Kinetics Of Dye Sorption: Effect Of Dyebath Flow On Dyeing Uniformity

By J. N. Etters, The University of Georgia, Athens, GA

Abstract A common goal of all dyers is to achieve uniform dyeings. Much attention therefore is given to the development of dye formulas that consistently result in uniform distribution of dye in the textile substrate being dyed. But no matter how well a given formula behaves during its development in laboratory dyeing equipment, that formula may fail in the production environment. Often the reason for such failure is found in the irregular dyebath flow through the textile mass in production dyeing machines. A theoretical kinetic basis for the influence of dyebath flow on dyeing uniformity is reviewed. Introduction International competitiveness in textiles is not likely to diminish in the near future. It is essential, therefore, that those who would compete successfully in such a pressure-packed environment make use of all elements of technology available. It is well recognized that a critically important quality attribute by which textiles are judged is the uniformity of color distribution. Only in those cases where the fad of a novel appearance is sought is mal-distribution of color actually tolerated. Dyeing technologists expend much effort in the selection of dyes, chemicals, auxiliaries, and procedures that will result in consistently uniform coloration of the textile substrate. More often than not the selection is based on the results of laboratory dyeings and other tests. It is, of course, rarely possible for production processing to be interrupted for experimentation on bulk equipment. Sometimes the perfection of a laboratory dyeing process is reproduced exactly in practice but not always. As has been noted, even when the 38

Figure l-Diffusion of dye from the dyebath (1) through the diffusional boundary layer (2), followed by sorption onto the fiber surface (3) and diffusion into the fiber interior (4).

Four Fundamental Steps in Dyeing

textile substrates, dyes, chemicals, auxiliaries, liquor ratios, temperaturetime ramps, and procedures are exactly the same in production as they are in the laboratory, transfer of laboratory dyeing results to production may not be successful. A compelling explanation for this failure can be found in the differences in patterns and velocities of dyebath flow in laboratory and production dyeing machines. The purpose of this article is to re-

view a theoretical basis of the influence of dyebath flow on the kinetics of dye uptake.The data presented is Intended to reiterate the importance of efforts to maintain uniform dyebath flow in production equipment. Such efforts are second to none for the promotion of consistently level dyeings. Sorption processes There are at least four fundamental steps involved in sorption of dyes by textile materials.: In the present examAmerican Dyestuff Reporter 3 January 1995

ple, which is illustrated sche-matically in Figure 1, the substrate is assumed to consist of uniformly accessible fibers. As shown in Figure 1, the steps are summarized as: 1. Diffusion of dye in the external medium (usually water) toward the diffusional boundary layer at the fiber surface. 2. Diffusion of dye through the diffusional boundary layer that exists at the fiber surface, 3. Sorption of the dye onto the fiber surface, and 4. Diffusion of dye into the fiber interior. In the case of disperse or vat dyes, an additional step consisting of dissolution of particulate dye must be added as a prerequisite-before step one. For all other conventional classes of dye, e. g., acid, basic, direct, naphthol, reactive, and pre-reduced sulfur, the initial state of the dye in the dyeing medium is that of a molecular or associated molecular form. It should be noted that the four steps given above are simply reversed for desorption processes, indicating the importance of each of the steps in migration or levelling processes. Physico-chemical parameters: The rate of sorption or desorption of dye by textile fibers is controlled by several fundamental physico-chemical parameters. At a given dyeing temperature, these parameters include the: 1. Denier, which is proportional to radius of the cylindrical fiber or the apparent radius of the non-cylindrical fiber; 2. Liquor ratio, i. e., the ratio of the volume of the dyebath to the volume of the fiber mass; 3. Distribution coefficient or ratio of the equilibrium concentration of dye in both the application medium and the fiber; 4. Diffusion coefficient of the dye in both the application medium and the fiber; 5. Fundamental nature of the dyeing system, i. e., is dyeing ng from an infinite or a finite dyebath; and 6. Thickness of the diffusional boundary layer at the fiber surface. It is useful to discuss the above parameters in detail. fiber Denier - When all other fiber morphological characteristics are identical, the rate of dyeing for a given sysJanuary 1995 American Dyestuff Reporter

tem is inversely proportional to the denier of the fiber. This fact is easy to comprehend from a simple geometrical analysis. As the denier of a given fiber increases, the surface area decreases for a given mass of fiber available for dye sorption. In the case of an endless cylindrical fiber, the relationship is given by:3

where S is the surface area in cm2 per gram of fiber; a is a constant having a

value of 6 x 10z5; p is the fiber denier, and o is the specific gravity of the fiber. Since the length to diameter ratio for useful fibers usually is greater than 100 to 1, the surface area contribution from the ends of the individual fibers is relatively small and usually is ignored. Accompanying the increased surface area that is associated with decreasing fiber radius is a decreased distance that the dye on the exterior fiber surface must diffuse to fill the fiber to an equilibrium fixation level. Diffusion of dye into the fiber from the ends of the fiber may be treated as a

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constant, since fiber radius has no statistically significant effect on this contribution to dye uptake for real systems. From the effect of fiber radius on both available surface area and diffusion distance, it is, therefore, understandable why decreasing radius causes an increased rate of dye uptake. In Figure 2 the influence of both fiber denier and specific gravity on fiber surface area is illustrated for cylindrical polyester fiber. As revealed in Figure 2, as the fiber denier is reduced to values below about 1 (microdenier fibers), the fiber surface area increases dramatically. The extremely high surface area of microdenier fibers can lead to high strike rates, and is partly responsible for associated levelness problems often encountered with such fibers. Liquor ratio and distribution coefficient For finite bath systems, i. e., for systems in which the concentration of dye at the fiber surface decreases during the course of dyeing, the equilibrium dyebath exhaustion, E, is a function of both liquor ratio, Q, and distribution coefficient, K. The relationship is given by:
E =

Figure 2-Fiber surface area as a function of fiber denier and specific gravity.

Surface Area (cm2 /g) (Thousands) 7.5

Data Points for Identification Only +Sp.G. = 0.75 +Sp.G. = 1.00 +Sp.G. = 1.25 +Sp.G. = 1.5

5.5

3.5

0.1

0.5

0.9

1.3

1.7

2.1

2.5

2.9

Denier

K+Q

Figure d-Fractional equilibrium exhaustion as a function of distribution coefficient, K, and liquor ratio, Q.

Even though the parameter, K, given above is assumed to be a constant, concentration-independent- a condition rarely encountered in practiceequilibrium exhaustion of many exhaustion dyeing processes can be roughly approximated by the use of Equation 2. Equilibrium exhaustion is important because the rate of dyeing is determined to very great extent by the magnitude of the parameter, E. As shown in Figure 3, the equilibrium exhaustion, E, approaches zero as the liquor ratio, Q, approaches infinity (l/Q approaches zero) for several different values of the distribution coefficient. Diffusion Coefficients A diffusion coefficient is a measure of the rapidity of movement of a molecule through a given medium. As the numerical value of the diffusion coefficient increases, the speed of movement of a molecule through the medium also increases. At a given temperature, the diffusion coefficient of a

Fractional Equilibrium Exhaustion

0.8

0.6

0.4 0.2

!
O
0.01

0.02

0.03

0.04

0.05

Reciprocal of Liquor Ratio (1/Q)

American Dyestuff

Reporter : January 1995

Figure 4-Fractional uptake of dye as function of fractional equilibrium exhaustion and (dimensionless) time when no diffusional boundary layer exists.

Fractional Dye Uptake (M t/M oD )

0.8

0.6 0.4
High Flow Rate 1E=.98 2: E = .84

0.2

3: E = .68 4: E = 0 0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Square Root of Dimensionless TimevDt/r2

molecule in an air medium is much higher than it is in a medium of water, and the diffusion coefficient of the same molecule in water IS much higher than it is in a solid fiber. In practice, apparent diffusion coefficients often are used, since the value of the true diffusion coefficient rarely is known. In fact, it is argued in some quarters that the diffusion coefficient of a dye in a fiber is really the same as it IS in the surrounding aqueous medium. The smaller value of the measured diffusion coefficient in the fiber is attributed to the tortuous pathways that the dye must take on its way to the fiber center. No matter whether or not the tortuosity theory is correct, it is clear that the apparent diffusion coefficient of dye in fiber is much, much lower than the diffusion coefficient of dye in the dyebath itself. The rate of dyeing is controlled, therefore, by the rate of diffusion of dye in the fiber, unless a significantly thick diffusional boundary layer exists at the fiber surface. If such a layer does exist, the rate of dyeing is influenced by the rate of diffusion of dye in the dyeing medium, as January
1995 Amerlcan Dyestuff Reporter

well as in the fiber. Infinite vs Finite Dyebaths As shown in Figure 3, equilibrium exhaustion of a dyebath is influenced strongly by the liquor ratio. If the liquor ratio is high enough, no significant degree of exhaustion occurs. Dyebaths having infinitely high liquor ratios are referred to as infinite dyebaths and equilibrium exhaustion from such baths is equal to zero. Since dye that is adsorbed at the fiber surface is in equilibrium with dye in the dyebath, diffusion of dye into the fiber interior will occur from a constant surface concentration. In practice it is not necessary for the liquor ratio to be infinite for infinite bath conditions to prevail. For example, in the early stages of disperse dyeing, the particulate dye will act as a reservoir that supplies fresh dye to the bath as dye is taken up by the fiber. In addition, during the early stages of dyeing acrylic fibers with basic dye, the negatively charged fiber surface will tend to be saturated with positively charged dye that is replenished from the bath as dye diffuses into the fiber. Circle 21 on Reader Service Card

Figure 5-Simplified schematic of relationship between dyebath flow rate and Indigo dyeing of cotton cables in conventional indigo dye ranges O C C U r S b O U n d a r y l a y e r t h i c k n e s s . from an infinite bath, since dye is continually added to the bath to replenish dye that is taken up by the cotton fiber. Conventional liquor ratio dyeing with other classes of dye occurs under finite bath conditions. In this form of dyeing, the concentration of dye in the dyebath and at the fiber surface continuously decreases during the course Boundary Layer Thickness of dye uptake, until an equilibrium is established. With the exception of some reactive dye classes, equilibrium bath exhaustion for finite bath systems tends to be quite high in practice. The reason that the fundamental form of a given dyebath is important is that the dyebath form dictates the type of sorption kinetics that will prevail and the associated appropriate diffusion equation used to describe the kinetics of dye uptake. In Figure 4, the Increasing Flow Rate rate of dye uptake is shown for a dyeing system in which the only variable is the fractional dyebath exhaustion that has been dictated by distribution coefficient and liquor ratio. It is revealed in Figure 4 that the rate of dye uptake increases as the fractional equilibrium exhaustion increases. The computed rate of uptake curves shown in Figure 4 are for a Figure 6--Rate of dye uptake as a function of fractional equilibrium dyebath exdyeing system in which no diffusional haustion and dyebath flow rate. boundary layer exists. The term, Dt/r2 consists of the diffusion coefficient, D, (cm2/second); the dyeing time, t, (seconds); and the fiber radius, r, (cm). Since all of the dimensions cancel, the term Dt/rZ is referred to as a dimensionless quantity, with time being the only variable. Diffusional Boundary Layer The diffusional boundary layer has been the subject of numerous publications6-0 and is discussed in detail by McGregor. As has been pointed out, a dyebath that is flowing past the surface of textile fibers develops velocity gradients. As the fiber is approached more and more closely by the flowing bath, the velocity of the bath decreases from that which exists in the mainstream to that which exists at the fiber surface. The region of velocity change is referred to as a hydrodynamic Within the hydrodynamic boundary layer is a region in which the concentration of dye decreases from that which exists in the dyebath mainstream to that which exists at the fiber surface. This region of concentration
42 American Dyestuff Reporter January 1995

change is referred to as the diffusional boundary layer. The thickness of the diffusional boundary layer is proportional to the thickness of the hydrodynamic boundary layer, and the thickness of the hydrodynamic boundary layer is inversely proportional to velocity of flow of the bath past the fiber surfaces, as schematically illustrated in Figure 5. The importance of the diffusional boundary layer is found in the layers influence on sorption and desorption rates. Diffusional boundary layers act to impede or decrease rates of sorption or desorption of dye by the fiber, with the effect increasing with increasing thicknesses of the layer. When dyebath flow velocity is not uniform throughout the textile mass, the rate of dye uptake will not be uniform, leading to dyeing unlevelness. The influence of the diffusional boundary layer is illustrated in Figure 6 by the use of computed rate of dyeing curves. The dashed lines in Figure 6 represent dye uptake under very low rates of liquor flow that result in a relatively thick diffusional boundary layer. Such a boundary layer corresponds to a dimensionless L value of 5.0, discussed elsewhere. As shown in Figure 6, the effect of the diffusional boundary layer increases with increas-

ing equilibrium bath exhaustion. This fact is consistent with the observed behavior of commercial dyeing systems. For example, it is widely known that high affinity dyes result in high equilibrium exhaustion and are difficult to apply uniformly. It is believed that a very large proportion of the observed unlevelness is caused by flow rate differences in various regions of the textile material. When the influence of the boundary layer is superimposed on the nonuniformity of dyeing caused by diverse regions of the flowing dyebath being starved of dye, the importance of the boundary layer is emphasized even more. Conclusions It is critical that efforts be made to ensure that the rate of dyebath flow is uniform throughout the textile mass in exhaustion dyeing processes. However, even with the best of efforts, uniformity of dyebath flow cannot be guaranteed in all cases. In such instances, the dyer must employ methods that will tend to level out the inevitable unevenness that occurs in the early stages of the dyeing process. As previously noted,13 perhaps the most effective method is to raise the energy level of the system by the use of high-

er dyeing temperatures and/or suitable chemical auxiliaries that promote migration of dye. q

References
1. J. N. Etters & S. J. English, Textile Chemist and Colorist, 20, No. 6, 21 (1988). 2. J. N. Etters, Textile Chemist and Colorist, 26, No. (1994). 3. A. Urbanik & J. N. Etters. Textile Research Journal, 43, No. 11, 657 (1973). 4. R. McGregor, Dyeing Primer, AATCC, Research Triangle Park, p35, (1981). 5. P. Rys & H. Zollinger. Fundamentals of the Chemistry and Applicatlon of Dyes, Wiley-Interscience, New York, p160. (1972). 6. A. B. Newman, Transactions of the American institute of Chemical Engineers, 27, 203 (1931). 7. J. N. Etters, Journal of the Society of Dyers and Colorists. 97, No. 4, 170 (1981). 8. J. N. Etters, Journal of Applied Polymerscience, 42, No. 3, 1519 (1991). 9. J. N. Etters, Industrial and Engineering Chemistry Research, 30, No. 3, 589 (1991). 10. J. N. Etters, Journal of the Society of Dyers and Colorists,, 107, No. 3. 114 (1991). 11. R. McGregor, Diffusion and Sorptlon in Fibers and Films, Academic Press. New York, ppl72-192, (1974). 12. M. Hou. A. K. Sarkar & L. Fang, rn Book of Papers (Proceedings), 1991 AATCC ICE. AATCC, Research Triangle Park, pp4248, (1991) 13. J. N. Etters. Textile Research Journal, 64, No. 7, 406 (1994).

News... [Continued from page 33]

duced at the biennial trade show and conference in 1993. The Showcase booths will be centrally located within a 2,500-square-foot area on the show floor. Ninety-five percent of the space had been contracted for by December 1994. The show will feature some 55,000 square feet of exhibits, said to be a significant increase since the 1993 show. By December 1,1994,70 percent of the available booth space had been contracted for by exhibitors. Sewn Products Expo 95 is expected to draw 5,000 to 7,000 attendees during its three days. The show was renamed Sewn Products Expo beginning in 1995 to better reflect our expanded emphasis in the past few years to serve the greater sewn products industries-such as apparel, automotive, home products and marine products-in the U.S. and Mexico, said Karen Schaffner, publisher of Apparel Industry Magazine.
January 1995 American Dyestuff Reporter

The three-day concurrent educational Conference program also is being expanded to appeal to a wider range of manufacturing executives from these industries. In the Partnership 2000 Pavilion, [TC] and its partners will install a T-shirt production line, kiosks for participating part-

ners, a classroom for training of six technicians at a time, a presentation auditorium with 30 seats and a video auditorium with 25 seats. T-shirt orders will be taken from attendees and the cash register information will drive the production line all the way through delivery of the product.

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