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3733-3746 (1973)
synopsis
The accelerated rate of diffusion of disperse dyes into synthetic fibers caused by various
dyebath additives (“carriers”) has been correlated with their plasticizing action. The
rate of change in length of Acrilan filaments with temperature under dyebath conditions
enabled the effects of the carrier on the Toof the filaments to be measured, and the results
for different concentrations of carrier a t one temperature could be superimposed on a
common curve by employingsuitable shift factors. The shift factors, BS well as the vari-
ations of the diffusion coefficients of dyes with temperature and carrier concentration,
bothmatched a WLF relationship, confirming that the dyeing process is controlled by the
segmental mobility of the polymer. Indirect experimental evidence suggests that the
same relation will describe the effect of carriers on the dyeing of poly(ethy1eneterephthal-
ate) substrates with disperse dyes.
INTRODUCTION
Earlier diificulties associated with the coloration of synthetic fibers made
from polyacrylonitrile and poly(ethy1ene terephthalate) , using nonionic
dyes, were due to the unacceptably slow rate of diffusion of the dyes into
the fiber. These practical problems were eventually overcome by ap-
plying the dyes in specially developed pressurized machines which operate
at temperatures greater than 100°C, or by the addition to the dyebath of
organic compounds such as phenols, primary amines, hydrocarbons, and
esters, which have the effect of increasing the rate of diffusion of the dyes
in the fibers to an acceptable level of temperatures below 100°C. The
latter compounds are referred t o as “carriers” and their mode of action is
discussed in this report.
Various aspects of the action of “carriers” have already been examined
in an attempt to elucidate the mechanism by which they operate and
various theories have been put forward. Some workers’ suggest that the
enhanced rate of dyeing is a result of an increase in the low solubility of the
disperse dyes in the dyebath, while others2 claim the action of water-in-
soluble carriers to be due to the formation of a surface layer of carrier
around the fiber in which the dye is very soluble and from which movement
into the fiber is rapid due to the intimate contact between dye and fiber.
It has also been noted that some carriers cause swelling of the fibers, and
this leads to the theory that a more vigorous movement of the fibrous
3733
@ 1973 by John Wiley & Sons, Inc.
3734 INGAMELLS, PETERS, AND THORNTON
where aT is the shift factor for the viscoelastic properties of the fiber, A and
B are constants, and D is the diffusion coefficient at the temperature indi-
cated by the subscript.
Adherence of the variation of the diffusion coeEcient with temperature
to eq. (1) demonstates that the segmental mobility of the polymer chains,
which controls the viscoelastic properties, also controls the movement of
dye through the substrate. Consequently, eq. (1) should also be applicable
when the glass transition temperature is reduced by the incorporation of
CARRIER DYEING 3735
1.0
L
LO
1.0
X Phenol
A 2091, Phenol
0 3091, Phenol
I
I.o - 25
I
Temperature, OC
TABLE I
Glass Transition Temperatures of Acrilan
Filaments When Immersed in Different Solutions
Concentration,
Solution g/l. I
Water - 57.0
Phenol 10 46.0
Phenol 20 35.0
Phenol 30 25.0
Toluidine 2.3 43.0
Ni trobenzene 1.0 52.5
Nitrobenzene 2.0 49.5
Dimethylformamide 10 53.0
TABLE I1
Effect of Temperatureon the Partitionof Phenol Between Acrilan and Water
~~ ~~ ~
I.5-
-
c-
e
1 Io9/1 1 --I#
1
0
P
-W 0 Woter
+ 591, Phenol
/JO/
J0
A 10g/lPhcnol
0 2 0 g / 1 Phenol
X Jog/, Phenol
0 10. I I
0 2
CARRIER DYEING 3739
TABLE III
Shift Factors Used to Superimpose the Rate of Elongation Onto a Common Curve
Concentration of phenol in Shift factor
solution, g/l. log10 aT
0.00 0
5.00 -1.46
10.00 -2.04
20.00 -2.64
30.00 -3.25
/
x
7 -9
.-
C
E
N
t
d
0
-v -
0
1
0
P 0
+
Water
Sg/t phenol
A phenol
-11. P X
0
0
0
0
lsgh phenol
2 . 3 9 ~Toluldenc
2911 Nitrobenzene
lgiL Nitrobenzene
10g/l Dimcthylformamidc
I I
10 20 30
(T-Tg)
Fig. 3. Effect of different carriers on the diffusion cm5cient of phoazobenzene in
Acrilsn fiber at 7OoC, expressed aa a function of T - Tg.
CARRIER DYEING 3741
-
CI Disperse Red 1
The appartus used was similar to that described elsewhere.22 The
samples of filament (0.1 g) were contained in small, stainless steel wire
cages secured on a stainless steel rod.
The rate of dyeing was plotted and the diffusion coefficient calculated
according t o Hill’s equation for diffusion into a semi-infinite cylinder.2s
The radius of the 3-denier filaments was calculated assuming a density of
1.17 g/cc and that the adsorption of phenol did not result in a change in the
radius of the fiber.
Dyeing Poly(ethy1ene Terephthalate) Film
Samples of poly(ethy1ene terephthalate) film, secured in stainless steel
frames, were dyed in a infinite dyebath after a pretreatment a t 95°C for 24
hr in a blank dyebath of appropriate composition. Vigorous agitation of
the dyebath during dyeing ensured that the necessary linear relationship
between C,and t’/*was maintained. After dyeing, the dyed films were
weighed, dissolved in metacresol of orthochlorophenol, and the dye content
estimated colorimetrically. The diffusion coefficients were determined
from the rate of dyeing data using McBaine’s equation.
DISCUSSION
The concept upon which this investigation into the mechanism of carrier
dyeing is based, relates the increase in the rate of dyeing to the additional
free volume which the carrier introduces into the fiber. The associated
increase in segmental mobility of the polymer chains in the fiber may then
3742 INGAMELLS, PETERS, AND THORNTON
lT-19)
Fig. 4. Acrilan filament: matching the diffusion data and the physical properties to the
WLF equation, Eq. (l), using A = 10.8 and Y = 28.5.
TABLE IV
Effect of Phenol on the Activation Enthalpy ( - A H ) for thc Diffusion of
pAminoazobenzene Into Acrilan in the Presence of Phenol
~~~ ~-
Calculated value
Phenol concentration, g/l. of AH*, kcal/mole
0 72.5
5 61.4
10 54.4
15 46.0
20 44.2
Dyeing of Poly(ethy1eneTerephthalate)
Unfortunately, the mechanical methods used for the determination of the
Toof Acrilan filaments in a dyebath were not feasible for poly(ethy1ene
terephthalate) in film form. Nevertheless, it was possible to produce in-
direct evidence that the mechanism of dyeing for poly(ethy1ene terephtha
late) was also dependent upon segmental mobility. This was accom-
plished by assuming that the lowering of the T,caused by the incorporation
of phenol in the dyebath was directly proportional to the concentration of
phenol in the bath and then matching a plot of log D againstphenol con-
centration to a curve of log aT against T - T, calculated using eq. (1).
Once the appropriate scale for the concentration of phenol had been chosen,
only a vertical shift of the experimental points was needed to fit them on to
the WLF curve (Fig. 5).
I 1 I
20 40
(T-Tg) OC 6o
I I I
0 20 40
phenol concentrotfon in dyeboth (g/Kg) of solution
Fig. 5. Poly(ethy1ene terephthalate)film: matching the diffusion data for different
dyes to eq. (1) using A = 10.8, B = 28.5.
CARRIER DYEING 3745
TABLE V
Comparison of Predicted Values of T,for PlasticizedPoly(ethy1ene Terqphthalate) Film
with Experimentally Determined “Dyeing Transition Temperatures”
Transition temp., “C
Concentration of
phenol in the Predicted Experimental
dyebath, g/l. values values
p-Aminoazobenzene 0.0 70 70-75
9.9 60 55-60
19.6 50 46-5 1
29.1 41 3641
CI Disperse Orange 3 9.9 60 56-62
CI Disperse Red 1 19.6 50 45-50
CONCLUSIONS
The evidence presented confirms that the diffusion of disperse dyes into
Acrilan filaments is controlled by the segmental mobility of the polymer
chains and that in the presence of carriers, the segmental mobility is en-
hanced due to the associated increase in the free volume of the system.
Indirect experimental evidence suggests that even with a highly crystal-
line poly(ethy1ene terephthalate) substrate, the dyeing process, in the
presence of carriers, may be expressed by a WLF relationship, suggesting
that the dyeing process is governed by a small proportion of the polymer
material not involved in a highly ordered molecular arrangement.
References
1. C. L. Zimmerman, I. M. Mecco, and A. J. Carlino, Amer. Dyestuff Rep., 44, 296
(1955).
2. T. Vickerstaff, Hexagon Digest, 20 (No. 7), (1954).
3. V. S. Salvin, Amer. Dyestuff Rep., 49,600 (1960).
4. V. S. Sdvin, ibid., 53,64 (1964).
3746 INGAMELLS, PETERS, AND THORNTON