SODIUM CARBOXYMETHYL CELLULOSE

Chemistry, Functionality, and Applications

Andrew C. Hoefler Food Ingredients Group, Hercules Incorporated Wilmington, Delaware 19808

http://www.herc.com/foodgums/index.htm

Figure 1 is a diagrammatic representation of a cellulose molecule. Note that each glucose unit in the cellulose chain has three hydroxyl groups, each of which is capable of hydrogen bonding to an adjacent molecule. In the bottom of Figure 1, we indicate cellulose more pictorially as a series of circles connected together in a long, linear chain.

Figure 2 shows a group of cellulose molecules in water. Because of the abundance of hydroxyl groups, and their ability to hydrogen bond to a neighboring molecule, the chains are bound tightly together. Water molecules, at any temperature, cannot force their way in between the chains to hydrate them, thus cellulose is water insoluble ( which is just as well, since most of our houses are made of wood. I certainly would not want my house to dissolve the next time it rains! )

Figure 3 illustrates the reaction for the manufacture of CMC. It is essentially a two step process. In the first step, cellulose is suspended in alkali to open the bound cellulose chains, allowing water to enter. Once this happens, the cellulose is then reacted with sodium monochloroacetate to yield sodium carboxymethyl cellulose.

An idealized unit structure of CMC is depicted in figure 4. The CMC shown here has a D.S.( Degree of Substitution ) of 1.0. If the remaining two hydroxyl groups on this unit became substituted, the D.S. would be 3.0. A D.S. of 3.0 is the theoretical maximum one could attain.

Figure 5 is a pictorial representation of CMC molecules. Note that the carboxymethyl groups protrude from the cellulose backbone, such that the hydroxyl groups of the backbone cannot get close enough to hydrogen bond to each other. The result is that even in the dried state, water can slip in between the CMC molecules and hydrate them, causing them to "peel apart" from each other and go into solution.

Figure 6 depicts the nomenclature for Hercules cellulose gum. The specific product described is cellulose gum type 7H3SXF. The "7" stands for the degree of substitution. In the food industry,

there are "7" and "9" types of substitution. The pharmaceutical industry also has a "1.2" type to work with. The "H" signifies a high viscosity grade, and the "3" is a reference point which defines the maximum viscosity of the gum in a 1% solution at 25C (in this case, 3000 centipoise). There are "L", "M", and "H" types, representing low, medium, and high viscosity respectively. The "S" stands for special rheological properties (smooth flow). There are "S" types for smooth flow, and "O" types for tolerance in acidic systems. Both of these types show considerably less thixotropy than the randomly substituted regular types of cellulose gum (more will be said about this later). The "X" stands for fine grind material, while a "C" would indicate a coarse particle size, and no letter would indicate a "regular" particle size. The "F" represents food grade (FCC), while a "P" would be pharmaceutical grade (USP).

Some typical viscosity values are shown in Figure 7. Please note that "L" and "M" types are measured at a 2% concentration, while "H" types are measured at 1%. Figure 8 shows the concentration versus viscosity relationship in a more visual fashion.

The effect of the Degree of Substitution on the properties of CMC is shown in figure 9. Tolerance to salt increases and tendency towards thixotropic behavior decreases as the degree of substitution increases.

There is another factor which is as important as the Degree of Substitution, and that is the "Uniformity of Substitution", which is shown visually in Figure 10. The "smooth" or non-substituted regions of a non-uniformly substituted molecule behave just like cellulose because they are still cellulose! These regions can hydrogen bond to a similar region on an adjacent molecule, leading to the buildup of a loose gel network ( Figure 11 ).

This buildup is time dependent, and is called "thixotropy". The loose gel network can be disrupted by shearing the CMC solution, but upon standing under no shear conditions the network will reform over time. Visually, the difference between uniformly and non-uniformly substituted CMC solutions can be seen in Figure 12. Smooth flowing CMC types are desirable for food systems such as syrups or frostings where smooth consistency is a must. Thixotropic CMC would find use in structured, grainy foods such as sauces or purees.

Cellulose gum is probably the fastest gum to hydrate in cold water. Consequently, it is the gum most like to form lumps when dispersed into water, due to it's rapid swelling in water. To overcome the problem described above, four procedures are recommended in Figure 13: Method 1: direct addition: Here the gum is added directly to the vortex of a vigorously agitated body of water. The rate of addition should be slow enough to keep the particles separated, but fast enough so that all of the gum is added before the vortex disappears. The reason for this is that it is extremely difficult to thicken an already viscous solution of cellulose gum by adding more dry powder. The direct addition method is usually encountered in highly controlled processing situations. Method 2: dry blending: In this method, the CMC is dispersed with other dry ingredients, such as sugar, prior to their addition to aqueous systems. The other particles serve to keep the CMC particles away from each other. Commonly, one part of CMC is mixed with five to ten parts sugar to effectively prevent lumping. The dry mix beverage is a classic example of this dispersion technique. Method 3: dispersion in a water miscible non-solvent: Cellulose gum may be dispersed in glycerine, ethanol, or propylene glycol and the slurry is then added to water. An off-shoot of this method is to disperse the gum in corn syrup, and then add the mixture to water with the aid of agitation.

Method 4: mixing device: Another method for the addition of cellulose gum to food systems in plant operations is the use of a stainless steel mixing device (figure 14). The gum is fed through a smooth wall funnel into a water jet eductor, where it is dispersed by the turbulence of water flowing at high velocity. Each particle is individually wetted out to give a uniform solution. Under optimum conditions, cellulose gum leaving the eductor is about 80 - 90% hydrated.

ADD THE GUM FIRST! (Figure 15) This is a general rule to follow when adding cellulose gum to water in all food formulations.

As an example of the importance of order of addition, Figure 16 is a graph of CMC viscosity versus salt concentration. In one case, the CMC was dissolved in the water before the salt, and the salt had a minimal effect on the viscosity of the solution. In the other case, the CMC was dissolved AFTER the salt, and the resulting final viscosity was much lower, especially as the salt concentration increases.

Figure 17 gives an idea of how cellulose gum is effected by increasingly stronger salt solutions, and by the uniformity of substitution. Going from distilled water to 4% sodium chloride drops the viscosity by a factor of about 12 for 7HF, and by about 3 for the more evenly substituted 7H3SF. The proportions are similar when going to a saturated salt solution ( last column ).

Figure 18 shows the effect of some other ions on the viscosity of a CMC solution. The Aluminum salt actually increases the viscosity of CMC because it has the steric capability of gelling CMC. Unfortunately, for taste reasons, this has little application in the food industry.

Figure 19 shows the effect of water / non-solvent mixtures on the viscosity of CMC. In this case, the non-solvent is glycerin. The maximum viscosity is reached with a 30/70 mixture of water and glycerin. At higher than 70% concentrations of glycerin, the CMC is not fully in solution and thus does not give as much viscosity. At lower than 50% glycerin, there is less "crowding" and more availiable water for hydration, thus the CMC viscosity is lower.

Figure 20 shows that the viscosity of CMC, like most other water soluble polymers, decreases with increasing temperature. Under normal conditions, this effect is reversible (ie: raising or lowering the solution temperature has no permanent effect on the viscosity characteristics of the solution). However prolonged heating at extremely high temperatures will permanently degrade the cellulose gum (depolymerization) which results in a viscosity decrease. What this means to the food technologist is that CMC is not particularly retort stable.

Figure 21 indicates that CMC, like most food gums, is pseudoplastic. This means that the apparent viscosity will decrease at increasing shear rates, but the effect is totally reversible. As soon as the shear is stopped, the viscosity returns to it's original value.

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CMC is more tolerant to the presence of ethanol than most other food gums (Figure 22). This makes cellulose gum useful for cordials and other low alcohol content beverages which require optical transparency.

CMC will give a synergistic viscosity increase with other hydrocolloids such as guar or locust bean gum ( Figure 23 ). If one were to mix a 1% guar solution of 3800 centipoise with a 1% CMC solution of 4000 centipoise, the net result is not the 3900 centipoise average of the two; it will be closer to 6500 centipoise. There are more average "collisions per second" between unlike molecules, which results in this synergistic viscosity increase.

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Food applications ( Figure 25): The availability of cellulose gum in different viscosity grades, particle sizes, special rheological grades, and combinations thereof permits tailor-made application of CMC to many different food systems. The following is a brief discussion of some of these applications:

Cake mixes CMC is used to improve the moisture retention in cake mixes, as a dried out cake is quite objectionable organoleptically. High D.S. types are preferred in cake mixes for maximum moisture binding. CMC also controls batter viscosity, imparts tolerance during mixing, protects against leavening loss, improves cake volume, and controls the uniformity of the cross sectional grain of the cake. For ease of mixing, fine grind types of CMC are preferred in cake mixes for rapid entry into solution. The homemaker does not want to spend all day mixing a cake. Frostings and Icings CMC may be used in frostings and icings to toughen the film prevent sticking to the package and reduce sugar crystal growth (graininess). In ready-to-spread frostings CMC helps stabilize the emulsion and adds creaminess. Most important, CMC prevents the icing or frosting from drying out. Uniformity substituted CMC (S types) are recommended to give a smooth icing or frosting. Pie fillings In starch based pie fillings, the addition of a small amount of CMC will prevent cracking control syneresis and firm the texture. The use of uniformity substituted 0 types of CMC are preferred for stability in acidic fillings such as in a lemon pie filling.

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Dairy products CMC was originally pioneered in ice cream and today this application still remains as one of the largest single uses for the gum. In ice cream CMC prevents ice crystal growth, inhibits lactose crystal growth (sandiness); imparts mix viscosity and body to the finished product, gives correct meltdown, and provides freeze/thaw stability (heat shock control). The use of coarse particle size types of CMC are preferred for ice cream applications (dispersion) because of poor mixing conditions commonly encountered in dairies. CMC is utilized as a stabilizer in many other dairy products such as egg nog, soft serve ice cream, milk shakes, and ice cream ripples. Pancake syrup CMC enjoys widespread use in regular, reduced calorie and dietetic pancake syrups. Here the excellent clarity, viscosity ability compatibility with sugar and non caloric characteristics of the gum are put to good use.

Dry mix beverages The ability of CMC to hydrate rapidly and viscosity in aqueous systems for body and mouthfeel is used in instant breakfast drinks instant fruit drinks hot cocoa mixes and low calorie dry mix beverages. Uniformity substituted low or medium viscosity fine grind types of CMC are most frequently used in these products in order to minimize "fish eye" formation. High viscosity types of CMC are not recommended in these products regardless of particle size since higher molecular weight types take longer to dissolve and are more prone to form fisheyes if dispersion and energy input (stirring) are not optimum. Pet foods and animal feed In semi-moist pet foods, CMC facilitates extrusion, binds moisture, and improves the cosmetic appearance of the product. In dry gravy-forming pet foods CMC is "dusted" onto tallow coated "kibble" with other ingredients, so that upon reconstitution a rich viscous shiny gravy evolves. Another animal food application for CMC is its use as a physical binder in pelleted animal feeds. A small amount of low viscosity CMC in the product holds the pellet together and prevents accumulation of fines in the product package during shipment. Additionally, the gum assists the extrusion process during manufacture of the pellets and helps reduce energy consumption by the pellet mill.

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CMC greatly modifies the behavior of water in sugar solutions (figure 26). Combinations of sugar and CMC display a significant "boost" in viscosity which is believed to be the consequence of a crowding mechanism. Cellulose gum decreases the tendency towards syneresis in high sugar food systems by serving as a water binder. Most importantly, CMC also reduces the rate of sugar crystal growth and crystal size in concentrated sugar systems. This functionality becomes important in confectionery applications such as fondants ( Figure 27 below).

Just as CMC controls sugar crystal growth in confectionery applications, it controls ice crystal growth in ice cream the same way ( Figure 28 ). Texturally, it is desirable to have a large number of small ice crystals (smooth) rather than a small number of large ones (sandy).

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A few cautions about using cellulose gum in food products: Exposure to UV light and entrained air in a food system should be minimized to prevent degradation of the gum. Molecular oxygen will cause the gum to breakdown by a free radical mechanism similar to that which occurs during the autoxidation of lipids. The presence of cations (calcium, iron, aluminum) will accelerate the process. Therefore it is recommended that a sequestrant such as sodium hexametaphosphate be used in systems where CMC is exposed to air and cations.

To summarize, cellulose gum is a very useful hydrocolloid for the food industry. It's water binding ability is second to none, and it is completely transparent in solution. CMC can add viscosity or mouthfeel, control syneresis, and control the rate / size of crystal growth.

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