Академический Документы
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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
N A M E ^ D ADDRESS OF USER
BORROW ING^^IBRARY
^
\
~~
DATE
slifjlS
=^V5_
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7/25/68
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Approved:
Chairrnan-
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
10
EXPERIMENTAL PROCEDURE
12
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
38
2.
Calculations
45
3.
46
4.
48
Versus Ct/Co)
51
52
LIST OF ILLUSTRATIONS
Figure
Page
20
21
3.
22
4.
23
5.
25
6.
26
27
8.
29
9.
7.
...
30
10.
31
11.
33
12.
34
35
39
13.
14.
vi
SUMMARY
CHAPTER I
INTRODUCTION
It was then
one that can be dyed only with disperse dyes, and one that can
There is an abundance
Sodium 3,5-di(carbomethoxy)ben-
CH2-CH2-O-C-
-1
-C-0 +
Jn
SO3 Na
The re-
, respectively.
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.
in dyeing polyester fibers by using an isooctane system which was an excellent solvent for disperse dyes and carriers.
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.
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
Contraction
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.
i^/{p]f)
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.
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
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.
known, but the magnitude in the system under investigation is not revealed in the literature.
10
CHAPTER II
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.
"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 Gerald K.
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.
12
CHAPTER III
EXPERIMENTAL PROCEDURES
^'
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.
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).
tion was diluted with water and methanol such that the solution was 50/50
methanol/water.
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.
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.
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.
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.
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.
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.
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
17
suits. When the flasks were removed, the fibers were withdrawn and placed
in a beaker where they were rinsed with methanol.
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.
About 30 fibers
18
*S
19
CHAPTER IV
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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28
exhausted.
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 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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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.
33
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function of Dt/r . The relationship between C^/Cco and Dt/r was also
presented graphically.
37
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
all the data points in Table 3 were easily determined and are presented
in Table 6 in the Appendix.
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
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
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
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?
-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.
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.
42
Because
T$
43
CHAPTER VI
RECOMMENDATIONS
In this work the biphenyl and the dye were simultaneously added
to the dyebath.
?S
The literature
4A
APPENDIX
-v1
45
Table 2. Calculations
B = A-
C = V (c - A_Ll)
w
^
a
46
Table 3.
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.
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 0
00 ENT EXT
05
Oa
10
15
la
5
CHG SON
1
0
7
FMT
YTO
STOP
UP
1
0
7
FMT
YTO
2
UP
UP
1
0
8
FMT
PI
STOP
UP
1
0
8
20 FMT
25
2a
30
35
3a
YTO
3
UP
UP
1
0
9
FMT
PI
STOP
UP
1
0
9
FMT
YTO
CLR
1
1
1
FMT
YTO
2
FMT
GTO
1
0
40 7
45
4a
50
55
5a
FMT
PI
UP
1
0
8
FMT
PI
X
1
0
9
FMT
PI
UP
X
DN
+
1
CHG SGN
X
1
1
0
FMT
YTO
1
60 FMT
80 IF X<Y
GTO
X
DN
DN
65 UP
UP
1
1
0
6a FMT
PI
X
DN
5
d
1
1
85 1
FMT
PI
UP
4
8a CHG SGN
X
1
+
90 UP
DN
DN
END
70 eX
XEY
DIV
UP
DN
75 1
1
1
FMT
+
7a RDN
ENT EXP
6
CHG SGN
49
Table 4.
PROGRAM 1
00
05
Oa
10
15
la
1
0
1
FMT
PI
UP
1
0
6
FMT
YTO
1
0
0
FMT
+
FMT
PI
UP
CLX
XEY
UP
3
FMT
GTO
RDN
1
0
20 3
FMT
YTO
1
0
25 6
FMT
PI
UP
1
2a 0
0
FMT
40 YTO
1
0
3
FMT
45 PI
UP
lYl
30 FMT
DIV
1
4a 0
4
FMT
PI
50 UP
PI
UP
CLX
XEY
35 UP
3
FMT
GTO
RDN
3a 1
0
4
FMT
DIV
DN
X
55 CLX
IF X<Y
7
5
1
5a 0
6
FMT
PI
lYl
60 UP
1
0
CHG SGN
DIV
65 1
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 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.
51
-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
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
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.
3.
4.
5.
6.
7.
)
8.
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.
11.
12.
13.
Vogel, T., De Bruyne, J. M. A., and Zimmerman, C. L., American Dyestuff Reporter, 47, 581 (1958).
14.
15.
16.
Felchtmayr, F., and Wurzi A., Journal of the Society of Dyers and
Colourlsts, 77, 626 (196^).
55
17.
18.
19.
20.
21.
22.