent
50.00

this type of product, sometimes referred to as open pack dog brawn, is shown in Table 10. Inclusion of preservatives such as sodium metabisul te and potassium sorbate allows distribution of the product at ambient temperatures.

Part B
Manugel GHB Sodium Alginate Sodium Metabisul te Potassium Sorbate Sodium Hexametaphosphate Water

Percent
1.40 0.15 0.15 0.05 41.74

Water-Based Dessert Gels

One of the purposes of this brochure is to demonstrate that through a deeper understanding of the factors involved in alginate gelation, it is possible to formulate dessert products where alginates can be used to unique advantage. An example is a hot water, alginate-based dessert that gels without refrigeration. e product types covered in this section all use the internal setting gelling mechanism and can be classi ed as follows:
Instant Water Gels High G Alginate High Ca2+ Aerated Gels High G High Ca2+ Foamed Gel Soft Gels Lower G High Ca2+ Shear Reversible Gels High M Low Ca2+

Part C
Glucono- b -Lactone (GDL) Dicalcium Phosphate Dihydrate Water Total

Percent
1.10 0.41 5.00 100.00

Fruit Pie Fillings High G High Ca2+ (Broken Gel)

Table 10. Open pack brawn formulation. Note: Parts A, B, and C are prepared separately. After combining A and B, C is added with thorough mixing. Part C should be used immediately after make-up to minimize hydrolysis of the GDL. *Manugel is a trademark of ISP Corp.

Figure 7. In uence of calcium ion level on alginate rheology.

Figures 7 and 8 indicate where these product types occur in the spectrum of alginate gelation properties. Figure 7 shows the typical e ects of increasing the calcium ion concentration during reaction with a high M alginate. At low levels of calcium/alginate conversion, a thickening or false viscosity occurs. In the middle region, soft, thixotropic, and in some cases, shear reversible gels occur. Finally at higher calcium levels, moldable, continuous, strong gels are obtained. Variations in alginate concentration, pH, soluble solids and temperature greatly change the boundaries of these three zones. Generally, the lower the pH and the higher the level of soluble solids, then the less calcium is needed to e ect the changes from false viscosity to continuous irreversible gel formation. Figure 8 depicts the position of many alginate gelling applications in relation to these three zones. As can be seen, the majority of the gelling applications table jellies, aerated desserts, fruit pie llings, structured fruit and dog brawns - fall in a narrow range of alginate concentration and calcium conversion; namely, 0.4 to 0.8 percent alginate concentration and around 80 percent calcium conversion.

12 ISP Food Ingredients Alginate/Calcium Reaction

Only one commercial product, an ice cream containing jelly, falls in the nongelling zone shown in Figure 8. is at rst glance may seem anomalous. However, in practice the avored alginate syrup solution is lled into the middle of an ice cream mix and both are frozen. e low temperature, coupled with a soluble solids level of around 25 percent to 30 percent and some calcium exchange from the surrounding milk product, sets the gel and relocates it to the middle zone of gel behavior the thixotropic gel region. is gelling technique of using high M alginate, low calcium conversion and low temperature can also be utilized in a non-bake imitation jam application where the appropriate alginate is dissolved in a cold fruit puree, which is then lled into suitable containers and frozen in a domestic freezer. After gelling, the non-bake imitation jam is stored at approximately 5C (41F). e product has good spreadability, excellent fresh fruit avor and, of course, is much lower in calories than conventional jam. A similar product, cake topping, is formulated to produce a cutable gel when chilled or frozen and, because of the high M alginate and low calcium alginate conversion, the gel does not exhibit syneresis. erefore, softening of the cake sponge does not occur. Air freshener gels and structured pimiento, also indicated in Figure 8, are both high alginate concentration gels to give strength in use, but the calcium alginate conversions are quite di erent. For air freshener gels the conversion is around 45 percent, giving an irreversible gel with very low potential syneresis. On the other hand, the structured pimiento, made by a di usion process, has a 100 percent conversion using high G alginate and as pointed out earlier, requires guar gum addition to reduce syneresis. A comparison of gelling behavior, as illustrated in Figure 9, between high G and high M alginates highlights some interesting points. As expected, the high G alginate has a greater gel strength at optimum calcium conversion. However, there are two crossover points on the graphs, indicating that at lower conversions the high M alginate gives a more homogenous and stronger gel. Also, on over-converting by using excess calcium it is the high G alginate that tends to precipitate sooner, again leaving a region where the high M alginate yields a superior gel.

Figure 8. Relationship between alginate gelling applications and calcium ion levels.

Figure 9. Gel strengths of high G and high M alginates at different calcium conversions.

ISP Food Ingredients Alginate/Calcium Reaction 13

Instant Water Gels Instant water gels prepared with cold water can be made with Manugel L98 mixed with sugar, color and avor. is is whisked in cold water and allowed to set. e product is ready to eat within 15 to 20 minutes. Advantages for this type of alginate gel are: cold make-up ease of make-up does not melt in hot conditions good clarity if required ready-to-eat in minutes excellent avor release easily demoldable

setting time independent of ambient temperature (from 5C - 35C; 42F -95F)

Figure 10. Comparison of gel strength buildup in aerated and unaerated gels in different water hardnesses (ppm CaCO3).

Care needs to be taken with the formulation of such instant water gels to take into account di erent water hardnesses. In Europe, for instance, water hardness can range from 50 ppm as calcium carbonate to over 400 ppm and in certain areas can approach 1,000 ppm. e normal test range, however, is taken as 50 ppm to 350 ppm calcium carbonate. Although the level of calcium carbonate may appear insigni cant, it can radically alter the strength of the alginate gel, especially at the nominal usage rate of 0.4 percent, as shown in Table 11. Higher concentrations of alginate are less a ected. In addition to careful formulation, variations in water hardness may be overcome by producing aerated gels or soft gels.
Conversion %

Figure 11. Variations in gel strengths with different alginate blends as measured on FIRA Gel Strength Tester.

Alginate %
0.40 0.40 1.20 1.20

Water Hardness ppm CaCo3

50 350 50 350

Contributed from water

5.0 37.0 1.6 12.6

Total
70.0 102.0 66.6 77.6

Table 11. Effect of water hardness. Assuming percent conversion in each case, from added calcium, to be 65.

Aerated Gels ese are prepared by adding a whipping agent, usually a hydrolyzed protein, to the gel formulation. Comparative formulations are shown in Table 12.
Ingredient
Manugel L98 Alginate product Citric Acid, Anhydrous Whipping Protein Sugar Color and avor Water Total

Instant Gel %
1.69 0.42 Nil 13.50 q.s. 84.39 100.00

Aerated Gel %
1.68 0.42 0.50 13.43 q.s. 83.97 100.00

Table 12. Aerated and unaerated instant gel formulations. *Manugel is a trademark of ISP Corp.

e leveling out e ect of aeration is clearly seen in Figure 10, where the gel strengths of the unaerated Manugel L98 based system are compared with those of the aerated Manugel L98 based system in three di erent water hardnesses (50, 250, 400 ppm calcium carbonate) and at various times after make-up.

14 ISP Food Ingredients Alginate/Calcium Reaction

e aerated product is, of course, quite di erent from a normal gel and is described as a mousse. It has a light, pleasant texture and can be adjusted for body by varying the concentration of whipping agent and by the addition of a pregelatinized starch. Useful spino products can be made using this mousse or whipped gel as a base. e whipped, but still liquid, aqueous portion can be further blended with various previously whipped creams, either natural or synthetic, to yield gelled, rich tasting products of high quality, especially when served chilled. Although these products require a two-stage make-up, they are not di cult to prepare and have excellent quality. Soft Gels Another approach to overcoming variations in water hardness is to use certain high M alginate blends along with formulation changes, such as changes in calcium conversion level and replacement of citric acid by adipic acid. e resultant gels are much softer than the originally marketed alginate gels, but still have an acceptable texture. Figure 11 shows the range of gel strengths possible through blending di erent types of high G and high M alginates. ese gels, although demoldable, will not stand up strongly compared to a gelatin gel or the early alginate gels. ey are, however, very useful in layered desserts, such as tri e, either for domestic or large scale make-up. A typical formulation for a soft gel is shown in Table 13. e e ect of using a special blend of high M alginate in this type of formulation is illustrated in Figure 12, which shows that although the nal gel strengths obtained are much lower than those obtained with a high G blend, there is much less di erence in the gel strengths in the various water hardnesses. Shear Reversible Gels Reversibility is not a phenomenon normally associated with alginate gels. Nevertheless, by proper formulation and alginate selection, commercially acceptable gels can be obtained. ese gels are designed to be made and stored asceptically until needed, which may be a few hours, days or even weeks. ey are then subjected to a pumping shear and deposited to form a layer of instant gelled dessert. Gel reformation is very rapid once the shearing action is removed. Since the gel at this point is processed at ambient temperatures, this enables layered desserts consisting of heat sensitive materials such as whipped cream or ice cream to be added almost immediately to the gel layer without the

Ingredient
Manucol JKT Alginate product Sodium Citrate Dihydrate Dicalcium Phosphate, Anhydrous Adipic Acid Sugar Water Total
Table 13. Soft gel formulation.

Instant Gel %
1.38 0.10 0.14 0.51 13.50 84.37 100.00

*Manucol is a trademark of ISP Corp.

Figure 12. Comparison of gel strengths obtained with high G and high M alginate blends in various water hardnesses (ppm CaCO3).

ISP Food Ingredients Alginate/Calcium Reaction 15

necessity of a cooling period. Further, since the alginate gel does not melt, the addition of hot custard, for example, can also be tolerated. ese properties allow energy savings and more rapid processing of these ready-to-eat layered desserts. Figure 13 shows typical viscosity recovery speeds after shearing these gels. Fruit Pie Fillings ese products are commercially important in the U.S. and Europe. e particular gelling system used in this application is unusual since, unlike the majority of applications, the gel is formed and then deliberately broken, either by further mixing or by passage through the depositor head. It is this broken gel that is used in the nal product. By breaking up the gel, problems connected with di erences in water hardness can be overcome. e syneresis that can occur on breaking the gel can be controlled by using a pregelatinized starch, or in some cases, guar gum. Although the broken gel (especially if it contains fruit pulp) does resemble natural fruit puree, it should not be considered as a means of merely extending the product. is is far from the case. ere are other more positive bene ts to be gained such as: no tailing from depositor heads no boil-out of lling good volume ll throughout shelf life reduction of moisture transfer into the pastry control of uidity of the lling if consumed hot excellent avor release due mainly to a reduction in the concentration of gums normally used ability to formulate new products, such as mini-turnovers, which would be extremely di cult using a more conventional lling thickener e elimination of tailing and boil-out keeps the processing lines free from burned on deposits, and therefore keeps the standard of hygiene of the line high, without a requirement for extra labor. e earliest commercial success in this eld was in apple turnovers. In largescale processing, considerable boil-out was encountered with all starch llings. Boil-out was eliminated by changing to an alginate two-stage make-up formulation. A typical formula for this type of lling is shown in Table 14 . e dry ingredients, together with the alginate blend, are dissolved rst in the water using a high speed stirrer for three to ve minutes. e ingredients in part B are then added, resulting in lower pH and dissolution of the insoluble calcium salt contained in the alginate blend. With the initiation of gelling, mixing time becomes critical, and mixing is only continued for one to two minutes. A longer time could break the gel as it begins to form, resulting in a soft, useless sludge. e gel is allowed to stand 30 to 45 minutes and is then transferred to the depositor head for lling. e shear during lling from the depositor and passing through the lling head is enough to break up the gel to the required consistency. After the gel is deposited on at squares of pu pastry, the turnover is formed and baked. e ambient shelf life requirement is only three to four days.

Figure 13. Rate of recovery of gel strength after shearing.

Ingredient Part A
Manugel PTJ Alginate Product Pregelatinized Starch Cinnamon Sugar Water Total

Percent
0.70 1.35 0.03 26.84 17.39 46.31

Part B
Apples, Sliced Adipic Acid Apple pulp Total

Percent
51.93 0.54 1.22 53.69

Table 14. Apple turnover lling formulation. *Manugel is a trademark of ISP Corp.

16 ISP Food Ingredients Alginate/Calcium Reaction

Another product where an alginate-based lling has proven extremely successful is in the small fruit- lled pie. As the required shelf life is three weeks at ambient temperature, maintenance of an acceptable lled appearance can be a problem. e problem has been successfully overcome by using a modi ed apple turnover formula and processing technique. A typical formulation is shown in Table 15. As in the preparation of the alginate gelling system shown in Table 14, stage one of the two stage apple lling is made up and allowed to set. is rst stage is incorporated into the second stage or nished apple lling as indicated in the formula shown in Table 15. ere are two primary advantages of including the structured fruit gel in this manner. is gelled phase reduces heat transfer, thereby keeping the temperature lower during the baking time. is reduces moisture loss and also boil-out. e second bene t is a reduction in the rate of moisture loss for an increase in shelf life. Figure 14 compares rates of moisture loss from a 50 percent sugar solution, a 50 percent sugar solution thickened with 0.3 percent alginate and a 50 percent sugar solution gelled with 0.3 percent alginate and calcium. It can be clearly seen that the rate of moisture loss is much less from the gelled system; and it is this property and related e ects that have led to the widespread use of alginate in all types of fruit pie llings.

Stage One Ingredient

Manugel PTJ Alginate Product Pregelatinized Starch Corn Syrup, high fructose Corn Syrup, 62 D.E. Water Adipic Acid Apple pulp Total

Percent
1.00 2.00 12.00 5.50 28.75 0.75 50.00 100.00

Stage Two Ingredient

Structured Apple (from Stage One) Apples, diced Pregelatinized Starch Corn Syrup, high fructose Corn Syrup, 62 D.E. Preservative (as desired) Total

Percent
25.00 42.00 2.50 20.75 9.75 100.00

Milk-Based Products
Milk contains calcium salts that can reduce, or even completely inhibit, alginate solubility. erefore, alginate products designed for use in cold milk must contain a calcium sequestrant, usually a phosphate or citrate. With hot milk no sequestrant is required. Sodium alginate will dissolve directly into the milk at 90C (194F) by agitating for ten minutes, or during pasteurization. Gelation will begin once the temperature has dropped below 60C (140F). A sample formula for a soft milk gel is shown in Table 16. e mix is added to milk, whisked for 30 seconds, then poured and allowed to set. e product is ready-to-eat within 15 minutes. is type of milk set involves the formation of a calcium alginate gel. e reaction sequence is a rapid dissolution of the sequestered alginate, followed by controlled release of calcium ions from the calcium sulfate and milk. Controlled release of calcium is obtained by slowly lowering the pH with the weakly acidic potassium hydrogen tartrate, and by the sodium citrate acting as a bu er and weak sequestrant. e nal product is a smooth, continuous, milk gel. As with alginate water gels, both the gel character and reset properties of alginate milk gels can be altered. By combining a calcium alginate gelling reaction with a pyrophosphate/starch/milk protein gelling reaction, useful products are obtained that have found wide market acceptance. Using this technique, formulations can be adjusted to obtain textures suitable for products ranging from soft cream-type llings, to soft aerated mousse products, to heavy cheesecake textures. Because reduced-calorie products have a wide market appeal, these milk-based products also can be formulated with reduced levels of fat, salt, and cholesterol. (See Table 20 for a low-calorie chocolate pudding formulation.)

Table 15. Two stage apple lling formulation.

Figure 14. Rates of moisture loss from systems containing 50% sugar.

Ingredient
Manucol JKT Alginate product Calcium Sulfate Dihydrate Cream of Tartar Sodium Citrate Dihydrate Pregelatinized Starch Salt Flavor and color Sugar ( ne particle) Milk (cold) Total

%
1.33 0.10 0.07 0.09 2.10 0.03 q.s. 12.25 84.03 100.00

Table 16. Alginate milk gel formulation. * Manucol, Lacticol and Dariloid are trademarks of ISP Corp.

ISP Food Ingredients Alginate/Calcium Reaction 17

Ingredient
Lacticol F336 Non-fat dry milk solids Sugar Potato Starch Dry Vanilla Yellow coloring #5 & #6 Tap water Total

%
3.00 13.00 14.53 2.50 0.30 0.01 66.66 100.00

e formulations shown in Tables 17 and 18 utilize these principles. e custard bakery lling is made by adding the dry ingredients to water and mixing for three minutes until the texture is smooth and consistent. e custard can then be poured into containers and allowed to set, or piped into pastry. e chocolate chi on lling produces an exceptionally rich and tasty chi on which can be served as a mousse dessert, frozen dessert, or pie lling. e dry ingredients are added to cold milk in a small mixing bowl and blended at low speed until mixed. e mixture is then blended at high speed for four minutes to reach the desired chi on-like texture. Consumer convenience is a desired feature in food preparation today. Two popular foods which can be made with little preparation and cooking are instant cheesecake and instant pudding. e instant cheesecake mix formulation (Table 19) uses Dariloid QH alginate. When blended with the cold milk, this formula produces a product similar to a baked cheesecake, yet requires no baking. e alginate provides the set, body, and creamy texture to the nished product. To prepare the cheesecake, thoroughly blend the dry ingredients, add the dry mix to the milk in a small bowl and mix at low speed until blended. Increase the speed to medium and blend for three additional minutes. Pour the mixture into a 7-inch graham cracker crust and chill one hour before serving. Reduced-calorie and fat products also are in demand as consumers seek to eat healthier foods. e low calorie chocolate pudding formulation (Table 20) uses a mixture of alginate and xanthan gum to produce a low-calorie pudding with excellent mouthfeel, texture, and body. e level of sugar can be lowered by substituting a non-caloric sweetener for the sugar. To prepare the instant lowcalorie chocolate pudding, the dry mix is dispersed in water using high shear mixing for 10-15 minutes until fully hydrated. A slurry of starch and milk is added to the rst solution and heated to 88C (190F) while continuing to mix. Once starch is fully gelatinized, the mix is removed from heat and cooled. e pudding will thicken and form a soft thixotropic gel several hours after cooling.

Table 17. Instant custard formulation.

Ingredient (Dry)
Sugar, ne granular Whip powder base Dutch Cocoa Dariloid QH Alginate Calcium Gluconate Tetrasodium Pyrophosphate, Anhydrous powder Salt, ne Vanilla avor Total Milk (1 cup/236 ml.)

%
60.17 27.13 8.14 2.17 1.63 0.38

0.27 0.11 100.00

Table 18. Chocolate Chiffon formulation.

Ingredient (Dry)
Sugar, ne granular Whip powder base Cream Cheese powder Cheese powder Dariloid QH Alginate Calcium Gluconate Tetrasodium Pyrophosphate Lactic Acid powder, 60% Salt Cream Cheese avor Total Whole Milk (1 cup/236 ml.)

%
43.76 23.79 12.07 11.89 3.57 1.50 1.19 1.08 0.60 0.55 100.00

Structured Potato Products

e increasing demand for convenience foods and for new and more varied ways of presenting potatoes has provided important new market opportunities. Recent sales increases are mainly due to the popularity of frozen french fries at fast food catering outlets. Greater retail sales have been attributed to innovations such

Table 19. Instant cheesecake mix formulation. *Dariloid and Keltone are trademarks of ISP Corp.

Figure 15. Structured potatoes from different ingredients.

18 ISP Food Ingredients Alginate/Calcium Reaction

as oven ready and microwaveable products and the introduction of ethnic dishes. It is thought that new textures and avors could further stimulate expansion of this market. e alginate/calcium reaction has been used in our laboratories to give novel structured potato products. e process involves dissolving the alginate in potato and gelling the mixture with a sparingly soluble calcium salt, such as calcium sulfate dihydrate. Product texture is varied by altering the quantities and ratios of the alginate and calcium salt, and the reaction is controlled with a phosphate-based calcium sequestrant. e type of alginate (high M or high G) and the amounts of calcium salt and sequestrant employed also depend on the source of the potato raw material. shows the various techniques to be used with di erent potato starting materials. Maximum e ciency from the alginate is obtained by predissolving it in water and then adding the seasoning, calcium salt, phosphate and potato ake or mash. However, the equipment and time required to dissolve the alginate may be inconvenient. erefore, in our developments, alginate addition was simpli ed as much as possible to t in with present manufacturing processes and to maintain production versatility. A dry blend of the ne-mesh alginate, seasoning, calcium salt and phosphate is used with each process. Where dehydrated potato ake or powder is used, the dry ingredients are simply dry blended and mixed with water for about two minutes. Some manufacturers limit the mixing time to as little as 35 seconds to prevent excessive starch breakdown, which subsequently gives a sticky product. However, even under these conditions, the ne alginate powder hydrates and performs well in the nal product. After mixing, the potato is left for a few minutes to allow the mixture to hydrate and then it is piped, extruded or molded into the nal product shape. With potato mash as the main ingredient, the alginate blend is dispersed throughout the mix by mixing with steamed potato pieces. If required, a little potato starch may be used to help disperse the alginate throughout the potato. If shredded potato or potato o cuts are the raw material, they are blanched before adding the alginate blend. In these situations, some potato starch is necessary to ensure that the alginate is adequately mixed. Some sample formulations for mixtures based on potato ake are shown in Table 21. e various recipes provide di erent potato textures. Duchesse potatoes have a soft mash consistency, whereas the croquette mix has a rmer
Ingredient
Sodium Alginate Potato Flake Salt Calcium Sulfate Dihydrate Tetrasodium Pyrophosphate Water Total

Ingredient
Skim milk Water Sugar Modi ed Starch Cocoa powder Salt Xanthan Gum Sodium Stearoyl Lactylate Keltone HV Alginate Vanilla avor Total

%
40.00 38.70 15.00 3.00 2.50 0.20 0.20 0.20 0.15 0.05 100.00

Table 20. Low-calorie chocolate pudding.

Duchesse %
0.35 20.00 0.60 0.20 0.10 78.75 100.00

Croquette %
0.35 23.00 0.60 0.20 0.05 75.80 100.00

French Fry %
0.50 25.00 0.60 0.45 0.10 73.35 100.00

Roast %
1.00 23.00 0.60 0.60 0.10 74.70 100.00

Table 21. Structured potato formulations.

ISP Food Ingredients Alginate/Calcium Reaction 19

texture. Both of these mixtures contain a product such as Manucol DMF alginate to hold the product together without contributing a noticeable gel texture. e french fry formulation has increased levels of both alginate and ake to give a rm, mealy texture. In this recipe, and in the one for roast potatoes, a di erent alginate, such as Manugel DJX or Manugel DMB may be used to give the more rmly gelled consistency normally associated with these products. e french fry and roast potato formulations also contain higher levels of calcium salt to obtain the desired product texture. Although calcium sulfate dihydrate is given in these recipes, other calcium salts may be used. Calcium citrate has also produced successful products. Whey powder, which contains a small amount of calcium, may be used although relatively high levels are required, which may result in a detectable avor in the cooked product. Tetrasodium pyrophosphate is used to control the alginate/calcium reaction. It is quite an e cient sequestrant; however, many dehydrated potato suppliers already include disodium dihydrogen pyrophosphate in their formulations to prevent discoloration of the rehydrated product from iron contamination in the potato and lower levels of the tetrasodium salt may be required to obtain acceptable setting times. e ability to use relatively high levels of water in these formulations is of interest, since replacement of some potato ake by water and alginate o ers possibilities of technically superior products without additional cost. Furthermore, reducedcalorie potato products is another potential development area. Alginate-based structured potatoes have other advantages. Since alginate is cold or hot water soluble, processing may be carried out equally well at any temperature. e potato ingredient does not have to be warmed or cooled for alginate to be used. As indicated previously, the product texture may be varied by selecting the alginate type and level to give consistencies ranging from a soft mash through to the rm, almost gel-like texture of an undercooked roast or baked potato. e tenuous alginate network that forms in the early stages of gel formation means that the extruded shape is retained. e alginate gel also ensures that the shape is maintained throughout the various stages of processing, including handling, chilling, freezing and cooking. Bursting or distortion during cooking is also minimized as a consequence of the gelled structure. A problem in any layered product containing, for example, meat or

20 ISP Food Ingredients Alginate/Calcium Reaction

sh, is moisture transfer into the potato, which gives a sloppy, wet product. e cohesion of an alginate-containing product generally overcomes this problem, and moisture loss from the potato during prolonged heating is also reduced. Alginates also reduce oil transfer into the interior of the potato and reduce moisture loss from the potato to the skin which helps to maintain the freshly cooked crispness. A close examination of frozen potatoes will show superior shape de nition in products containing alginate over cellulosic stabilizers due to the weak gel that holds the extruded shape. When the potatoes are cooked, this alginate gel holds the product shape throughout the thawing and heating cycle so that sagging does not occur. With the cellulosic stabilizers, the gelling/thickening properties do not operate below about 50-60C (122-140F). Consequently, there is ample time for shape loss and sagging to take place during the early stages of cooking. e ability to control and modify texture is a key bene t of the use of alginates in structured potato products. For example, by using alginates, croquettes can be produced without the traditional batter and crumb coating. Normally, the batter is needed to retain the product shape and integrity. When alginate is incorporated, the gel network extends throughout the mixture so that the product may be cooked directly in deep fat without batter. If batter is used, the gelled structure reduces the steam build up inside the batter casing that can cause the croquette to explode. French fry textures may be varied using the alginate system. With lower levels of alginate and high amounts of potato solids a dry, mealy texture is obtained. Reducing the potato ake and using higher levels of alginate produces a rm, almost under-cooked consistency. Roast potatoes represent the rmest texture generally encountered in cooked potatoes. e alginate-structured product may be cooked by deep frying only, which reduces cooking time from about 1 1 hours to around 10 minutes. An interesting texture can be achieved using shredded potato. A mix is made by sprinkling a dry blend of alginate, seasoning, calcium salt, phosphate, and potato starch (used as a dispersing aid) over blanched potato shreds. is mixture may then be extruded into a variety of shapes which can be fried (e.g., croquettes, potato cakes) or boiled (e.g., dumplings). Use of alginates in combination with potato technology permits the development of a range of novel products that may provide new marketing opportunities. For example, potato shells with a range of llings could be a potential fast food product. e shells are shaped for consistent portion control, eliminating the processing problems caused by the irregular shapes and sizes of natural potatoes. e shells may be coated with a solution of caramel and dextrose, which improves the appearance of the frozen product. is treatment also darkens the outside of the shell when it is cooked, simulating the potato peel. Scotch egg, a product consisting of a hard boiled egg encased in sausage meat, is well known in the United Kingdom. A similar product could be obtained using alginate-structured potato as the outer casing.

ISP Food Ingredients Alginate/Calcium Reaction 21

Meat lled turnovers represent another possible product opportunity. ese are made by rolling out the potato like pastry, cutting it into rectangles and crimping two sections together to encase a range of llings. Di erent sizes may be used for snack and main course variations. Various advantages of the alginate stabilizer are that the alginate maintains product shape during cooking, the gel acts as a barrier to moisture transfer from the lling so that the potato and meat lling remain distinct and retain their original texture and avor, and the moisture control assists in the production of a short, crisp skin. ese properties may be used in other layered foods such as shepherds pie (potato and minced beef) and shermans pie (potato and sh) and in battered products where a layer of meat or sh and potato are encased in batter. Another application of structured potato foods is co-extruded products. e algin allows the structured potato to be readily pumped and extruded. Several novel concepts using potato and vegetable combinations have been prepared in our laboratories.

Appendix
Products
Manugel L98 a ne-mesh alginate product for instant cold water aerated desserts Manugel DMB a ne-mesh, high-gel strength sodium alginate Manugel GHB a medium to low-viscosity, medium-gel strength sodium alginate Manugel DJX an extra ne-mesh, high-gel strength sodium alginate Manugel PTJ an alginate product for pie llings Manucol JKT a medium to low-gel strength alginate product for instant water gels Manucol DM a low-calcium, medium-mesh, high-viscosity sodium alginate Manucol DMF a low-calcium, ne-mesh, high-viscosity sodium alginate Lacticol F336 an alginate product for bakery custards and other cold milk-based systems Keltone HV a ne-mesh, medium-gel strength sodium alginate Dariloid QH a ne-mesh alginate product for milk-based systems

Terms
Aerated gels gelled foams with overruns of over 200 percent Algin collectively describes alginic acid and alginates Alginates salts of alginic acid Alginate/calcium reaction calcium-induced association of alginate molecules, which under the proper conditions produces a gel network Bakefast heat stable under baking conditions Bakery custard custard-type lling for baked goods Conversion or calcium conversion amount of calcium required to replace the sodium ion in a carboxylate group of a unit of sodium alginate, i.e., 20 parts calcium to 198 parts sodium alginate unit or roughly 1:10 calcium:sodium alginate Croquettes cylinder shaped, breaded potatoes Di usion setting setting brought about by allowing calcium ions to di use into an alginate solution or by the di usion of hydrogen ions into an alginate solution containing insoluble calcium salts in suspension Duchesse potatoes mashed potatoes piped into swirls and browned in the oven

22 ISP Food Ingredients Alginate/Calcium Reaction

FIRA Food Industries Research Association High G alginates that contain high proportion of guluronic acid High M alginates that contain high proportion of mannuronic acid Internal setting setting brought about by controlled release of calcium ions already in the system sometimes initiated by lowering of the pH of the system by slowly soluble acids also in the system Instant water gels water-based gelled dessert Piping decorating baked products by squeezing a lling from a tube onto the product Setting by cooling certain alginate gel formulations can be kept liquid at elevated temperatures; on cooling, these formulations set to give continuous gels Shear-reversible gels gels that become liquid upon shearing, but that revert to their original state when shear is removed Structured foods products that have been made by use of alginate gel technology Tri e layered dessert consisting of sponge cake, fruit- avored gel, real fruit pieces, and cream Vanilla slices iced pastries containing vanilla custard

Technical Service
As indicated at the outset, the purpose of this brochure is to provide an insight into the alginate/calcium reaction and, in particular, to outline the chemical principles involved and how these can be utilized in a wide variety of product situations. Alginates reactivity with calcium is complex but the food technologist with an appreciation of these principles will nd alginate to be an extremely useful tool for product development. Technical Service USA: 1 (888) 472-5446 For other global contact information, please see the back cover of this brochure.

ISP Food Ingredients Alginate/Calcium Reaction 23

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INTERNATIONAL SPECIALTY PRODUCTS 1361 Alps Road, Wayne, New Jersey 07470, USA Tel: +1 973 628-4000 Fax: +1 973 628-3311 www.ispcorp.com info@ispcorp.com CUSTOMER SERVICE Toll Free: 1 (800) 622-4423 Fax: +1 973 628-4001 info@ispcorp.com SAMPLE CENTER Toll Free: 1 (800) 243-6788 isp@chemicalmarketing.com

USA & CANADA REGIONAL SALES OFFICES PERSONAL CARE LOMBARD, ILLINOIS Toll Free: 1 (800) 323-2272 Tel: +1 630 932-4022 Fax: +1 630 495-0245 personalcareinfo@ispcorp.com PHARMACEUTICALS WAYNE, NEW JERSEY Toll Free: 1 (877) 389-3083 Fax: +1 973 628-4117 pharmaceuticalinfo@ispcorp.com PERFORMANCE CHEMICALS WAYNE, NEW JERSEY Toll Free: 1 (877) 389-3083 Fax: +1 973 628-4117 perfcheminfo@ispcorp.com FOOD INGREDIENTS USA Tech Service: 1 (888) 472-5446 Cust Service: 1 (800) 622-4423 Fax: +1 973 628-4001 foodinfo@ispcorp.com FOOD INGREDIENTS CANADA Tech Service: 1 (888) 472-5446 Cust Service: 1 (800) 465-5094 Fax: +1 905 607-9086 ispcanada@ispcorp.com

LATIN AMERICA CUSTOMER SERVICE ARGENTINA Tel: +54 11 4314-8971 +54 11 4314-0659 +54 11 4314-3293 Fax: +54 11 4314-8976 ispargentina@ispcorp.com BRAZIL LATIN AMERICA REGIONAL OFFICE Tel: +55 11 3649-0469 +55 11 3649-0477 Fax: +55 11 3643-1585 ispbrasil@ispcorp.com CHILE Tel: +56 2 229-9601 +56 2 229-9547 +56 2 229-9483 Fax: +56 2 229-1098 ispchile@ispcorp.com COLOMBIA Tel: +57 (1) 636-0618 Fax: +57 (1) 691-8540 ispcolombia@ispcorp.com MEXICO Tel: +52 55 5276-6110 Fax: +52 55 2614-2939 isp_mexico@ispcorp.com VENEZUELA Tel: +58 212 991-4545 +58 212 992-9703 +58 212 991-7775 Fax: +58 212 991-9705 ispvenezuela@ispcorp.com

EUROPE, MIDDLE EAST, & AFRICA CUSTOMER SERVICE AFRICA Tel: +49 (0) 2236 9649-237 Fax: +49 (0) 2236 9649-212 info.africa@ispcorp.com AUSTRIA Tel: +43 (0) 1 360 27-71220 Fax: +43 (0) 1 360 27-71221 info.austria@ispcorp.com BELGIUM Tel: +32 (0) 2 626-49 30 +32 (0) 2 626-49 34 Fax: +32 (0) 2 626-49 32 info.belgium@ispcorp.com BULGARIA Tel: +359 (0) 2 958-2596 Fax: +359 (0) 2 850-5480 info.bulgaria@ispcorp.com CZECH REPUBLIC Tel: +420 272 123 332 Fax: +420 272 123 305 info.czech@ispcorp.com FRANCE Tel: +33 (0) 1 49 93 21-58 +33 (0) 1 49 93 21-59 Fax: +33 (0) 1 49 93 21-62 info.france@ispcorp.com GERMANY EUROPE REGIONAL OFFICE Tel: +49 (0) 2236 9649-260 +49 (0) 2236 9649-264 +49 (0) 2236 9649-266 Fax: +49 (0) 2236 9649-295 info.germany@ispcorp.com HUNGARY Tel: +36 1 209 2629 Fax: +36 1 466 2550 info.hungary@ispcorp.com ITALY Tel: +39 0275 419 642 Fax: +39 0275 419 644 info.italy@ispcorp.com NETHERLANDS Tel: +31 (0) 20 65 45-361 Fax: +31 (0) 20 65 45-368 info.netherlands@ispcorp.com NORDEN (Denmark, Estonia, Iceland, Finland, Norway, Sweden) Tel: +46 (0) 8 519 920-10 Fax: +46 (0) 8 519 920-12 info.norden@ispcorp.com POLAND Tel: +48 (0) 22 607 25 20 Fax: +48 (0) 22 607 25 22 info.poland@ispcorp.com RUSSIA Tel: +7 495 981 39 53 Fax: +7 495 981 39 54 info.russia@ispcorp.com SPAIN & PORTUGAL Tel: +34 93 298 07 00 Fax: +34 93 298 07 05 info.spain@ispcorp.com info.portugal@ispcorp.com SWITZERLAND Tel: +41 (0) 1 439 53-66 Fax: +41 (0) 1 439 53-68 info.switzerland@ispcorp.com TURKEY & MIDDLE EAST Tel: +90 216 538 0800 Fax: +90 216 538 0880 info.turkey@ispcorp.com info.middleeast@ispcorp.com UK Tel: +44 (0) 207 519-5054 +44 (0) 207 519-5055 Fax: +44 (0) 207 519-5056 info.uk@ispcorp.com

ASIA PACIFIC CUSTOMER SERVICE AUSTRALIA Tel: +612 9648-5177 Fax: +612 9647-1608 salderson@ispcorp.com BEIJING, CHINA Tel: +8610 6515-6265 Fax: +8610 6515-6267 tltan@ispcorp.com GUANGZHOU, CHINA Tel: +8620 3758-9970 Fax: +8620 3758-9907 tltan@ispcorp.com SHANGHAI, CHINA Tel: +8621 6249-3900 Fax: +8621 6249-3908 tltan@ispcorp.com HONG KONG Tel: +852 2881-6108 Fax: +852 2895-1250 tltan@ispcorp.com HYDERABAD, INDIA Tel: +9140 5584-4000 Fax: +9140 2331-1090 ekalyanpur@ispcorp.com MUMBAI, INDIA Tel: +9122 2837-0472 Fax: +9122 2837-0449 ekalyanpur@ispcorp.com INDONESIA Tel: +6221 530-7181 +6221 530-7182 Fax: +6221 530-7183 mchondrodihardjo@ispcorp.com OSAKA, JAPAN Tel: +816 6838-5752 Fax: +816 6838-5566 myamashita@ispcorp.com TOKYO, JAPAN Tel: +813 5566-8661 Fax: +813 5566-8682 myamashita@ispcorp.com KOREA Tel: +82 2 554-6622 Fax: +82 2 554-6944 ksoh@ispcorp.com MALAYSIA Tel: +60 5513-1498 Fax: +60 5512-8311 atye@ispcorp.com PHILIPPINES Tel: +632 848-7188 Fax: +632 848-7191 rcomagon@ispcorp.com SINGAPORE ASIA PACIFIC REGIONAL OFFICE Tel: +656 223-3778 Fax: +656 226-0853 atye@ispcorp.com TAIWAN Tel: +886 2 2508-0212 Fax: +886 2 2504-3543 cchiang@ispcorp.com THAILAND Tel: +662 267-8103 Fax: +662 236-0041 spordi@ispcorp.com

Trademark registration applied for Registered trademark of the ISP group International Specialty Products. 2007 Designed & Printed in USA.

Product Code: FOIN_C1003 09/2007

The information contained in this brochure and the various products described are intended for use only by persons having technical skill and at their own discretion and risk after they have performed necessary technical investigations, tests and evaluations of the products and their uses. While the information herein is believed to be reliable, we do not guarantee its accuracy and a purchaser must make its own determination of a products suitability for purchasers use, for the protection of the environment, and for the health and safety of its employees and the purchasers of its products. Neither ISP nor its afliates shall be responsible for the use of this information, or of any product, method, formulation, or apparatus described in this brochure. Nothing herein waives any of ISPs or its afliates conditions of sale, and WE MAKE NO WARRANTY, EXPRESS OR IMPLIED, OF MERCHANTABILITY OR FITNESS OF ANY PRODUCT FOR A PARTICULAR USE OR PURPOSE. We also make no warranty against infringement of any patents by reason of purchasers use of any information, product, method or apparatus described in this brochure.