67

Carboxymethylcellulose
67.1 Introduction ......................................................................67-1 67.2 Coating Application ..........................................................67-1 67.3 Coating Formulation ........................................................67-2 References .....................................................................................67-4

Richey M. Davis
Hercules Incorporated

67.1 Introduction
Carboxymethylcellulose (CMC) is a charged, water-soluble polysaccharide derived from cellulose found in plants. It is used extensively in aqueous paper coatings for controlling coating viscosity. Aqueous paper coatings are colloidal suspensions consisting primarily of pigment, such as kaolin clay, and binders such as starch or latex. The solid concentrations typically range from 55 to 70%. The properties of a coating are determined by colloidal forces acting between particles and by the properties of the suspending aqueous phase. CMC affects the colloidal forces by adsorbing on clay pigment and by increasing the viscosity of the aqueous phase. These effects will be discussed after a brief description of the coating process.

67.2 Coating Application

For the best performance in a paper blade coating machine, a coating should have a shear thinning viscosity that decreases as the shear rate increases. Typical viscosities range from about 3000 mPas at shear rates below 1000 sec1 when the coating is mixed and pumped to less than 100 mPas at shear rates above 1,000,000 sec1 when the coating is applied to the paper. The linear velocity of paper in a coating machine can vary from less than 450 m/min to greater than 1400 m/min. Once the uid coating has been applied to the moving paper web, the paper passes through a section of the machine in which the excess coating is removed, often by a doctor blade. As the coating passes under the doctor blade, the paper adsorbs water from the coating. The paper then goes to a dryer section, where most of the water is removed to form a solid coating layer on the paper. If the coatings water phase viscosity is too low or if the coating particles form large aggregates with a porous structure, too much water is lost prematurely from the coating under the blade. Solid aggregates form under the blade and scratch the coated paper. Excessive water loss also raises the coating solids until the coating becomes shear thickening (the viscosity increases with the shear rate). This causes undesirable streaking on the paper. Shear thickening occurs as a result of increased collisions between the colloidal particles in the coating. These collisions form aggregates that raise the viscosity. For good coating performance, it is important to control the viscosity the water phase and to suppress the tendency of the solid particles to aggregate upon collision. The viscosity of the water phase increases as the concentration of CMC increases.1 Particle aggregation is a direct consequence of the colloidal forces acting between the particles. These forces and the role of CMC in affecting them are discussed next.

67-1
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Coatings Technology Handbook, Third Edition

25

mg Adsorbed CMC/g Clay

20

15

10

0 0 1 2 3 4 Parts CMC/100 Parts Clay

FIGURE 67.1 Adsorption isotherm for kaolin clay and CMC at pH = 7 and 25C. [Adapted from R. M. Davis, TAPPI J., 70(5), 99 (May 1987), with permission.]

67.3 Coating Formulation

The colloidal chemistry of paper coatings is governed by the attractive and repulsive forces between the clay, binder, and polymer. Kaolin clay comes in the form of the thin platelets that have negative charges on the edges and faces at pH values exceeding 7.2 Paper coatings are used typically at a pH of 8 to 9. Clay particles are attracted to each other by van der Waals forces, which are particularly strong when platelets approach to within 1 nm of each other.3 Most clays are treated with an anionic dispersant such as a low molecular weight polyacrylate, which adsorbs on the clay surface. This increases the net negative charge on the platelets and causes them to repel their neighbors, thus reducing the tendency for particle aggregation. A polymeric dispersant also imparts stability through steric stabilization, in which adsorbed polymer chains on one clay platelet repel polymer chains on neighboring platelets as a result of osmotic pressure.3 Negatively charged CMC adsorbs onto kaolin clay and acts as a stabilizer. Figure 67.1 shows the adsorption isotherm for CMC with molecular weight of 110 kg/mol onto clay.4 The amount of adsorbed polymer per mass of clay increases as the added polymer concentration increases. This polymer adsorption increases the amount of negative charge and hence the zeta potential on the clay, as shown in Figure 67.2. The zeta potential, which is the electrostatic potential near the surface of a clay aggregate, ranged from 20 to 30 mV, which is typical for suspensions that are moderately stabilized by electrostatic repulsion. The effect of CMC on coating viscosity at high shear rates is illustrated by the rst curve in Figure 67.3, where a concentration kaolin clay suspension without CMC begins to shear thicken at a shear rate of 18,000 sec1.4 Adding 0.10 part of CMC per 100 parts clay increases the viscosity and also slightly reduces the shear thickening tendency. As the CMC concentration increases to 0.21 part, the suspension becomes shear thinning. The adsorbed CMC increases the degree of electrostatic and steric stabilization, thus inhibiting collision-induced occulation. There are no quantitative models that predict accurately the onset of shear thickening viscosity in paper coatings at very high shear rates. There are, however, numerous theories for the viscosity of concentrated suspensions at low shear rates. These were reviewed by Metzner.5 A useful, general model was developed by Krieger.6 The suspension viscosity is correlated with the water phase viscosity s and the solid volume fraction as 1 = s m
Bm

(67.1)

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Carboxymethylcellulose

67-3

where is the ratio of the solids volume and the total volume; m and B are dimensionless parameters determined by tting viscosity data to Equation 67.1. An analysis of viscosity data using Equation 67.1 suggests that paper coatings, like other concentrated suspensions, ow in ordered layers along streamlines rather like cards in a deck sliding over each other.4 At low shear rates, this ordered structure results in a low viscosity. Above a critical shear rate, this ordered structure breaks down and the particles in the suspension collide far more frequently, resulting in owinduced agglomeration and the resulting shear thickening viscosity is suppressed by treating the coating with CMC.

36 34 32 Zeta Potential, mV 30 28 26 24 22 20 0 1 2 3 4 5 6 Parts CMC/100 Parts Clay

FIGURE 67.2 Zeta potential of kaolin clay with adsorbed CMC at pH = 7 and 25C. [Adapted from R. M. Davis, TAPPI J., 70(5), 99 (May 1987), with permission.]

50 45 Viscosity, mPas 40 35 30 25 20 1000

10,000 Shear Rate, 1/sec

100,000

FIGURE 67.3 High shear viscosity for kaolin clay and CMC; < clay volume fraction = 0.39. distilled water control: 0.10 part CMC/100 parts clay; = 0.21 part CMC/100 parts clay; O 0.31 part CMC/100 parts clay. [Adapted from R. M. Davis, TAPPI J., 70(5), 99 (May 1987), with permission.]

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Coatings Technology Handbook, Third Edition

References
1. Aqualon Cellulose Gum (Sodium Carboxymethylcellulose), (product bulletin), Aqualon Company, Wilmington, DE 198505417. 2. A. E. James, and D. J. A. William, Adv. Colloid Interface Sci., 17, 219 (1982). 3. H. Van Olphen, An Introduction to Clay Colloid Chemistry, 2nd ed. New York: Wiley-Interscience, 1977, p. 48. 4. R. M. Davis, TAPPI J., 70(5), 99 (May 1987). 5. A. B. Metzner, J. Rheol., 29, 739 (1985). 6. J. W. Goodwin, in Science and Technology of Polymer Colloids. G. W. Poehlein, Ed. Dordrecht: Kluwer, 1982, p. 552.

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