C95g-13 1

Fundamental Investigation of Ultrasonic Effects in

Textile Wet Processing

W.W. Carr, S. Michielsen, and H.W. Beckham

Georgia Institute of Technology

Gary Mock and Bob McCall

North Carolina State University

Project Goals: To identify the mechanisms responsible for the observed advantages gained by

employing ultrasound in textile wet processes and to access the relative importance

of the effects of ultrasonic irradiation on basic transport phenomena occurring in the

dye solution, in the polymer, and in the textile.

Abstract
The use of ultrasound in textile wet processing offers many potential advantages. Previous work

has shown that the use of ultrasonics in dyeing provides the following benefits: (1) energy savings and

reduced processing times, (2) environmental improvements, (3) process enhancement, and (4) lower

overall processing costs. A fundamental understanding of the operative processes are needed so that

meaningful application of ultrasonics in textile processing may be made. This project is directed at

determining the phenomena responsible for the effects of ultrasound in textile wet processing and the

relative importance of phenomena occurring in the bulk solution and in the fiber. Our studies show that

ultrasound increases the swelling of both unmercerized and mercerized cotton. Although the beneficial

effects of ultrasound are also observed to occur in polyester, no effect of ultrasound on the glass

transition temperature was observed. An experimental approach has been developed that will enable a

direct determination of the effect of ultrasound on the diffusion coefficient of the dye within polyester.

Research including modeling is being conducted to determine the effect of ultrasound on the partition

coefficient and enhancement of dye transport to the fiber surface by reducing the boundary layer

thickness. The effect of ultrasound on the particle size of insoluble dyes is being studied. Ultrasound
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reduces the average particle size of vat dyes in their insoluble form suspended in water and eliminates the

larger particles.

Introduction

There are many potential advantages offered by the use of ultrasound in textile wet processing.

The following benefits due to the use of ultrasonics in dyeing were shown by previous researchers [1-4]:

(1) energy savings by dyeing at lower temperatures and reduced processing times, (2) environmental

improvements by reduced consumption of auxiliary chemicals, (3) process enhancement by allowing

real-time control of color shade, and (4) lower overall processing costs, thereby increasing industry

competitiveness. A fundamental understanding of the relative operative processes is needed so that

meaningful application of ultrasonics in textile wet processing can be made.

Although several fundamental studies [5-9] on the effects of ultrasound in various

physicochemical processes have been conducted, the mechanisms responsible for the effects of

ultrasound on textile processes have not been established. This project is directed at determining the

phenomena responsible for the effects of ultrasound in textile wet processing and establishing the relative

importance of phenomena occurring in the bulk solution and in the fiber. The mechanisms under

investigation include: (1) increasing swelling in water, (2) reducing glass transition temperature of the

fiber (dilation of amorphous regions), (3) increasing the diffusion coefficient of dye in the polymer, (4)

increasing the fiber/dye bath partition coefficient, (5) enhancing transport of the dye to the fiber surface

by reducing the boundary layer thickness, and (6) breaking up of micelles and high molecular weight

aggregates into uniform dispersions in the dye bath.

Cotton Fiber Swelling (G. Mock, R. McCall, D. Klutz)

The swelling of both mercerized and unmercerized cotton fibers with water alone and with

ultrasound has been studied. Ultrasound causes significant fiber swelling compared to water alone.

Since cotton fibers are very nonuniform and hard to measure, the tests were repeated numerous times and

the results averaged. Several methods of measurement were used to confirm the results.
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For unmercerized cotton, the swelling with water alone ranges from 10% to 20%, but with

ultrasound the range is from 25% to almost 50%. For mercerized cotton, the swelling with water alone is

only about 3% but with ultrasound is about 35%. Remember, the mercerization process causes

permanent swelling of the cotton fiber. Of interest here is that ultrasound still causes additional swelling.

The fiber swelling is observed for at least an hour after the removal of the ultrasound, as long as the fiber

remains in water. When removed from water and allowed to dry, the fiber returned to its original

diameter.

Dye Particle Size (G. Mock, R. McCall, D. Klutz)

Vat dyes were examined in their insoluble unreduced form suspended in water to determine if

ultrasound changed the dye particle size. Five different vat dyes of known structure were examined,

most of which had previously been used in ultrasound dyeing trials. A 5-g/L solution of each dye was

prepared, then divided in half to give two samples for each dye. One sample of each dye was treated

with 20 kHz ultrasound at 25oC for 60 minutes; the other sample was used as a control untreated sample.

The dye samples were measured with a Honeywell Microtrac Particle Size Analyzer. This instrument

measures each sample twice and averages the results to produce an average particle size and a particle

size distribution. The results of the particle size analysis are shown in Table 1.

Vat Violet 1 was effected most by ultrasound. The particle size distribution was initially

bimodal, but when treated with ultrasound, became unimodal (Figure 1). The large particles were

reduced in size, and the smallest particles were increased in size.

Table 1. The Average Particle Size Of Vat Dyes

Dye Manufacturer Without With Avg. Size
Ultrasound Ultrasound Decrease
(microns) (microns) (microns)
Vat Violet 1 Catawba Charlab 2.447 0.606 1.841
Vat Black 25 Catawba Charlab 0.462 0.405 0.057
Vat Black 25 Sunbelt 0.516 0.514 0.002
Vat Green 3 (Dyeing) Catawba Charlab 0.941 0.268 0.673
Vat Green 3 (Printing) Catawba Charlab 1.434 0.292 1.142
Vat Green 1 Catawba Charlab 0.454 0.392 0.062
Vat Violet 13 Sunbelt 0.444 0.431 0.011
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9.0

8.0

7.0

6.0
Percent of Whole

5.0
W/O US
With US
4.0

3.0

2.0

1.0

0.0
3

5
6

3. 9

11 2

14 0
70
0

4
13

17

22

28

37
48

63

81

31

99

54

48

0
06

37

78

88

04

.0

.2
0.

0.

0.

0.

0.
0.

0.

0.

2.

2.

6.

8.
1.

1.

1.

5.

Particle Size (microns)

Figure 1. The Particle Size Distribution of Vat Violet 1

Ultrasound reduced the average size of the dye particles for each of the dyes tested. The effect

ranged from virtually nothing in the case of Vat Black 25 to greater than 1.75 microns in the case of Vat

Violet 1. The effect of ultrasound on particle size is most evident when examining the before and after

graphic distributions drawn by the analyzer. Ultrasound had the greatest effect on vat dyes with a

bimodal particle distribution. After these dye samples were treated with ultrasound the large particles

were completely eliminated. Without ultrasound vat dyes may contain particles larger than 14 microns,

but when vat dyes are treated with ultrasound the largest dye particles are smaller than 2 microns.
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45.000

40.000

35.000
Total % of Particles In Each Size

W/O US
30.000
With US

25.000

20.000

15.000

10.000

5.000

0.000
3

11 2
00

70
0

4
13

17

22

28

37

48

63

81

31

99

54

48
06

37

78

88

04

.0

.2
0.

0.

0.

0.

0.

0.

0.

0.

2.

2.

6.

8.
1.

1.

1.

3.

5.

14
Particle Diameter (microns)

Figure 2. The Summed Particle Size Distributions of the Untreated and Treated Dye Samples

Figure 2 shows a combined plot of all the untreated and treated samples. The solid bars are

untreated dyes, and the open bars are the ultrasound treated dyes. It can be seen that ultrasound

completely eliminates the larger particles (> 2 microns). Treating vat dyes with ultrasound shifts the

particle size distribution toward smaller particles.

An investigation into dye structure and the particle size change with ultrasound was conducted.

The vat dye base structures are given in Table 2. Using the vat dye base structures and comparing them

with the diameter differences in Table 1, a pattern can be seen. The two dyes which had the greatest

change in average particle diameter, Vat Violet 1 and Vat Green 3, are both benzanthrone derivatives.

These two dyes also had bimodal particle size distributions before treatment with ultrasound. The two

dyes with the smallest change in average particle diameter caused by ultrasound, Vat Black 25 and Vat

Violet 13, are both anthraquinone derivatives. Vat Green 1, a dye between these two extremes is a
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violanthrone derivative. Samples of Vat Orange 9 and Vat Blue 19 were unavailable for measurement.

Benzanthrone derivatives are effected the most by ultrasound, then violanthrone derivatives, and then

anthraquinone derivatives.

Table 2 Vat Dye Base Structures

Vat Dye Base Structure
Vat Violet 1 Benzanthrone
Vat Black 25 Anthraquinone
Vat Green 3 Benzanthrone
Vat Green 1 Violanthrone
Vat Violet 13 Anthraquinone
Vat Orange 9 Anthraquinone
Vat Blue 19 Violanthrone

Glass Transition Temperature (H. Beckham, J. Good, and J. Zhan)

One proposed mechanism responsible for the effects of ultrasound in textile wet processing was

the possible dilation of amorphous regions, i.e. decreasing the effective glass transition temperature in

synthetic fibers. Before dye can penetrate into the amorphous regions of synthetic fibers, the fiber must

be heated above its effective glass transition temperature. In commercial dyeing, plasticizers are often

added to lower glass transition temperatures. Since ultrasound allows fibers to be dyed at lower

temperatures, it was thought that ultrasound might lower the glass transition temperature. A dynamic

mechanical analyzer was used to obtain tan delta loss curves for polyester films in a water bath exposed

to ultrasound at 20 kHz. The results reveal that ultrasound does not affect the glass transition

temperature.

Diffusion Coefficients and Partition Coefficients (S. Michielsen, W. Carr, P. Das, and E.

McFarland)

We are investigating the effects of ultrasound on the diffusion coefficient for dye diffusing into

fibers and films. Previous reports [10, 11] have suggested that ultrasound increases dye diffusion
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coefficients in cellulose films; however, the model used in the investigation assumes that ultrasound does

not affect either partition coefficient or dye transport to the fiber surface from the dyebath.

To measure diffusion coefficients, we first attempted to use a water soluble fluorescent disperse

dye in combination with Raman and fluorescence microscopy to establish the concentration of dye in the

PET film as a function of position. Once the concentration as a function of position is determined,

diffusion coefficient is then calculated from the mass diffusion equation for one-dimensional diffusion

through a stationary membrane. The film was dyed for times ranging from 0 to 24 hours with C.I.

Disperse Blue 79 in a 1 L aqueous dye bath containing 10 mg/L of dye, 10 g/L benzoic acid carrier, and 2

g/l TritonTM X-100 at 100°C. After dyeing, the film was rinsed with water and dried. Then the film was

potted in a PMMA casting resin. Samples were cured for 24 hours, microtomed, and examined under a

Zeiss Axiovert 100 microscope fitted for fluorescence measurements. A 100 W Hg lamp was used as the

light source. Incident light was filtered so that only blue and UV light were transmitted. The sample

fluorescence was filtered, and only light with wavelengths greater than 510 nm was allowed to pass.

Since fluorescence intensity is directly proportional to the concentration of dye in the polymer,

fluorescence intensity was measured at various positions across the film to give a concentration versus

position profile.

Although this technique measured concentration as a function of position, problems were

encountered with this technique. Previously, we reported that the C.I. Disperse Blue 79 appeared to

degrade. Concentration measured with a SpectronicTM-20 decreased with dyeing time. Through

discussions with a dye expert, we learned that disperse dyes should not degrade at 100°C (12). One

possible explanation for the apparent degradation of C.I. Disperse Blue 79 was that the dye was actually

aggregating. If the dye aggregates, the solution will not absorb as much radiation in the

spectrophotometer. We were previously measuring the absorption of a dye sample

spectrophotometrically after diluting the sample with water. If we instead dilute the dye solution with

10% dimethyl formamide or ethyl alcohol, the dye aggregates should break up. Another possibility is
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that the dye solution degraded due to a pH that was too high. The dye solution should be held at a pH of

5 when dyeing polyester with disperse dyes. If the dye solution is held at a pH of 5, the degradation

should be prevented.

Another problem encountered with our technique is that the dye did not reach equilibrium even

after 24 hours. When measuring partition coefficient, the dye-fiber system must reach equilibrium.

Possible reasons for this have been discovered. The benzoic acid carrier used previously is a poor

carrier. Pres-carTM carrier is a much better carrier and allows for faster dyeing times.

The Raman and fluorescence microscope did not accurately pinpoint the concentration at each

position. Calculations reported previously have shown small errors in measuring concentration as a

function of position can cause big errors in diffusion coefficient. Even bigger errors are encountered

when exactly the same position can not be determined for two different times. Unless the Raman

technique can be further developed to include improved accuracy, this method will not be useful for our

measurements.

Current Work and Plans for the Future

New techniques for measuring dye concentration gradients in films and fibers are being

investigated. On a current NTC project [13], a Laser Scanning Confocal Microscope is being used to

determine dye concentration as a function of position. The technique is promising for our application

since it provides high resolution.

A technique is being considered for estimating diffusion coefficients and mass transfer rates.

The method uses solutions to Fick’s Second Law for diffusion through cylinders and slabs. The

diffusion coefficient and mass transfer rate can be related to average concentration of the dye in the

substrate. The dyed substrate can be dissolved, and the average dye concentration

spectrophotometrically measured. The validity of this method depends on how well the boundary and

initial conditions of the model are met.

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A steady-state experiment may be better for measuring diffusion coefficients due to the huge

errors generated when the same position can not be established in the fiber/film for two different times.

A method was reported [11] in which a polymeric film was placed between two sides of a diffusion cell.

One side contains a dye solution held at a constant concentration, and the other side contains a blank

solution. As dye passes through the film, the rate of dye diffused through the film is monitored until

steady state is reached. If mass flow rate and the dye concentration gradient in the film can be measured,

the effects of ultrasound on the diffusion coefficient and mass transfer coefficient can be determined.

The method requires that the effect of ultrasound on partition coefficient be previously established.

We will determine the effect of ultrasound on partition coefficient, which can be measured by

either adsorption or desorption techniques. The method of Gilbert (a desorption technique) is a

promising technique for use in this application [14].

Once the best method is established, the effect of ultrasound on the diffusion coefficient and

mass transfer coefficient will be measured. Work has already begun on establishing models for several

approaches.

[Other Contributors: Pronab Das, Post Doc (Georgia Tech); David Klutz (NC State), Elizabeth
McFarland (Georgia Tech), J. Zhan (Georgia Tech), Graduate Students, John Good, Undergraduate
Student (Georgia Tech)]
Industry Interactions: 12
Other Interactions Outside NTC: 10

References

1. Klutz, D., Master’s Thesis, North Carolina State University, 1993.

2. Thakore, K.A., Smith, C.B., and Clapp, T.G., American Dyestuff Reporter, 30, October, (1990.

3. Thakore, K.A., Indian Journal of Textile Research, 13, 133 and 208 (1988).

4. Shimizu, Y., Yamamoto, R., and Shimizu, H., Textile Research Journal, 59, 684 (1989).
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5. Suslick, K., ed. Ultrasound, Its Chemical, Physical, and Biological Effects VCH: New York, (1988).

6. Liu, L-S., Kost, J., D’Emanuele, A., and Langer, R., Macromolecules, 25, 123 (1992).

7. Henglein, and A., Gutierrez, M., J. Phys.Chem., 94, 5169 (1990).

8. Cost, M., Mills, G., Glisson, P., and Lakin, J., Chemosphere, 27, 1737 (1993).

9. Riesz, P., and Kondo, T., Free Radical Biology & Medicine, 13, 247 (1992).

10. Thakore, K.A., Smith, C.B., and Hite, D., Textile Chemists and Colorists, 22(11), 21 (1990).

11. Smith, C.B., Clapp, T.G., Thakore, K., Cato, M.J., and Hite, D., EPRI Final Report, TR-101379,

Phase I, Research Project 2782-06, November 1992.

12. Tincher, Wayne, Personal Communication, August 3, 1998.

13. McGregor, R., et al. “Fundamentals of Dye Diffusion Variance in Polyamide and Polyester Fibers,”

National Textile Center Annual Report: November 1997, 255-264.

14. Gilbert, G.A., Proceedings of the Royal Society of London, A183, 167-181 (1944).

Presentations/Publications

1. J. Good, J. Zhan, D. Klutz, G. Mock, and H. W. Beckham, Fundamental Investigations of

Ultrasound-Enhanced Dyeing, AATCC International Conference and Exhibition, Atlanta, GA; 8–11
October 1995.
2. Klutz, D.S., “Ultrasound Aided Exhaustion Dyeing,” M.S. Thesis, NCSU, 1993.
3. Klutz, D.S., Ph.D. Thesis, NCSU, 1997.