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THE SORPTION OF CATIONIC DYES

BY POLYESTER FIBERS

A THESIS
Presented to
The Faculty of the Division of Graduate
Studies and Research
by
Larry Clifford Kelley

In Partial Fulfillment
of the Requirements for the Degree
Master of Science
in the A. French Textile School

Georgia Institute of Technology


March, 1972

GEORGIA INSTITUTE OF TECHNOLOGY LIBRARY


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credit must be given in subsequent written or published work.
Extensive copying or publication of the thesis in whole or in
part requires the consent of the Dean of the Graduate Division
of the Georgia Institute of Technology.
This thesis by
Larry Clifford Kelley
has been used by the following persons, whose signatures attest
their acceptance of the above restrictions.
A library which borrows this thesis for use by its patrons
is expected to secure the signature of each user.

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BORROW ING^^IBRARY

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\

~~

DATE

slifjlS

In presenting the dissertation as a partial fulfillment of


the requirements for an advanced degree from the Georgia
Institute of Technology, I agree that the Library of the
Institute shall make it available for inspection and
circulation in accordance with its regulations governing
materials of this type. I agree that permission to copy
from, or to publish from, this dissertation may be granted
by the professor under whose direction it was written, or,
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and does not involve potential financial gain. It is understood that any copying from, or publication of, this dissertation which involves potential financial gain will not
be allowed without written permission.

=^V5_

JI
7/25/68

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"

SORPTION OF CATIONIC DYES


BY POLYESTER FIBERS

Approved:

Chairrnan-

Date approved by Chairman:_

ii

ACKNOWLEDGMENTS
I would like to express my appreciation to my thesis advisor,
Dr. Walter C. Carter, whose guidance and counsel has made this thesis
possible.
I wish to thank Dr. James L. Taylor for the financial assistance
provided through the School of Textiles.
Dr. Charles L. Liotta and Mr. R. K. Flege served on the reading
committee and I am grateful to them.
I am grateful to Dr. L. Howard Olson for his generous assistance
in formulating the calculator program.

iii

TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS
LIST OF TABLES

iv

LIST OF ILLUSTRATIONS
SUMMARY
CHAPTER
I.

INTRODUCTION

Statement of the Problem


Review of the Literature
II.
III.

INSTRUMENTATION, EQUIPMENT, AND CHEMICALS

10

EXPERIMENTAL PROCEDURE

12

Analysis of Dye and Carrier Solutions


Equilibrium Studies
Rate Studies
Determination of Fiber Radius
IV.

DISCUSSION OF THE RESULTS

19

Calibration Curves
Isotherms
Rate Studies
Apparent Diffusion Coefficients
V.
VI.

CONCLUSIONS

41

RECOMMENDATIONS

43

APPENDIX

44

BIBLIOGRAPHY

54

IV

LIST OF TABLES
Table

Page

1. Average Diffusion Coefficients Versus Carrier


Concentration

38

2.

Calculations

45

3.

Results of Rate of Dyeing Experiments

46

4.

Program for the Hewlett-Packard Calculator

48

5. Calculator Output, Dt/r


6.

Versus Ct/Co)

Apparent Diffusion Coefficients for All Points in the


Rate of Dyeing Experiments

51

52

LIST OF ILLUSTRATIONS
Figure

Page

1. Spectrum of Basic Blue 22 in 50/50 Methanol/Water

20

2. Absorbance-Concentration Relation for Basic Blue 22


in 50/50 Methanol/Water (1.00 cm Cell at 635 nm)

21

3.

Spectrum of Biphenyl in 50/50 Methanol/Water

22

4.

Absorbance-Concentration Relation for Biphenyl in


50/50 Methanol/Water (1.00 cm Cell at 248 nm)

23

5.

Sorption Isotherm for Dye in Polymer

25

6.

Langmuir Plot of Sorption Isotherm for Dye in


Polymer

26

Cross Section of Fiber After Sorption of 10 Percent


Dye Based on the Weight of the Fiber

27

8.

Sorption of Biphenyl by Teflon Liner (95C)

29

9.

Sorption of Biphenyl by Teflon Liner and Fibers (95C)

7.

...

30

10.

Sorption Isotherm for Biphenyl in Fiber (95 C)

31

11.

Percent Dye Decomposition Versus Time (95 C)

33

12.

Dye Sorption-Square Root of Time Curves With and


Without Carrier (95C)

34

Dye Sorption-Time Curves With and Without


Carrier (95C)

35

Log of Diffusion Coefficient Versus Amount of Carrier


in Bath

39

13.
14.

vi

SUMMARY

This work involves a study of the dyeing behavior of polyester


fibers which have been modified so that they will sorb cationic dyes.
The equilibrium state and the kinetics of the dyeing process have been
determined as well as the effect of chemical dyeing accelerants called
dye "carriers" on the dye diffusion process.
It is concluded that this dyeing system obeys a Langmuir type
sorption process where the dye uptake is dependent upon the number of
sorption sites in the fiber. The rate of dyeing is low but can be
greatly increased when a dyeing carrier such as biphenyl is added to the
dyebath.

The apparent diffusion coefficient is shown to increase with

increasing amounts of carrier in the dyebath, the log of the diffusion


coefficient being linearly related to the amount of carrier sorbed by
the fiber.

CHAPTER I

INTRODUCTION

Statement of the Problem


When polyester fibers were introduced in the late 1940's, their
density and impermeability presented special dyeing difficulties. It
was found that only nonionic disperse dyes could be used on the highly
hydrophobic fibers; however, under the usual dyeing conditions the rate
was extremely slow and higher dyeing temperatures were required to increase the rate of diffusion of the dye into the fiber.

It was then

found that certain organic compounds, commonly referred to as "carriers",


when added to the dyebath, caused an acceleration in the diffusion of
the dye (1). Today, polyester fibers are normally dyed either at temo
o
peratures. in excess of 100 C or at approximately 100 C in the presence
of carriers.
Even with the satisfactory dyeing rate by these methods the latitude of polyester fibers in the apparel industry was somewhat hampered
because of the restricted selection of available colors using disperse
dyes.

In the mid 1950*s the E. I. duPont de Nemours Company (2,3)

introduced a modified polyester fiber capable of accepting cationic


dyes, thus presenting a new selection of brilliant and varied colors.
Since only general information of a practical nature is available
concerning the dyeing of cationic dyeable polyester fibers, it is the
purpose of this study to determine experimentally the characteristics
of the dyeing process, namely, the equilibrium state and the effect of

carriers on the kinetics of the dyeing process.


Review of the Literature
With respect to dyeing behavior, polyester fibers are of two
types:

one that can be dyed only with disperse dyes, and one that can

be dyed with cationic as well as disperse dyes.

There is an abundance

of information on the disperse dye-polyester fiber system, but very


little on the cationic dye-polyester fiber system which presumably resembles the cationic dye-acrylic fiber system.

Therefore, this review

of the literature will include information on the dyeing of polyester


fibers with disperse dyes, the effect of carriers in accelerating the
dyeing process, and information on the dyeing of acrylic fibers with
cationic dyes.
Modifications of Polyester Fibers
Almost all of the polyester fibers on the market today are made
from a condensation polymer of terephthalic acid and ethylene glycol.
Polyester fibers chemically modified so that they can be dyed with cationic dyes are now available (2,3).

Sodium 3,5-di(carbomethoxy)ben-

zenesulfonate as a modifier is added to the polymerization process


providing acid groups as dye sites. Concentrations of 1 to 5 mol percent of the modifier are regarded as optimum and preferred.
sulting structure is as follows:

CH2-CH2-O-C-

-1

-C-0 +
Jn

SO3 Na

The re-

Dyeing Polyester Fibers


Mechanism of Dyeing. Waters (4) has determined the saturation
values and the relative diffusion coefficients of disperse dyes in
polyester, nylon, and cellulose acetate fibers. At 85 C, the polyester
fiber was found to sorb a little less dye than the cellulose acetate but
twice as much as nylon.

The relative diffusion of C. I. Disperse Orange

3 at 85 C was 680 times faster in nylon than in polyester, and at 100 C


this dye diffused into the polyester 48 times faster. Waters concluded
that the behavior of disperse dyes in polyester resembled their behavior
in nylon and cellulose acetate, and that the polyester fibers opened up
at higher temperatures allowing the dye to penetrate the fiber.
Remington and Schroeder (5) studied the equilibrium distribution
of disperse dyes between polyester fibers and water. Using three different disperse dyes, they found in each case a direct proportionality
between the concentration of dye in the water phase and the concentration of dye in the fiber which held until saturation occurred in both
phases. When two dyes were equilibrated simultaneously, each acted
independently of the other. The heat of dyeing for the polyester fiberdisperse dye system was calculated to be only 4 kcal/mol. These results
indicated that the dyeing mechanism involved simple solution of the dye
in the fiber.
Patterson and Sheldon (6) have described work in which the diffusion coefficients were derived from the rates of dyeing. At 95 C, the
diffusion coefficients of C. I. Disperse Red 1 and C. I. Disperse Red 15
I A 9
1
12?
into polyester staple were 8.5 X 10
cm sec
and 1.32 X 10
cm
sec

, respectively.

From other experiments the diffusion coefficients

were shown to be independent of concentration.

They also found that

when additional dye particles were added to a saturated dye solution,


the rate of dyeing remained constant.

It was their conclusion that only

single disperse dye molecules could diffuse within the fiber.


Vickerstaff (1) and Salvin (7) have conjectured that the dye molecules can diffuse only in the amorphous regions of a fiber.

In the case

of disperse dyes, Glenz et al. (8) and Salvin (7) concluded that the
forces of attraction linking the dye to the fiber are short range forces
such as hydrogen bonding, dipole interaction and Van der Waals forces.
In a study using seventeen disperse dyes, Glenz et al. (8) found that an
increase in the number of groups available for hydrogen bonding on the
dye molecule decreased the diffusion rate.
Effect of Carriers.

Schuler (9) investigated the role of carriers

in dyeing polyester fibers by using an isooctane system which was an excellent solvent for disperse dyes and carriers.

Surprisingly, the addi-

tion of water to an isooctane dye bath increased the rate of dyeing six
fold indicating that water itself was a powerful carrier. When equimolar
concentrations of widely differing carriers were sorbed by the fiber, the
rate of dyeing was relatively independent of the structure of the carrier,
and increasing the concentration of the carrier in the fiber increased
the rate of dyeing.

Schuler concluded that the mechanism of carrier

activity varied little and that the carriers entered the amorphous retions of a fiber and loosened the polymer interchain forces.
Glenz et al. (8) tested Schuler's hypothesis in an aqueous medium
by determining the diffusion coefficient of disperse dyes when equimolar
concentrations of benzoic acid and trichlorobenzene were actually inside

the fiber. They found an increase of the diffusion coefficient by a


factor of 10-100, and concluded that the effect of a carrier depended on
the number of molecules present in the interior of the fiber.
Vickerstaff (10) observed that water insoluble carriers such as
biphenyl were 50 times more effective on a weight basis than soluble
carriers in increasing the dyeing rate of disperse dyes in polyester
fibers. Also, a fiber which had been pretreated with biphenyl exhibited
a much higher initial rate of dyeing than a fiber where biphenyl was
merely added to the dyebath. An explanation of this was that the biphenyl in the pretreated fiber modifies the fiber structure thus giving
a higher initial rate, but when the biphenyl is in the dyebath, the rate
can be accelerated only after the biphenyl has penetrated the fiber.
When a carrier modifies a fiber by loosening interchain forces,
the fiber will swell as the carrier molecules penetrate between polymer
chains.

Rawicz et al. (11) studied the contraction of fibers, which is

a measure of its swelling, as a factor in carrier dyeing.

Contraction

was shown to be dependent upon the concentration of carrier added to the


bath, and water-insoluble carriers tend to shrink polyester fibers more
than water-soluble carriers. A study of X-ray diffraction patterns disclosed significant deorientation after a fiber had been treated with one
percent o-phenylphenol based on the weight of the fiber.
Balmforth et al. (12) examined the effect of carriers oil the
equilibrium uptake of disperse dyes in polyester fibers. They discovered that increasing the biphenyl concentration increased the equilibrium uptake, but only up to a biphenyl concentration of 7 percent based
on the weight of the fiber. Higher concentrations of the carrier re-

duced the amount of dye sorbed by the fiber. They theorized that 7
percent biphenyl was the amount necessary to saturate both the fiber and
the dyebath, and any further additions led to a third phase consisting
of biphenyl containing the dissolved dye.
Dyeing Acrylic Fibers
Vogel et al. (13) investigated the equilibrium state of Orion 42
acrylic fiber obtained by dyeing fibers at 100 C with three cationic
dyes.

When the reciprocal of the concentration of each dye in the fiber

i^/{p]f)

was plotted against the reciprocal of the concentration of dye

in the bath (l/[D]g) straight lines were obtained which extrapolated to


approximately the same point on the 1/jjDJf axis.

They concluded that

this system exhibited a Langmuir type isotherm and the maximum amount
of dye sorbed corresponded to the number of sulfate or sulfonate end
groups in the polymer.
Balmforth et al. (14) confirmed the findings of Vogel et al. and
stated that cationic dyes were sorbed by an ion exchange mechanism where
dye cations replaced the hydrogen or metallic cations present in the
fiber.

Their results showed that the amount of dye sorbed decreased

with increasing concentration of electrolytes since the cations of the


electrolyte compete for the sites with the dye cations.
Beckmann (15) has stated that adsorption of the cationic dye on
the surface of the acrylic fiber is due to the negative electrical
potential at the fiber surface. He quotes a value of -44 mV for this
potential.

This negative charge attracts the positively charged dye

to the surface of the fibers where sorption occurs.


Once the dye molecule is in the fiber the dye is transferred

from site to site progressively into the fiber.

Feichtmayr and Wurz (16)

point out that energy must be applied to the dye molecules to lift them
out of the energy wells corresponding to anionic sites and push them
into adjacent sites. Cegarra (17) has measured this energy and found it
to be between 60 and 80 kcal. per mol which is the highest activation
energy encountered in any dyeing process.
Measurement of the diffusion coefficient of cationic dyes into
the acrylic fibers has been impeded by the difficulty of the mathematical
treatment and the irregular cross section of commercial acrylic fibers
(15).

However, Peters et al. (18) in work with nylon and acid dyes have

shown by microdensitometric studies that the diffusion coefficient is


not constant, but increases as the concentration of dye in the fiber increases.

As the ratio of the filled sites to the number of sites in the

fiber approaches unity, the diffusion profile will tend to form a sharp,
slowly advancing line. Using photomicrographs Goodwin and Rosenbaum
(19) confirmed this observation for cationic dyes in acrylic fibers and
concluded that difficulties in the experimental procedure and interpretation limited the scope of microdensitometric determination of the diffusion coefficient.
In an earlier study, Rosenbaum (20) found apparent diffusion
coefficients for cationic dyes in acrylic fibers using an equation which
included the number of sites available in the fiber and the external
surface area of the fiber. The apparent diffusion coefficients he
found were of the order of 10"" cm sec" at 97*^C.
Summary
From a survey of the.literature, it can be stated that disperse

dyes enter polyester fibers by a simple solution mechanism which continues until the system is saturated with dye. The diffusion of single
dye molecules takes place in the amorphous regions of the fiber, and
the diffusion coefficient is independent of dye concentration. Because
of the compact nature of polyester fibers, the diffusion of dye is
extremely slow, and once in the fiber the dye is held by short range
electrical forces.
Carriers enter the amorphous regions of fibers by the solution
mechanism where they loosen interchain forces and swell the fiber allowing dye molecules freer movement into the fiber. The efficiency of
a carrier depends on the number of molecules inside the fiber; however,
after the system is saturated the dye uptake is reduced.
The sorption of cationic dyes by acrylic fibers obeys the
Langmuir isotherm where the number of anionic sites control the amount
of dye in the fiber.

Dyeing can be explained as an ion exchange between

dye cations and metallic or hydrogen ions on the sulfate or sulfonate


groups in the fiber. The dye diffuses by traveling from site to site
progressively into the fiber. The speed of diffusion is dependent upon
the concentration of dye molecules in the fiber; the higher the concentration, the faster the diffusion.
The purpose of this study is to determine the sorption mechanism
and measure the apparent diffusion coefficients of a cationic dye, with
and without carrier, into modified polyester fibers.

From this survey

of the literature, it is believed that this system will closely resemble


the cationic dye-acrylic fiber system.

As pointed out in the literature,

diffusion of disperse dyes is extremely slow in polyester fibers.

Therefore, it is to be expected that cationic dyes will also diffuse very


slowly.

The effect of carriers in increasing the diffusion of dyes is

known, but the magnitude in the system under investigation is not revealed in the literature.

10

CHAPTER II

INSTRUMENTATION, EQUIPMENT, AND CHEMICALS

Dacron type 161 "12 denier" staple was used in this work. This
fiber is manufactured by the E. I. duPont de Nemours Company.

The dye

used throughout this study was C. I. Basic Blue 22 also obtained from
the E. I. duPont de Nemours Company.

The commercial name of the dye is

"Sevron" Blue 2G. The biphenyl carrier, 99 percent purity, was obtained
from the Monsanto Company.
The constant temperature bath used in this work consisted of an
insulated metal tank filled with polyethylene glycol, A Fisher Proportional Temperature Control which included a heater and a thermistor
probe achieved temperature control to +.01C.

A constant source of heat

was provided by a 750-watt flexible immersion heater regulated with a


120-volt Staco Variable Autotransformer (type 2PF1010).

A Gerald K.

Heller Company GT21 laboratory stirrer and accompanying motor controller


was used to insure a uniform temperature in the bath.
Agitation of flasks was provided by a Burrell Wrist Action Shaker.
When complete immersion of the dyebath was required, a tumbler device
provided constant rotation of 8-inch pressure tubes obtained from Ace
Glass Incorporated.

The pressure tubes were sealed using standard

bottle caps with 5 mil Teflon film as a seal.


Absorbance measurements of dye and carrier solutions were made
using a Beckman DB-G grating spectrophotometer equipped with a Beckman

11

10-inch recorder.
Weighings were made with a Mettler H6T balance. Water purification was accomplished by passing tap water through a Corning LD-2a
demineralizer.
For determining the diameter of the polyester fibers, a Carl
Zeiss Microscope with an American Optical Filar Micrometer Eyepiece was
used.

Calibration of the eyepiece was made with an American Optical

Company 2 mm micrometer slide.


Reagent grade methanol, acetone, glacial acetic acid, and N,
N-dimethylformamide were obtained from the Fisher Scientific Company.
Triton X-100 was obtained from the Rohm and Haas Company.

12

CHAPTER III
EXPERIMENTAL PROCEDURES

^'

In order to determine the dyeing behavior of cationic dyeable


polyester fibers and the effect of carriers on the dyeing behavior, it
was necessary to develop analytical methods for estimating the amounts
of dye and carrier sorbed by the fiber. In the determination of the
sorption isotherms for the dye, this is usually accomplished by either
a sorption or a desorption technique.

In this work, the sorption tech-

nique was used and the amounts of dye in the two phases were determined
by measuring spectrophotometrically the amounts of dye initially present
and the amount present at equilibrium.

Thus, the amount of dye sorbed ;

could be calculated from the change in dye concentration, i.e., by


difference. This procedure was used since more direct methods for
measuring the concentration of dye in the fiber were unsuccessful. The
dye could not be easily "stripped" from the fiber, and no good solvent
for the dyed fiber was available.
An identical procedure was used for determining the amounts of
the carrier, biphenyl, sorbed by the fiber.
In studying the rates of dyeing, both in the absence and presence
of carrier, the amounts of dye sorbed were determined in a similar
manner, i.e., by measuring spectrophotometrically the dye concentration
initially and after specified times of dyeing.
In order to use the analytical method described, spectrophotom-

13

etric calibration data for both the dye and carrier were required. This
is described below.
Analysis of Dye and Carrier Solutions
A stock solution of the dye was prepared having a concentration of
.5 g/1 and a pH of 4.5 (2.5 g/1 glacial acetic acid).

This stock, solu-

tion was diluted with water and methanol such that the solution was 50/50
methanol/water.

It was then examined spectrophotometrically, the ab-

sorbance values being recorded between 400 and 700 nanometers. The
maximum absorption peak was selected, and the absorbance values at the
absorption peak were plotted against the concentration of dye adjusted
so that the absorbance values would be between zero and one (1.0) when
using a one centimeter cell.

In all cases the reference cell of the

spectrophotometer contained a solution identical to that in which the


dye was dissolved.
A stock solution of .2 g/1 biphenyl was made by dissolving the
carrier in 500 milliliters of methanol, then adding water until the
liter mark was reached in a volumetric flask.

The procedure for

determining the wavelength for maximum absorbance and the calibration


curve was the same as for the dye except that the region between 200
and 300 nanometers was examined spectrophotometrically.
Equilibrium Studies
Dye in the Polymer
Preliminary experiments revealed that the sorption of the cationic
dye by the fiber was so slow that several hundred hours at the boil
would be required to reach equilibrium.

One means of circumventing this

14

long contact time was to increase the surface area by dissolving the
fibers and then precipitating the polymer in a finely divided form.
First, to remove impurities from the polyester fibers, 20 grams
of the fiber were scoured with 4 percent Triton X-100 based on the
weight of the fiber for 15 minutes at the boil (liquor ratio of 40:1).
The fibers were washed thoroughly with water, air dried and conditioned
at room temperature. The fibers prepared in this way were used throughout the study.
Two grams of the fiber were dissolved in 125 milliliters of
boiling N,N-dimethylformamide and diluted to a liter with water containing acetic acid. Twenty-five milliliter portions of this solution containing .05 grams of the polymer were pipetted into six 100 milliliter
volumetric flasks. Differing amounts of the dye stock solution were
then pipetted into the flasks so that they contained 20, 30, 40, 50, 60,
and 70 percent dye based on the weight of the polymer. When the dye
solutions contacted the solution of the dissolved polymer, precipitation
. of the polymer occurred in the form of a fluffy mass. All of the flasks
were filled to 100 milliliters with water, stoppered, and allowed to
equilibrate at room temperature for two days.

Then the contents of each

flask were filtered through glass filters to remove the dyed polymer.
The filtrates were diluted with methanol and water to achieve a 50/50
methanol/water solution. These solutions were analyzed spectrophotometrically.
Biphenyl in the Fiber
To relate the effect of the biphenyl on the diffusion of the dye
into the polymer, it was necessary to ascertain the amount of biphenyl

15

in the fiber.

In the course of this study biphenyl was found to steam

distill making complete immersion of the dyebath mandatory; however,


the Teflon liner required when using pressure tubes was found to sorb
biphenyl.

It was therefore necessary to determine the amount sorbed by

the Teflon liner.


Stock solutions of biphenyl dissolved in acetone were prepared
in concentrations of .1, .2, .3, and .4 g/1 so that when five milliliters
of these solutions were pipetted into a pressure tube, they would yield
2, 4, 6, and 8 percent biphenyl based on a weight of .125 grams of fiber.
Eight pressure tubes were used, two for each concentration, and the
acetone was evaporated by means of a water aspirator leaving a residue
of carrier in the bottom of the tubes. Twenty-five milliliters of water
were added to each tube, and .125 grams of fiber were placed in four of
the tubes resulting in one blank where only the Teflon liner would be
in contact with the biphenyl, and in one containing fiber (liquor ratio
of 200:1) for each carrier concentration.

A two-inch square Teflon

liner was placed over the mouth of each tube which was capped and fastened onto the tumbler device. The tubes were immersed in the 95 C oil
bath and rotated at 48 r.p.m. for 22 hours.
When the tubes were uncapped, the Teflon liners and the fibers,
where applicable, were removed and rinsed in a beaker containing methanol
to dissolve any biphenyl on the fiber surface.

The carrier solutions

in the tubes were poured into 100 milliliter volumetric flasks, and the
tubes were rinsed with methanol to dissolve any remaining biphenyl. The
biphenyl solutions were diluted with water and methanol such that the
final solutions were 75/75 methanol/water.

These solutions were

16

analyzed spectrophotometrically.

Rate Studies
Dyeing Without Carrier
Cationic dyes have been found to be unstable at normal dyeing
temperatures, and decompose after prolonged dyeing times even in an
acidic dyebath. The dye used in this study, C. I. Basic Blue 22, has
been reported to be one of the most stable cationic dyes; nevertheless,
preliminary work, indicated that decomposition was occurring when dyeings
were conducted at times up to 25 hours.
To determine the percent dye decomposition, 50 milliliters of the
.5 g/1 dye stock solution (pH 4.5) were pipetted into each of the 100
milliliter volumetric flasks. The flasks were stoppered, attached to
o
the shaker, and placed in the 95 C oil bath. The action of the shaker
was carefully controlled to insure the same amount of agitation throughout the experiment.
After contact times ranging from one to 25 hours the flasks were
removed, and diluted with methanol and water giving a 50/50 methanol/
water solution. These solutions were examined spectrophotometrically.
Once the amount of dye decomposition was known, the rate studies
were performed with the procedure being the same. Again, 50 milliliters
of the dye stock solution (10 percent dye based on the weight of the
fiber) were pipetted into each flask.

To give a standard liquor ratio

of 200:1, .25 grams of the fiber were placed in each flask. They were
then attached to the shaker and placed in the oil bath.

Several trials

were performed at each time interval to insure reliability of the re-

17

suits. When the flasks were removed, the fibers were withdrawn and placed
in a beaker where they were rinsed with methanol.

The dye solutions were

diluted with methanol and water to give a 50/50 methanol/water solution.


These solutions were analyzed spectrophotometrically.
Dyeing with Carrier
As mentioned above, steam distillation of the biphenyl at 95 C
necessitated the complete immersion of the dyebath; therefore, the rate
experiments utilizing carrier required the use of the tumbler device
and pressure tubes. The effect of the biphenyl on the amount of dye
uptake was investigated using concentrations of 2, 4, 6, and 8 percent
biphenyl based on the weight of the fiber.
Five milliliters of the appropriate biphenyl stock solution were
evaporated in each pressure tube as described previously.

Twenty-five

milliliters of the dye stock solution and .125 grams of the fiber were
added to the tubes giving a 200:1 liquor ratio and 10 percent dye based
on the weight of the fiber. As in the biphenyl sorption experiment,
the tubes were tumbled in the oil bath at 48 r.p.m.
After varying dyeing times the tubes were removed and the dyebaths were poured into flasks. The Teflon liners and the fibers were
removed and rinsed with methanol. The dye solutions were diluted to
obtain 50/50 methanol/water solutions which were analyzed spectrophotometrically.

Determination of Fiber Radius


The average radius of the polyester fibers was determined so that
the apparent diffusion coefficient could be derived.

About 30 fibers

18

were placed on a slide with a drop of mineral oil as the immersion


medium.

Twenty diameter measurements were made microscopically using

a calibrated micrometer eyepiece.

*S

19

CHAPTER IV

DISCUSSION OF THE RESULTS


Calibration Curves
The peak, absorbance of Basic Blue 22 was discovered to occur at
635 nanometers as shown in Figure 1. When experiments on the absorbanceconcentration relationship were performed, a linear dependence of absorbance on concentration was found only if the dye solutions contained 50
percent methanol. At the higher concentrations the dye molecules
probably aggregated causing lower absorbance readings and thus a nonlinear relationship. However, when methanol was used a linear relationship was obtained as is shown in Figure 2. The specific absorbance for
the dye (impure, commercial) was found to be 8.04 (1.00 g/1, 1 cm cell
thickness).
The spectrum of biphenyl revealed that the peak absorbance was at
248 nanometers as shown in Figure 3. The calibration curve when the
solvent was 50/50 methanol/water is shown in Figure 4, An excellent
linear relationship between absorbance and concentration was observed.

Isotherms
Dye in the Polymer
Figure 5 shows the sorption isotherm for the dye in the precipitated polymer at room temperature. The equations for conversion of
the dyebath absorbance values to grams of dye per kilogram of fiber and
grams per liter left in the dyebath are given in Table 2 in the Appendix.

20

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24

The curve obtained is characteristic of a Langmuir type isotherm


where dye sorption is a function of the sites available, in this case,
the sulfonate groups. The equation for a Langmuir isotherm is:
1
1
1
[D]^ = k[S]^ [D]g + [S]^

where [D]

is the concentration of dye in the fiber at equilibrium, k is

a constant, [S],. is the number of sites in the polymer available for


sorption of dye, and [D]
equilibrium.

is the concentration of dye in the bath at

In Figure 6, l/[D]f is plotted against l/[D]g giving a

straight line which extrapolates to .0027 on the 1/[D] axis.

The above

equation reveals that this point corresponds to the reciprocal of the


number of sites; thus, the polymer has enough sites to sorb 370 grams of
impure dye per kilogram of polymer.
To determine the moles of pure dye sorbed, it was necessary to
derive the purity of the commercial dye. Using the absorbance relationship between known concentrations of pure and impure dye, the purity was
calculated to be 20 percent. Balmforth et al. (14) have found the
molecular weight to be 455. After appropriate calculations, the polyester fibers were found to sorb 0.16 moles of pure dye per kilogram of
fiber. Thus, the modified polyester fibers have extremely high site
content when one considers that nylon and acrylic fibers sorb approximately .04 eq/kg and .05 eq/kg of dye, respectively.
Figure 7 gives an indication of the high affinity of Basic Blue
22 for modified polyester fibers. The photomicrograph shows the penetration of dye into the fiber after a 10 percent dyebath had been

25

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27

Figure 7. Cross Section of Fiber After Sorption of 10 Percent Dye


Based on the Weight of the Fiber

28

exhausted.

A contact time of 81 hours at 100C was required. The

fibers are narrowly ring dyed because most of the dye molecules are
captured by the sulfonic acid groups on and near the surface of the
fiber.
Biphenyl in the Fiber
Since the Teflon liner used to seal the dyeing tubes was found
to sorb the biphenyl, it was necessary to measure the amount sorbed.
The sorption by the Teflon is shown in Figure 8, and the sorption by the
Teflon liner plus the fibers is shown in Figure 9.

By subtracting the

effect of Teflon, the isotherm for the sorption of biphenyl by the fiber
was determined as shown in Figure 10. The points on the curve represent
initial carrier concentrations of 2, 4, 6, and 8 percent based on the
weight of the fiber, and it can seen that at 8 percent carrier the fiber
appears to be approaching saturation.
When establishing the isotherms the fibers were left in contact
with the biphenyl for 22 hours at 95C. At the end of this time it was
noted that fiber segments one-eighth of an inch long remained in the
bath after the main fiber mass had been removed.

The number of fiber

segments ranged from a few for the 2 percent carrier concentration to


10 or 15 for the 8 percent concentration.

It appears that the plasti-

cizing action of biphenyl coupled with hydrolysis of the polymer leads


to severe fiber damage. During the study, an attempt was made to
establish an isotherm for the biphenyl under the same conditions of pH
which existed in dyeing, namely 4.5.

After 22 hours in this acidic bath

the fibers were completely broken down into minute segments. It was
concluded that under this acidic condition, hydrolysis is more severe.

29

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32

and biphenyl, because of its plasticizing action enhances the degradation of the fiber.

Rate Studies
o
The percent decomposition of the dye for various times at 95 C is
plotted in Figure 11. The amount of decomposition was subtracted from
all the points in the rate of dyeing experiments without carrier because
of the long dyeing times. The decomposition was ignored in the experiments with carrier since the longest dyeing time was eight hours where
only 3.2 percent of the dye decomposed.
Figure 12 and 13 show the rate of dyeing curves without carrier
and with carrier in concentrations ranging from 2 to 8 percent based on
the weight of the fiber. The points in both figures are an average of
the points at each dyeing time. Table 3 in the Appendix lists all the
values for various times and carrier concentrations. Figure 12 reveals
a linear relation between the amount of dye in the fiber and the square
root of dyeing time. The slopes of these curves are proportional to the
square root of the diffusion coefficient.

Figure 13 gives a better

picture of the rate process. It appears that if no carrier is present


the surface sites are filled within two hours, and then the rate of
dyeing becomes much slower as the dye molecules move into the fiber.
When the biphenyl is added to the dyebath, the effects are very apparent
because the biphenyl immediately begins to penetrate the fiber loosening
the interchain forces and swelling the fiber. The dye molecules travel
to the sites in the interior of the fiber at a rate which increases with
carrier concentration. The increase in the rate of dyeing between 4 and

33

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36

6 percent carrier may be because the 6 percent concentration yields


enough biphenyl molecules to completely penetrate the fiber, or because
of experimental variability.
Apparent Diffusion Coefficients
The diffusion of dye in the fiber is the process which governs
the dyeing rate and may be regarded as a characteristic measure of the
dyeing rate. In this study the apparent diffusion coefficients were
determined by using Hill's (21) equation:

C^/CcD 1 - .692 exp (-5.785 Dt/r^) + .190 exp (-30.5 Dt/r^)


+ .0775 exp (-74.5 Dt/r^) . . . J
In this equation C^ is the grams of dye per kilogram of fiber sorbed
after time t, COD is the grams of dye per kilogram of fiber sorbed at
saturation or equilibrium, D is the diffusion coefficient in cm2 sec-1,
t is given in seconds, and r is the radius of the fiber in centimeters.
Hill's equation allows the diffusion coefficient to be calculated using
the rate of dyeing curves if the fiber cross sections are circular, and
the concentration of dye at the surface is constant. As seen in Figure
7 the polyester fibers used in this study were circular, and the concentration was kept nearly constant by utilizing a long liquor ratio
(200:1) and short dyeing times in the rate studies to maintain a small
dyebath exhaustion.
In his work Hill presented a table which expressed C^/Cco as a
?

function of Dt/r . The relationship between C^/Cco and Dt/r was also
presented graphically.

Since the times of dyeing and the radius of the

37

fibers are known, the diffusion coefficient can be calculated quite


simply. However, in this study C

values for dyeing without carrier were

so low that the C^/CCD ratio fell below the points in Hill's table. This
problem was solved by using a computer to calculate small values of C^/CcD
2
and the corresponding Dt/r values. The program and the output are given
in the Appendix in Tables 4 and 5, respectively.
Since the average radius of the polyester fibers was calculated
to be 1.73 X 10

centimeters, the apparent diffusion coefficients for

all the data points in Table 3 were easily determined and are presented
in Table 6 in the Appendix.

Because of the variability of the points,

it was believed that choosing several points from the rate curves in
Figure 12 would yield more valid diffusion coefficients. The averages
of these points are shown in Table 1 revealing that the diffusion of
dye into the fiber is 17.6 times faster when 8 percent biphenyl based on
the weight of the fiber is in the dyebath as against no carrier. When
the log of the diffusion coefficient was plotted against the percent
carrier based on the weight of the fiber in the dyebath, a straight
line resulted as shown in Figure 14. Since the amount of biphenyl in
the fiber is proportional to the amount in the dyebath, it is concluded
that the log of the diffusion coefficient is proportional to the amount
of biphenyl in the fiber, a relationship similar to that exhibited by
nylon dyed with disperse dyes in the presence of phenol (22) .
The diffusion coefficient obtained for dyeing with no carrier,
4.4 X 10~

cm

sec~ , compares favorably with results obtained by

Patterson and Sheldon (6) who found diffusion coefficients for disperse
dyes in polyester fibers at 95C to be from 6.02 X 10 ^^ to 8.5 X 10^-14

38

Table 1. Average Diffusion Coefficients Versus


Carrier Concentration

Percent Carrier Based on


the Weight of the Carrier

Average Diffusion
Coefficients (cm sec" )

4.40 X 10

-14

-13
1.04 X 10
-13
1.66 X 10
5.50 X 10
7.76 X 10

-13
-13

39

pq

(3

n4

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0)
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40

?
-1. Glenz et al. (8) found diffusion coefficients ranging from
cm^sec
-13
-12
2
-1
3.3 X 10
to 6.2 X 10
cm sec
when dyeing polyester fibers at
100 C with disperse dyes.

They also discovered that the diffusion

coefficients were 10 to 100 times higher when carriers were used.

41

CHAPTER V

CONCLUSIONS
The sorption isotherm for a cationic dye by a precipitated
polyester polymer revels that a saturation value is reached. When
the reciprocal of the amount of dye in the polymer is plotted against
the reciprocal of the amount of dye in the bath, a linear relationship
results which is characteristic of a Langrauir type isotherm. The
amount of dye sorbed is dependent upon the number of sulfonic acid
groups in the modified polyester.

The precipitated polymer sorbed .16

eq/kg of Basic Blue 22 which is a high value compared to nylon and


acrylic fibers where the maximum sorption is .04 eq/kg and .05 eq/kg
of dye, respectively.
The amount of biphenyl sorbed by the fiber is proportional to
the amount initially in the dyebath until a concentration of 8 percent
carrier based on the weight of the fiber (.4 g/1) where the fiber
approaches saturation. After a contact time of 22 hours at 95C, the
biphenyl causes slight degradation of the fibers, and the degradation
is more pronounced with increasing concentrations of biphenyl. Under
the same conditions except at a lower pH of 4.5, the fibers are completely degraded.

It is concluded that the plasticizing action of the

biphenyl causes an enhancement in the hydrolysis of the ester linkages


in the polymer chain.
The rate of dyeing at 95 C is slow without the aid of a carrier.

42

The rate is accelerated by the addition of biphenyl, and it increases


as higher concentrations of biphenyl are employed in the dyebath.
o
The apparent diffusion of the dye in the fiber at 95 C is con-14
2
-1
stant and very low (4.4 X 10
cm sec ) . The addition of biphenyl
to the dyebath increases the speed of diffusion, and the diffusion
coefficient is 17.6 higher with 8 percent biphenyl based on the weight
of the fiber than with no carrier.

The increase in the diffusion coeff-

icient is proportional to the amount of biphenyl in the dyebath.

Because

disperse dyes have similar diffusion coefficients, it is concluded that


the diffusion of dye in a polyester fiber is controlled by the fiber
structure and the changes in structure which occur when a carrier such
as biphenyl is sorbed by the fiber.

T$

43

CHAPTER VI

RECOMMENDATIONS

In this work the biphenyl and the dye were simultaneously added
to the dyebath.

The effect of pretreating the fibers with biphenyl

would be an interesting and necessary study.


The determinination of the activation energy for the cationic
dye-polyester fiber system would be a valuable investigation.
It was found that biphenyl causes slight degradation of the
polyester fibers after long contact times at an elevated temperature,
and severe degradation in an acidic medium.

An interesting study would

be to determine the effect of various dyeing accelerants on textile


fibers as a function of pH, time, and temperature.

?S

The literature

fails to mention this deleterious effect of carriers, presumably because


practical dyeing times have durations of only several hours.

4A

APPENDIX

-v1

45

Table 2. Calculations

Determination of Amount of Dye in Fiber and in Bath


B = Dye in bath (g/1)
C = Dye in fiber (g/kg)
Cj = Initial concentration of dye (g/1)
A = Absorbance at 635 nm
f = Dilution factor
a = Specific absorbance for the dye (8.04
for 1.00 g/1, 1 cm cell)
V = Volume of dyebath (ml.)
w = Weight of fibers (g)

B = A-

C = V (c - A_Ll)
w
^
a

46

Table 3.

Results of Rate of Dyeing Experiments

Amount of Carrier
In Dyebath
(percent o.w.f.)

Time of Contact
(hours)

Amount of Dye in
the Fiber (g/kg)

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
6
6
6
6
6
6
6
6

4
4
4
4
9
9
9
9
16
16
16
16
25
25
25
25
1
2
2
4
4
6
6
1
1
2
2
4
4
8
8

12.2
10.4
14.8
13.4
16.0
14.8
17.2
18.6
28.0
24.2
22.4
21.8
34.4
34.4
35.2
31.4

0.75
0.75

2
2
4
4
6
6

8.0
13.4
15.4
18.4
19.4
25.4
24.4

9.4
10.0
15.4
15.4
22.8
23,8
40.4
37.8
16.4
16.4
28.4
30.4
44,2
43.2
52.2
52.2

47

Table 3.

Results of Rate of Dyeing Experiments (Continued)

Amount of Carrier
in Dyebath
(percent o.w.f.)

Time of Contact
(hours)

0.5
0.5
1
1
2.75
2.75
4
4

Amount of Dye in
the Fiber (g/kg)

16.4
15.4
24.8
25.4
39.4
41.4
49.2
50.2

48

Table 4.

Program for the Hewlett-Packard Calculator

PROGRAM 0

00 ENT EXT

05

Oa

10

15

la

5
CHG SON
1
0
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FMT
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20 FMT

25

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30

35

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9
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1
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40 7

45

4a

50

55

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9
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80 IF X<Y

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70 eX
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CHG SGN

49

Table 4.

Program for the Hewlett-Packard Calculator (Continued)

PROGRAM 1
00

05

Oa

10

15

la

1
0
1
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6
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DIV
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7
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0
6
FMT
YTO
6a (Yl
1
0
5
70 FMT
PI
IF X>Y
8
5
75 1
0
4
FMT
PI
7a UP
1
0
3

80 FMT
YTO
GTO
2
3
85 1
0
0
FMT
PI
8a UP
UP
FMT
STOP

50

Table 4.

Program for the Hewlett-Packard Calculator (Continued)

PROGRAM 2

00 CLR
1
0
0
FMT
05 YTO

'v-

Oa

10

15

^5

la

20 YTO
,
FMT
END
*

1
UP
1
0
1
FMT
YTO
ENT EXP
5
CHG SGN
UP
1
0
5
FMT
YTO
CLR
1
0
2
FMT

PROGRAM 3
Hewlett-Packard library routine for the 9100A calculator
computing the Bessel function of the first kind of order
n.

This is Part # 09100 - 70025

51

Table 5. Calculator Output, Dt/r Versus C^/CcD

-J

.00001
.00002
.00004
.00007
.00010
.00020
.00040
.00070
.00100
.00200
.00400
.00700
.01000
.02000
.04000
.07000
.10000
.20000
.40000
.70000
1.00000

0141881
0157251
0186014
0221853
0251091
0333939
0459591
0596739
0709559
0992999
1388350
1818374
2154950
2985829
4095999
5227611
6058242
7821475
9315687
9879283
9978705

52

Table 6.

Amount
of
Carrier
in Bath
(percent
o.w.f.)

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
6
6
6

Apparent Diffusion Coefficients For All Points


in the Rate of Dyeing Experiments

Time
(sec X 10~ )

CjCm

D t / r 2 ( x 10^)

Diffusion
Coefficient
9

(cm'' sec"-*- X 10

1.44
1.44
1.44
1.44
3.24
3.24
3.24
3.24
5.76
5.76
5.76
5.76
9.00
9.00
9.00
9.00
0.36
0.72
0.72
1.44
1.44
2.16
2.16
.36
.36
.72
.72
1.44
1.44
2.88
2.88
.27
.27
.72

.0329
.0281
.0400
.0362
.0432
.0400
.0464
.0502
.0756
.0654
.0605
.0589
.0929
.0951
.0848
.0929
.0216
.0362
.0416
.0497
.0524
.0686
.0659
.0254
.0270
.0416
.0416
.0616
.0643
.1091
.1021
.0443
.0443
.0767

93
30
97
37
50
97
10
20
15.50
85.00
7.40
7.00
17.50
18.00
14.70
17.50
0.65
37
25
75
35
35
8.65
03
20
25
25
50
8.20
20.50
21.00
4.00
4.00
11.70

01
,70
,17
,92
24
,75
,80
,82
8.03
40
83
63
81
81
98
81
40
84
13.50
9.86
11.10
12.90
12.00
8.55
9.97
13.50
13.50
15.60
17.00
21.30
21.80
44.30
44.30
48.60

14

53

Table 6.

Amount
of
Carrier
in Bath
(percent
o.w.f.)

6
6
6
6
6
8
8
8
8
8
8
8
8

Apparent Diffusion Coefficients For All Points


in the Rate of Dyeing Experiments (Continued)

Time
(sec X 10"^)

.72
1.44
1.44
2.10
2.10
.18
.18
.36
.36
.99
.99
1.44
1.44

CjCCD

Dt/r^(x 10^)

.0821
.1194
.1167
.1410
.1410
.0443
.0416
.0670
.0686
.1064
.1118
.1329
.1356

35.00
29.30
27.80
41.50
41.50
4.20
3.60
9.00
9.50
20.30
22.00
36.50
38.00

Diffusion
Coefficient
(cra^ sec"^ x lO-'-'^)

46.00
60.80
57.70
59.10
59.10
69.80
59.80
74.80
78.90
61.30
66.40
75.80
78.90

54

BIBLIOGRAPHY
1. Vickerstaff, T., The Physical Chemistry of Dyeing, 2nd ed., Oliver
and Boyd, London (1954), pp. 484-493.
2.

Griffin, J. M., and Remington, W. R., U. S. Patent No. 3,018,272


(1962).

3.

Griffin, J. M., U. S. Patent No. 3,057,827 (1962).

4.

Waters, E., Journal of the Society of Dyers and Colourlsts, 66,


609 (1950).

5.

Remington, W. R., and Schroeder, H. E., Textile Research Journal,


21, 177 (1957).

6.

Patterson, D., and Sheldon, R. P., Transactions of the Faraday


Society, 55, 1254 (1959).

7.
)
8.

Salvln, V. S., American Dyestuff Reporter, 49, 600 (1960).

9.

Glenz, 0., Beckmann, W., and Wunder, W., Journal of the Society of
Dyers and Colourlsts, 75, 141 (1959).
Schuler, M. J., Textile Research Journal, 27, 352 (1957).

10.

Vickerstaff, T., Hexagon Digest, 20, 7 (1954).

11.

Rawlcz, F. M., Gates, D. M., and Rutherford, H. A., American Dyestuff


Reporter, 50, 320 (1961).

12.

Balmforth, D., Bowers, C. A., Bulllngton, J. W., Gulon, T. H., and


Roberts, T. S., Journal of the Society of Dyers and Colourlsts, 82,
405 (1966).

13.

Vogel, T., De Bruyne, J. M. A., and Zimmerman, C. L., American Dyestuff Reporter, 47, 581 (1958).

14.

Balmforth, D., Bowers, C. A., and Gulon, T. H., Journal of the


Society of Dyers and Colourlsts, 80, 577 (1964).

15.

Beckmann, W., Journal of the Society of Dyers and Colourlsts, 77,


616 (1961).

16.

Felchtmayr, F., and Wurzi A., Journal of the Society of Dyers and
Colourlsts, 77, 626 (196^).

55

17.

Cegarra, J., Journal of the Society of Dyers and Colourists. 87


149 (1971).
"~

18.

Peters, R. H., Petropoulos, J. H., and McGregor, R. , Journal of the


Society of Dyers and Colourists, 77, 704 (1961).

19.

Goodwin, F. L., and Rosenbaum, S., Textile Research Journal, 35,


439 (1965).

20.

Rosenbaum, S., Textile Research Journal, 33, 159,291 (1964).

21.

Hill, A. v., Proceedings of the Royal Society, B104, 39 (1928).

22.

Jeschke, W. D., and Carter, W. C , "Diffusion Characteristics of


Disperse Dyes in Nylon-66 and Their Relationship to Poljmier
Structure," Paper, Fiber Society Meeting, Charlotte, North Carolina,
April 16-17, 1964.

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