Appendix A

Problems With Fiber Reactive

Dyeings Not Repeating -
. A Look at Five Typical Cases

By:
Brent Smith,
Keith Beck, and
Tod Uadderra
College of Textiles, NCSU
Raleigh, NC

Reprinted with permission f”

American Dyestuff Reuorter (September 1990)
 Problems With Fiber Reactive
Dyeings Not Repeating-
A Look At Five Typical Cases
- ! By Brent Smith, Keith Beck,
Tod Madderra
School of Textiles, N.C.S.U.
Raleigh, NC

Introduction igure 1-Data acquisition system. demonstrated by our real-time data

While it’s a fact that the fiber reac- acquisition system.
tive dyeing of cellulosic materials is
of great commercial importance, it is
also one of the most difficult batch Case I: A “Normal” Dyeing with
prdcesses to control. As part of a Triazines
Consortium for Research in Apparel, Dyeings known to have good pro-
. . Fiber and Textile Manufacturing duction history generally use dye
(CRAFTM), the authors have de- combinations with similar exhaus-
: I veloped a system for acquiring real- tion and substantivity characteris-
time on-line data from batch dyeings. tics. A typical case is shown in Figure
Actual production dyeing problems 2 for a combination of two mono-
can now be diagnosed in our own chloro triazine dyes, Orange 13 and
laboratory using data from this data Violet 1. The kinetics of exhaustion
acquisition system. This information as well as the substantivity of the
’. I is a great asset to both laboratory
and production dyers in establishing
dyes clearly produce similar exhaust
curves up to the time of alkali addi-
dye recipes and procedures which, tion (25 minutes). Addition of alkali,
due to their inherent design, repeat which in this case produces essen-
consistently and resist shade varia- tially no further exhaustion of the
tions. le dye procedures and recipes. bath, initiates the reaction phase of
The data acquisition system is de- To control fiber reactive dyes, onc the dyeing. The overall reaction rate
scribed in more detail elsewhere’.*. lust consider many important fac is controlled by several factors: con-
Data from this system include infor- )rs, such as diffusion, reactivity anc centration of dye present, concentra-
mation about dye concentration in Jbstantivity. In addition, there arc tion of nucleophile (i.e., cellulose or
the dye bath at any time, conductiv- nportant differences between type! hydroxyl anions), and reaction rate
ity, pH and temperature. In addition ‘hich must be taken in account constant. The fixation efficiency de-
to diagnosis of dyeing problems, hese differences are graphicall) pends on the relative reaction rate of
. -. .
these data can be used for other pur-
..
. . poses such as modelling and study-
ing dyeing processes, and real time igure 2-Dye exhaustion vs. time-Violet 1 and Orange 13.
. .
process control.
The system consists of sensors to
detect pH. conductivity, temperature,
dye and chemical concentrations in
the dyebath on a real time basis; sig-
nal- conditioners; micro and mini
computers; displays and peripherals,
as shown in the block diagram in
Figure 1. We have used this appa-
.. ratus to examine dyeing recipes and
procedures with exceptional produc-
tion history (good and bad). Data
from such dyeings show exactly why
some dyeings “went wrong,“ and
also indicate how to improve the per-
formance of these shades in terms of I

The dye with cellulose compared to
water, which in turn depends on the
relative amounts of dye in the fiber
and in the dyebath respectively. Note
that, at the time of alkali addition, ex-
haustion has essentially reached a
steady state, thus the timing of the
alkali addition is not critical. Also,
the exhaustion is moderate to high
for fiber reactive dyes-about 60% at
the time of alkali addition. Under
these conditions, reaction of the dye
with the fiber occurs reproducibly
and efficiently.
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~~~
Case II: Triazine Dyes of Differe
Substantivity
Figure 3 shows another combin
tion shade of two monochloro tri
zine dyes, Yellow 135 and Blue 5. I
in case I, exhaustion of each dye hi
reached a relatively steady state pril
to alkali addition. But in this cas
the yellow component is nearly 80
exhausted at the time of alkali adc
tion, compared to just over 40% fl
the blue.
This has important practical imp
cations to the dyer because the re1
. ?xact,since any deviation in the tim-
The Results
Improved productivity-no straight-
ening is required; and this design
feature costs less than specialized
static dye machines.
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~ lecome highly path dependent and
IY
P132a
American Dyestuff Reporter
tive efficiency of fixation of the two
dyes will depend on their relative r e
action rates which in turn depend on
their relative concentrations in the
fiber. Even with all other factors (e.g.,
reactivity of the dyes) being equal,
the fraction of blue dye in the fiber is
about half as great, giving much
lower fixation efficiency and more
hydrolysis. Thus, the “hot patch”
taken before washing will contain
much more unfixed hydrolyzed blue
dye, which will wash out and the
shade will wash down to a more yel-
low cast. The dyer will be faced with
a hot patch decision requiring con-
siderable judgment as to how much
the shade will change on washing.
Case 111: Alkali Added Too Soon
Figure 4 shows a combination of
!wo dichloro triazine dyes, Yellow 7
and Blue 4. Although alkali was
added after the same time (25 min-
Jtes) as in the two previous cases,
:he data clearly indicate that, in this
:ase, dye is still exhausting. There-
‘ore, the timing of the alkali add has
f great effect upon the ultimate
shade. If alkali is added slightly ear-
ier than specified, more dye will re-
nain in the bath and thus relatively
ess of the dye will be fixed. Control
If the alkali add must be almost
ng of alkali addition or even at the
ime it takes to circulate the alkali
hroughout the dyeing machine
:ould well produce shade variation.
lther factors (e.g., fabric prepara-
ion, temperaturehate of rise, salt
:oncentration) might well advance
)r retard dye exhaustion slightly, and
hereby significantly affect shade re-
jeatability.
In cases I and IIexhaust to a steady
tate existed prior to alkali addition.
:or those processes, ultimate dye
lxhaustion depends primarily on the
inal conditions in the exhaust
ihase, e.g.. temperature, salt con-
entration and liquor ratio. Mo-
nentary fluctuations do not substan-
ially affect the final exhaustion. But,
i this case, dye continues to ex-
laust after the addition of alkali, giv-
i g simultaneous exhaustion and re-
ction. The dyeing results then
ny fluctuation in the factors previ-
usly mentioned is likely to result in
poor shade repeat or unlevel dye-
ig. This is a higher risk situation and
?quires more careful control to
chieve good shade repeats.
0 September 1990
 a
. --
Gigure &Dye exhaustion vs. time-Yellow 135 and Blue 5. Figure &-Dye exhaustion vs. time-Yellow 7 and Blue 4.

YOllOW 135 -
--- Yellow 7 -
0
BlrU.5 Blue4 --- a- --- -__ I

0 10 20 30 40 50 60 70

Tlm (Minuter)

:igure -ye exhaustion vs. time-Blue 3R and Blue 21 Figure &Dye exhaustion vs. time-Blue 19 and Red 180.

,
0
.-

I
0

ElW33R - T-
---
Elm21 --- Blue19
Red180 -
m
0 .

0 10 20 30 40 50 60 70

T I M (Mlnuter)

:ase IV: Vinyl Sulfones of Different

leactivlty
Figure 5 shows the performance of
combination of two sulfatoethyl
ulfone dyes, Remazol Blue 3R (no
.I. Number) and Blue 21. (Note-
ue to pH sensitivity of the dyes in
lis reme, a scale factor adjustment
was made at the time of addition of
ilkali.) These dyes have very compat-
ble exhaustion prior to alkali addi-
ion and reach a fairly steady state.
3ut, in contrast to the triazine dyes
fescribed in the preceding, these
fyes commence exhaustion again

42

don similar
y!, .-_-
to cases Ill and IV. Thi:
m u i r e s careful control of many fac
tors, e.g.. temperature and alkali ad
dition, to achieve good shade re
peats and level dyeings.
Conclusions
Fiber reactive dye formulation:
and procedures vary greatly in theii
performance. Even if dyers had e s
sentially perfect control over theii
processes, shade variations would
still result from uncontrollable fac.
tors such as fiber maturity, ambienl
conditions, water quality, dye and
chemical variances. Therefore, it is
important t o devise dyeing protocols
which a l e highly resistant to varia-
tions. Situations which lead to inher-
Selecting Dyes.. . 3) Houser, Nelson. Direct Dyes. Clemson
:Continuedfrom page 751
~ u m e rthe diversity of product mix
lor styling and differentiation.000
‘ I ) J. Gordon Cook, Handbook of Textile
=ibers2. Man-made Fibers, p. XXVIII.
2) C. H. Giles, The Theory of Coloration
)f Textiles, p. 41.
leferences
1) Cook, J. Gordon. Handbook of Textile
fibers, 1. Natural Fibers, 2. Man-made
Fibers, Durham, Merrow, 1984.
AATCC, Dyeing Primer. Research (7)COLOR INDEX. Third Edition. York-
Triangle Park, AATCC, 1981.
2) Giles, C.H. “Dye-Fibre Bonds and Their
Investigation.” The Theory of Coloration (8) Weigle. Palmy. Ancient Dyes for Mod-
of Textiles, West Yorkshire, The Dyers
Company Publications Trust, 1975.
News
[Continued from page 141
Acquisition Agreement
C r o m m n & Knowles Corp. Stam-
d, CT. recently announced i t has
ned a definitive agreement to ac-
uire the business and certain asse.ts
f Atlantic Industries, Inc., a Nutley,
ased producer of dyes for the
e industry.
hough details of the proposed
action were not revealed, C&K
mber 1990 0 American Dyestuff Reporter
I
ently unstable shade repeats can b
identified by examination of dyebat The Textile
data. Dye recipes and procedure
which are high risk can be identifie1 Industry’s
in advance using real time dyebatl
data acquisition. Air
In these studies the authors suc
cessfully identified several specifit
Pollution
-Solution
situations leading t o higher risk o
poor shade repeats in fiber reactivc
dyeing as demonstrated by thesc
_-----
- - -
---.
cases. A few of the most prominen
problems included (a) selection o
1 -
dyes of different affinity o r reactivit!
and (b) addition o f alkali toc
soon. 0 0 0
leferences
1) Madderra. Tod. Development of a Rea
Time Data Acquisition System for Batct
Dyeing, Master’s Thesis, NCSU College
of Textiles, 1990.
2) Beck. Keith, Madderra. Tod and Smith,
Brent. Real-Time Data Acquisition in
Batch Dyeing, in press, Proceedings oi
the 1990 AATCC National Technical Photo: Third precipitator on the far
Conference and Exhibition. right is shut off to show the difference
in smoke emission compared to the
other two operating units.
POLTTUBE by
University, Continuing Education Sym- BELTRAN
posium on ”Dyeing Fundamentals.” Wet Electrostatic
September, 1989. Precipitator
1) “Modest Increases in Production and
Earnings Offset by Imports,” Textile
Operates wet or dry
Chemists and Colorist. Research Trian-
gle Park, February 199ONol. 22, No. 2. High Collection efficiency at
p. 2. high veloclty
“2.4 Billion and Growing,” ATI, April Low energy use
1988, p. 67. Rigid electrode
i) Park, J. A Practical Introduction to Yarn Economical operation -
Dyeing, West Yorkshire, The Society of low pressure drop
Dyers and Colourists, 1981. Fabricated from corrosion
i) Trotman, E.R. Dyeing and Chemical resistant materials such as:
Technology of Textile Fibers. Sixth Edi- Fiberglass Reinforced
tion. New York, John Wiley and Sons. Plastic
1984. Upgrade scrubber systems
increasing efficiency and
shire, The Society of Dyers and Colou- reducing horsepower.
rists. 1971.
ern Weavers. New York. Watson-Gup- Eliminates Smoke,
till, 1974. Odor, Particulate and
Fumes from Wet
Processing Operations.
Beltran with over 500
installations worldwide, is the
textile industry’s most
experienced supplier of air
pollution control equipment.
did announce that the acquisition
would be made for cash and is ex-
pected to be completed in the third
quarter of 1990.
BELTRAN ~~
BELTRAN ASSOCIATES INC.
Atlantic Industries, Inc., is an indi- 1 133 East 35 Street,
rect, wholly-owned subsidiary of Brooklyn, New York 11210
Great American Management and In- 71 8-338-331 1
vestment, Inc. FAX: 71 8-253-9028
[Continued on page 1061
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