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Chemistry, Functionality, and Applications
Andrew C. Hoefler Food Ingredients Group, Hercules Incorporated Wilmington, Delaware 19808
allowing water to enter. and their ability to hydrogen bond to a neighboring molecule. Note that each glucose unit in the cellulose chain has three hydroxyl groups. thus cellulose is water insoluble ( which is just as well. each of which is capable of hydrogen bonding to an adjacent molecule. the chains are bound tightly together. I certainly would not want my house to dissolve the next time it rains! ) Figure 3 illustrates the reaction for the manufacture of CMC. cannot force their way in between the chains to hydrate them.Figure 1 is a diagrammatic representation of a cellulose molecule. Water molecules. Once this happens. since most of our houses are made of wood. Because of the abundance of hydroxyl groups. cellulose is suspended in alkali to open the bound cellulose chains. at any temperature. Figure 2 shows a group of cellulose molecules in water. linear chain. we indicate cellulose more pictorially as a series of circles connected together in a long. It is essentially a two step process. 2 . In the first step. the cellulose is then reacted with sodium monochloroacetate to yield sodium carboxymethyl cellulose. In the bottom of Figure 1.
The specific product described is cellulose gum type 7H3SXF. The "7" stands for the degree of substitution. Figure 5 is a pictorial representation of CMC molecules.S. Note that the carboxymethyl groups protrude from the cellulose backbone. causing them to "peel apart" from each other and go into solution.0.0. of 3. water can slip in between the CMC molecules and hydrate them. Figure 6 depicts the nomenclature for Hercules cellulose gum. the D. such that the hydroxyl groups of the backbone cannot get close enough to hydrogen bond to each other. A D.An idealized unit structure of CMC is depicted in figure 4.0 is the theoretical maximum one could attain. The result is that even in the dried state. In the food industry.S. would be 3. 3 .S.( Degree of Substitution ) of 1. The CMC shown here has a D. If the remaining two hydroxyl groups on this unit became substituted.
Tolerance to salt increases and tendency towards thixotropic behavior decreases as the degree of substitution increases. 4 . The pharmaceutical industry also has a "1. There are "L". "M". and the "3" is a reference point which defines the maximum viscosity of the gum in a 1% solution at 25C (in this case. while "H" types are measured at 1%. and "O" types for tolerance in acidic systems. The "X" stands for fine grind material. while a "P" would be pharmaceutical grade (USP). and no letter would indicate a "regular" particle size. The effect of the Degree of Substitution on the properties of CMC is shown in figure 9. There are "S" types for smooth flow. while a "C" would indicate a coarse particle size. and high viscosity respectively. Some typical viscosity values are shown in Figure 7. and "H" types. Figure 8 shows the concentration versus viscosity relationship in a more visual fashion. 3000 centipoise). The "F" represents food grade (FCC). The "S" stands for special rheological properties (smooth flow). Both of these types show considerably less thixotropy than the randomly substituted regular types of cellulose gum (more will be said about this later). medium.there are "7" and "9" types of substitution. representing low. The "H" signifies a high viscosity grade. Please note that "L" and "M" types are measured at a 2% concentration.2" type to work with.
This buildup is time dependent. and that is the "Uniformity of Substitution". Smooth flowing CMC types are desirable for food systems such as syrups or frostings where smooth consistency is a must. the difference between uniformly and non-uniformly substituted CMC solutions can be seen in Figure 12. 5 . but upon standing under no shear conditions the network will reform over time. which is shown visually in Figure 10. The loose gel network can be disrupted by shearing the CMC solution. leading to the buildup of a loose gel network ( Figure 11 ). Visually. Thixotropic CMC would find use in structured.There is another factor which is as important as the Degree of Substitution. 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. and is called "thixotropy". grainy foods such as sauces or purees.
due to it's rapid swelling in water. it is the gum most like to form lumps when dispersed into water. Method 3: dispersion in a water miscible non-solvent: Cellulose gum may be dispersed in glycerine. but fast enough so that all of the gum is added before the vortex disappears. An off-shoot of this method is to disperse the gum in corn syrup. 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.Cellulose gum is probably the fastest gum to hydrate in cold water. one part of CMC is mixed with five to ten parts sugar to effectively prevent lumping. such as sugar. Method 2: dry blending: In this method. and then add the mixture to water with the aid of agitation. Commonly. the CMC is dispersed with other dry ingredients. To overcome the problem described above. The rate of addition should be slow enough to keep the particles separated. 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 dry mix beverage is a classic example of this dispersion technique. ethanol. or propylene glycol and the slurry is then added to water. 6 . The other particles serve to keep the CMC particles away from each other. The direct addition method is usually encountered in highly controlled processing situations. Consequently. prior to their addition to aqueous systems.
ADD THE GUM FIRST! (Figure 15) This is a general rule to follow when adding cellulose gum to water in all food formulations. 7 . cellulose gum leaving the eductor is about 80 . Under optimum conditions.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.90% hydrated. Each particle is individually wetted out to give a uniform solution. where it is dispersed by the turbulence of water flowing at high velocity.
In one case. and by the uniformity of substitution.As an example of the importance of order of addition. the CMC was dissolved in the water before the salt. the CMC was dissolved AFTER the salt. Figure 17 gives an idea of how cellulose gum is effected by increasingly stronger salt solutions. and the resulting final viscosity was much lower. Figure 16 is a graph of CMC viscosity versus salt concentration. In the other case. 8 . especially as the salt concentration increases. The proportions are similar when going to a saturated salt solution ( last column ). and the salt had a minimal effect on the viscosity of the solution. 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 maximum viscosity is reached with a 30/70 mixture of water and glycerin. Figure 19 shows the effect of water / non-solvent mixtures on the viscosity of CMC. At lower than 50% glycerin. Unfortunately. for taste reasons. the non-solvent is glycerin. there is less "crowding" and more availiable water for hydration. 9 . the CMC is not fully in solution and thus does not give as much viscosity. this has little application in the food industry. thus the CMC viscosity is lower.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. In this case. At higher than 70% concentrations of glycerin.
the viscosity returns to it's original value. like most other water soluble polymers. Figure 21 indicates that CMC. What this means to the food technologist is that CMC is not particularly retort stable. As soon as the shear is stopped. decreases with increasing temperature. this effect is reversible (ie: raising or lowering the solution temperature has no permanent effect on the viscosity characteristics of the solution). This means that the apparent viscosity will decrease at increasing shear rates. However prolonged heating at extremely high temperatures will permanently degrade the cellulose gum (depolymerization) which results in a viscosity decrease. but the effect is totally reversible. is pseudoplastic.Figure 20 shows that the viscosity of CMC. like most food gums. 10 . Under normal conditions.
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.CMC is more tolerant to the presence of ethanol than most other food gums (Figure 22). CMC will give a synergistic viscosity increase with other hydrocolloids such as guar or locust bean gum ( Figure 23 ). it will be closer to 6500 centipoise. This makes cellulose gum useful for cordials and other low alcohol content beverages which require optical transparency. which results in this synergistic viscosity increase. 11 . There are more average "collisions per second" between unlike molecules.
particle sizes.Food applications ( Figure 25): The availability of cellulose gum in different viscosity grades. the addition of a small amount of CMC will prevent cracking control syneresis and firm the texture. CMC also controls batter viscosity.S. 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). types are preferred in cake mixes for maximum moisture binding. and controls the uniformity of the cross sectional grain of the cake. For ease of mixing. Most important. The following is a brief discussion of some of these applications: Cake mixes CMC is used to improve the moisture retention in cake mixes. imparts tolerance during mixing. special rheological grades. and combinations thereof permits tailor-made application of CMC to many different food systems. protects against leavening loss. as a dried out cake is quite objectionable organoleptically. Uniformity substituted CMC (S types) are recommended to give a smooth icing or frosting. 12 . The use of uniformity substituted 0 types of CMC are preferred for stability in acidic fillings such as in a lemon pie filling. CMC prevents the icing or frosting from drying out. High D. The homemaker does not want to spend all day mixing a cake. fine grind types of CMC are preferred in cake mixes for rapid entry into solution. improves cake volume. Pie fillings In starch based pie fillings. In ready-to-spread frostings CMC helps stabilize the emulsion and adds creaminess.
soft serve ice cream. Additionally. CMC is utilized as a stabilizer in many other dairy products such as egg nog. reduced calorie and dietetic pancake syrups. binds moisture. Pet foods and animal feed In semi-moist pet foods. In ice cream CMC prevents ice crystal growth. CMC facilitates extrusion. 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. 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. 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. and provides freeze/thaw stability (heat shock control). Here the excellent clarity. inhibits lactose crystal growth (sandiness). Another animal food application for CMC is its use as a physical binder in pelleted animal feeds. 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. milk shakes. 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. 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.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. gives correct meltdown. the gum assists the extrusion process during manufacture of the pellets and helps reduce energy consumption by the pellet mill. Pancake syrup CMC enjoys widespread use in regular. and ice cream ripples. 13 . and improves the cosmetic appearance of the product. imparts mix viscosity and body to the finished product. viscosity ability compatibility with sugar and non caloric characteristics of the gum are put to good use.
14 . This functionality becomes important in confectionery applications such as fondants ( Figure 27 below). it controls ice crystal growth in ice cream the same way ( Figure 28 ). Most importantly.CMC greatly modifies the behavior of water in sugar solutions (figure 26). Cellulose gum decreases the tendency towards syneresis in high sugar food systems by serving as a water binder. Texturally. it is desirable to have a large number of small ice crystals (smooth) rather than a small number of large ones (sandy). Just as CMC controls sugar crystal growth in confectionery applications. Combinations of sugar and CMC display a significant "boost" in viscosity which is believed to be the consequence of a crowding mechanism. CMC also reduces the rate of sugar crystal growth and crystal size in concentrated sugar systems.
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. To summarize. iron. cellulose gum is a very useful hydrocolloid for the food industry. 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. It's water binding ability is second to none. and it is completely transparent in solution. The presence of cations (calcium. 15 . control syneresis. CMC can add viscosity or mouthfeel. Molecular oxygen will cause the gum to breakdown by a free radical mechanism similar to that which occurs during the autoxidation of lipids. and control the rate / size of crystal growth.